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Synthesis and metal cation-promoted hydrolysis of (hydroxyimino)phosphonoacetic acid derivatives

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Synthesis and metal cation-promoted hydrolysis of (hydroxyimino)phosphonoacetic acid derivatives

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Content SYNTHESIS AND METAL CATION-PROMOTED HYDROLYSIS OF (HYDROXYIMINO)PHOSPHONOACETIC ACID DERIVATIVES BY Mari Fujimoto A Thesis Presented to the FACULTY OF THE GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree Master of Science (Chemistry) May 1997 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. UNIVERSITY O F S O U T H E R N CALIFORNIA T H E G R A D U A T E S C H O O L U N IV E R S IT Y P A R K LO S A N G E L E S . C A L IF O R N IA 8 0 0 0 7 This thesis, written by under the direction of hj^Jd..„Thesis Committee, and approved by all its members, has been pre sented to and accepted by the Dean of The Graduate School, in partial fulfillment of the requirements for the degree of Jfc l& ri h Q jx d L Z s . D*4M Date. THESIS COMMITTEE R eproduced with perm ission of the copyright o w n e r Further reproduction prohibited without perm ission TABLE OF CONTENTS CHAPTER ABSTRACT I INTRODUCTION H RESULTS AND DISCUSSION A. Synthesis of Bis-DCHA+ Salts of (£)- (Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid B. Synthesis of Anilinium salts ofp-Nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate C. Fragmentation of (E)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid D. Hydrolysis chemistry of anilinium salts of /j-nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate ID EXPERIMENTAL SECTION A. Preparation of Bis-DCHA+ Salts of (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (1) Preparation of (dimethoxyphosphinyl)acetic acid (MFJI-78A) (2) Preparation of Trimethyl a- (Hydroxyimino)phosphonoacetate via nitrosation of dimethyphosphonoacetylchloride followed by methanolysis (MFJI-8 8 A) (3) Preparation of sodium salt of methyl (Hydroxyimino)- (hydoxymethoxyphosphinyl)acetate (MFJI-89B) (4) Preparation of Bis-DCHA+ Salt of (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)- acetic acid via hydrolysis of sodium salt of Methyl (Hydroxyimino)(hydroxymethoxyphosphinyl)acetate (MFJI-93B2) (5) Preparation of (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)- acetic acid(MFJI-103A) R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. B. Preparation of Anilinium p-nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate (1) Preparation of p-Nitrophenyl (dimethoxyphosphinyl)- acetate(MFJI-l 14F) (2) Preparation ofp-Nitrophenyl(dimethoxyphosphinyl)- (hydroxyimino)acetate (MFJI-115C) (3) Preparation ofp-Nitrophenyl (dihydroxyphosphinyl)- (hydroxyimino)acetic acid (MFJI-10C) (4) Preparation of Anilinium p-nitrophenyl (dihydroxyphosphinyl)(hydroxyimino)acetate (MFJH-11A) C. Fragmentation of (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (1) pH dependence of the stability of (E)-(Hydroxyimino)(hydroxymethoxyphosphinyl) acetic acid (MFJI-103A) (2) Stability of the Bis-DCHA salt of (£)-(hydroxyimino)(hydroxymethoxyphosphinyl) acetic acid in different solvents D. Fragmentation of p-Nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate (1) pH dependence of the stability of p-nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate (2) Mg2+ ion metal effects on the hydrolysis of p-nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate at pH=8.5 (3) Ca+ ion metal effects on the hydrolysis of p-nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate at pH = 8.5 (4) Mg2 + ion metal effects on the hydrolysis of p-nitrophenyl acetate at pH = 8.5 (5) Ni2 + ion metal effect on the hydrolysis of p-nitrophenyl (E)-(dihydroxyphosphinyl)- (hydroxyimino)acetate at pH = 7.1 of the copyright owner. Further reproduction prohibited without perm ission. (6 ) pH dependence of the hydrolysis of p-nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate (7) pH dependence of the hydrolysis of p-nitrophenyl (£)-(dihydroxyphosphinyl)- (hydroxyimino)acetate with Ni2 + ion metal effect (8 ) pH dependence on the hydrolysis of 54 55 CONCLUSION APPENDIX A APPENDIX B APPENDIX C (hydroxyimino)acetate with Ni2 + ion metal effect 56 N 58 NMR SPECTRA 60 MFJI-78A A1 61 MFJI-8 8A A2-A4 62 MFJI-89B A5-A7 65 MFJI-93B2 A8-A10 6 8 MFJI-113B A11-A12 71 MFJI-114F A13-A14 73 MFJI-115C A15-A17 75 MFJH-11A A18-A20 78 Hydrolysis of MFJII-11A A21-A22 81 KINETIC DATA 83 Summary of rate constants BI-B2 84 pH-Dependent experimental data B3-B21 8 6 Ca" Saturation data B22-B30 105 Mg2 + Saturation data B31-B39 114 N i2 + Saturation data B40-B45 123 p-Nitrophenyl acetate data B46-B47 129 Standard curve for p-nitrophenol data B48-B52 131 Buffer base catalysis data B53 136 Nonlinear regression data analysis B54-B64 137 ESTIMATION OF pKa FOR MFJD-11A 148 tv R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ABSTRACT Two derivatives of (£)-(hydroxyimino)phosphonoacetic acid (£-troika acid 1), (£)-(hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (P-ester 2) and (E)-p- nitrophenyI(hydroxyimino)(dihydroxyphosphinyl)acetic acid (C-ester 3), have been synthesized and evaluated for phosphorylation capabilities under different conditions. Both esters (2 and 3) are activated by acid, base, or heating to undergo ultimate fragmentation, resulting in the formation of a putative metaphosphates intermediate which phosphorylates protic solvents. However only C-ester 3 phosphorylates (greater than 80%) at neutral pH whereas with the P-ester, acid-dependent isomerization is favored, resulting in a low yield of solvent phosphorylation. In addition, aided by conjunction of chelating groups (oxime and phosphonate), in C-ester 3, the hydrolysis of can be significantly enhanced by divalent metal cations. For example, Ni2 + ions catalyzed the hydrolysis by 700-fold at neutral pH (50 °C). Thus, C-ester 3 can serve as a metal cation-activated phosphorylating agent under mild aqueous conditions. OH O N' O OH O N' O HO^II I I I I / P - C - C - O H HO Troika acid 1 P-ester 2 C-ester 3 v R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. CHAPTER I INTRODUCTION A molecule containing the phosphate functional group dominates biological systems as one of the most important intermediary metabolites. Similarly, phosphorylation, the transfer of phosphoryl group (-PO3 ), makes up a large class of en2ymatic reactions which are central to biological metabolism and biosynthesis. One of the important aspects of phosphorylation is to provide the thermodynamic driving force for reactions which are otherwise endergonic. For instance, chemically unreactive substrates are often enzymatically activated by forming phosphate esters with oxygen of acyl, or an alcohol group from good chemical phosphorylating agents, before they can be used for biosynthesis. The premier biological phosphorylating agent is adenosine triphosphate (ATP), whose phosphoric-anhydride linkage acts as a reactive donor of the phosphoryl group. Once such acy 1-phosphate intermediates are formed, the transfer of an acyl group to nucleophilic acceptors can be achieved with displacement of the phosphoryl group. 1 Phosphorylation can also couple thermodynamically with unfavorable biological processes, such as active transport, in which the cations are pumped against their concentration gradients. In addition, phosphorylation can control the concentration of hydrophobic molecules in a cell by increasing their water solubility with phosphate linkages, thereby preventing them from leaving the cell through the membrane. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Because of this significant involvement of enzymatic phosphorylation in regulatory processes, there is considerable interest in obtaining chemically synthesized phosphorylating agents which may have substantial economic and clinical potential. As mentioned above, many phosphorylating agents used in biological phopsohrylation all make use of the favorable properties of phosphoric anhydrides. These compounds are kinetically stable in water since they are protected by negative charges, yet due to their thermodynamic instability, they can drive a phosphorylation reaction to completion in the presence of a suitable catalyst.2-3 For synthetic organic chemistry, however, the use of such phosphoric anhydride intermediates are not practical due to their low reactivities (poor leaving groups in SnI and Sn2 reactions or in elimination) in the absence of a catalyst such as an enzyme. Therefore, in order to perform phosphorylation without a catalyst, it is necessary to synthesize phosphorylating agents which produce reactive phosphorylating intermediates such as monomeric metaphosphate.2 The formation and the reactivity of monomeric metaphosphate has attracted much attention over the years due to its role as a highly reactive, electrophilic phosphorylation intermediate.4 Although there has been a vigorous debate over the free existence of monomeric metaphosphate in water, Westheimer and others have demonstrated convincing evidence for the generation of monomeric metaphosphate species as well as their biological importance.2-4-5-6 Such unstable intermediates can be generated, among other ways, by the chemical hydrolysis of phosphate-monoester monoanions which proceed by a dissociative mechanism. The maximum rate of the hydrolysis occurs at pH 4. It is postulated that the process involves either synchronous 7 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. protonation of the leaving group or a fast preequiliblium protonation followed by the rate determination step. 1 HO- pH = 4 :P — OR O O ^ 1 1 H / P — OR O + PO 3' + ROH In the presence of water or other nucleophiles, such as alcohol solvents, monomeric metaphosphates rapidly yield orthophosphates. PO3' + h 2o ------------------- H2 P 0 4' In the presence of aprotic solvents, they immediately polymerize to P-O-P derivatives.7 PO 3' P —O— P The other example is by the Conant-Swan fragmentation of P-halophosphonates in which methyl metaphosphate and metaphosphate are generated by base.8 0 Ph H-CCL " 1 Base ^ / P — CBr— CHBr-CHj ------------- BrC6I^C=CHCy + Br' + CHjOPQ 'O O Ph + -n 1 1 1 Base / P — CBr — CHBr— CHj ------------ BrC6l-^C=CHC^ + B r '+ PQ' 'O CH3OPO2 + H20 CH30 P 0 3H' + H+ PQ' + hfeO H2P Q The main disadvantage of these metaphosphate precursors, or many others, is that these compounds can only generate monomeric metaphosphate under harsh R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. conditions, either strongly acidic or basic, which would severely limit the application of such phosphorylating agents. Present studies have focused their efforts to design precursor molecules which will generate monomeric metaphosphate anions under physiological conditions. Recent investigations on the generation of metaphosphate have found that a- hydroxyiminophosphonate derivatives are precursors to monomeric phosphates over wide ranges of pH and thus serve as potential phosphorylating agents.9,10-11 In addition to their metaphosphate generating capabilities, these derivatives have unique metal binding properties due to the combination of both oxime and phosphonic bifunctionalities which could influence greatly in their course of reactions. Leading researchers who have been working on phosphorylating agents using hydroxyiminophosphonic derivatives include Eli Breuer and his group. Breuer reported that a-hydroxyiminobenzylphosphonic acids undergo fragmentation to benzonitrile and orthophosphate via monomeric metaphosphate with \\n 0.2-2 hours at pH 1.5- 9.2. 12 OH ✓ HO M tli Fast fragmentation Fast phosphorylation HO ° ] > — C— Ph--------------------------- ► R -C = N + P O j' ---------------------------------- ► ^ P — OR HO Mild conditions Solvent ROH FIO The main problem in using this type of compound as a phosphorylating agent is that it is highly unstable and undergoes spontaneous fragmentation over wide ranges of pH, therefore, structural modifications must be required to control its fragmentation process. Consequently, Breuer and his group have made several attempts to modify this parent compound (a-hydroxyiminobenzylphosphonic acid) to make more stable precursors, 4 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. from which the parent compound, or its analog, can be reproduced under certain activation conditions. One of his attempts was to add a simple alkyl group to the phosphonate. However, unlike dianions of this type, which exhibit a tendency to undergo fragmentation, simple monoesters were too stable to undergo fragmentation even after 30 hours of refluxing in acetonitrile. As a result, a following attempt added polyhaloalkoxy groups on phosphonate with the assumption that they would exert an influence on P-C bond breaking through their electron-withdrawing effect. The contribution of the hexavalent phosphorus resonance form was much more significant for dianions compared to the simple monoester, resulting in higher electron density on the phosphorus, which in turn would assist in C-P bond breaking. 13 Trihaloethyl and hexafluoro-2 -propyl(a-hydroxyiminobenzyl)phosphonates are such examples. 1 3 o n'° H CX3CH2O.11 || Heat ROH CXjCHzO. || > — C— Ph ----------- PhCN* CXzCHjjOPQ, ♦ OH ----------------------- > - O R HO Activation HO Phosphorylation Breuer demonstrated that both compounds undergo fragmentation through generation of alkyl metaphosphate in both refluxing aprotic solvent (MeCN) and protic solvents (EtOH or 2-PrOH). However, no fragmentation in refluxing water, or MeOH (100 % of starting materials were recovered) was observed which they explained as the result of stabilization of starting materials by solvent effects. Recently, his group has developed precursors with 2 -cyanoethyl and p-nitrophenethyl ester as protecting groups for methoxyimino-phosphonates. 14 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. H OCHj xO C H j XH^ O N ■ H z C t Qj i ii Ph PhCN * POj" * OCHj X = CN, — Q - N Q 2 They have shown that these compounds can be activated by means of dealkylation to produce the parent compound under strong alkaline conditions, through /^-elimination with the respective formation of acrylonitrile and /7-nitrostyrene by-products. The following solvent phosphorylation can only be achieved by lowering the pH which facilitates fragmentation of the parent compound to metaphosphate. As previously mentioned, one of the main purposes in developing this type of phosphorylating agent is its potential use in the field of biochemistry or possibly medicinal chemistry. Therefore, it is important to activate such phosphorylating agents and perform phosphorylation in an environment that is compatible to the physiological conditions. In the context of continuing interest in hydroxyiminophosphonate derivatives, McKenna and Kashemirov have introduced (hydroxyimino)phosphonoacetic acid. "troika acid", as a new class of parent compound for phosphorylating agents. 15 One of the interesting characteristics of troika acids is their trifunctional system in which phosphonic, oxime, and carboxylic acid groups are connected to a common carbon atom. Troika a c id s OH HO N . HO O II — c OH HO N O II II OH HO HO E - isom er Z - isomer 6 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. The second characteristic is their geometric isomerism. The oxime OH group can be trans to the phosphonic acid group, (£-isomer) or cis (Z-isomer). The third characteristic is their stereospecific fragmentation process, especially the stereospecific fragmentation of E isomer which results in generation of metaphosphate under mild conditions. Because of the unique location of oxime in the system, its chemical behavior is controlled by the stereochemical status of the hydroxyimino moiety. The oxime hydroxy group can interact with either of its neighboring groups (phosphonic or carboxylic group), depending on E or Z orientation, therefore it will significantly influence the course of reaction taken by the molecules under specific conditions. While both isomers are stable at pH > 12, only E isomers undergo metaphosphate fragmentation and produce exclusively orthophosphoric acid (ti/2 < 10 min for H2O), consistent with solvent phosphorylation, whereas the Z isomers gave a product with an intact P-C bond, identified as phosphononitrile ((tj/2 - 15 min for H2O) at room temperature. Stereospecific fragmentation of troika acids O N O HO O l H II — C — C — OH / O H pH >12 NaOH sta b le o E - isomer pH <12 h 2 o pH > 12 sta b le o N o HO~ II II II — c — c — OH HO _ . NaOH Z - isomer pH <12 H 2 0 HO O HO^II ^ P — CN 7 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Finally, compared to other a-hydroxyiminophosphonate derivatives, troika acids have more flexibility in designing precursors due to the unique combination of its trifunctional system. Parent Troika Acid §H O N O HO ^ J l II || c C OH HO P-monoester isomer C-monester isomer Troika Acid Derivatives By simply changing the position of alkyl group (whether P-monoester or C-monoester) or the type of alkyl group used, activation conditions for precursors might be greatly adjusted to meet requirements for particular phosphorylating agents. 16 Especially for activation of C-monoesters to produce troika acids, it can be readily achieved not only by chemical hydrolysis, but also by enzymatic hydrolysis which are prevalent in nature. 16 Furthermore, such activation rates might be catalyzed or enhanced by exploiting the metal-binding properties of oxime and phosphate groups. 16 Recently, Dr. B. A. Kashemirov in the McKenna laboratory synthesized the first « troika acid derivative, the C-methyl ester of troika acid, and examined its fragmentation behavior in aqueous and non-aqueous solvents as well as in phosphorylating properties. 1 5 It was found that the C-methyl ester was stable at pH 2-8, at 22 °C. The activation conditions for the reproduction of parent compounds required ester hydrolysis 8 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. under alkaline conditions (pH 13-14) followed by a lowering in pH to generate metaphosphate for the further solvent phosphorylation. Thermolysis in protic or aprotic solvents was also used for activation. Fragmentation of C-methyl ester of troika acid by thermolysis in various solvents and alkaline hydrolysis o n"°o 11 Heat(79 - 84'c ) 1 b R 0H o OCHA* * O ^ H II II ROH H O . I I ^ , P — C — C — OCH 3 ----------------------------------------- ► [H P O 3 J----------------------------- ► ^ P — OR £ - isom er ** NaOH H2O (pH = 13-14, 25 *C) (pH = 6-7, RT) R = Et, i-Pr, t-Bu, H metaphosphate which is then phosphorylated by solvent. The second possibility is that the C-methyl ester (£-isomer) is directly attacked by nucleophile, here water, to produce orthophosphoric acid (associative mechanism). When the C-methyl ester (£-isomer) was refluxed in an aprotic solvent (acetonitrile), the products (81 %) with 31P NMR 5 = - 10 and -2 2 , were identified as polyphosphate, which is a known self-condensation product of metaphosphate. Similar experiments in protic solvents (1:1 EtOH-/-BuOH) gave a product ratio of ~ 2 : 1 ethyl phosphate : /-butylphosphate. Lack of selectivity of a primary alcohol versus the sterically hindered /-butyl alcohol is a well-known characteristic for a dissociative mechanism (metaphosphate). If, in fact, an associative- elimination phosphorylation mechanism took place then a much larger EtOH-t-BuOH selectivity ratio can be expected. Therefore, the above results strongly suggest a metaphosphate generating mechanism for the C-methyl ester (£-isomer). Although both R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. activation conditions (ester hydrolysis under alkaline condition or direct thermolysis) resulted in high phosphorylation rates with the C-methyl ester (> 80%), as with other precursors discussed earlier, its activation still requires strong alkaline conditions to produce the parent compound, (£)-troika acid. In exploring the further effect of structure on the chemical properties of troika acid derivatives, one of the main goals has been the synthesis of compounds which could be activated and perform phosphorylation under physiological conditions. 16 In the research presented in this thesis, the following two compounds have been synthesized and evaluated for their activation conditions as well as their phosphorylation properties under mild aqueous conditions. 1) P-monomethyl ester of troika acid. H 3 CO HO . OH O N O ^ I I (I II - C — C - OH (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid. 2) p-Nitrophenyl C-mono ester of troika acid .OH HO n m n HO (E)-p-Nitrophenyl (hydroxyimino)(dihydroxyphosphinyl)acetate 10 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. References 1 Walsh, C. Enzymatic Reaction Mechanisms; W.H. Freeman and Company: New York, 1979. 2 Westheimer, F.H. Science 1987,235, 1173-1178. 3 [a] Knowles, J. R. Anu. Rev. Biochem. 1980,49, 877; [b] Bachwald, S. L.; Hansen, D. E.; Hassett, A.; Knowles, J. R. Methhods Enzymol. 1982, 87, 279 [c] Calvo, K.C. J. Am. Chem. Soc. 1985, 107, 3690. 4 Westheimer, F.H. Chemical Reviews 1981, 81, 313-326. 5 Regitz, M.; Maas, G. Top. Curr. Chem. 1981, 97, 71. 6 Freeman, S.; Friedman, J. M.; Knowles, J. R. J. Am. Chem. Soc. 1987,109, 3166-3168. 7 Quin, L. D.; Bourdieu, C.; Quin, G. S. Tetrahedran Lett. 1990, 31, 6473-6776. 8 Westheimer, F. H. Phosphorus Chemistry 1981, 81, 65-68. 9 Breuer, E.; Karamon, R.; Goldblum, A.; M.;Gibson, D.; Leader, H.; Potter, B. V. L.; Cummings, J. H. J. Chem. Soc. Perkin. Trans. 1 1988, 3047-3057. 10 Breuer, E.; Schlossman, A.; Muhammad, S.; Gibson, D.; Chorev, M. Leader, H. J. Chem. Soc. Perkin. Trans. 1 1990, 3263-3269. 1 1 Breuer, E.; Mahajna, M.; Quin, L. D.; Quin, G, S. J. Org. Chem. 1991,56,4791-4793. 12 Breuer, E.; Karamon, R.; M.;Gibson, D.; Leader, H.; Goldblum, A. J. Chem. Soc. Chem. Comm. 1988, 504-506. 1 3 Mahajna, M.; Breuer, E. J. Org. Chem. 1993, 27, 7822-7826. 14 Mahajna, M.; Breuer, E. J. Chem. Soc. Perkin Trans. 1 1994 1847-1849. 1 5 Kashemirov, B. A.; Ju, J.; Bau, R.; McKenna, C. E. J. Am. Chem. Soc. 1995, 117, 7285-7286. 1 6 McKenna, C.E.; Kashemirov, B.A. In preparation. 11 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. CHAPTER II RESULTS AND DISCUSSION A. Synthesis of Bis-DCHA+ salts of (E)- (Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (MFJI-93B2) Trimethvl a-fhvdroxviminolphosohonoacetate via nitrosation of (dimethoxyphosphinvDacetvl chloride followed by methanolvsis fMFJI-8 8 A) Scheme 1 CHA^I? “ ° KOH C h .o J ' F I? H * ChbO^ff P ° S0C1: CH»CXI? P I? H 2SPC. 24 h H H H OHO '°H CH,° ^ _ £ J < L C| 1NOCI M U CH.O' I ► ^ p - c- c - o c h H ZCHfcOH CHiO 4 The synthesis shown in Scheme 1 was done according to a previously published method. 17 The nitrosation reaction was carried out first with the conversion of trimethylphosphonoacetate to the corresponding chlorocarbonyl compound in which the methylene group was activated, as the a proton became more acidic, for the subsequent electrophilic attack by the nitrosyl chloride. (Dimethoxyphosphinyl)acetyl chloride was prepared by the alkaline hydrolysis of trimethylphosphonoacetate with, an equimolar amount of KOH in methanol, which selectively attacks the methoxy carbonyl group without affecting the methoxy group on I f i the phosphonate group. After rotary evaporation, the corresponding potassium salt was 12 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. converted to (dimethoxyphosphinyl)acetic acid in 65% yield by acidification using ion exchange resign (Dowex 50WX8, H+ form) in methanol which was then refluxed with 20 % excess thionyl chloride in CH2CI2 for 3 hours, giving the corresponding chlorocarbonyl compound. The nitrosation was achieved by the addition of excess nitrosyl chloride in which the electrophilic nitrogen atom of nitrosyl chloride attacks the activated methylene group of the acid chloride, resulting in the initial formation of the corresponding nitroso group, which was then tautomerized to the oxime compound since as a rule nitroso compounds are stable only when there is no a hydrogen. 19 The progress of the reaction was followed by observing the disappearance of the doublet in 'H NMR (5 3.43 ppm) corresponding to the methylene group of the acid chloride. Methanolysis produced trimethyl a - (hydroxyimino)phosphonoacetate which was further purified by column chromatography on silica gel in 48 % yield (7 : 3 mixture of E and Z isomers) Characterization data:20 Compound Data Obtained ^ ft ^ ^ p - c - c - 0 K 3 h MFJI-113B 1 H NMR (D20): 5 (ppm) 2.7 (d, 2 JH P = 21.5 Hz. CH2 ), 3.5 (d, VH P = 1 1 .2 Hz, OCH3). 3 IP NMR (D20): 8 (ppm) 30.0 (Appendix A11-12) C H 3O v m ^ ft _ u _ ^ P —C — C — OH c h 3c t ^ MFJI-78A 31 ? NMR (D20): 5 (ppm) 27.0. (Appendix Al) 13 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Characterization data: continued OH I •HNMRCCDCb)^ (ppm) 3.7- 3.9 (m, 9H, OCH3), 12.4 (s, 1H, OH). 1 3 C NMR (CDCI3): 6 (ppm) 143.5 MFJI-8 8 A (£), (d , 1 * / CP = 224 Hz, P-C=N), 143.1 (Z), (d , l J C p =164 Hz, P- C=N). 3lP NMR (CDCI3); 6 (ppm) 7.7 (£), 6.2 (Z). (Appendix A2-4) Elemental analysis : C5H 10NO6P Calcd : C, 28.45; H, 4.77; N, 6.63. Found: C, 28.09; H, 4.79; N, 6.48. Preparation of sodium salt of methyl (hvdroxvimino)(hvdoxvmethoxyphosphinvDacetic acid (MFJI-89B) Scheme 2 The sodium salt of methyl (hydroxyimino)(hydroxymethoxyphosphinyl)acetate was obtained by reaction of trimethyl a-(hydroxyimino)phosphonoacetate with 2 0 % excess Nal in dry acetone. Due to the non-basic, nucleophilic character of I', this reaction selectively monodealkylates the phosphonodiester groups without affecting the methyl ester of the carboxylic group. In addition, in dry acetone the product precipitates while the rest of compounds are still dissolved in the reaction mixture, therefore making purification easier. After 24 hours, the precipitates were filtered and washed by dry R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 14 acetone and ether, giving the corresponding sodium salt of P-monoester in 70.0% yield, of (2 :1 £ : Z mixture). Characterization data: 20 Compound Data Obtained Literature Reference OH O N O CH O JI II I I p _ C- C - OChj NaCf MFJI-89B mp 143 °C (Sodium salt) NMR (D20): 8 (ppm) 3.42 (£), (d , V hp = 11.5 Hz, OCH3), 3.39 (Z), (d , Vhp=1 1.5 Hz, OCH3), 3.71 (£), (s, OCH3), 3.68 (Z), (s, OCH3). 13C NMR (D20): 5 (ppm) 52.4 (d , 2J C p = 5.4 Hz, OCH3), 52.7 (s, OCH3), 150.0 (d J j cP = 193 Hz, P-C=N), 164 (d , 2J Cp = 20 Hz, C=0). 3 IPNMR(D20 ):8 (ppm) 2.14 (£),-0.75 (Z). (Appendix A5-7) Reference20 Preparation of bis-DCHA~t ~ salt of (£y(Twdroxvimino)fhvdroxvmethoxyphosphinvl)acetic acid via hydrolysis of sodium salt of methyl (Tivdroxvimino)fhvdroxvmethoxvphosphinvDacetate CMFJI-93B2) Scheme 3 £)H r0H r0H /0H - r O N O O N O P N D O N O O N O O N O lr (r NaOH C H ,0 ^ n II IT H* C H jO ^II II II OCHA C H jO O ' 1 1 1 1 ' ; P - C - C - O C H i --------- > . v p _ p _ 0 N a --------- ^ . P - C - C - O H ---------► , p - c - c - o - *OCHA NaO NaO* H 0 OCHA- -O 25«C. 24 h This compound was prepared according to the method of Dr. Kashemirov, Fujimoto and Dr. McKenna.20 The bis-DCHA+ salt of (£)-(hydroxyimino)- (hydroxymethoxyphosphinyl)acetic acid was prepared by alkaline hydrolysis of the 15 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. sodium salt of methyl (hydroxyimino)(hydroxymethoxyphosphinyl)acetate using 2 molar equivalents of NaOH, giving the P-monoester disodium salt which was then acidified using Dowex 50WX8 (H+ form), followed by the addition of 3 equivalents of dicyclohexylamine at 5°C. The pure bis-DCHA+ salt of (£)-(hydroxyimino)- (hydroxymethoxyphosphinyl)acetic acid was obtained by recrystallization from ether in 58% yield. Characterization data: 20 Compound Data Obtained ,0H C H 3O v f ? 1 / 1 ? ,p— C — C-O- ♦ D C H A O C H A * -O £ -3 MFJI93-B2 mp 140-141 °C1 H NMR (D20): 8 (ppm) 1.0-2.1 (m,40H, CH2) 3.19 (m, 4H, CH), 3.54 (d , 3H, V hp= 1 1 Hz, 0CH3) 13C NMR (D20): 5 (ppm) 23.8, 24.4, 28.9, 53.0 (cyclohexyl), 52.4 (d . 2J c P = 5.4 Hz, OCH3), 156.4 (d , X J C p = 185 Hz, P-C=N), 168.8 (d , 2 /C p = 18 Hz, C=0). 3 JP NMR (D20): 8 (ppm) 4.2 (Appendix A8-10) Elemental analysis: C27Hs2N3 0 6 P Calcd: C, 59.43; H, 9.60; N, 7.70. Found: C, 59.17; H, 9.74; N, 7.65. Preparation of (EVChydroxviminolfhydroxvmethoxvphosphinvDacetic acid (MFJI-103A) Scheme 4 , 0 H o n' o CHjO^II II I I P— O -C -O ♦ D O H A O C H A * -O E-3 16 M e O H H O O H O N r O C H 3O - II II I I P-C-C-OH R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Generation of (£)-(hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid was achieved by ion exchange on a resin (Dowex 50X8, H+ form) in methanol. The solvent was removed by rotary evaporation, giving the product in 89 % yield as a 1 : 1 mixture of E and Z isomers. Characterization data: 20 Compound Data Obtained Literature Reference r0 H O N O CHj O ^ II II H , P - C — C - OH HO MFJI-103A 13C NMR (CDCI3, C2D6O): 5 (ppm) 146.8 ( 8 , lJ C p = 212 Hz, P-C=N) (£), 144.4 (5 , C P = 157 Hz, P-C=N) (Z). 31P NMR (D20): 5 (ppm) 2.4(£), -0.2 (Z)2 1 Reference"0 17 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. B. Synthesis of Anilinium salts of p-Nitrophenyl (£)- (dihy droxyphosphiny l)(hy droxy imino)acetate (MF JI-11 A) Preparation of p-nitrophenvl (dimethoxvphosphinvDfhydroxviminolacetate via direct nitrosation of (dimethoxvphosphinvnacetate ester (MFJI-115C) eviously reported nitrosation procedure required the conversion of dimethoxyphosphinylacetic acid to the corresponding chlorocarbonyl compounds to activate the methelene group of the acid prior to nitrosation. However this approach to synthesis ofp-nitrophenyl (dimethoxyphosphinyl)(hydroxyimino)acetate (MFJI-115C) does not work because of the low' reactivity of p-nitrophenol with chlorocarbonyl compounds (Scheme 5, Method 2). Alternatively, when esterfication of dimethoxyphosphinylacetic acid with p-nitrophenol was conducted before direct nitrosation of the resulting p-nitrophenyl (dimethoxyphosphinyl)acetate (MFJI-114F) in the presence of aluminum triisopropoxide, a good yield of MFJI-115C was obtained. (Scheme 5, Method 1). Esterification of dimethoxylphosphinylacetic acid with p-nitrophenol requires the combination of carboxyl activation of equimolar dicyclohexylcarbodiimide (DCC) and catalysis by 4-pyrrolidinopyridine (10% molar) which provided a useful method for in situ activation of the corresponding carboxylic acids for reaction at room temperature with alcohol which are less nucleophilic, such as p-nitrophenol. The mechanism of this reaction is considered to involve the conversion of the acid to anhydride by DCC, which forms an acyl pyrridium species with the catalyst, followed by nucleophilic attack by p- 18 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. nitrophenoxide. During the course of reaction, thin layer chromatography (5 : 1 mixture of toluene and acetone as solvent) was used to monitor the reaction. After being stirred for 4 hours, the solution was filtered to remove the dicyclohexylurea precipitate, giving MFJI-l 14F in 78% yield with 90 % purity. The product was characterized by both lH NMR; 7.27, 8.26 (the appearance of p-nitrophenol (4H, C6H4 ) and disappearance of methyl ester (3H, OCH3) and 31P NMR (D2O): 6 (ppm) 21.5 which was in agreement with previous unpublished work.23 Scheme 5 p-Nitrophenyl (dimethoxyphosphinyl)acetate(MFJI-l 14F)2 4 was first converted to its aluminum salt by the addition of aluminum triisopropoxide which activates the methylene group, followed by the electrophilic attack of nitrosyl chloride to form the corresponding nitroso group which then tautomerized to the more stable oxime group. During the reaction, thin layer chromatography (5 : 1 mixture of chloroform and acetone) and 3 lP NMR were used to monitor the reaction to determine the optimum time for C H jO ^ n C H jO O H O ^ „ 0 H O CHj O ^ i | || C-O CHjO 1 1. KOH 2. H H Y DCC Y OH 1 NOCI A l(0/-Prp M ethod 1 OH M eth od 2 19 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. reaction since this reaction was accompanied with transesterification with isopropanol which was produced in the reaction mixture after the formation of the aluminum salt complex with aluminum triisopropoxide. After 30 min (optimum reaction time), pure p- nitrophenyl (dimethoxyphosphinyl)(hydroxyimino)acetate (MFJ-115C) was obtained in 25 % yield as a mixture of E and Z isomers which were assigned by the NMR. The composition and structure were consistent with elemental analysis and NMR ('H 13C. 31P). Characterization data: Compound Data Obtained C H 3 0J? ? ft /= \ cH3o> H r 0 ~o" Q ~ N° 2 H MFJI-114F ’H NMR (D20): 5 (ppm) 3.22 (dd, 2H, CH2 ), 3.75 (dd, 6 H, OCH3), 7.27, 8.26 (dd, 4H, C6H4 ). 31P NMR (CDCI3): 6 (ppm) 21.5 (Appendix A 13-14) PH CH3 0 J ? N ff / = \ c h 3o - p ~ c ~ c ~ 0 ~ ^ ~ N 0 2 MFJI-115C mp : 135-136 °C lH NMR (CDCI3): 5 (ppm) 3.95 (dd,6 H, OCH3) 7.45,8.34 (dd, 4H, C6H4). I3C NMR (CDCI3, C3D60): 5 (ppm) 143.5 (£), (5 , Ucp = 220 Hz, P-C=N), 143.3 (Z) ( 6 , L ^p = 166 Hz, P-C=N). 31P NMR (CDCI3): 5 (ppm) 6.42 (£), 6.18(Z). Elemental analysis: CioHj 1N2O8P Calcd: C, 37.75; H, 3.48; N, 8.80. Found: C, 37.87; H, 3.55; N, 8 .6 6 (Appendix A 15-17) R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Preparation of the anilinium salt of p-nitrophenvl fdihvdroxyphosphinvl)flivdroxvimino)acetate via regioselective didealkvlation with Me.SiBr fMFJII-1 1A) Scheme 6. OH OH I Q^| CH,Ov l? H / = v 1. BTMS HQ |? M I? / = v C.H jNHj O N O The reaction of p-nitrophenyl (dimethoxyphosphinyl)(hydroxyimino)acetate with 3 eq. of bromotrimethylsilane (BTMS) dealkylated phosphonate ester selectively without affecting the carboxylate ester.25 In addition, when this reaction proceeded in polar solvent, more E isomer of the corresponding trimethylsilyl phosphonate was obtained (in acetonitrile the E : Z ratio was 3 : 1, in methylene chloride 1:1), which were then readily hydrolyzed by neutral H2O to give p-nitrophenyl (dihydroxyphosphinyl)- (hydroxyimino)acetate (MFJII-10C). The anilinium salt of p-nitrophenyl (E)-(dihydroxyphosphinyl)- (hydroxyimino)acetate (MFJII-11 A) was obtained by treatment of the corresponding phosphonic ester with 1.5 eq. of aniline in acetonitrile. The crystallization occurred after the mixture was allowed to stand for 5 min and the crude product was obtained in 55% yield after being washed by 5 ml of ether. Recrystallization from methanol and ether produced pure MFJII-11A in 33 % yield. The composition and structure were consistent with elemental analysis and NMR I1 !! l3C, 3 lP). 21 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Characterization data: Compound Data Obtained on O N O MFJII-11A mp : 148-149 °C *H NMR (D2O): 6 (ppm) 13-1A (m, 5H, C6H5) 7.27, 8.23 (dd, 4H, C6H4) 13C NMR (D2O, C3D6O): 5 (ppm) 151 (£), ( 6 , ly C p = 195 Hz, P-C=N). 3lP NMR (D2O, C3D6O): 5 (ppm) -2 .2 . Elemental analysis:26 Ci4Hi4N30gP(H20)0.5 Cald: C, 42.87; H, 3.85; N, 10.71. Found: C, 43.01; H, 3.77; N, 10.74. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C. Fragmentation of (E)-(Hydroxyimino)(hydroxymethoxyphosphinyI)acetic acid (MFJI-93B2) Fragmentation of fg)-(hydroxvimino)fhvdroxvmethoxvphosphinvnacetic acidCMFJI- 103 A): pH dependence of the stability and thermolysis in different solvents (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid was stable in water at pH 7 for 24 hours. However at pH 1.5, MFJI-103 A decomposed over 2.5 hours, unlike its C-methyl-isomer which was stable under the same condition. The major product was methyl phosphorocyanidate (85 % 3IP NMR -17.4 ppm) which corresponded the Ca-Cp cleavage product, and the minor product was methyl phosphate (15 % 3 IP NMR 2.1 ppm) which corresponded from P-Ca cleavage product. There was also a small 3IP NMR peak at 8 -0.2 ppm which was assigned to the Z-isomer of MFJI-103 A in reaction mixtures containing the incompletely decomposed E isomer of MFJI-103 A. Summary of Results for pH-dependent Study pH Products pH 7 pH 1.5 stable Methyl phosphorocyanidate O CH3OOI ^P — C N H O (85 % 31P NMR -17.4 ppm) Methyl phosphate O CH3O O I y.P — O H HO (15 % 31P NMR 2.1 ppm) A thermolysis study showed that the E-isomer of MFJI-93B2 in refluxing MeCN mainly decomposed to the Ca-Cp cleavage product methyl phosphorocyanidate (84% 3 IP NMR), and the minor product (16%) was identified as dimethyl pyrophosphate, which is known as a P-Ca cleavage phosphorylation product (Scheme 7). 23 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Scheme 7. OH O K O C H 3 0 _ii I I l l DCHA • - o ' e- 3 • O C H A 1 0 * c [ ^P-OCH,] H O v _ O ' N O C H jO -ll II II 0> _ c _ c - 0- 0 0 I I I t CH jO —P — O P OCH 3 1 I 11% o CH jO^N - o '" - " DCHA • -O OH EtOH . ii ii ii J p — C— C - O ' *OCHA [ > - o c h» J HO O ' N 0 o^ o CH 30 . II , P — OEt O 11% o CH 30_ |I ^P— C N 0 8 1 % Similarly, in refluxing EtOH (Scheme 7), the E-isomer of MFJI-93B2 gave the P-Ca cieavage phosphorylation product, ethyl methyl phosphate (19%) and the Ca-Cp cleavage product methyl phosphorocyanidate (81%). Replacement of the EtOH by 1 : 1 EtOH-/-BuGH gave a 1 : 1.3 product ratio of ethyl: t-butyl methyl phosphate (total 24%). Summary of Results for thermolysis in different solvents Solvents Products MeCN Methyl phosphorocyanidate 0 1 0*— P— ‘OCH^ ( I n (84 % 3 1 P NMR -17.8 ppm) Dimethyl pyrophosphate 0 o ii ii C H sO - P — 0 — P — O C H 3 1 l 0 o r (16 % 3IP NMR -9.3 ppm) 24 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Summary of Results for thermolysis in different solvents (continued) Solvents Products EtOH Methyl phosphorocyanidate 0 I 0— P — O C H j C N (81 % 3lP NMR -17.8 ppm) Ethyl methyl phosphate o ch3ovii _ P— O E t -o (16 % 31P NMR 2.2 ppm) EtOH/ tBuOH (1 :1) Methyl phosphorocyanidate 0 1 0— P — O C H , ( I n (76 % 3IP NM R-17.8 ppm) Ethyl methyl phosphate o -f-o a (5 6%) t-Butyl methyl phosphate 0 C H aO ^ II otB u •o' ’ (18.4%) ( total 24 %) From observation of th e 3 lP NMR peak of the Z-isomer during the pH-dependent fragmentation study and the previously reported data for troika acid, showing that the production of the corresponding phosphorocyanidate was only observed from the Z- isomer of troika acid, it is likely that activation by acid fragmentation induced the acid- dependent isomerization of the £-isomer of MFJI-103 A to the Z-isomer, therefore the majority of product was phosphorocyanidate (Scheme 8 ). This is also consistent with the previous finding that a-hydroxyiminocarboxylic acids predominately transform to nitriles via tram elimination.20 Scheme 8. 0 P — OH O O L ° I HO C H jO^i i U U H » P — C— C— O- -DCHA — — C HO DCHA * - O ' ' S . O N O 0 C H ,0 ^ I I || || C H jO ^H £.3 > - C - C - O H ► ? — CN c J HO HO Z-3 10 The question as to whether or not the production of methyl phosphate indeed involved the generation of metaphosphate intermediate can be answered from the result that extensive selectivity in solvent phosphorylation between 1° and 3° alcohol was not observed. As previously mentioned, if in fact the process was an associative fragmentation which involves elimination-phosphorylation via an intermediate adduct. 25 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. then the selectivity between those two solvents would be significantly higher (. In addition, the formation of pyrophosphate in aprotic solvents by thermolysis again supports the idea of dissociative fragmentation which is likely to involve the generation of a methyl metaphosphate-like intermediate. From the product distribution between phosphorocyanidate and methyl phosphate, it is apparent that the overall process: E- isomer MFJI-103A — > Z-isomer MFJI-103A — > methyl phosphorocyanidate competes favorably with a direct dissociative fragmentation. It should also be noted that while fragmentation via acid-dependent isomerization at low pH was only observed in MFJI- 103 A, the C-methyl isomer was stable under the same conditions, which indicates that acid-dependent isomerization of MFJI-103 A may be facilitated by intramolecular protonation of the oxime OH by the carboxyl proton. Furthermore, the stability of MFJI- 103 A and the fragmentation of Troika acid at pH 7 can be explained on the basis of stereoelectronic effects. According to the stereoelectronic theory,27 the fragmentation of P-Ca bond process would be controlled by the number of lone pairs on oxygen directly bonded to phosphorus which are antiperiplana (app) to the breaking bond (P-C). Therefore, it is consistent that at pH 7, troika acid, having the higher number of app lone pairs with respect to its P-C bond, is more reactive towards fragmentation than MFJI- 103 A which has fewer app lone pairs at the same pH. Due to above reasons, activation of MFJI-103 A by acid or thermolysis could only give a low yield of phosphorylation for P-monoester derivatives. In order to make the P- monoester a more effective phosphorylating agent, the appropriate choice of ester group must be made to provide a more suitable activation condition. 26 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. D. Hydrolysis chemistry of anilinium salts of /7-nitrophenyl (£)- (dihydroxyphosphinyl)(hydroxyimino)acetate (MF JII-11 A) Fragmentation of aniliniuni salts of p-nitrophenvl fiTWdihvdroxvphosphinvl¥hvdroxviniinofacetate (MFJII-11A): pH dependence of stability and phosphorylation chemistry The anilinium salt ofp-nitrophenyl (£)-(dihydroxyphosphinyI)- (hydroxyimino)acetate (MFJII-11 A) was monitored by 3IP NMR to evaluate activation conditions as well as phosphorylation capabilities. MFJII-11A was stable at storage, but in HiO it slowly undergoes hydrolysis followed by fragmentation. At pH = 3.1 (T = 25 °C), less than 4.1 % was decomposed over 52 hours and 100% of the product was phosphoric acid, the likely solvent phosphorylation product. At pH = 6.5 (T = 25 °C), 92 % of the product was phosphoric acid and 8 % of the product was phosphorocyanidate (ti/2 ~ 30 hours). At pH = 8.5 (T = 25 °C), 80 % of product was phosphoric acid and 20 % of the product was phosphorocyanidate (tm ~ 0.5 hours). To examine whether this phosphoric acid came from metaphosphate (dissociative mechanism), a solvent phosphorylation selectivity test was conducted. MFJII-11A was first placed in the solvent mixture of 1 : 1 water : methanol and then monitored by 1 3 P NMR. (AppendixA 21) The solvent phosphorylation product ratio was 1.2 : 1 mixture of phosphoric acid and methyl phosphate, respectively (34 % of product was from solvent phosphoiylation and 6 6 % was re-esterfication product-scheme 9). A similar experiment in a mixture of 8:1:1 water : EtOH : t-BuOH gave a solvent phosphorylation product ratio of 10 : 1 : 27 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 0.6 (total 65 % of the product was from phosphorylation and 35 % of the product was from re-esterfication, AppendixB 22). It is apparent that this lack of selectivity between solvents, especially between ethanol (1°) and t-butanol (3°), supports a dissociative mechanism (metaphosphate mechanism). In addition, in the presence of Mg2 + metal ions, an additional peak with 8 -0.35 ppm 3 1 P NMR was observed assigned to the E troika acid. It is clear that MFJII-11A can be activated by hydrolysis to produce the E troika acid, which then undergoes solvent phosphorylation via metaphosphate (scheme 9). Although MFJII-11A will undergo reesterfication when the solvent contains a significant amount of an alcohol with high nucleophilicity, such as ethanol and methanol, it is clear that when MFJII-11 A was activated by means of alkaline hydrolysis under mild aqueous conditions, it will undergo solvent phosphorylation via a metaphosphate-generating mechanism with a high phosphorylation rate (> 80%). Scheme 9. P ^ Activation P ^ Solvent O N O .— . by hydrolysis O N O phosphorylation O HO^_*_S_ 0 -/^S -N O , - - ■ ► H 0 .jU _ S_o. ----------HO^_OR ' ° ° ROH ° MFJI-11A £ troika acid Orthophosphate or its drivatrve Re-estenfication ROH OH ONO HO £ _ £ _ S _ o r O re-estenfication product 28 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Kinetic study on the rate of hydrolysis of the anilinium salt of p-nitrophenvl (E)-(dihvdroxyphosphinvl)flivdroxvimino)acetate (MFJII-11 A): pH- dependent activation and metal ion catalysis The pH dependence of the rate of formation of p-nitrophenoxide from p- nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate (MFJII-11A) was examined. Because of the low reactivity of MFJII-11A at pH < 8.7, studies at pH between 8.7 and 4.2 were carried out at 50 °C (ji = 0.5 M with NaCl) and studies at pH between 8.7 and 10.3 were carried out at 25 °C (p = 1.0 M with NaCl). In Figure 1 is shown a plot of log K obsd vs. pH for the hydrolysis of (MFJII-11 A). 0.6 o £ E -0.6 S * 2 - 1.2 o -2.4 3 4 5 6 7 8 9 10 11 pH Figure 1. Plots of logAC ^ ) vs. pH for the hydrolysis of p-nitrophenyl (£> (dihydroxyphosphinyl)(hydroxyimino)acetate (MFJII-11 A) in the presence of 0.01 M Ni2+(A) at 50 °C, in the absence of metal (0) at 25 °C and (O) at 50 °(ji = 0.5-1.0 M with NaCl) The plot at 8.56 < pH < 10.3 at 25 ° C has a linear slope of 0.99 (± 0.09) which indicates that an hydroxide ion-catalyzed reaction is occurring. No pH-independent reaction was observed over the pH range where the study was conducted at 25 °C. For the same 29 -Cl P o o — q R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. reaction at 50 °C (Figure 1), the plot represents a transition with increasing [H+] from negative one to zero. Such lines with “upward bends" can be analyzed in terms of a mechanism with two independent pathways. One of the pathways can be seen at pH > 8.2 where the plot has a linear slope of 0.95 (±0.1). Therefore, this pathway likely represents a OH" catalyzed reaction. The other pathway can be observed at 7.2> pH > 4.2 where the reaction is nearly pH-independent (the slope is close to zero) with a possible inflection point around pH 5. This pH-independent reaction likely indicates a water reaction, or kinetic equivalent. To determine the rate expression for these reactions, it is important to consider all ionizable species. There are three functional groups present in MFJII-11 A. Due to the reactivity with water, the exact values for pKa2 and pKa3 could not be determined by titration. However work done by Dr. Kashemirov in the McKenna laboratory with Professor Gerhard Haegele (Institute of inorganic chemistry and structural chemistry) and a preliminary correlation between electrostatic potential, (MacSpartan) and experimentally determined pKa values of methyl (dihydroxyphosphinyl)- (hydroxyimino)acetate indicates that the values of pKai, pKa2, and pK^ are around 0.35, 5.3, and 10.83, respectively, and pKa is likely to correspond to the oxime group. With this assumption, the only possible species present at this pH range (8.7 < pH < 10.3) would be dianion MFJII-11A (A2'). Therefore, the reaction at T = 25 °C (8.7 < pH < 10.3) can be written as Ar + O K -> P (I) 30 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. in which case the rate of reaction is given by d[P]/dt = £ ’bH[Otf][^2 '] (2 ) where A T ”O H is the second-order rate constant for hydroxide ion catalysis. Since [A2-] is close to the total concentration of MFJII-l 1 A, At, equation (2) can be modified as d[P]/dt = £ ”0H [OH\[A^ (3) where the presudo-first-order rate constant can be described by A obsd s /T ’ oh / [aH] (4) Where Kw and an are water ionization constant and activity coefficients, respectively. The experimental data gives a good fit to equation (4) with K ”oh = 1.05 * 104 M‘ 1 min*1 . For the reaction at T = 50 °C (4.2 < pH < 8.7), the general mathematical expression (K) for this type of upward bent correlation line can be described as K=C,+C 2 /[a H ] (5) where the first term, Q represents the pH-independent reaction and the second term, C2/[aH] represents a reaction with an linear slope of one via a logarithm which indicates the occurrence of hydroxide catalysis. To formulate this reaction in more detail, all ionizable species must again be considered. As mentioned before, there are three functional groups present in MFJII-11 A, thus there are four possible species. There is a possible inflection point around pH 5 which could represent an apparent pKa for the monoanion of MFJII-11A (pK^). The reaction is shown in scheme 10. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Scheme 10 CH CH O' O' . ^ O l ' / O v. OI^O „ 0 ^ 0 - 0 O AH A K - & where Ka i, K^, and K ^ represent acid dissociation constants for the neutral species, monoanion, and dianion of MFJII-11 A, respectively, K ’ m 0 and K ' ’ ^ q represent the rate constants for the pH-independent reactions of monoanion and dianion, respectively, and K ’ oh represents hydroxide reaction of dianion. Like the reaction at 25 °C, the reaction at 50 °C also indicates a linear slope of 1 at higher pH ( pH > 8.2 ) therefore, the rate of reaction where the slope is one can be written as equation (2 ) d[P]/dt = K ”0H [Off][A2 -] (2) The fraction of dianion of MFJII-11 A, [A2'] is designated as fA 2~ It is given by f * A 2- = [A2-]/[At] = jKa.K^faul) ([aH ]3+K.al[aH]2+KaiKa 2[aH ] +KaiKa2Ka3) (6 ) Therefore equation (2) can be modified as d [P]/dt= (K ’ oh f(9/nKa,Ka 7raH irAtl) ([aH ]3+Ka,[aH]2+KaiKa2[aH ] +KaiK a2K .a3) (7) where ^obsd = (K ”nnK,,iKX 7 Kw ) ([aH ]3+^al[aH ]2+^aI^a2[aH ] (8 ) The explanation for the pH-independent reaction (the first term of equation 4, Ci) is more complex. In figure 1 , the plot of log K obsd vs. pH for the hydrolysis of MFJII- 11A at 50 °C show a nearly pH-independent reaction at 4.2 < pH < 7.2. The slope is 32 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. nearly zero with possibly an inflection point near pH 5 indicating of apparent pK^. There are two possible cases which would fit this scheme. The first case is that only the monoanion is participating in the water reaction in the pH independent range. The second possibility is that both the monoanion and dianion are involved in the water reaction. Therefore for the first case, the total reaction ( both hydroxide and pH- independent reactions) can be written as where K'klo is a rate constant for the water reaction of monoanion. The fraction of monoanion of MFJII-11 A, [A‘] is designated as fA .. It is given by A2 ' + [OHI— > P A- + [H20 ] - * P (9) in which case the rate of reaction is given by d[P]/dt = £ ”0H [O /T H ^ I+ K ’ hzoK ] (10) fA . = [A']/[At] = (Kai [aH ]2)([aH ]3+Kal [aH ]2+Ka,Ka2[aH ] +KalKa2Ka3) (11) Therefore equation (10) can be modified as d [P]/dt = K ’ wn(K^U»}2 ) fA ,1 ([a^+^a.N p+ATa.^faH] +^alM a 3 ( 12) where ([aH]3+^al[aH ] ^ a i ^ a 2[aH ] + K ^ K ^ ) (13) Similarly, for the second case, the reaction can be written as A2 ' + [OH*]-* P A2 ’ + [H20 ]-> P A- +[H 20 ] - * P (14) 33 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. in which case A T 0b S d is given by i^obsd = (A i' ’ctnK alK a2 ATw)+ AT' H2Q K ^ K n-)\2Lu\+ K '» 7 n K n l\S L » ] 2) ([aH ] +^al[aH]2 +ATal^a 2 [aH] +Ka iKa 2 K a 3 ) (15) where K " hio is the rate constant for the water reaction of dianions. Between the two equations above (15) and (13), the better fit to the experimental A T 0b sd data was to equation (15) with apparent p A T al, pA^ and pA^ values of 1.28, 5.45 and 10.4 respectively (Table I & II - AppendixBl ).29 It is important to point out that a reaction such as the one above can also be derived from other, kinetically equivalent cases. For example, the major species existing at 5.3 < pH < 7.2 is the dianion A2 " where the rate is pH-independent. There is a possibility of having a kinetically equivalent pH-independent reaction when the minor species, the monoanion A"’ is involved in a hydroxide reaction, such as in equation (16). A2 ' + [OH*]— > P ,4' + [OH']-> (16) in which case A T 0 b sd is given by A Tobsd = (K 'nuKatKaj Kw)+ ( K ’ nu\K ,\\aiu\ Aw) ([aH ]3+A T ai [an]7 A T ai A T a 2 [aH ] +Ki\Kt aK&) (17) where K oh is the second order rate constant of monoanions. The calculation from nonlinear regression curve fit to the experimental data indicates that A T ’ oh (p A ^ 4.0) must be greater than 109 which is significantly close to the diffusion limit ( 101 0 M-1 s-'). There is no basis for expecting a rate constant of that magnitude. In addition, the isotope effects, Kh20/ Kd20 between pH 4.2 and 5.3 gives around 2.5 ( Tablel, AppendixB 1) 34 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. which is well within the range of typical values (2-4) of solvent isotope effects for hydrolysis of esters. 1 Therefore, pH-independent reaction must involve water reaction of dianions or monoanions (or both), not the kinetically equivalent case (eq. 16 and 17) and thus equation (17) can be ruled out. A second possible case is in the pH region where the slope is one. One can consider the possibility that the trianionic species (A3-) reacts with water, where A3 - is a minor species (Kaj « [an]). A3' + [H20 ]-> P ^ - + [ H 20]->/> (18) in which case A T 0b S d is given by ^obsd = (K ”mcK*\Ktf K^)+ \ K*i) ([aH ]3 +^ai [aHl^ATai A T a 2[aH ] +Ki[KalKai) (19) where K"u2 0 and K" ’ h20 are the rate constants for dianions and trianions, respectively. However, if in fact this was the case, then the rate constant for trianions (A T ’ ’ ’ h 2o ) must be nearly 104 times greater than that for dianions, assuming that pK^\ pA T ^ and pa r e 1, 5.5, and 10.5. Furthermore, if in fact trianions were involved in the water reaction, then A T o b s d should saturate as the pH gets closer to 10.3, which was not observed in this case. Thus, considering the fact that this is in the high pH region, the only reasonable assumption in the region where the slope is one would be hydroxide-catalyzed reaction of dianions. The effect of various divalent metal ions on the hydrolysis of MFJII-11A was also examined. In the presence of nickel ion Ni2+, there is a marked enhancement of A obsd. Saturation effects are achieved for Ni2+ as shown in Figure 2. The corrected 35 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. second-order rate constant (Ks- (K** - A ToVfOH'1 ]3 0 , where in the observed pseudo- first-order rate constant in the presence of divalent cations and Kq is the first-order rate constant in the absence of metal ions) for Ni2+ shows a hyperbolic dependence on Ni2+ concentrations at constant pH (7.1). 4.00E+07, 3 .5 0 & 0 7 ^ 3.Q0E+07 | 2 .5 0 B 0 7 | 2.00E+07 r : 1 .5 0 E+ 0 7 * 1 .OOE+07 5.00E+06 O.OOE+OO 0 0.005 0.01 0.015 0.02 Ni(ll) ion (M) Figure 2. EfTect of Ni:+ metai ion on the hydrolysis ofp- nitrophenyl(dihydroxyphosphinyl)(hydroxyimino)acetate (MFJII-11 A). The ordinate is the corrected second-order rate constant (Ks), {Ks = ( K ^ -Ko)/iOIT], where ICbm is the pseudo-flrst-order rate constant in the presence of metal and K o is the pseudo-first-order rate constant in the absence of metal ion. Reaction conditions: T = 50 °C, p = 0.5M (NaCl), pH = 7.1 (0.01 M N-ethylmorphoiine buffer), [MFJII- 11 A| ~ 50 pM. The curve represents a theoretical fit to equation (20). The expression for Ks for metal binding is given in equation (20)31 Ks = K""<KU ( ^ ] / < l +KJM*']) (20) where Km is the metal ion association constant and Klim is the limiting rate constant for metal ion catalysis. The experimental metal association constants Km and Klim were 3.01 X 102 M- 1 and 4.57 x 107 M-‘ min-1 respectively for Ni2+ at pH 7.1 (iV-ethylmorpholine buffer, 0.02 M). Due to the low solubility of Ni2+ ion in pH range studied, the 80 % saturation concentration of 0.01M (the concentration required to reach 80 % of rate enhancement) was used for the pH-dependent experiment. In Figure 1, the plot of log 36 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. £obsd vs. pH for the hydrolysis of (MFJII-11 A) in the presence of Ni2+ 0.01 M at 50 °C indicates the occurrence of apparent hydroxide ion catalyzed reaction at a pH greater than 5.3 and a pH-independent reaction at a pH less than 5.3. Since this experiment was conducted at a pH where pA^ (assuming that pA T^ is around 10.4) is much greater and p^ai (assuming that p A T ai is around 1) is much smaller than the pH, thus, equation (15) can be simplified to A nsbsd = (K ”nuK*7 Kw)+ K ' "mo K ’ mnla.u]2) ([aH ]2+^a2[aH] ) (2 1 ) The data gives a good fit to equation (21), where K ’ oh ,K ’ ’ mo and A T ’ H 20 are 4* 107 , 0.01, and 0.015, respectively ( apparent pKa2 is 5.5). This clearly indicates the metal ion- promoted hydroxide-catalyzed reaction due to the stabilization of MFJII-11A caused by metal ion binding to the chelating groups (oxime and phosphoric groups) of MFJII-11 A. The enhancement in A(”oh at 50 °C is nearly 700-fold at this non-saturating concentration of Ni“+ and the rate constant of the dianion (A T ’ Wo) for the pH-independent region also increases by 7.5 times, however there is no significant rate enhancement for the pH- independent reaction of the monoanion (K ’ h2o) at a pH less than 5.0 in the presence of Ni2 + ion. This can be explained from the fact that at a pH below 5.0 (which is around p A T a 2) the concentration of monoanion starts to increase, therefore the effect of metal ion binding must decrease since the second acid group (oxime group) of MFJII-11A must be ionized to form the site of strong metal binding. The values for the observed pseudo-first- order constants A^sd in pH dependence experiments are summarized in Table 1 37 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. (AppendixB 1) and the values for the second-order rate constants and the rate constants for the pH-independent reaction are summarized in Table 2 (AppendixB 1). Additional divalent metal ion effect studies were conducted with Mg2+ and Ca2 ' at a constant pH of 8.5. Unlike Ni2 + , both these metals showed weak effects. 8.00E+04 7.00 E+04 6.00E+04 ’ c" 5.00E+04 E Z 4.00E+04 M * X 3.00E+04 2.00E+04 1.00E+04 0.00E+O0 i / T / ► / ' / f / J / / 8.00 E+04 7.00E+04 6.00E+04 "c 5.00E+04 E | 4.00E+04 £ 3.00E+04 2.00E+04 1.00E+04 O.OOE+OO i ► I ' / + i / / / / ► " 4 t / / / . J 0.2 0.4 0.6 0.8 Mg(ll) ion (M) 0.2 0.4 0.6 0.8 Ca(ll) ion (M) Figure 3ab. Effect of Mg2 * (a) and Ca2 + metal ion (b) on the hydrolysis of (MFJII-11 A). The ordinate is the corrected second-order rate constant (Ks), {Ks = (K^^d -Ko)/[OIT1, where Ko^d is the pseudo-flrst-order rate constant in the presence of metal and Ko is the pseudo-first-order rate constant in the absence of metal ion. Reaction conditions: T = 25 °C, p = 0.5M (NaCl), pH = 8.5 (0.01M borate buffer), [MFJII-11 A| - 50 pM. The curve represents a theoretical fit to equation (20) Figure 3a shows that the slope of a plot the corrected rate constants A Tobsd' vs. Mg2 + concentration is linear which suggests saturation effects are not observed near 0.8 M Mg2 + at pH 8.5 (borate buffer, 0.01 M), however the corrected second-order rate constant Ks increases by 500 % at 0.8 M Mg2+ at pH 8.5. In the case of Ca2+ ion (Figure 3b), the experimental data followed equation (20) with Km =1.33 M' 1 and Klim = 1.43 x 38 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 10' 5 M' 1 min*1 at pH 8.5 (borate buffer, 0.01 M). The rate enhancement in the corrected second-order rate constant Ks was 500 % at 0.8 M Ca2 + (50 % saturation concentration). The rate of formation of p-nitrophenoxide from p-nitrophenyl (£)- (dihydroxyphosphinyl)(hydroxyimino)acetate(MFJII-l 1 A) was compared with the rate of formation of p-nitrophenoxide from p-nitrophenyl acetate , which lacks chelating functional groups such as oxime and phosphonate groups, in the presence of divalent metal and the absence of metal. In the absence of metal, the rate of hydrolysis of MFJU- 11A was 20 times faster than that of p-nitrophenyl acetate at pH 8.5 , 25 °C (borate buffer, 0.01 M). At 0.2 M Mg2+, the observed first-order rate constant for MFJII-11A increased by 1 0 0 %, whereas there was no significant increase in the rate of hydrolysis for p-nitrophenyl acetate at pH 8.5, 25 0 C. This results clearly indicates that oxygen of oxime group and oxygen groups of phosphonic acid must be involved in coordination of the metal ions, not the oxygen of carbonyl group. It is important to point out that although the above issues have been considered, an exact mechanism in pH-independent region can not be determined by kinetic data and solvent isotope effects alone, especially because experimentally determined pKa values are not available (only estimates from electrostatic potential correlation data were available). Further measurements are necessary to make such distinctions. However, it is clear that the activation of MFJI-11A can be catalyzed by OH' ion at pH > 8.0 and at near neutral, the activation can be fairly slow unless it is catalyzed by metal-ion promoted hydroxide. Nickel cation is much more effective in this respect than the alkaline earth dications Mg2 + and Ca2+ . 39 with perm ission of the copyright owner. Further reproduction prohibited without perm ission. References 17 Kashemirov, B. A.; MiKityuk, A. D.; Strepikheev, U. A.; Khokhlov, P. S. J. Gen. Chem. USSR (Engl.) 1986, 56, 843. 18 Malevannaya, R. A.; Atsvetkov, E. N.; Kabachnik, M. I. J. Gen. Chem. USSR (Engl.) 1971,41, 1432. 19 March, J. Advanced Organic Chemistry; John Wiley & Sons, Inc.; New York, 1992. 20 Kashemirov, B. A.; Fujimoto, M.; McKenna, C. E. Tetrahedron Lett. 1995, 36.9437- 9440. 21 Due to missing NMR spec, can not be presented. 22 Hassner, A., Alexanian V. Tetrahedron Lett. 1973, 46, 4475-4478. 23 Unpublished work from Dr. McKenna’s laboratory. 24 Khokhlov, P. S., Kashemirov, B. A., Strepikheev, Yu. A. J. Gen. Chem. USSR (Engl..) 1982,2468-2469. 25 McKenna, C. E.; Schmidhauser, J. Am. Chem. Soc. 1979, 739. 26 Water was used prior to crystalization and hydroscopic nature of MFJII-l 1 A, it was impossible to remove it. However water was not detected by ‘H NMR. 27 Gorenstein, D. G. Chemical Reviews 1987, 87, 1047-1077. 28 Details of pH determination work are explained in Appendix C. 29 Detailed kinetic calculations as well as data are shown in Appendix B54-64. 30 Shames, S. L.; Byers. L. D. J. Am. Chem. Soc. 1980, 103, 6177-6184. 31 Fife, T. H.; Pujari, M. P. J. Am Chem. Soc. 1990, 112, 5551-5557. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. CHAPTER III EXPERIMENTAL SECTION A. Preparation of Bis-DCHA+ salts of (£)- (Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid All reagents used were AR from Aldrich, Inc. NMR spectra were recorded on a Bruker AM 360 spectrometer. 1 H and 13C NMR chemical shifts were obtained using tetramethylsilane as an external reference. 31P NMR chemical shifts were referenced to external 85% H3PO4 . Elemental analysis was performed by Galbraith Laboratories Inc. Melting points were determined on a Thomas Hoover Capillary Melting Apparatus. (1) Preparation of (dimethoxvnhosphinvDacetic acid fMFJI-78A) The synthesis was performed according to previously published methods. 17 A solution of 56.11 g (0.2 mole) of potassium hydroxide in 30 ml of methanol was placed in a 200-ml Erlenmeyer flask with a solution of 36.4g (0.2 mole) of the trimethyl phosphonoacetate in 30 ml of methanol and left overnight at room temperature. After the solvent was removed by rotary evaporation (water pump, 15-30 mm, 40°C), the white crystals obtained were washed with ether. The corresponding potassium salt18 was dissolved in 2 0 ml of methanol and poured into a 60-ml glass filter with pre-washed ion exchange resin (Dowex 50WX8, H+ form) for acidification. Additional (20ml) methanol was added while the filtrate was checked with pH paper for acidity. This process was repeated twice for complete acidification and the solvent was then removed by rotary evaporation, giving 23.1 g (65.0%). 41 with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Characterization data: (Appendix A-1) !3C NMR (CDCI3): 8 (ppm) 27.0. (2) Preparation of trimethvl a-fhvdroxvimino)ohospho noacetate via nitrosation of dunethvphosphonoacetvlchloride followed bv methanolvsis (MFJI-8 8 A) The synthesis was performed according to a previously published method.32 In a 50-mi round-bottom flask equipped with a condenser, dimethylphosphonoacetic acid (2.0 g, 0.012 mole) was dissolved in 20 ml of dry methylene chloride. Thionyl chloride (1.6 ml, 0.018 mole) was added dropwise to the reaction mixture and refluxed for 3 hours. The reaction mixture color changed from clear to yellow. The excess thionyl chloride was removed by charging nitrogen gas under reduced pressure (water pump 10-30 mm, 40° C), giving the corresponding chlorocarbonyl compound. The reaction mixture was then allowed to stand for 3 minutes after 10 ml of dry methylene chloride was added. Nitrosation was achieved by the addition of a solution of 1 g nitrosyl chloride in 8 ml of methylene chloride and stirred for 4 hours at room temperature. The reaction mixture was again flushed with nitrogen gas under reduced pressure (water pump, 10-30 mm, 40° C) to remove excess nitrosyl chloride until its color changed from reddish orange to light yellow. The reaction mixture was then cooled in an ice bath and 10 ml of methanol was added. After mixing for 10 minutes, the methanol was removed by rotary evaporation, giving 1.8 g (71%) crude product. One g of the product was further purified by column chromatography on silica gel with a 5 : 1 mixture of chloroform and acetone as solvent. While collected samples were continuously checked by thin layer chromatography with 42 with perm ission o f the copyright owner. Further reproduction prohibited without perm ission. UV light, this process was repeated twice and 0.35 g (25 %) of a 7 : 3 mixture of E and Z isomers of trimethyl a-(hydroxyimino)phosphonoacetate was obtained.33’ 34 Characterization data: 20 (Appendix A2-A4) *H NMR (CDC13): 8 (ppm) 3.7-3.9 (m, 9H. OCH3), 12.4 (s, 1H, OH). 1 3 C NMR (CDC13): 8 (ppm) 143.5 (E), (8 , ]J Cp = 224 Hz, P-C=N), 143.1 (Z),(5,lJ C p =164 Hz, P-C=N). 3lp NMR (CDCI3); 8 (ppm) 7.7 (E), 6.2 (Z). Elemental analysis: C5H 10NO6P Calcd : C, 28.45; H, 4.77; N, 6.63. Found: C, 28.09; H, 4.79; N, 6.48. (31 Preparation of sodium salt of methyl (hvdroxviminoKhvdoxvmethoxvphosphinvllacetate (MFJI-89B) Trimethyl a-(hydroxyimino)phosphonoacetate (350mg, 0.00165 mole) in 5 ml of dry acetone was mixed with 298 mg of sodium iodide in 5 m of dry acetone in 25-ml round bottom flask and left overnight at room temperature, giving a white precipitate. The solid product was then filtered and washed with dry acetone and ether. After being dried in the desiccator for 24 hours, 249 mg (70.0%) of the sodium salt of methyl (hydroxyimino)(hydroxymethoxyphosphinyl)acetate was obtained (2:1 E :Z mixture) .33,34 Characterization data: 20 (Appendix A5-A7) lH NMR (D20): 8 (ppm) 3.42 (£), (8 , V H P = 11.5 Hz, OCH3), 3.9 (Z), 43 R eproduced with perm ission o fth e copyright owner. Further reproduction prohibited without perm ission. (5 , V hp = 11-5 Hz, 0CH3), 3.71 (£), (s, OCH3), 3.68 (Z), (s, OCH3). 13C NMR (D20): 6 (ppm) 52.4 (5 , 2J CP = 5.4 Hz, OCH3), 52.7 (s, OCH3), 150.0 (8 , ! j C p = 193 Hz, P-C=N), 164 ( 6 , 2J C ? = 20 Hz, C=0). 31P NMR (D20): 5 (ppm) 2.78 (£), 0.90 (Z). (4) Preparation of Bis-DCHA+ salt of (Fl-divdroxviminoKhvdroxvmethoxvphosphinvnacetic acid via hydrolysis of sodium salt of methyl (TivdroxviminolthvdroxvmethoxvphosphinvOacetate (MFJI-93B2) The sodium salt of methyl (hydroxyimino)(hydroxymethoxyphosphinyl)acetate (207 mg, 0.946 mmole) was dissolved in 3 ml HzO and placed in an ice bath. After a solution of 75.7 mg (0.00189 mole) of sodium hydroxide in 2.5 ml of H20 was added and stirred for 5 min., the reaction mixture was removed from the ice bath and allowed to hydrolyze at room temperature for 24 h. The solvent was first removed by rotary evaporation with a water pump (10-30 mm, 30°C) and further in vacuo, giving the corresponding P-monoester disodium salt. The salt was then dissolved in 0.5 ml of H20 and 1 ml of methanol for acidification using Dowex 50WX8 (H+ form). The filtrate was immediately treated with 515 mg (0.00283 mole) of dicyclohexylamine in 3 ml of methanol at 5°C. After mixing for 10 min, the solvent was removed by rotary evaporation with a water pump (10-30 mm, 40°C), giving a yellowish viscous liquid. The residue was then recrystallized from ether 300 mg (58%) of the bis-DCHA+ salt of (£)- (hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid. 44 vi R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Characterization data: 20 (Appendix A8-A10) >H NMR (D20): 5 (ppm) 1.0-2.1 (m, 40H, CH2) 3.19 (m, 4H, CH), 3.54 (5 , 3H, J hp=H Hz, OCH3). 13C NMR (D20): 5 (ppm) 23.8, 24.4, 28.9, 53.0 (cyclohexyl), 52.4 (8 . 2J C? = 5.4 Hz, OCH3), 156.4 ( 8 , lJ cp = 185 Hz, P-C=N), 168.8 ( 8 , 2 J C p = 18 Hz, C=0). 31P NMR (D20): 8 (ppm) 4.1. mp : 141-142 °C Elemental analysis: C2 7H52N30 gP Calcd: C, 59.43; H, 9.60; N, 7.70. Found: C, 59.17; H, 9.74; N, 7.65 (5) Preparation of f.EVfhvdroxvimino')- (hvdroxvmethoxvphosphinvl)acetic acid (MFJI-1Q3AN ) The DCHA+ salt of (£)-(hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (60 mg, 0.112 mmole) was dissolved in 2 ml of methanol and poured into a 5 ml glass filter with resin (Dowex 50X8, H+ form) for acidification. The solvent was removed by rotary evaporation (water pump, 10-30 mm, 40°C), giving 18 mg (89 %) of (£)- (hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid as a 1 : 1 mixture of E and Z 33 34 isomers. Characterization data: 20 1 3 C NMR (CDC13, C2D60): 8 (ppm) 146.8 ( 8 , lJ c? = 212 Hz, P-C=N) (£), 144.4 (8 , !yC p = 157 Hz, P-C=N) (Z). 3!P NMR (D20): 8 (ppm) 2.4(£), -0.2 (Z). 45 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. B. Preparation of Anilinium salts of p-Nitrophenyl (£)- (dihydroxyphosphinyl)(hydroxyimino)acetate (1) Preparation of p-nitrophenvl (dimethoxvphosphinvl)acetate (MFJI-114F) In a three-necked flask equipped with a thermometer, a dropping funnel and a drying tube, 5.0 g (0.030 mole) of dimethylphosphonoacetic acid in 40 ml of dry methylene chloride was placed. After a solution of 4.1 g (0.030 mole) ofp-nitrophenol and a solution of 0.45 g (0.0030 mole) of 4-pyyolidinopyridine in 20 ml of dry methylene chloride were added, the flask was placed in a water bath at 25°C. From a dropping funnel, a solution of 6.1 g (0.0030 mole) of dicyclohexylcarbodiimide22 in 20 ml of dry methylene chloride was added dropwise in the course of one hour while the temperature was kept constant at 25°C. During the course of reaction, thin layer chromatography (5 : 1 mixture of toluene and acetone as solvent) was used to monitor the reaction. After being stirred for 4 hours, giving a cloudy and white yellowish color, the solution was filtered to remove the dicyclohexylurea precipitate. The filtrate was then washed twice with 100 ml of cold water and dried with sodium sulfate until the solution became a clear yellow. The solvent was removed by rotary evaporation (water pump 10-30 mm, 30°C), giving a viscous liquid with some precipitate. The liquid was mixed with 10 ml of ether and filtered again to remove additional dicyclohexylurea precipitate. After ether was removed by rotary evaporation (water pump 10-30 mm, 25°C), 7.11 g (78%) ofp-nitrophenyl (dimethoxyphosphinyl)acetate (MFJI-114F) was obtained. Characterization data: (Appendix A13-A14) *H NMR (CDCI3): 6 (ppm) 3.21 ( 8 , 2H, CH2) 3.74 (dd, 6 H, OCH3) 7.27, 8.26 (dd, 4H, C6H4) 31P NMR (D20): 6 (ppm) 21.4. 46 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. (2) Preparation of p-nitrophenvl (dimethoxvphosphinvO(hvdroxvimino)acetate (MFJI-11 5 0 A solution of 2.35 g (0.0081 mole) ofp- nitrophenyl(dimethoxyphosphinyl)acetate (MFJI-114F) in 100 ml of dry methylene chloride and a solution of 1.24 g (0.0089 mole 1.1 eq) of aluminum triisopropoxide in 20 ml of dry methylene chloride were mixed in a 250 ml round bottom flask. After the mixture was stirred for 1 0 min at room temperature, 1 .0 g (0.015 mole 2 eq) of nitrosyl chloride in 10 ml dry methylene chloride was added. During the reaction, thin layer chromatography (5 : 1 mixture of chloroform and acetone) and 31P NMR were used to monitor the reaction. After 30 min. (optimum reaction time) of stirring, the solution was washed first with 100 ml of 5% aqueous solution of acetic acid , then 100 ml of aqueous sodium bicarbonate and finally 1 0 0 ml of cold water to remove any aluminum triisopropoxide residue. The methylene chloride layer was dried with sodium sulfate for 40 min and filtered. After rotary evaporation (water pump 10-30 mm, 40°C), 950 mg (37%) of yellow crystals formed. The crude product was further purified by being dissolved in 3 ml of acetone and filtered. The acetone was then removed from the filtrate by rotary evaporation (water pump, 10-30 mm 30°C), giving yellow crystals. The product was finally washed with ether and toluene to remove extra p-nitrophenol and placed in a evacuated desiccator overnight, giving 500 mg (20%) of pure p-nitrophenyl (dimethoxyphosphinyl)(hydroxyimino)acetate as a mixture of E and Z isomers. 33,34 Characterization data: (Appendix A15-A17) mp : 135-136 °C lH NMR (CDC13): 8 (ppm) 3.95 (dd, 6 H, OCH3) 7.42, 8.31 (dd, 4H, C6H4) 13C NMR (CDCI3, C3D60): 8 (ppm) 143.5 (£), ( 8 , lJ cp = 220 Hz, 47 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. P-C=N), 143.3 (Z) (5 , >yCp = 166 Hz, P-C=N). 31P NMR (CDC13): 5 (ppm) 6.4 (£), 6.3 (Z). Elemental analysis: C 1 oH 11N2O8P Calcd: C, 37.75; H, 3.48; N, 8.80. Found: C, 37.87; H, 3.55; N, 8 .6 6 . (3) Preparation of p-nitrophenvl (dihvdroxvphosphinvOfhydroxviminolacetic acid TMFJI- 100 In a 25-ml round bottom flask, 100 mg (0.314 mole) ofp-nitrophenyl (dimethoxyphosphinyI)(hydroxyimino)acetate was dissolved in 3 ml of acetonitrile. Bromotrimethylsilane (122 p i, 0.943 mmole) was added via a 20-pl syringe and the mixture stirred for 3 hours at room temperature. Excess bromotrimethylsilane and volatile side products were removed by rotary evaporation (water pump, 15-30 mm, 40°C), giving 85.4 mg of yellowish liquid (trimethylsilane ester). The trimethylsilane ester (85.4 mg, 0.235 mmole) in a 5 ml round-bottom flask was placed in an ice bath and cooled for 5 min. After few drops of cold water (5°C) were added to the solution, the reaction mixture turned cloudy and then soon became clear. Cold acetonitrile 3ml (5°C) was then added and the reaction checked by 31P NMR. Characterization data 31P NMR (D20): 5 (ppm) -0.5 (£), -3.0 (Z). (4) Preparation of the anilinium salt of p-nitrophenvl (dihvdroxvphosphinvDChvdroxvimino iacetate (MFJII-11A) Aniline (35 pi, 0.705 mmole) was added to a solution of/7-nitrophenyl (dihydroxyphosphinyl)(hydroxyimino)acetic acid in 3 ml of acetonitrile. Crystallization occurred after the mixture was allowed to stand for 5 min. The solvent was removed by rotary evaporation (water pump, 10-30 mm, 40°C). After the crystals were washed by 5 48 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ml of ether, 50 mg (55%) of the crude product was obtained. Methanol and ether were used for recrystallization giving 30 mg (33 %) of the pure anilinium salt of p-nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate. Characterization data: (Appendix A18-A20) m p: 148-149 °C >H NMR (D2 0): 5 (ppm) 7.3-7.4 (m, 5H, C6H5) 7.27, 8.23 (dd, 4H, C6H4) 1 3 C NMR(D20 , C3D60): 5 (ppm) 151 (£), (8 , [J Cp = 195 Hz, P-C=N). 31P NMR (D20 , C3D60): 5 (ppm) -2.2. Elemental analysis: Ci4Hi4N3OsP(H2O)0 .5 Calcd: C, 42.87; H, 3.85; N, 10.71. Found: C, 43.01; H, 3.77; N, 10.74. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C. Fragmentation of (£)-(Hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid (MFJI-103A) (1) pH dependence of the stability of fEVfhvdroxvi mino V (hvdroxvmethoxvphosphinvl)acetic acid (MFJI-103A). These experiments were carried out in 5 mm glass NMR tubes at 25°C. with a concentration of (E)-(hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid of 0 .1 % in D2O and 85 % of H3PO4 was used as a external reference. pH = 1.5 (9 hours) :20 methyl phosphate (15%) 31P NMR (D2O): 6 (ppm) 2.1. methyl phosphorocyanidate (85%) 31P NMR (D2O): 8 (ppm) -17.8. (2) Stability of the bis-DCHA salt of (E)- (hvdroxvimino)(hvdroxvmethoxvphosphinvl)acetic acid in different solvents. The bis-DCHA+ salt of (£)-(hydroxyimino)(hydroxymethoxyphosphinyl)acetic acid, 40 mg, was dissolved in 5 ml of solvent (acetonitrile, ethanol or ethanol-r-butanol) and refluxed for 24 hours while the reaction was monitored by 3IP NMR (0.3 % solution in D2O and reference to external 85 % H3PO4 ). In acetonitrile:20 jym-dimethyl pyrophosphate (16%) 31P NMR (D2O): 5 (ppm) -9.3. methyl phosphorocyanidate (84%)3 lP NMR (D2O): 5 (ppm) -17.8. In ethanol: ethyl methyl phosphate (19%) 3 *P NMR (D2O): 8 (ppm) 2.2. methyl phosphorocyanidate (81%) 31P NMR (D2O): 8 (ppm) -17.8 50 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. D. Hydrolysis chemistry of anilinium salts ofp-nitrophenyl (£)- (dihydroxyphosphinyl)(hydroxyimino)acetate The rates of hydrolysis of p-nitrophenyl (£)- (hydroxyimino)(dihydroxyphosphinyl)acetate (MFJI-11 A) were determined by a SHIMAZU UV-260 spectrophotometer. The temperature was controlled (± 0.1 °C) with a VWR model 1165 circulating constant-temperature bath which was connected with **** cell block in SHIMAZU UV-260 spectrophotometer. The temperature in the cell compartment was calibrated with a Brooklyn Themo Co-thermometer. Reaction mixture pH values were measured at 25 and 50°C with a Beckman Model 1165 pH meter. For nonmetal ion-assisted reactions, a few buffer solutions were prepared with EDTA (2 x 10' 5 M) as a precaution against trace metal ions in the buffer and salts, but the same results were yielded as the non EDTA-containing buffers. Over buffer concentrations of 0.02- 0.01 M the buffer did not have a significant catalytic effect. (AppendixB 53) The ionic strength was 0.5-1.0 M, maintained with NaCl. Kinetic parameters were calculated with a nonlinear regression program (Mathcad). (1) pH dependence of the stability of anilinium salt of p-nitrophenvl (EVf dihvdroxvphosphinvl)fhvdroxviminolacetate . These experiments were carried out in 5 mm glass NMR tubes at 22°C; the concentration of the anilinium salt of />-nitrophenyl (E)-(dihydroxyphosphinyl)- (hydroxyimino)acetate was 0.1 % in D2O (W/V). (2) Mg2+ ion metal effects on hydrolysis of g-nitrophenvl (E)- (dihvdroxvphosphinvl)(hvdroxvimino)acetate at pH=8.5 (AppendixB 31-39) 51 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. The buffer employed for this reaction was 10 mM borate buffer containing 1 M of NaCl for constant ionic strength. Boric acid, sodium chloride and sodium hydroxide were AR grade from Sigma, Inc. and MgCl2 was reagent grade from Aldrich, Inc. To initiate a kinetic run, 1 0 0 pi of stock solution of the anilinium salt of p-nitrophenyl (£)- (dihydroxyphosphinyl)(hydroxyimino)acetate in 1M NaCl (0.002 M) was injected into 1.9 ml of pre-reaction mixture containing 10 mM borate buffer and Mg2+ ion at the desired concentration. The initial concentration of the anilinium salt was 45-60 pM. While the reaction mixture was maintained at 25 °C and pH = 8.5, the rate of hydrolysis was determined by monitoring the appearance of /7-nitrophenoxide at 400 nm. The reaction followed pseudo-first-order kinetics for at least three half-lives. The concentration of Mg2+ ion was varied from 0 to 0.8 M with an increment of 0.1 M .. All reaction runs were done in duplicate or triplicate. The product spectra were quantitatively identified with those of equivalent concentration of />-nitrophenol under the same conditions except the concentration of Mg2+ ion was kept at 0.1 M since there was no significant difference in the spectra of p-nitrophenol over various concentrations of Mg2+ ion (AppendixB 49). (3) Ca2+ ion metal effects on the hydrolysis of p-nitrophenvl (E)-(dihvdroxyphosphinvO- (hvdroxviminoiacetate at pH = 8.5 (AppendixB 22-301 The buffer employed for this reaction was 10 mM borate containing 1 M of NaCl for constant ionic strength. Boric acid, sodium chloride and sodium hydroxide were AR grade from Sigma, Inc. and CaCl2 was reagent grade from Aldrich, Inc. To initiate a kinetic run, 100 pi of stock solution of the anilinium salts in 1 M NaCl (0.002 M) was 52 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. injected into 1.9 ml of pre-reaction mixture containing 10 mM borate buffer and Ca2+ ion at desired concentration. The initial concentration of the anilinium salt was 45-60 pM. While the reaction mixture was maintained at 25°C and pH=8.5, the rate of hydrolysis was determined by monitoring the appearance of p-nitrophenoxide at 400 nm. The reaction followed pseudo-first-order kinetics for at least three half-lives. The concentration of Ca2+ ion was varied from 0 to 0.8 M with a increment of 0.1 M. All reaction runs were done in duplicate or triplicate. The product spectra were quantitatively identified with those of equivalent concentration of p-nitrophenol under the same conditions except the concentration of Ca2 + ion was kept at 0.1 M since there was no significant difference in the spectra of p-nitrophenoxide over various concentrations of Ca2 + ion (AppendixB 48). (4) Mg2 * ion metal effects on the hydrolysis of p-nitrophenvl acetate at pH = 8.5 (AppendixB 46-471 The buffer employed for this reaction was 10 mM borate containing 1 M of NaCl for constant ionic strength. p-Nitrophenyl acetate was AR grade from Sigma, Inc. To initiate a kinetic run, 30 pi of stock solution of p-nitrophenyl acetate in acetonitrile (0.005 M) was injected into 2.97 ml of pre-reaction mixture containing 10 mM borate buffer and 2+ . Mg ion at the desired concentration. While the reaction mixture was maintained at 25 °C and pH=8.5, the rate of hydrolysis was determined by monitoring the appearance of p- nitrophenoxide at 400 nm. The concentration of Mg2 + ion was varied from 0 to 0.2 M with an increment of 0.05 M . The initial concentration of p-nitrophenyl acetate was 50 pM. All reaction runs were done in duplicate. The product spectra were quantitatively 53 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. identified with those of equivalent concentrations of p-nitrophenol at 400 nm under the same conditions. (5) Ni2 + ion metal effect on the hydrolysis of p-nitrophenvl (E)- fdihvdroxvphosphinvl)(hvdroxvimino)acetate at pH = 7.1 (AppendixB 40-45) The buffer employed for this reaction was 20 mM TV-ethylmorpholine (pH = 7.1) containing 0.5 M of NaCl for constant ionic strength. N- ethylmorpholine was AR grade from Sigma, Inc. To initiate a kinetic run, 100 pi of stock solution of the anilinium salt (0.002 M in 0.5 M NaCl) was injected into 2.9 ml of pre-reaction mixture containing 20 mM ^/-ethylmorpholine buffer and Ni2 + ion at the desired concentration. The initial concentration ofp-nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate was between 40-80 pM. While the reaction mixture was maintained at 50°C, the rate of hydrolysis was determined by monitoring the appearance of p-nitrophenoxide at 400 nm. The concentrations of Ni2+ion at which the hydrolysis was observed were 0.001,0.0025, 0.005,0.0075, 0.01,0.02 M. All reaction runs were done in duplicate. The product spectra were quantitatively identified with those of the standard curve from the equivalent concentrations of p-nitrophenol at 400 nm under the same conditions. (6) pH dependence of the hydrolysis of p-nitrophenvl (E)- rdihvdroxvphosphinvl)flivdroxvimino)acetate (AppendixB 3-15) The pH dependence of the rate of formation of p-nitrophenoxide from p- nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate was examined at 25°C for pH=8.7, 9.0, 9.5, 9.8, & 10.3, and at 50°C for pH = 4.2, 5.0, 5.3, 5.8, 6.3, 6.7, 7.2, 8.2, & 8.7. The buffers employed were 10 mM borate containing 0.5 M of sodium chloride for 54 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. pH> 8.2, 20 mM Af-ethylmorpholine containing 0.5 M of sodium chloride for pH = 6.7 and 7.2,20mM of cacodylate containing 0.5M of sodium chloride for pH = 6.3 and 5.8 and 20 mM of acetate containing 0.5 M of sodium chloride for pH = 4.2 and 5.2. Acetic acid, cacodylic acid and TV-ethylmorpholine were reagent grade from Sigma, Inc. Kinetic runs were initiated by injecting 100 pi of ester stock solution (0.002-0.003 M in 0.5-1 M NaCl) to 2.7 ml of pre-reaction mixture containing appropriate buffers at the desired temperature. The reaction was followed by monitoring p-nitrophenoxide at 400 nm for pH> 6.7, at 317 nm for pH = 6.3 and 5.8, and at both 317 nm and 271nm for pH = 4.2 and 5.2. For the hydrolysis at pH > 5.8, the product concentrations were identified by standard curves from equivalent concentration of p-nitrophenol under the same conditions. For pH = 4.2 and 5.2, the equations (22) and (23)3 5 were used to determine the product. A3 17 = 8e 3 1 7b[MF JD-11 A] + E p3 17b[p-nitrophenol] (22) A217 = E e 217b[MFJn-l 1 A] + sp 2 1 7 b [p-nitrophenol] (23) where Ax is the absorbance at X nm, sx is the extinction coefficient at X nm and b is path length of the cuvette (I cm). The reactions were pseudo-first-order for 3 half-lives. (7) pH dependence of the hydrolysis of p-nitronhenvl (E)-(dihvdroxvphosphi nyQ- (hvdroxvimino)acetate with Ni2 '1 ' ion metal effect (AppendixB 17-211 The pH dependence of the rate of formation of p-nitrophenoxide from p- nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate with Ni2+ ion was examined at 50°C for pH = 4.2, 5.3, 5.9, 6 .6 ,7.1. The buffers employed were 20 mM N- ethylmorpholine containing 0.5 M of sodium chloride for pH = 6 .6 and 7.1, 20 mM of cacodylate containing 0.5 M of sodium chloride for pH = 5.9 and 20 mM of acetate buffer 55 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. containing 0.5 M of sodium chloride for pH = 4.2 and 5.3. Kinetic runs were initiated by injecting 100 pi of ester stock solution (0.002 M in 0.5 M NaCl) to 2.9 ml of pre-reaction mixture containing the appropriate buffer with 0.01 M of Ni2+ (non-saturated concentration) at 50°C. The reaction was followed by monitoring p-nitrophenoxide at 400 nm for pH = 6 .6 and 7.1, at 317 nm for pH = 5.9, and at both 317 nm and 271 nm for pH = 4.2 and 5.3. The product concentrations were identified by standard curves from equivalent concentrations of p-nitrophenol under the same conditions (Ni = 0.01M). For pH = 4.2 and 5.3, the equations (22) & (23) were used to determine the product. The reactions followed pseudo-first-order kinetics for at least 3 half-lives. (8 ) Solvent isotope effects on the hydrolysis of anilinium salt of p-nitrophenvl (in-(dihvdroxvphosphinvl)fhvdroxvimino)acetate CMFJII-11 A). The solvent isotope effect on the rate of formation of p-nitrophenoxide from p- nitrophenyl (£)-(dihydroxyphosphinyl)(hydroxyimino)acetate (MFJII-11 A) was examined at 50°C for pH=4.2 and 5.3. The buffers employed were 20 mM acetate buffer which was prepared from D-acetic acid (CHjC(O)OD) and D2O adjusted by NaOD; 0.5 M of sodium chloride was added for constant ionic strength. Acetic acid and NaOD were reagent grade from Sigma, Inc. Kinetic runs were initiated by injecting 100 pi of ester stock solution (0.002-0.003 M in 0.5-1 M NaCl / D2O) to 2.7 ml of pre-reaction mixture at 50 °C. The reaction was followed by monitoring p-nitrophenoxide at 317 nm and the product concentrations were identified by standard curves from equivalent concentrations of p-nitrophenol under the same conditions. The reactions were pseudo-first-order for at least 3 half-lives. 56 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. References 32 Zhang, Y.; Takeda, S.; Kitagawa, T.: hie, H. Heterocycle, 1986,24,2151-2153. 3 3 Structural assaignments of the oxime isomers in this research were done on the basis of correlation between 3 1 P NMR 8 and l3C NMR ‘j cp values. 3 4 McKenna, C. E.; Kashemirov, B. A.; Ju, J.-Y. J Chem Soc. Chem. Comm. 1994, 1211- 1212. 35 Harris, D. Quantitative Chemical Analysis; New York, 1987. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Chapter IV CONCLUSION In conclusion, two derivatives of troika acid, a P-ester and a C-ester, were synthesized and evaluated for their activation conditions as well as their phosphorylation capabilities. Both derivatives were stable around neutral pH. The P-ester can be activated by either acid or direct thermal fragmentation resulting in the formation of methyl metaphosphate, which then undergoes solvent phosphorylation. However, the P-ester also undergoes a more favorable pathway; acid-dependent isomerization which in turn produces phosphorocyanidate from the Z-isomer of troika acid, thus, yielded low phosphorylation (<20 %). On the other hand, the C-ester could be activated as a means of hydrolysis, producing £-troika acid which underwent solvent phosphorylation via a dissociative mechanism. The hydrolysis can be catalyzed by hydroxide and divalent metal ion. The use of Ni2 + metal ions catalyzed the hydrolysis by 700-fold at neutral pH. In addition, these effects were observed at non-saturating concentrations. It is likely that for a good leaving group such as p-nitrophenol (pKa = 7.1), nucleophilic attack is the rate- determining step rather than breakdown of a tetrahedral intermediate to products. The strength of metal binding to the chelating groups such as phosphoric and oxime groups stabilized the transition state, thus enhancing the rate of reaction.36,37 Finally, although the C-monoester faces the possibility of re-esterfication when hydrolyzed in solvents containing a strong nucleophiles such as ethanol or methanol, its activation by Ni2 + and other metal cations is of considerable interest since it gives high solvent phosphorylation yield (80 %) under mild aqueous conditions. 58 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. References 36 Fife, T. H.; Theodore, T. J. J Am. Chem. Soc. 1982, 104,2251-2257. 37 Fife, T. H.; Theodore, T. J. J Am. Chem. Soc. 1982, 107, 1141-1047. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. APPEN D IX A Calibration conditions 'H NMR external CDC13 in D20 jlP NMR external 83% conc. H3PO4 |JH NMR external CDCI3 in D2 0 MFJI-78A (D20 , 3.0 % w/w) MFJI-8 8 A (CDCI3, 2.5 % w/w) MFJI-89B (D20 , 3.0 % w/w) MFJI-93B2 (D20, 2.5 % w/w) MFJI-113B (D20 , 3.0 % w/w) MFJI-114F (CDCI3, 1.5 % w/w) MFJI-115C (CDCI3, 1.4 % w/w) MFJII-1 1 A (D2 0 (85 %) + CD3COCD3 (15 %), 1.3 % w/w) AppendixA 21 (r-BuOH (80 %) + EtOH (10 %) + D20 (10 %), 2.0 % w/w) AppendixA 22 (D20 (44 %) + MeOH (56 %), pH = 8.5) R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ppm Start # Start Stop Integral 1 27.09 26.98 foo.00 2 26.72 26.65 1.85 File created: Thursday, March 27, 1997 12:27 PM 2 peaks found in MARlP2Jmport peak ppm freq amp 1 27.040 3942.14 10478625.00 2 26.688 3890.87 190330.61 100.00 1.85 27.00 26.0 ppm MFJI-78A (3,P NM R) O H O CH30 .{i_ ( ! ;_ g _ OH cH3c r ^ Appendix A I €l R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ---A- ■ V r ~ v. \ _ 13.0 12.0 H.O 10.0 9 .0 ■ " i..........‘ ■ -i......... a.o 7.0 PPM 1 1 . J. 1 1 6.0 1 .......t 11 1 • 1 5.0 4.0 3.0 MFJI-88A ('H NMR) OH CHjO..° « ° C H jO '" '0 - 0 - 0 0 ^ Appendix A2 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. O S 0 ' P - ° — C - O C H , / J J ^**1 'of 'o' i —i —i —i —i — i —j — Z '. 2 2 2 0 IB 1—1 —i —1 — i —1 —r 16 V . ~r~ 12 10 B PP*! ■ i—1 —i -1— i - 6 * 2 I 1 I 1 1 -2 -< -6 M FJI-88A (3,P NMR) OH 0 N 0 C H iO Ji ii ii ^p— C— C— o c h 3 ChfeCT Appendix A3 63 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. U -U |L " ’ I " - ........ " " I "" " T " .. I....................I .....................I --------------- I ------- -- > 1 1 -------- ! --------'--------r 200 1B0 160 140 120 100 80 60 40 20 0 PPM M FJI-88A (l3C NMR) OH O N O C H 30.n_n_u _ 0 C H 3 CH3O" Appendix A4 * 4 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. V 4.0 3.B 3. E 3.4 3 .2 3.0 2 .8 2.S PPM MFJ1-89B ( lH NMR) OH O N O c ^ ° ^ p - c - c - o c h 3 Na O ' Appendix A5 €5- R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. WdJ 0 N O MFJI-89B (3lP NMR) OH O N O Appendix A6 G£ R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. MFJI-89B (,3C NM R) OH CH3OJ? » ft n ^ 0 ; p - c - c - o c h 3 Appendix A7 e n R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. MFJI-93B2 (lH NMR) O H O N O ch3 o j D C H A * '0 ^ P — C — C — O D OHA Appendix A8 t o R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. n I n 1 ------! 1 I - - - - -1 - - - - -1 > - I - - - - -r- I ------,- - - - -,- - - - -, ------1 ------r- — -r 1 - - - - -1 - - - - -- 1 ---------r - -- - - - E * 2 0 -2 -t> -e -.0 - .2 -.fr - .6 -2D M FJI-93B2 (JlP NMR) p H C H 3O x? 1 1 ° ^ p — C — C —O DCHA D CH A < " 0 ' ' Appendix A9 61 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 200 :eo ie.o i .0 J20 lOO an- ■ SO E O -0 MFJI-93B2 (1 3 C NMR) 0 H r u n O N 7 0 c h 3 ° n I| I I L I DCHA'O'' D C H A Appendix A 10 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 6 p e a k s found in MARI.HI .Im p o rt p e a k p p m freq am p 3.616 3.612 3.S81 3.S24 2.802 2.743 1302^1 1300.74 1289.51 1269.01 1009.24 987.76 12209.58 20880.45 23682.83 703.13 948S33 9540.75 rile c re a te d : Friday. February 28. 1997 12:39 PM ppm Start 3.67 2.84 2.72 5.26 1.96 MFJ1-113B ( ‘H N M R ) CH3 0.1? ? ° CH3 O' 1 1 1 I I . ■ P — C— C— O K H 1 ------1 ----- 1 ----- 1 ----- 1 ----- ] ------1 ----- 1 ----- 1 ----- 1 ------1 ---- 3.50 3.00 2.50 apm A p p e n d ix A ll R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 2 peaks found in M A RLP1 .Invort peak ppm freq amp 1 30.000 4373.73 869453.06 2 1S.967 2327.83 60536.66 ~ \ 1 I _ , | * * ' 40.00 p p m # £Sn S to p Integral 1 32.01 28.14 100.00 2 17.52 14.62 4.27 1 100.00 4.27 t ] i r — i 1 j i i i i 1 1 : i 1 — 30.00 20.00 10.00 MFJ1-113B (J1 PNMR) O H O C M sO 'ji-i-fi-O -'K ch3o' ^ Appendix A I2 W . R e p r o d u c e d with perm ission of the copyright owner. Further reproduction prohibited without perm ission r'wh 'iz ir h ? - - n .* * “:i o ^ u j j ,5Pj:‘ ?so»^K.*tjTr«vr*vCvo{&v- O'* — V'inM -Jrtf* • v .* * “ xo “ A O . - » * r > r r r \x * ^ 'V 3 f .'L liV 'r'.'H n o O '"'" i : n o N / " ; - S i ; rr/.n»ov 'Si-Q. - r r r m » * • nnnrm nnnnnrM nn > ' t m iy i > ) i *!/' I, | « \ » \ ■ri M F JI-II4 F ('H NMR) CH30 ^ ” I I _ CH30 9 C~ ° ~ O ~ N 0 2 H Appendix A 13 =« R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. . 3.9(>SW_ F B e • <£J? Stop integral ApriJ 2 .1 9S7 2 24.07 23.99 “ .64 1 21.48 21.23 100.00 I 100.00 I r 2.64 ! > i | • * » i j ■ » * » j f » i * I i i r ' ! t j i i- j j i t j j i { p i | i i i i j ■ r"i'“ i 1 r * r r i j r " i r i | i ^ T p p i ”! r ■ j r i t t 28.00 27.00 26.00 25.00 24.00 23.00 22.00 21.00 20.00 19.00 18.00 17.00 16.00 15.00 jpm M FJI-I14F (3IP NMR) n u ^ 0 H 0 CH30 x ii i || CH3O ? - c - ° - \ J ~ n ° 2 H Appendix A 14 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Dpm Pile created: 5 lnt* 9 £ i Wednesday, April 2, 1997 2 8.39 8.26 2.04 1 3 4 PM 3 7.49 7.36 2.08 1 4.00 3.90 6.00 MFJI-115C ( ‘H NM R) PH ch3<x$ N $ / = \ 2.04 2.08 1 1 ' r 9.00 3pm 1 r~ 6.00 8.00 7.00 5.00 4.00 T-1— 1 3.00 Appendix A15 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. * ^ Stop kitM ni F i e created: 2 6-22 6.14 To.OO ^ 5 j> g p y . April 2, 1997 M F JI-1 1 5 C (3,PN M R ) PH CH30 ^ff ff 9 /= \ CH30-P c C- ° H > N 0 2 9.B9 / 10.00 8-00 ' 7-M t o o 1 1 1 i.M 1 1 ^ - 1 1 apn, — « a.oo 4.00 3.00 t r - 2-00 1.00 A p p e n d ix A16 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. u - 0 0 r> O « n 0 or: « . O -n 0 op: 0 0 * 0 o r •D 0 O fO fO O — * 0 o- • !“ * - * £ :. OO w O I POC-XO OO rj.'.so V • C J O*- - o*« * « “ j rj 0 PTntv — r » . C M ■ :» ; L . * • u * - J r, 3 CwTl- • . * » O w H k C ! w r * . * T if ' _ — • 1 O4 ^ ron'j oonouiff o o o o n -71 r-i G O O O . * ■ * 'M " .1 rj .. C i C i C i u 1 in Tgrrer ^r^zer ST-gF r r ~ <;r a: S z u & X 0 = 0 = Q- I j. 2 = 0 u. 2 I 0 = C L / \ o o « * > m X X o o Appendix A17 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ci” or: 0.: w . o-j: t: a E p j 5 P a c c < « Z c o - — M 5 E J£ & I * _ V « a o 0 ) ( 0 o 0 ) p j q C O Pw N . N . i n p j P 0 o ' T p j p j p j IP) © o CO ad m © p* o to IP) p . i r > ( 0 m 0 0 ** r — 00 IP) p j 0 0 o 0 ) P0 P* ♦ IP) P " > 00 o c o P0 coi p )0 ) 0 ) too' p j p j ( 0» t p j 0 ) ( 0 <0 ( 0 ip ) (O IP) i n *■ o o ) 0> 0)0)(0( 0t oC 0 c o P J p j P J p j P J P J p j P J p j U1 ao 0 ) p j P J ( 0 p j r —p» PO V — 0 ) P» IP) ' J - P J p j r \ j p j r n r o 0 ) c n p j 0 0 adad 0 0 p jp jp jp jp j p j pr> t o< 0 P«. 00 0) a o 0 > 00 Pso_ 00 2 z JF x o=o < i _ z=o o o < \i o o _fj o o _ad u. 2 o = o - / \ o o x ; rt I z b E a . O Appendix A18 l ^ h ^ h p em iission o f m e copyright owner. Further reproduction prohibited without perm ission. b n o o o — v T > xjc o o r; cn * a) 0 o rj cn alWOQQO«< O I ' ' o o ^ a o acu — --5NNO n*v^jruo *n.n to ^cu *:u e -£»- 's* * A * I i t . > • » * • T»n w T u»0<n** v f l O W N oocn •rocu ^ 3 0 0 'ij : -tft -Tr- o o w o o O O Q O w tiO 0 0 0 0 " • c o o o o c ^ n r j rj -nn w -T > 'jj* i * \ V *Vi o 1 V o ■Si V -> C Tscsr^-- l : i j g 0=c^ s • — ^ter O = F . — r^ B l A p p e n d ix A 19 R eproduced with perm ission of the copyright ow ner. Further reproduction prohibited without perm ission. « M F Jn -l 1 A (I3C NMR) c r OH O N O r ° ^ - c - o - o - N ° 2 . n h 3 O ' Appendix A20 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. e o a E l© o Z a. 2 E < < 0 2 .£ O ' "O 2 c 3 £ E (A § • ra a i .* d ra « to a cvi < o m to to co csj B o m m n o') . - rs. L f> .— N S O O O r - S I N ' f t O I v o '- t v m — cm •“ C O © 0* (V I D O V ) “1 JT O in in © > . O in id cm « cm cm v 0 9 * • i 5 , (5 N O W ® * * i f 04 as f ^ ^ r 0 0 7 7 ? '■ N n t w « o N » *• C M I CO . "V argofvjto* q QOCVJIOQOCNJ 5)0077? ct<nK>-ioin = { jo in m io .- a « d d 7 T co * f c co cm * - m ^ o o C O o o C M o o o o o - o o E a. a. Appendix A21 2/ R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Appendix A22 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. APPENDIX B R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced with permission o f th e copyright owner. Further reproduction prohibited without permission. Table I . Sum m ary of K obsd (pseudo-flrst-order rate constants) for hydrolysis of I X I F J I I -1 1 A I n p H dependence experim ents No m etal (T = 25°C) No m etal (T » 50°C) A dded Ni m etal io n s (0.01M.T = 25°C) pH Kobsd(1/min) Ave. Kobsd(1/mln) PH Kobsd(1/mln) Ave. Kobsd(1/min) pH Kobsd(1/min) Ave. Kobsd(1/mln) 8.70 0.051 0.0535 4.20 0.0067 0.0069 4.20 0.0151 0.0158 8.70 0.056 4.20 0.0070 4.20 0.0164 9.00 0.108 0.104 5.00 0.0106 0.0107 5.30 0.041 0.0402 9.00 0.100 5.00 0.0107 5.30 0.040 9.50 0.338 0.345 5.30 0.0110 0.0119 5.90 0.160 0.161 9.50 0.352 5.30 0.0128 5.90 0.161 9.80 0.637 0.632 5.80 0.0101 0.0104 6.60 0.768 0 69 3 9.80 0.687 5.60 0.0107 6.60 0.618 10.3 2.120 2.04 6.30 0.0099 0.0099 7.10 2.26 2.15 10.3 1.960 6.30 0.0099 7.10 2.04 No m etal (T = 50°C in D20 6.70 0 0085 0.0086 pH Kobsd(1/mln) Ave. Kobsd(1/mln) 6.70 0.0087 4.20 0.0028 0.0027 7.20 0 0119 0.0119 4.20 0.0026 7.20 0.0119 5.30 0.0047 0.0048 8.20 0.0570 0.0814 5.30 0.0048 8.20 0.0657 8.70 8.70 0.176 0.180 0 178 3 a S’ Table 1 1 . Summary of rate con stan ts for hydrolysis of MFJII-11A In pH d ep en d en ce experim ents No m etal (T = 25°C) Appendix B54-55 Equation # k a1 ka2 ka3 K' H20(1/M) K" OM (1/M min) K" H 20 (1/M) error (4) 10A -5.45 2.60*10A -11 I 1.05*10A 4 5.19‘10*-4 No m etal (T = 50°C) Appendix B56-61 Equation # ka1 ka2 ka3 K1 H20(1/M) K" OH (1/M min) K" H 20 (1/M) error (15) (21) 10*1.28 10A -5.45 10-A 5.45 10A -10.38 0.0073 0.00998 3.44*10A 4 3.38*10A 4 0.0083 0.00898 2.15‘10*-5 2.56*10A -4 A dded Nickel m etal Ions ( = 50°C) Appendix B62-64 Equation # ka1 ka2 ka3 K' H20(1/M) K" OH (1/M min) K” H 20 (1/M) error (21) 10A 5.50 0.012 2.0*10A 7 0.06 1.32*10A -4 Table I I I . Summary ot rate constants an d metal association constants for metal saturation data (equation 20) OOr)n(D(DNSU)lflM O O t O f f l r r N N P ) 05 05 C O C O G 5 05 05 C O Cn W < D < O N •^T-ooco«5ir)r^r^05 oo-»— ^ “C O id m * ttcm c m c m c o c o ^ C M 0 5 0 5 h- f * - O ' co o* o ' ^ o* o o in : o * O ' ^ -o ' * . O' Tf 0 5 0 5 0 5 0 5 0 5 O ' O' f» - r- < * - O O C M C M fl> ^ ^ w <o C O N I O IO O C 5 N N o cn in co co O O C O 05 f x . rx . C D ▼ - C D C D in C O o O C D C D V h- o C D C D in G O f X . h- O O in C M O rx. O G O C O O r* - a d O o C O d C M 05 C O C O in C O C D O 05 o 0 5 C O o o in O C D 05 0 5 G O 0 5 in O ' o C M C O O O C D r-* 05 C M in C O in m r*. in o T — G O C O 05 05 05 o d o o C M 05 O C M O C O a o o O C M d in m c o c o c o a 5 '« -c o m ^ c o c 5 r-<-CDNOO>OOIAM> C S C O -io^-^CM^-^-CMCM^ToOO d o d o o’ o d 2 o o 05 G O 05 05 C M C M U ) lO O O i- r P P d o d d o o 0 0 < “^N CM o* o o d O C O m U 5 C D C D N S C O C O d d d d d d o d d o o* o * oom m cocococo ^ o o v o — ■ ■ “ C M C M V O' C O C O C D C O O O 05 05 C M C M O ' O ^ O ' O' C O C O C O 0 0 * - ■ * “ C O C O o o ■ * - -V C O C O 05 05 o o C O C D c d c d 05 05 G O 00 o o O ' O * C M C M C D o o i n r»vflO co co C O C O co 05 05 C M h-l** O h- C M 05 05 h- o o- in co cn in m co co co coco pw coco co coco C M * 05 05 O G 5 05 c m m m rx * co co in coco c m c m co co O O C O co 05 05 C O C O O O C O C O 05 05 P P r- r-.«- o o in in 05 05 C O 00 C O C O C O C O r - h» 3 O 0 5 C M in m C O * x » 0 5 p * * * C D O C O C M C O C D G O f x » in C D 0 5 ’ C D in C D C O * cd o 0 5 * r x .' in' r - * * C D in O G O in m C M C O G O C O C O O C D in C D r- C O 0 5 C M o o C M C O o in C D f x . rx. n m in m m in in in o o O r x . C M C M C D n ▼ * * C M C M o C M 3 d o o o o o o in 05 C M o G O G O C O G O C O C O o O o O o O U J in U J U J U J U J O 05 C O O P- 0 5 C D o 0 5 O C O O in G O in fx . O rx . r- in 0 5 in co C O C M C M O O O O O O O O C O C O O O O O o o o o o o co co o o in in O O O ’ O'CMCMCOCOt- t- r - C O C O C O C O C O co C O C O cd cd co co O O I A I A S C D C O C O in * in* c o * 05 05 in C O o ^ C O C O C D G O C O C O in in co o O 05 r - in 00 1 ^ g o * o m *- o- C D co rx. C O C D C O O ' 05 r » - r - C M m co co r * * » r— 1^05 05 05 05 d r- ihih m m c m c m C O G O G O 05 05 r- g o co co co (D N h O O O ' C O C O C O C O r-» ▼ “ O’ v C M C O C O C O C O C O C O o o d o ' O v C O C O 05 05 G O C O 05 05 C O C O 3 O ' O C D C M G O C D C M O G O in o G O C O in C D m fx . rx . C M O C O in o 00 C D m O C O C O in C D C O C O 0 5 o 0 5 C D C O G O T — C M C O C O C O 3 O 0 5 in G O C O in 8 m 0 5 o in C D ’ in 3 o o C O 0 5 3 - 2 0 o jj 35 O O 35 C O • * “ C M o m P P d o d d o o r - c o c M i - c o c M i n n c o o o o * -* -C M C M C M C M C M C M C M C M C O C M d d d d d o ' d d d d d d a a g O O ^-^-C M C M d o d o cocoooinincoior^^cqaq d d d d d d d d o d d o inr-comcO’ r-cD cococoin^-coin a oo m m 05 c n c o u r ’ N ffiO JO J o o o o d d o o o a * c U J o o ^ --* -m in in in in in ^ --r-c M C M O E M l~ OOCMNOONNOOOO =*?i o q o o o q o g o o o o o o 9 9 o o 9 9 o o o o AppendixB 2 8 T R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p H dependence experim ental d ata (N o metal T = 25C ) o CO « o 2 © 0 3 CL UJ in C O 00 O’ m C M C O o * CO CO C O 00 03 C M p- 03 03 C M 0 0 o C O 03 w P-- oo h - 03 p - m 00 03 IN 05 05 C M 03 C M O ’ oo C O C O I A O* 00 C O C M C M CO O oo C M in C O o C O C O O T -» P - C O r*- C M C O UJ i O' p - m 00 p-. O ' C O C O 00 U m 05 O' 00 O o O ' CN /< ■ ( o 00 C M C O CO CO in p - C M 5 UJ P - O ’ C O r— «o in C O IU 00 03 00 o m m r*- oo T~ o* o O O C M oo in p - C O CO C O UJ #r\ C O p - CO o * oo C M 03 05 00 00 r*» ./"i p - O ' o m in 0 0 m C O C O lO P-. r ^ 00 0 0 03 03 o C M C O O ' UJ C O C O o C M o ; f » o o d o o d o o o o ▼ J C M C M C M A • i i i v i *7 i • ▼ — 1 i 1 1 i i *7 i i i m 1 0 in m m in in in m m in in m in m C O C O C O C O C D CO o © o o o © o o o o © o o o o o q o o o O o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ L L i UJ UJ L L i UJ « p — O’ O ’ C O G O CO 03 CO r— O ' m C O 00 o ; C O in co C O CO 03 O’ oo C O o C O o CO O ’ o * 03 Is- r - C M /Tk 03 C M m p— CO in C O C M p- oo O C M C O 05 C M C O O ’ co CO UJ 05 p - 0 0 CO O ' CO C M o o 03 r— CO C O . CO CM o O ' p * ~ O O ' GO C M C M C M C M cvi C M * « “ * * “ * - • » “ C O CO cn o o (0 -O < CO m m in in in m m i n m in in in in in in in m m m in o o o o o o o o o o o o o o o o in o o o o o UJ UJ L L i UJ UJ UJ UJ UJ L L i UJ UJ iii L L i UJ UJ UJ UJ UJ UJ UJ UJ C O O ' O ' p^ 03 CO C M 0 0 UJ C M p- in C O C M p - P - m C M oo C O C O C O O' m C M C M r-- UJ 05 C O C O 05 P- o Is- C O O ' m cn C M T “ O) p - CO O p - C M 5 in C O m O ' «n oo C M o 05 C M C O o ; in in CO CO 03 a > C M . O’ m C O p - C U 03 C M in T — c m ' C M C M C M C M * C M C M C M C O CO C O P - Is* C O C M C O m 03 C O oo O’ m O' C M 0 0 O' C O m oo CO 03 O' C O p- O O C M C O C D o C M O’ m r - 05 r— C O i n T — C M C M C M C M C M CO C O C O O ' O ' o O’ o O' in in i n o o o o o o d d d d o d o o o o o o d d C L z C M O O O lO «n W < 9 r-i O lO C M C O 05 ^ d © C M C O o C O c UJ o c o UJ g g - O uj 2 y.r=- o c - o> " 0.0 £ z ® co < ^ ^ • A C L O C O O ' m O' 05 00 C O O O P^- C M C O in 05 Is- co 00 03 C M O ' 7 1 p - co C M P-. cn m r t Is- C M C O C M C O in r— C O C O O ' CO in G O cn 05 Is- 03 o O' p - o C M CO r - m 0 C O u 05 cn O’ C O C M C O o O ' P^ m r - 03 05 0 cn O’ C O C M 05 in O ' o 00 0 cn m 05 C M 03 m C M 00 r ^ v CO C M T — C M O ' 0 0 m m p - C O 05 o CO i n < DIs- a > C O d d d o o T — T — T “ c m ' C M C M 1 • v T “ 1 • * 1 i T — 1 1 T — 1 • 1 1 m m m m in in in in C O C O C O C O C O C O C O o o o o o o o o o q 0 0 0 O 0 Ui UJ L L i L L i L U UJ UJ UJ UJ UJ UJ Ui Ui UJ Ui m 03 T “ h- in r — O’ C O C M C O O ' 1 ^* C M p- 0 C O O co oo in r^. m C M co cn 0 0 C O Is- 0 0 O O’ O' G O in C M 03 C M 05 C M 05 O C O 0 C O in C M C O in O ' T “ 03 05 O ’ 0 cn C M C M * C M T~ 0 5* C O * 0 0 cd in o 1 cn A A IO r * » c o o o A C M in in in • a in in m in in in in m m m in 0 0 0 m O 0 0 0 0 0 0 0 0 0 0 q L L i L U UJ 1 111 UJ UJ UJ UJ UJ UJ Ui Ui UJ Ui UJ CO O ' in UJ O ' C M cn C M C O 05 cn C O m m m 05 (D r— 05 O ' r-* O ’ C O in O in C O 05 in in u O ' C O O 0 03 00 O ' 0 0 05 C O 03 q O ’ UJ O y — O ' C O C O r - 05 0 C M in T-’ C M C M C M C M C M C M C M cn cn cn cn < D Q j C O 03 05 C M O ’ O ' 03 m C O 0 0 C M in in cn 0 0 m C M C M m p - O ' C O 0 cn C O T — C M O cn cn cn O ' O’ O ’ > 4 m m in d O 0 d 0 0 d 0 d 0 0 0 0 C M C O o © in in in E 0 0 T “ d d d C O o d ^ CO 0 N CO O) d o d h d o d AppendixB 3 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. re *o re O E 10 -§ C M re ii x H- re *= g l § I c 2 0) Q. re ■ a X Q. O c o o to Ui a c o u oo o ’ 'cr' ii re X w CL Ui o c in r- tT C D 00 r*. in O O m CO 05 C D C O C M O ' m C D C D C O 05 G O CO C M 05 O’ C O in 05 05 G O T“ C O 05 co 0 T — 00 G O 05 r*^ CD 05 C O in in O 0 t— o> s C O C D in 05 G O 0 C M CO C M C M 0 r - C D G O co C O TT O C M 0 C M r^ 05 05 in G O C O 0 CO 05 0 G O C O 05 in C O C M O 05 t r G O O' C O O 0 t*- •O ' P*. •O' G O C M 05 m 0 C O O M1 •O' o - m C D C O r - r*- G O 05 05 C M C D h - 05 o ' 0 o ' 0 O ' 0 0 0 0 O o ’ o ' • r - T — C M 1 1 V 1 1 ( 1 * 7 1 1 1 v t r - 1 T v T — 1 ** 7 v 1 in i n i n m in in in m in in in i n i n i n m in C D C O C O CD 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O 0 0 O UJ L L i UJ UJ Ui UJ UJ L L i UJ UJ UJ UJ U i UJ UJ UJ UJ UJ UJ UJ in CO C M C M C O C D r^. C O C M CD T - G O C O G O CO G O CO C D C O G O C M C O 05 C M 0 05 03 G O C O in O G O C M * C M O C M in G O ^ 3 * G O 0 C O G O 05 r^- C O CO 0 C O 05 C M * C M C M * C O C M C M C M cvi O C M 05 T “ r*- T ”* C M T — 05 G O r^ f"- cd CO i n 0 0 o (O C M CL Z C O CD m i n m t A in m m • a in i n i n in in in in in i n in 0 O 0 0 0 in O 0 0 0 in O 0 0 i n 0 0 0 0 0 O 0 0 p Ui UJ UJ UJ LU 1 l it UJ UJ Ui 1 \ n UJ LU h i LU UJ UJ Ui L L i UJ UJ L L i C O CD in C D in 05 in n \ C O i n 05 CD to in C M in G O C O 05 CD C M in 0 m in w C O G O h - 0 •O' 05 m G O r-. 05 O 0 C D C M 0 r^» Tf (< n 0 C M C M in in 05 C M 0 O C O tf5 C O C O Is -* in 0 W J in r^ 05 0 * “ • C M G O G O 05 T — •r-' C M * C M C M C M C M C M C M C O cd CO cd c o •O C M % C L Z C O 05 m C O C O 05 T— C D m C M G O C O m C O G O C M 10 1 ^- C O C D N- G O O C M TT C D 0 C M C O C D 0 C M C D C M C M C M C M C O C O C O C O ^ r V in in in i n O O 0 O O 0 0 0 O 0 O * O O 0 O 0 O 0 0 0 * 0 C O C O o re in _ i n m in E q o T t-'N co -t l Z o ’ © o ' ° o ' c i s ® . - . riOOO 0 0 03> ^ C M O ’ v - t - co in ao cm m re c o c o o w re w Ui o <J re o o Ui 00 0 5 £ « O £ g ° CL Z C O G O C O C M 05 < D 05 r - C M CO C M M - G O C M r - G O C M N- 05 C M C D O T — 0 O' i n C M C O r^. O ' C M T* •O' O C M C O 0 05 C O 05 C D G O 0 N- C O i n C M 05 C M C M 0 in O G O C M in C M in C D 05 m G O O C O in C O 05 05 05 O C D 05 C M 05 in T — r - M’ 05 G O C M O’ 0 T— G O fN - 05 C M 0 C M •^r i n C O C O 0 ) C O C M 05 m O C M in G O C M C O C O C O C O co M- m C D C D G O G O 05 p C M C O in 05 0 0 0 * 0 O 0 O O 0 O O 0 v ^— * T T* 1 V 1 V 1 1 T- 1 1 • 1 r — 1 T • 1 1 T -“ in m i n in in in in in in in in i n i n in in in C D C O C D 0 0 0 0 p 0 0 0 0 0 0 0 p 0 0 0 O 0 O LU LU UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ LU O' C M 05 r ^ h- 00 C M 05 C M C O C O m G O G O 05 O' 1 ^- G O C D C O 5T TT 0 h- h- O C M C M C O C O C O C M r>- C M N- C M C M C D m 05 C O i n T T in O C D G O C M C D C M C M 05 in C M * C M T — 05 00 p C O C M O C M T — C O cd cd cd cd C M C M C M cvi y - y — T- 05 C O C D IO 00 0 5 C M n < o C O C D CD CD C D in in in in in in i n in in in in in in in O 0 O O O p 0 0 0 0 1 0 0 p 0 p 0 0 p 0 0 0 LU Ui UJ UJ UJ L L i LU L L i UJ UJ 1 UJ UJ UJ UJ UJ L L i L L i UJ UJ L L i C M CD 05 h - 05 C D in h- O' m CO C M C O in G O C M CO CO CO C M C D C O CO O v 0 C O V U t r \ CD m 0 C D O C D 0 G O O C M M * CO TT C D C M h* CO vU G O pw C M C D O T ” 05 C M in O i n O 0 C M in r * * * C O 05 O C M C D 05 O T — G O in C D CD 05 T- T ~ - T * “ cm’ C M C M * C M C M C M * cd cd cd Q. O C O < ® C N Z.0D w S © CL © in C O C M C O G O in in 05 G O C O C O 05 0 C M in 05 C O in 05 C M m 0 C M C M C M C M C O C O C O C O •O ' •O ' •O ' 0 0 * 0 0 0 0 O O ’ o ’ 0 0 0 O 0 0 0 m N it) ° O O co C O o ^-cN^reresoo© 0 0 0 0 0 0 0 0 m C M ^ C O 00 C M C D ^ ^ ^ < > » cm ’ >0 AppendixB *n R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p H dependence experim ental d a ta (N o metal T = 25C ) O c o o w B UJ o c o o in o> u X C L © C Q UJ O c o O C O p - N. m C O in C O CO 05 C N in C O C O r-. r - n * C N 05 C O m N- o i n co C O C O o C O in o> C O C O CN C N TT o o CO C N C O N in C O C N CO r - 05 05 C O i n C O C O o * — CO m C O 05 C O co C N h - in C O in C O TT ^ r ^ r Is- ^ r 00 o C O C O 05 C O CO C O C N 05 T “” CO 05 05 h - C N in 00 C O i n © C O CO 05 r— I s* - C O in h - **r C O C O ? * TN- i n in C O 05 05 O r-- O ■ N * © o d d o o d d o o T — t— cvi CN 1 *7 1 i i *7 *7 1 *7 T” 1 1 i i ■ * 7 i in i n i n in m m m in in m in m in C O C O C O C O o o p o o o p o o o o o o o o o o LU UJ UJ UJ UJ UJ UJ UJ L L i L L i LU UJ UJ UJ UJ UJ LU TT in C N C N CN C O ■o- I s- C N in 05 C N CN m •*r 05 C O in 05 05 05 05 r ^ V O G O P *. i n o 05 CO C O * o C O * 05 C M * C O C N * C N CO C N * in C N CN P m o C O CO in 05 C O C O C O C O C O m in i n in in i n i n in in in in O p p o C O o o o p o o o o o o o p LU UJ UJ L U lit UJ L L i LU UJ Ui UJ UJ L L i L U UJ L L i p*- C N C O UJ i n V — «tr in in «T C O 05 C O in T~ C O 05 G O oo C O 05 in C O C O o T ” co r*- C O m UJ i n in C O G O 05 C O C N C O C O o r*. p*- r*- C N C O 05 o C N C O p*- C O 05 C N in cd cd 05 t— C N C N cn C N C N cvi C O * C O Is- C O in o UJ CO © r*- (0 00 m in to 0) Q . O C O (0 «o << T- - GO CO ^ = a o z 05 N" T- 05 p * * - CO CN C N CN CO G O ^ r C N C N 05 C O in co CN CO N* C O G O o 1 ^ G O i n oo O T* T * * * o CN CN C O C O C O in m in O o o o d o o o d o d o o d d o in co 0) E o in C N C N p— r^. C N m i n p C N o o o 05 o o C N CO CO in r - GO CD o o d o o d o o T “ cvi c m ' ^ co in h - O O C O * C O c o y k . 0) 0 0 LU CN N CO N S (N CM U ) m co t- t- h - in tt co m o o N C N J CD GO O CM CO N CO CO CO m X £2 o S ^ § £ 2 £ £ 0 0 0 0 ^ 5 © o CJ^CMNNCOCONCOOON lOO)T-r-(ONCMT-fl)MW (0 CMO)COOOO^(ONa)(O r-lOCOCDVCOOCD^^^ COQ^W^OaCO^NO incotococsiCMGOinino>co O C O SO N V Sr C M ^-C O (OCOCDNCDOOMCDCM^ d o d d d d r r r N N C O in C M a> C O C O o c o o in ©• 1? ® X m a . Ui m in in in o o o o t n i n i n i n i n t n i n i o i n i n i n i n c o c o c o o o o o o p p p o p p p p p o p U J U J U J U J U J U J U J U J U j u J U J U J U J U J U J U J U J L U U J (OCOOOlOt-NCOCO^CMS^NWWflOT-© O ^ W N tf ) C O O t- N 0 I D O ) N O ) C O C D W M ^ CO-^COCOCJCOCONO^-COOCOV^’ COCON n C M — — C O CO CO O 0 ) C 0 ^ C 0 C 0 ( M 0 5 M O C 0 © © N o c o S i o C O C D C O C O C O C O co o O o o O o o UJ UJ UJ UJ UJ Ui L L i 05 TT C O C O in 05 in C O C O G O o in C O o G O C O G O T ~C O CO G O C O 05 N* o co in ^•* in in C O * fw * G O * 05 o o in o o C N C N CN T_ CO TT C O in in i n in in in in in in in in o o p o o o o o o o o UJ L L i UJ L L J L L i Ui L L J Ui Ui LU Ui C N in 05 CN 05 C N in r — N* in C O O CO 05 C O C O o C O C O 05 C O 05 r^. TT 00 N* N- 05 05 O C O m CO 05 C O in 05 C O lO C O T “ C N C N * C N C N * cd cd cd 0) a o C O CO CO CO CO CO CN 0 5 in CN CO r^* < r- CO in TT 0 0 CO in in N* CO 0 5 o CN CO CO in I s*- CO co O CO GO o o o o t — r - CN CN CN CN CO CO *T i n in CO o d o o o o o d o o o o o o o o o d o d C O i o 8 r § U 8 «r«CM IO©t“^ ^ ^ 0) 10( 0 CMN(D0) ^ 0) ^ 0) 0 0 0 ) 0 0 0 (DlOcri-OiOMU)^ir)fl0 ^ r N UJ £ « id r- C O C M C M C M C N C M C N C M C M ' r ~ m C O C N C M C N T " C O C O C O in in m in m m in i n in m in in in in in o o o o o o in o o o o o o p o o o o o UJ UJ UI Ui Ui UJ © UJ Ui UJ UJ UJ UJ Ui u i Ui u i UJ UJ C O in 05 m UJ in m p- CO C O C O 05 C O T“ 05 r^ C D in C O G O C O G O 05 "V p * - r r ▼ — G O 05 C O C O G O m 05 C M G O C O C M h - C O o oo C O ■ * * C M o C O C O o C O r _‘ < D h- C M C O C M C O N* in in C O C O G O cd od 05 T -" r - * — * C M C N cd cd cd cd cd cd cd cd n C O 05 in C O m in N. G O C O 05 C O G O ! * • » » C O ^ N » 05 C N C O C D r - o C M C O CO o 05 ^ r C O G O 05 C N cr- o O T “ . C N C N C N C M C O C O ^ r in in in C O C O C O ST © o o o o d o o O o o o d o d d d o o o 0 5 E o lO p*- o CO CO in 05 c o CO o CO P*. C N C M G O C M m T -J C M C M cd cd 05 0 5 f s . 0 5 0 5 C O C O CM CM CO 0 5 0 5 — O CO t o C O t- ' cri ^ iri n ^ CM CM CM CM CM o c o o 52 U5 UJ o o O 5 5 * o > 'tr I I 0) X w Q . UJ C O in co C M co C M m i n 05 C D C O Ml r*- 05 C M p * - u i C O p * ~ C N N* N * C M C O in TT T— ■ C M /SI C O <r UJ «n ' C M 05 a o G O C O C M C M C M C O C M C N C M IN G O C O m r j 05 O UJ G O in o C O O O in m C M 05 h- G O N. C M r^* P* N in G O ® o in G O N* O C O C M co C N C M U C M 05 r j 05 C M 00 05 C O C O C O 05 m C O O 05 C O (A m 05 G O U o C O «\t G O o C N h- 05 C O o 05 C O TT u i in C O UJ N o C M IN C N C O C O C O C O C O N * N“ in in C D G O O ' . C M cp C N l*J o o o d o d d o o o o o o o o r— r — C M C M T “ 1 i T - 1 1 i 1 1 • • 1 *7 i • 1 i i t— t i t « i 9 in in m in in in in in in in in in m in in in m in C O C O C O o p o o p o o o o o o o o o o o o o o o o o Ui Ui UJ UJ UJ UJ UJ Ui L U LU tu UJ UJ UJ UJ UJ LU UJ UJ UJ UJ 05 C M G O C N ^ r 05 C O 05 G O G O 05 C O C O 05 C M 05 TT C O C M 0 05 in O ^ r o m C O 05 C O G O O o o 05 C O C O C O in C O C O O C O G O C N 05 05 C O o 05 C N G O C O 05 •^r 05 CO C O ^ r ^ r cd C N C M o 05 P*- in C O p m C M o 05 C N cd cd cd cd cd cd cd c m ' c m ' C M C M C M *“ r— ad TT o c o o a z (O0(ofn{o<DfO0 0 lftinlotntoinifiifiir)tr5io o o o g o o g o o g o g o o o o o o o o UJUJUJnSUJujnjUJUJMjUjuSUJUJujuJujuJUJUJ lOCOCOSCCOlOicCOlOjs^iiiCM CM OSCOOS^^CO 05NtoS(OM, S l°0>ScoS,“ ^ ,"®r^NNN T -co^S N ^S m r-g^^cow co t-tn oto co c o ^ - w r c o c o v ^ ■ Q C N I M ’ W O O C O C O * ^ 10 id cd ^ od od *-* *-* W cvi cm cm c m ’ cm cd C O cn cn © o LU UJ C M G O C O c m in « < T C O cd cd C O J O < CO ^ o r ° ' z C O C M G O h- G O 05 r*- 05 p^ C M C M C O C M C O 05 C O r^- T — N T 05 T “ N * C O p- p^. G O 05 o C M C O G O 05 C O in C O T ” C O o GO 05 (0 o o o o o C M C M C O •*r •*T m m m CO o o o o o o o o o o d o o o d o o o d o d o CM CO m o CM in CO 05 GO CN CO in CN d o d o d o oo C D ui co t j- rr_ C M C N AppendixB 6 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p H dependence experimental data (N o metal T = 25C) o o © UJ y- C M ^ ID y - C O oo Jc * - cn id r- C M ^ O) C O N O) h* C D S : C O O C D uo C O (D m r r to co o cd ^ 2 n n ^ o c o O) m N C M CO O) ^ ID r O N N C O O) O 2 o o ' o ' o ' o' CO CO O ) t - CO N ID O ) GO O ^ 0 0 0 0 CO CM ^ C M O N CO CD ID CN TT O ) C O 0 CO CO CO N O © CM N CO 00 O O t- CM CN . 05 C M C D O ^ C D O) V (O ID f id N ; - o V Ifl N IV G O ^ ^ tn CN O S CN g M 1 0 05 C O 2 V N ^ CO S <n ^ p . co 03 o p - oo o C M P- p - p * C O ID p T r cm cvi o > C O p * C O C O « o | o o £ 0 5 UJ I C D g |w O ID in ID ID C D o o o o o I I I • I uj mi uj uj m ID 00 C M C O cn C M C M 0 C O N ’ n ’ Y “ 03 P- 0 M * C O t - O I D I D I D I D I D I D I D I D I D O O O O O O O O O U J I U U J U J U J U J U J U J U J © f W N O C M D C O N C M G O O S C O O T T C M C O C O C D lD lD C O r^ O C O lD C O C O f ^ C D lD ^ J 'T T ^ .C M t- ID C O C O C O C O C O o o o p o p UJ UJ LU UJ UJ UJ co cn o ) co ^ co O ^ ^ CO V N cn 05 o o co O CO 0 3 CM N CO C O o UJ C M o CO o> C M C M C M C M C M Y “ T “ ■ * ” r - P - C O C O ID cn 03 C O C D /A CD C O ID ID ID ID ID ID in ID ID ID ID ID ID ID O O UJ o O o C D O O O o O O O o O O O O © o O UJ UJ i i n LU UJ O i UJ UJ UJ LU UJ UJ UJ U1 UJ UJ UJ UJ UJ UJ UJ C M ID C D UJ 03 C O cn 03 03 T f Y — C O C D p- 5 C M cn C O C M cn TT C O P- p- C O o 03 C O Y — O Q0 r - p~ cn CO p- p- C O U J m C M o p. M ’ 03 ^T o ID r r cn y- cn C O cn ID cn C D ID P-* 03 o Y “ C M IV ID ID C D y* P-. O C M C M C M C M C M c m ' C M G O C M < 0 < /) JO < TT ID P- 03 cn p~ ID C M G O cn C O C O C M C M M * 03 C M 03 r — 03 G O ID C O G O C O G O o y» cn M * P- C O o ID C O C O G O C M G O © O o O ' . ' . y- C M C M C M C M C M C M cn cn cn C O cn • M - © o ' d o ' o o o ' o* o ’ o ’ o o ’ O © o o ' o ’ d o ’ o o ’ d a > E o cn ID ID cn C M M * o O .0 4 0 9 o O C M cn p - 00 03 ID y* CD ID ID P- CO O o Y “ 9 tt O CM CO o C M cn *- CO Y~ cn ID CD y- Y * T — C M C M CM C M cn o c o o C /3 U J o c o C O < ■ > ID ^ od 'cT H © X V > C L ill G O C M ID cn ID Y- O O p» G O 03 ID ^T cn C M G O C M C M O C M p - cn C M C M p - cn T “ cn o C M 03 ID 03 P- C M C M o C M C O O cn Y * M * 00 G O O O C O C0 ID ID p ~ C M G O u o ID P^ cn C M ID C M ID cn C M P^ C O ID o o cn a* cn 03 O CO C M C O 5 C M G O C D M- C M 03 P-. p - ID 03 ID cn ID C D G O C O G O ID P^ o P- G O ID P - G O 03 C D C O 03 o ID C M C M cn C M 00 Y — m C M C M C M cn 9 cn •<r ID ID C D C D C O G O 03 o C M ID ID 9 9 d O o ' o o d o ' d d d o o ' o ' O Y -J Y- yJ i i y * i i i V i i • i v 1 i Y ~ 1 T 7 r ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID C D C O C D C O C O O O O o O O O O O O o O O O O o O o O o o LU UJ UJ L U UJ UJ UJ LU LU UJ L U L U L U UJ LU UJ UJ L U UJ UJ UJ ID p- C M C M ID r - 03 P^ ID 03 C M P- C M G O P - C M C M 03 G O p- ID O C D O cn ID cn 03 O P- P*- C O C M 03 Tf P*- C M cn cn cn C M O G O C O G O O P - C O ID cn cn 03 C M C M G O 03 o O ID V cn Y~ o C M P - ID C M C M o 9 N. C O C O 03 C M 03 p- cn cn cn on cn cn csi C M C M C M •*- Y —Y -’ ▼ — 03 03 G O C O Y “ C M C M 03 C O o c o o co C O C O C O C O C O C O ID ID ID D ID ID D D ID to ID ID ID to o p O o o O o O O O O O O O O O O O O O o UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ L U UJ UJ UJ UJ L U UJ UJ UJ L U G O Y — cn p - C M P^ C O G O C O TT 03 G O 03 ^ r cn C M C M C M C O o 03 cn cn o C O ID Y ” C M 03 C M C O M * 03 cn C M Y ~ C O C O p - C M cn C D C O o O M * Y » C M ^r M * P «. cn 03 M * C M ID p- 03 o Y* C O m; p- 9 9 •<r p- C O C O 00 p- C M C M cn ID C O G O Y “ Y “ Y “ Y “ Y » Y “ Y- C M C M C M C M C M C M cn (0 JO < G O Y — 03 C O p- G O C M ID C D M * C M ID ID G O ID 03 ID ID cn vD ID p* 03 Y “ ID p- o cn ID 03 cn C O P *. C O 03 n- o o O O o o Y- Y “ C M C M C M C M cn cn cn ^ r C O d o o o o d o o o d o O o o o o d o o d o o © I ° d cn ID cn C M cn C M to C M ID C M o C O C O C M o ID ID o o d Y “ C M cn M1 to d G O * 03 AppendixB 7 7 * R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C O T3 C O S o E o ■c in 0) I I Q. X 0) C O a? a) C E ■ K ° a ; a . © * o X Q. O o © © U J c o u © © U J - g 09 O 4 8 - C L — ' a u C O o C O o> oo C O C O " M * I s- 03 G O C D O' r r M’ C D o T “” C D T “ 03 C O C D C O 03 ^r C M G O O r r h - C O C O C O in m C D C O o C M C D p C D r - d © d d o d o d o o T— T — C M C M 1 ■ i i T“ 1 i *7 • ■ * 7 T — 1 1 i r-“ I *7 *7 o « in m in m in lO m m in m in in C D C D C D C D o o o o o o o o o o o o o O O O o UJ UJ UJ u j u j u j u j u j u j L U U1 u j u j u j u j u j C M C O r r 00 in 03 in C O co C M C M C D C D N- m oo C D in r - C O 03 C O C O C D O C M C O r j 03 03 N» C O m p ID C O "O ' P — < C M C O C O * C M C M C M * C M C M C M * C O C D C O C D #o C D C D C D C D C O C D in m m in in in in in in O UJ o o O p © o o o o o o o o o o o © UJ 1 II1 UJ L U u j u j u j u j u j UJ u j u j u j u j L U u j u j Q. O O UJ C O C M in m 03 in 00 ^ r C O 03 C O in I s - O C M G O in o 03 o cp CO C D P —o M1 © * “ C O d in r-’ oo G O ■ * “ T~ r — C M C M C M C O C O C O C O in I s - o o 00 o C M C M r-* O O 03 C O C M O o o C M m C D 00 03 C O m G O in O O C M C O G O o o O o o o o v — C M C M C M C O C O ^ r M- d o o o d d d d d O d d d d o d d m C O o oo I s - o C D r- C M C M C M Q C M 75 o C D 00 o C O £ C M C M C M G O o v ^ « r ~ © d d o o C O •<r in 03 C M C O o o © U J o o © UJ o c 00 o i g ° C L — a © i s s-o a • z O O r - C O in C D p - C M C O C O C M p - «_ r - C M C O in 03 m O 03 M S in C O r - o* 03 M S C D r^- C D 03 C M 03 C M I s- 03 QJ M t o C O C M o u /A o £ C M C O rr> C M M * C O C O 03 03 T — o o m V U G O r - r— o - C M o* V i 03 O ' in C O Ml r - 03 C O C O AS C M p- C O C M C O UJ 03 C M p - 03 r - G O C O 03 G O U3 /A 00 r— 03 xr 03 Ift C D •o* o (13 C M o P- 03 C M < 4 3 fs» 03 co C O ^5 * U / in C D C D I s - V 3 C O r - p m N d d o o o d o o d o T— r- C M C M i Tp • i 1 1 T * “ 1 » 7" T r — i 1 i o in in in in in in in in in in m in C D C O C D CO o p o © o o o o o o o o O p o o u j L U UJ UJ u j UJ u j u j u j UJ UJ UJ u j UJ u j u j C O in C M 03 oo C O 03 p - M- T "" C O G O G O m r - -M * C D C D C O p - o C O Tf G O 03 03 in ^ r C M co r - C O p - o C O r - C M 03 C O C M C O C M m T — C D O C D C O C O co C M C D C M O C M T~ O 03 r— r— m TT C O C M f - M' C M r - C D G O C O C O C M C M C M C M * C M C M C M ■ * “ ’ r_ r— C D C O C M p- C O C D C D C D C D CO C O C D in m in in in in m in o O O O O O O o O o o o o o o o o © uj u j u j u j u j u j u j u j u j UJ u j uj u j u j u j u j u j a . in 03 m x- 03 m 03 m r - C M p- C M C O co 03 o o C M r— C M C O C M C O o in r - p in G O 03 * r— © C O C M C D I s-' C O 03 T ~ C M * C M C M C M CO O C M in r - 03 o C M 03 co C D C O in 03 O o o O O o o o T— T “ C M C M C O C O C O d d o o d o o o o o o o o o o d d ® o i n N o a D T - ( o o f f l T - S T - ( N » - ' - S J j ' « C O O ^ ^ O O O n V O N W N B O 0 ^ c s o d o d d o V ^ r V r i ^ i o s d S ! ? 5 AppendixB 7 / R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p H dependence experimental data (N o metal T=50C) o ^ < j) N In q > LU ' c o o C M ^ 00 ^ II * X w Q . UJ O c o O 00 CD CO C M N- C D 05 C O 05 C M N- CD 05 N* 00 05 o* 05 h* C O 05 CO G O CD C M 05 O 05 i n 05 in o C M r — M * CO V 05 C O CO o i d 05 CO C M < T l O T — i n m w . C M m C D CO o C M CO C O N . G O CD U 5 < T * 05 o o o d o d o T “ C M C M C M o 05 05 i 05* 1 Uj i 05 T — 1 i i ■ * • 1 i i v i ■ v i i i i o i m i n i n m m m m in m m i n i n in m i n i n CD C D CD CD C O CD CD m o o o o o o o o o p o o o o o p O O O O o O O o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ L U UJ UJ u j UJ C M CO to CO N C M 05 i n CD C M 05 05 CD CD M * 05 CO 05 N - m CO CO CO M * O T * “ i n C O O M* M * O C M C M r~ m i n 05 C M o C O * o C D to p CO CD N> O i n C O N- i n in* TT C O C M C M C M 05 CO P*J CD ih •^r i CD CO CO < o m m in m in m i n o ■ A in i n i n i n in i n i n in i n i n i n o o o 9 o o o o o o U; O o o p o o o o o o p o p © UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ * it i Lll UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ a . T» C O N 05 CO N* 05 05 CD lU LU C M N- i n M * CD in CD o CO G O n- 05 CD a > C O CO C O p 05 O C M C M CO •M * M* 05 V) C O i n 05 C M C M CO CO CO ’ O ' in i h i n i h i h i h in ’ < 5 c*- o S T © C M ■ M * C M C O C D 05 C M O O o T “ o o d o C O C M C D C O C O 05 in C M o o *— C M j W O ) Cl C O IO * . C M C M C O ^ ^ > 0 0 0 0 0 C O O > C O C O tD -r-C 0 * - ^ * N - CMC0 0 5 O C 0 C 0 1 0 CDC0 ( D ( D t O N S N S r * * S o o ' © o ' o o* © o ' o IT ) G O O C M C O C O TT in C D in C O 05 G O *- G O C O C D G O C M C O C M _ _ N- C O C M O N* O m o N » © C M 05 o T* N -‘ cd C M C O ih G O C O 05 v C M C M C M C M C M C O co C O C O g £ § ° O m w o © o to ip u i t"* rS'CO y 9 o UJ O 05 ^ C M s i . o> Jr C M © o p S ” c g o O a uj C 03 “ O ^ c\i in A 00 ♦ « ♦ i l ° a . ^ n- m o * - in h- a> o> co co o co ^ o in co co d a> n * ® S m rj § S o S5 < D 05 r ; t- « j C M S U) M * N lO C O C O S? C M M - C O 05 C O S lO N C D 05 C O S in ID ID C O C O 2 05 W C D C O C M S C O 05 ID (O N 2 • « “ * “ co in ^ o o o o o ■ r- C M C O C M rj », G ) ^ N 05 S ^ J tt 05 in o co 05 5 O C O 05 n. CO © * * “ ^ E r 2 C M S C O C M 5 05 © 2 C M T T 05 'O ’ 05 ® 05 05 05 O C M o d d 05 • t- 2 2 t 05 , r - T- co in in in in o m * o ▼ - C O 05 co ( O N © h- O M * ^ © m. C M 05 2 co o* 55 cm tn 1 ” r-» co co ^ ^ ^ 05 C D C M 05 C D V > 4 W m V X W l co w cd ” co co in m o o > i UJ UJ C D C O O C O o m T- C M m m m in o © UJ UJ 05 m i n cm 0 5 Tf C O C O 0 5 C D in C O C D o o I I UJ UJ I s- ^r C M C D in M- M- M- in in o o I I UJ UJ co in o co C D C O in ^ C O 05 C O m m o o UJ UJ cm m in co co co C O N- N- * - C O C O * in in o o UJ UJ C M C M N- ^ O 05 C D rJ © in m o o UJ UJ C O C O C M C M N- 05 C D C O C O C M in tn in o o o UJ UJ LU C D C O 05 C O 05 C O N- C O 05 05 N N N- • C O in m in co o © o o UJ u j UJ UJ N - CO M“ CO N- 05 05 O) m C O ^ N. *-* in C M r N T“ T* 05 i n in o © i i UJ UJ i n in o co in m © o « * 4 U J U J t* 4 U J U J «J U J uj OO£5 O££0 0 0 0 0 0 0 0 0 0 G?OC?OCp UJ UJ m UJ UJ U J U JU J U JU J LL JL JJ U JU J U JU J U JU J LU N- ^ <r- r- C O 05 C O O C M * © " f l o i n N ^ s o i n o o s © .M , © N O I C M © M 'N C O O C M C O C O C O ^ ^ ^ ^ lh C D C O tn C M C M C M C D C D C O in G O to 05 C O r - C M ao 05 C M co O C M 05 05 o C M O O C M C M C O C O M * m in m in C D C D o o o ' o ’ o ’ d d o o o ' o ' o ’ o ’ o ’ o ' o ’ N- C D •«- C O C D I s* o o d t i 1 • C O C D C D C O o O O o UJ u j u j L U ^ * * C O C O t — C D oo o in C D o C D o 00 o C D C M C O 05 oo' h~ C D m in in in o o o o UJ uj UJ u j C M oo T — ' C D T “ C O co ih ih ih ih co C D in C M C M O’ in N- N. N- N- o' o ’ o o TT C5 © C M oo C M C D C O G O E O T o o C M c m ' co' in 00 CM C O ao o C O CO ^r m oo CO G O CO O CO CO 05 CO CD in C M 05 00 o C M ih CO o C M C M C M CO 00 T — CM * “ V C M C M C M C M C O CO CO C O ^ — co ca I s * - ' co ^ AppenjjixB 9 ^oL R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p H dependence experimental data (N o metal T=50C) E o C O C M05 C O C O C O C MC M05 in in C O tn 05 u M * O O C O C O r-. C M r* - C O O O C O C MM * tn G O M * C O O o T — C Mtn C D G O C Otn o C M T “ © a 05 o o o o o o o d o o T ~ ‘ T - » * C MC M o to a i o > T “ 1 1 T * r* 9 UJ ' 1 1 * * ' * c * lO tn m tn in in in in in m tn in tn C O C OC O o o y o o o o o o o © o o o o o o o o UJ UJ UJ UJ U l UJ L U uj UJ uj uj uj UJ uj UJ uj o» ^T N . C O M * G O y — G O oo G O G ON - r^ - C MC M 05 C Mo N . r* - C O cd G O to C O C Mo O 00 q © r*. in C MT —0 5 C O ^r C O C M 0 5 C MC O G O to UJ m- ' O' M * cd cd cd C M 05 tn C M o c C O C OC O C O tn tn in tn in in tn in tn in tn tn tn r* -' o o © o o o o o o o o o o o o o o o © it X o Q UJ U J UJ UJ UJ L U UJ U J UJ UJ UJ UJ UJ uj UJ UJ UJ a r* - C Min 0 5 in C M C O to T " tn C Oin C M o Q. ,w■ 05 T * - C O © C M tn h- tn 05 C O o C M<D C M 0 5 C L C O A T T N - * 0 5 C MC M * C O * th r - CM C O C O C O in C O G O t — h- C M05 tn 0 5 C M C O o O o T “ * C O tn C O G O C O 05 C Otn G OG O o o o o o o o o O O T- C MC MC MC M S ' o © 1 o o' o d o o o d o o d d d o d d X time 0 0 0 o C O d 1 .8 6 5.97 1 0 .1 0 G O O ) 15.84 19.38 M * r^ C M 26.95 48.67 S929 77.62 116.23 134.11 178.81 196.69 final C O h- tn C O G O T “* C MC O h- in G O h» O 0 5 05 o C O C O C D tn tn 0 5 0 5 o 05 C O tn c C Mm o O' G O 05 in C O C M C D 00 C M C O C M C O o co tn tn C Min f* w T“ h - G O Is- o C O C O o C O h* C O C O tn Q 0 C O o to C OC M C D w C O C O co o 00 M * C O in G O m C Mo 00 £ C O 05 C M00 o tn o C O 05 C D C M u ^T C Mo to C O o o C MC MC Mtn h- 05 C O C Min L U o> 05 o d o o o o d o o o C MC M o _ C a i i 05 t i 1 i T * 1 « 1 ▼ “ i i • i r i o’ d tn tn in tn tn tn m tn tn tn in to tn C O C OC O o o o o o o o o o o o o o o o o c U J ■ i uj i • U l uj 1 uj 1 o L S J U J U J U J L U U J U J U J U J U J U J o 0 5 r- C OC O C O C D tn M * C D G O C O m C O G O < J 1 - ^ C O C O C O G OC D C O C M r ^ G O o r-. 0 5 M* h- C O M - O v G O 00 o 00 h * CM G Otn w o C O T “ 00 G O 05 C O h- 05 T — 0 5 C M r^» co M * o C O tn C O m CO T* h - 0 5 C O U J cd cd cd cd C M * C M T “ cd cd CM o g ; CO CO CO CO CO m in m in o m tn m tn tn m tn in o o o o o O o q o o o o o o o o q LU © it X o Q UJ UJ UJ uj UJ uj U J LU i U J U J uj UJ UJ UJ UJ uj a . CO C M CO 0 5 M* 05 CO CO 05 GO tn in 0 5 oo 05 r - o Q. tn CO tn r - CO CO M * M * 00 CM 05 m CO o ifi Q. C O * cd 00 05 ■ * “ C M * C M cd cd M 1 th C O .o < CO M * 0 5 CO tn 0 5 r- C O GO in r — r> . in T* o o C M CO CD CO GO CO CO GO CO tn o o ? 5 o o o O o o o O O O C M C M C M C M ST o o d o o o d o o o d d o o o o o d X time 0 0 0 0.85 1.96 9 2 9 10.63 o CO C M 16.67 2 0 39 22.87 28.35 51.20 65.91 81.65 122.27 CO o o C O * CD T~ 206.91 final AppendixB 10 93 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced with permission o f th e copyright owner. Further reproduction prohibited without permission. pH dependence experimental data (No metal T=50C) pH=6.7 PH=6.7 I time NP(t) Abs (t)Conc Ester(t) conc. ln(Ester conc.) Time NP(t) AbsMP (t)Conc Ester(t) con^Ester cont 0 -0.016 0 0 -0.03 0 0.9 -0.011 2.83E-06 5.08197E-05 -9.887227032 0.7 0.006 5.37E-06 6.617E-05 -9.6233 2.08 -0.006 3.58E-06 5.00745E-05 -9.901998349 1.62 0.009 5.81 E-06 6.572E-05 -9.6301 328 -0.001 4.32E-06 4.93294E-05 -9.916991134 2.98 0.015 6.71 E-06 6.483E-05 -9.6438 4.46 0.002 4.77E-06 4.88823E-05 -9.926095901 4.16 0.02 7.45E-06 6.408E-05 -9.6553 6.68 0.009 5.81 E-06 4.7839E-05 -9.947668386 6.12 0.028 8.64E-06 6.289E-05 -9.6741 11.3 0.024 8.05E-06 4.56036E-05 -9.995524407 8.48 0.037 9.99E-06 6.155E-05 -9.6957 13.4 0.031 9.09E-06 4.45604E-05 -10.01866594 11.9 0.051 1.21E-05 5.946E-05 -9.7301 17.72 0.045 1.12E-05 4.24739E-05 -10.06662033 15.84 0.066 1.43E-05 5.723E-05 -9.7685 24.32 0.064 1.4E-05 3.96423E-05 -10.1356132 25.94 0.102 1.97E-05 5.186E-05 -9.8669 26.34 0.069 1.48E-05 3.88972E-05 -10.1545891 30.04 0.11 2.09E-05 5.067E-05 -9.8902 33.32 0.088 1.76E-05 3.60656E-05 -10.23017178 38.5 0.142 2.56E-05 4.59E-05 -9.989 43.92 0.112 2.12E-05 3.24888E-05 -10.33461445 48.76 0.169 2.97E-05 4.188E-05 -10.081 54.44 0.132 2.41E-05 2.95082E-05 -10.43084248 58.92 0.183 3.17E-05 3.979E-05 -10.132 62.54 0.146 2.62E-05 2.74218E-05 -10.50417375 65.92 0.201 3.44E-05 3.711E-05 -10.202 70.08 0.158 2.8E-05 2.56334E-05 -10.57161503 72.64 0.218 3.7E-05 3.458E-05 -10.272 84.22 0.176 3.07E-05 2.29508E-05 -10.68215691 91.2 0.255 4.25E-05 2.906E-05 -10.446 86.82 0.179 3.11E-05 2.25037E-05 -10.70182967 93.24 0.253 4.22E-05 2.936E-05 -10.436 110 0.205 3.5E-05 1.86289E-05 -10.89079577 99 0.265 4.4E-05 2.757E-05 -10.499 130 0.225 3.8E-05 1.56483E-05 -11.06514916 121 0.295 4.84E-05 2.31E-Q5 -10.676 150 0.24 4.02E-05 1.34128E-05 -11.21929984 139 0.312 5.1E-05 2.057E-05 -10.792 180 0.258 4.29E-05 1.07303E-05 -11.44244339 162 0.338 5.48E-05 1.669E-05 -11.001 200 0.271 4.49E-05 8.79285E-06 -11.64157207 180 0.353 5.71E-05 1.446E-05 -11.144 220 0.28 4.62E-05 7.45156E-06 -11.8070865 191 0.361 5.83E-05 1 326E-05 -11.23 final 0.33 5.37E-05 0 final 0.45 7.15E-05 0 -0.008716989 slope -0.0085 Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission. pH dependence experimental data (No metal T=50C) pH=6.3 pH=6.3 Tlme(min) NP(t)Abs. NP(conc.) Ester conc. In(Ester) Time(min) NP(t)Abs. NP(conc.) Ester conc. In(Ester) 0.48 0.24 0.035526 0.127786455 -2.057394731 0.48 0.24 0.035526 0.1277865 -2.0574 7.1 0.334 0.046648 0.1166643 -2.148454697 6.7 0.36 0.049724 0.113588 -2.1752 12.44 0.41 0.05564 0.10767192 -2.228666452 11 0.41 0.05564 0.1076719 -2.2287 17.14 0.468 0.062503 0.100809314 -2.294524525 16.5 0.468 0.062503 0.1008093 -2.2945 22.48 0.524 0.069129 0.09418335 -2.362511866 22.4 0.518 0.068419 0.0948933 -2.355 27.18 0.566 0.074098 0.089213877 -2.416718684 28.65 0.55 0.072205 0.091107 -2.3957 33.16 0.61 0.079305 0.084007762 -2.476846082 34.5 0.6 0.078121 0.085191 -2.4629 39.78 0.65 0.084037 0.07927493 -2.534833339 38.56 0.625 0.081079 0.0822329 -2.4982 46.4 0.682 0.087824 0.075488665 -2.583772768 45.2 0.675 0.086995 0.0763169 -2.5729 55 0.731 0.093621 0.069690946 -2.663684868 55 0.731 0.093621 0.0696909 -2.6637 60 0758 0.096816 0.066496285 -2.710609202 60 0.758 0.096816 0.0664963 -2.7106 65.74 0.794 0.101076 0.062236736 -2.776809839 65 0.794 0.101076 0.0622367 -2.7768 66.88 0.862 0.111488 0.051824507 -2.959892141 85 0.882 0.111488 0.0518245 -2.9599 final 1.32 0.163312 0 final 1.33 0.164495 -0.001183 slope -0.00989 slope -0.00993 intercept -2.11479 intercept -2.11858 > • Q Reproduced with permission o f th e copyright owner. Further reproduction prohibited without permission pH dependence experimental data (No metal T=50C) > •o •o ( D 3 ^ x w C O pH=5.8 pH=5.8 Time(min) NP(t)Abs. NP(conc.) Ester conc. In(Ester) Tlme(min) NP(t)Abs. NP(conc.) Ester conc. In(Ester) 1.3 0.239 0.029794 0.115258993 -2.160573574 0.64 0.23 0.028851 0.1162012 -2.1524 2.554 0.257 0.031678 0.113374649 -2.177057464 1.92 0.246 0.030736 0.1143168 -2.1688 3.3 0.268 0.032829 0.112223106 -2.187266369 3.36 0.268 0.032829 0.1122231 -2.1873 7.4 0.32 0.038273 0.106779448 -2.236989805 8.9 0.337 0.040053 0.1049998 -2.2538 8.28 0.33 0.03932 0.105732591 -2.246842101 13.22 0.385 0.045078 0.0999749 -2.3028 9.6 0.346 0.040995 0.104057619 -2.262810504 15.42 0.409 0.04759 0.0974624 -2.3283 12.38 0.377 0.04424 0.100812361 -2.294494299 23.54 0.484 0.055442 0.089611 -2.4123 19.48 0.448 0.051673 0.093379674 -2.371081578 30.9 0.543 0.061618 0.0834345 -2.4837 24.38 0.491 0.056174 0.088878188 -2.420488524 39.66 0.603 0.067899 0.0771534 -2.562 29.2 0.53 0.060257 0.084795444 -2.467513463 52.48 0.694 0.077426 0.067627 -2.6937 35.6 0.576 0.065073 0.0799799 -2.525979922 58.78 0.734 0.081613 0.0634396 -2.7577 43.72 0.63 0.070726 0.074326871 -2.599282741 70.12 0.818 0.090407 0.054646 -2.9069 53.62 0.703 0.078368 0.066684812 -2.707778055 76.58 0.865 0.095327 0.0497257 -3.0012 58 0.729 0.08109 0.063962983 -2.749450752 90.04 0.9 0.098991 0.0460617 -3.0778 62.5 0.771 0.085486 0.059566182 -2.820667277 99.92 0.951 0.10433 0.0407228 -3.201 92 0.901 0.099096 0.045957037 -3.080048298 final 1.34 0.145053 0 final 1.34 0.145053 0 slope -0.01069 slope -0.01013 intercept -2 15791 intercept -2.16107 Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission. pH dependence experimental data (No metal T=50C) > T J a pH=5.0 pH=5.0 Time(min) NP(t)Abs. NP(conc) Ester conc. In(Ester) Time(min) NP(t)Abs. NP(conc ) Ester conc. In(Ester) 1.64 0.293 0.028324 0.094459339 -2.359585815 0.26 0.279 0.027072 0.0957105 -2.3464 3.16 0.309 0.029753 0.093029491 -2.374838733 5.6 0.336 0.032166 0.0906166 -2.4011 4.66 0.325 0.031183 0.091599643 -2.39032791 9.02 0.371 0.035294 0.0874888 -2.4362 6.1 0.342 0.032702 0.090080429 -2.407052353 14.36 0.425 0.04012 0.0826631 -2.493 10.8 0.39 0.036992 0.085790885 -2.455842517 20.34 0.482 0.045214 0.0775693 -2.5566 13.4 0.416 0.039315 0.083467382 -2.483299363 31.44 0.578 0.053793 0.0689902 -2.6738 16.76 0.449 0.042265 0.08051832 -2.519270544 39.98 0.643 0.059601 0.0631814 -2.7617 19.82 0.477 0.044767 0.078016086 -2.550840245 44.04 0.673 0.062282 0.0605004 -2.8051 28.5 0.554 0.051648 0.071134942 -2.643176615 54.2 0.743 0.068538 0.0542449 -2.9142 38.54 0.633 0.058708 0.064075067 -2.747699961 60.26 0.775 0.071398 0.0513852 -2.9684 44 0.672 0.062193 0.060589812 -2.803628513 71 0.838 0.077028 0.0457551 -3.0845 50.66 0.72 0.066483 0.056300268 -2.877055982 82.32 0.899 0.082479 0.0403038 -3.2113 53.92 0.742 0.068449 0.054334227 -2.912600919 90.44 0.939 0.086054 0.0367292 -3.3042 60.289 0.774 0.071308 0.051474531 -2.966668141 102.62 0.994 0.090969 0.0318141 -3.4478 70.9 0.838 0.077028 0.045755139 -3.084451176 126.9 1.09 0.099548 0.023235 -3.7621 80.34 0.888 0.081496 0.041286863 -3.18721091 final 1.35 0.122783 0 90.24 0.937 0.085875 0.036907954 -3.299328208 slope -0.01067 100.2 0.983 0.089986 0.03279714 -3.417413953 intercept -2.32678 110 1.027 0.093918 0.028865058 -3.545123478 final 1.35 0122783 0 -0.01067 p H dependence experimental data (N o metal T=50C) CO 03 TT CO 03 CO O ’ CO 0 3 pw t n CM t n C M d TT CO h«* o CO 03 CM c o o CO o CO N . c o > CM r*- O CO 03 CO C M CM CM O o m - O o CO CM C M CO TT o CO CO f^. o t n CO 03 GO p*- r*» C M o 0 3 CO GO r- O O 0 3 CO CO CO o CM CM CM o CO 5 © 03 O CO CO O' O' t n CO Q CM C M t n i n r*- p*. 0 0 o 0 3 N- 03 (O UJ a i 5 CO 03 p - CO 03 CO 0 3 03* 1 d O o c • 0 3 0 3 t 03 03 i 03 t 03 03’ i i i i d i t n i n t n m t n m t n m t n t n t n t n t n t n o o c © © o o o o o o o o o o o o o UJ UJ LU UJ UJ LU uj LU UJ UJ UJ uj UJ UJ o CO CO r^. p*- N . r*- p ^ CO CO CO o M- CO TT tT O ' t n 0 3 CO © oo C M CO CO CO GO 0 3 CO 0 3 tO II <D CO r ^ CO 0 0 CO O ’ CM t n 0 3 N- co CM X U) cd cd cd t n t n i n t n mt cd C M * ■ i-* Q. L U y CO CO m t n t n i n t n m i n t n t n t n t n t n C o o o o © o o o o o o o p o o o UJ UJ UJ u j u j L U u j UJ u j UJ LU u j u j LU u j CJ^ CO T f t n 03 0 0 0 0 G O G O CO CO 0 3 CO CM oo t n T “ 0 3 CO 0 3 p - o t n CO CO < D '— -r o i CO 0 3 •o* <9 CO 0 3 T— CM m CO o Tf C M Q. Q. t n cd r - T* C M CM CM cd t n t n O X tn f" * * t n 0 3 03 0 3 03 CO C M rr CO CO GO C M t n 0 0 CO t n 0 3 C M ■ O ' m CO CO CO i^- CO C M C M C M C M CO CO CO CO CO CO *<r m CO o d o o o o o o o d d d o d o £ 3 < h* o o CO CO CO 03 CO 0 3 CO 0 0 0 3 CO r ^ 03 CO CO t n CO CO CO CO CO r*. C O N* h - d n . CO CO CO CO o m TT d C M o O o o d o d o d o d o I n £ 3 < © o CO tn 0 3 ▼ — CO t n C O o CM t n § r — CM CM G O O (0 T — g~ P w T - CO 0 3 CO t n CO C O CO 03 CO e \ t n CO h* r - h - N» C O C M 03 w CO r - CO h - C M o C M Q o o 00 t n CO M * C O 0 3 o CO Q o o i n o o 0 3 o TT O) a > t n CO 03 o p*. CM 03 CO 0) o o t— CO C M CO r^* CO CO o t n 0 3 CO m CO C O II 1 CO o o O o a i • V- r r - d I z 1 i 1 1 1 1 1 t n i n t n tn m m CO CO CO O o f o o o o o o o o o o L U UJ UJ u j L U L U L U L U L U o 0 0 O' o o CM 0 3 N . CO CO m C M GO CO O CO C M GO 03 o oo C M C M r - r- m CO i n o* CO v CO T ~ 00 G O 0 ) t n CO C M CO C M C M cd to U i cd C M * c m ' <r“ 03' o i n t n t n i n t n i n t n t n t n c © o o o o o o o o o C O o e s UJ L U UJ L U LU L U u j LU L U L L l w CO 03 t n CO t n CO CO r^* W* CO C M CO r - CO r»- CO TT Q 3 II 0 3 r^. C M C M i n c o r ^ Q . X Q_ CL Z C M cd m - i n t n i n t n cd o cn CO t n C M CO N- CO i f 03 Is- t n t n t n 03 CO t n 03 o o CO CO CO t n o t n CO CO d (A o o o o d o o o X3 < CO t n 0 0 t n 0 3 CO CO M* f t. o oo t n C M CO t n o* C M T" o CM h - CO m - o CO CO CO co CO C O o* © o o o o d o d £ 1 < (D o oo o 00 C M C M C M o CO 15 E ▼ — CD o CO tn CO c I - U- AppendixB 15 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission. pH dependence experimental data (No metal T=50C) Ph=4.2 Ph=4.2 time Abs(271) Abs(317) NP (t)Conc Ester(t) conc. ln(Ester conc.) time Abs(271) Abs(317 NP (t)Conc Ester(t) conc. In(Esterconc ) 0 0.7766 0.153 8.046E-07 6.52535E-05 -9.637231137 0 0.706 0.153 2.35E-06 6.417E-05 -9.653974199 20 0.7601 0.205 7.216E-06 5.88418E-05 -9.740658894 20 0.691 0.211 9.427E-06 5.7093E-05 -9.770829188 60 0.6347 0.293 2.02E-05 4.58576E-05 -9.989970245 60 0.577 0.301 2.239E-05 4.4126E-05 -10.02847004 80 0.616 0.336 2.561 E-05 4.04449E-05 -10.11556994 80 0.56 0.345 2.789E-05 3.8634E-05 -10.16138298 106 0.5775 0.381 3.169E-05 3.43661 E-05 -10.27843876 100 0.525 0.381 3.284E-05 3.3679E-05 -10.29864013 130 0.5181 0.419 3.741 E-05 2.86444E-05 -10.46055174 130 0.471 0.428 3.949E-05 2.7028E-05 -10.51863258 170 0.4741 0.471 4.443E-05 2.16308E-05 -10.74139336 170 0.431 0.479 4.63E-05 2.0218E-05 -10.80891813 190 0.4972 0.501 4.741 E-05 1.86457E-05 -10.8898968 190 0.452 0.504 4.875E-05 1.7769E-05 -10.9380497 final 0.3311 0.63 6.606E-05 final 0.31 0.63 6.652E-05 T J p H dependence experimental data (added N i, T = 50C) gS O § « - 05 ® 05 ( O co U J C O ^05 v m i - i f l C M N i f l ^ N O ) r ) ^ c o w © o ( o N O J C O l f l N t - O O N V C O i r j C M ^ ^ C M N C O C O a 5 i - ^ - * - ^ - © i n C M C M G 5 C 5 C M O i f l V N N O N C m O N M O N i - ’t C O t < o c o o v c N O n n v ^ n i “ f » n < o o T C O C O N ^ - n o O C O f O C O O l f l r - O c O r - C O O l ©CMf-.os^r'-cMcococM^-coiococoin^' n^^^;u)W(p<pNqocNiu)cq®^o o 0 b o o o o ’ o o o oi co n * ® I w Q. U J m i A i f l i n i A i o i n i o i f l o o o o o o o o o L L I U J L L J U J L L I L L J L L J L L l L L J r - V O J l O O t - C O O N o t n n s c o N O ^ - c o 0) W ® 1 “ © W V C M C O ^ 0 0 ) © N ( p l f ) ^ C O c o ’ co cm cm csi cm c m ' c m ’ c m ’ o co in in in c o o o o in o uj uj uj uj 9 u a) in n © uj o s in « »- © cd r * * - co m q. co cs co tn ^ Z co co co m tn o o tn o U J U J □ * , U J 05 i- J* f C O 0> C O g 05 C O C O C O C O i 05 C O m tn to tn © o p o uj uj ui U J co co r- m 05 go n O 05 v C M 05 C D C O C M ^ ^ tn in tn tn o p o o uj uj u !i uj co co c m tn 05 O M * C O T- C O 0 0 o C M C O C O O ^ m 1 m * C O C O C O C O C O o o o o o U J L L J U J U J U J r* . 05 m c m co C O O - M - C D •* - N O f i O l O co g o C D C O C M tn tA tn tn tn o g p p o UJ in UJ UJ UJ co = m co oo ^ - S o o c o N S O M - i - C O C O 05 •« - m , tn m m co n < a. z C M © © C O C M © C O tn ffl^ © r* fr- C D *- m c o Q o a 5 ^ - c M ^ t n Q o o m o t n o 5 Q O c o c D M ; r M , M , m t n t n i n © © © N S N Q O © b b b b b b b b b b o o b b o o in o uj ® 05 aj o .2 C M 0 5 C O C D 05 O ® ^'C D 05rrtCOinCD_-.CD05C500COr^CMin*- t o N C M < M V ( O C O < O ^ M , ^ © © © 0) O C M © H » O O 0 ° 0 0 0 ^ 0 0 0 0 0 0 ^ “ ^“ ^- c o c C M C O O C O h- c h- C O o C M G O u C O 05 l-» O © C O To r - in LU C O 05 'c 05 05 o m in c o o o o UJ C O UJ tn tn N » w C O C O £ 05 tn UJ u tn m c o o o UJ UJ o C O . r» in N. * tn C M I I Q. ® X Q. z C O C M 05 co C D co r: 05 o 2 g S © ^ 5 9 5 3 " o ® o ’ c i 2 o o o o o U J L L I U J U J L U 05 © C M © N 05 C O C D C O ^ © r - ffl O © ^ G O C O C M M * C O * C O * C O O O L L J U J -c C O C O C O 05 C O C M C O o tn o ^ r-. C M C M C M C O m tn C O co m C O C O h- m C M C O tn tn M * C O 0 5 O ' 05 C M r-. C O C O /ft G O C O0 5 o C Mtn 05 m w C D in G O G O G OC O 2? o G O C M0 5 o G O C O Tf Ai A i r- G O C OC M5* ■ " S ' C O C D C D r - C M tn w 05 C MC O C O C D C O C O O © C O o 2 05 C O o O r * » m C O o tt C O o . . tn C O 0 0 . 05 o in C O o co co o O © o o o o o i-J C MC M * C M • » C M in tn in in in in tn m m m tn C O C O C O o o p o o o o o o o o o o o UJ UJ UJ U J U J Ul UJ uj U J uj L U uj uj L U C O m C M C O C D C O C O C M r - C O o C M C DC O r- f— tn N. C O tn G O r - 0 5 M * C OC D O r-- tn o C M05 5 o G O tn C O C Mo aq in o G O C M C O C Mc m ' C Mc v i C MT* T “ th C O m tn m tn in m m in in m tn tn m in in p o o o o p o o o o o o p o o UJ UJ UJ U J U J Ui UJ U J uj U J uj uj uj U J uj © m m C MC O in C O C O G O m C O & C O C Mo C D *• 0 5 in m h- tn C O o C MC O C M o G O C O 05 tj- m o ao C O 03 in O C O 0 5 < /) tn r* » o C Otn r*- C O o tn G O o C Mtn C O co' •*r •O ' M O' th tn th th C O C D C O 05 C O C O tn C O in C D r-» G O C O C M in C O tn C O • M * C D C O c n C O C M C O G O o C O tn o G O C M C O C M C M C O M * m tn tn C O C O C O C O N. f*. G O 00 C O O o o o d o o o d d o d o o o o O o O d o C O 05 O b- C O C D C M C O C M tn C O C O C O C O tn C O tn C O C O o tn C M C O in o G O r^ » o m 05 o C O h- Jz C O C D T- r— o C M C O T T M * w in tn C D C D r*. G O 05 w C O c o o o o d o o o b o o o o d o o iff AppendixB 17 io o R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission. pH dependence experimental data (added Ni, T = 50C) pH=6.6 Ni(0.01) pH=6.6 Nl(0.01) time NP(t) Abs NP (t)Conc Ester(t) conc. ln(Ester conc.) lime NP(I) Abs NP (t)Conc Ester(t) conc. ln(Esler conc.) 0 0 0 4.7761E-06 5.7164E-05 •9.769583095 0 3 5 0.003 5.2239E-06 5.3582E-05 -9.834295696 0.177 0.06 1.3731E-05 4.8209E-05 -9.939965761 0.75 0.07 1.5224E-05 4.3582E-05 -10.04086428 0.327 0.09 1.8209E-05 4.3731E-05 -10.03744548 0.85 0.09 1.8209E-05 4.0597E-05 -10.11181602 0.455 0.115 2.194E-05 0.00004 -10.1266311 0.95 0.11 2.1194E-05 3.7612E-05 -10.188189 0.632 0.135 2.4925E-05 3.7015E-05 -10.20418934 1.05 0.12 2.2687E-05 3.6119E-05 -10.22868036 0.69 0.145 2.6418E-05 3.5522E-05 -10.24534741 1.2 0.15 2.7164E-05 3.1642E-05 -10.36103181 0.9 0.181 3.1791 E-05 3.0149E-05 -10.40935039 1.6 0.2 3.4627E-05 2.4179E-05 -10.63002175 1.48 0.235 3.9851 E-05 2.209E-05 -10.72040581 1.85 0.23 3.9104E-05 1.9701 E-05 -10.83481616 1.637 0.252 4.2388E-05 1.9552E-05 -10.84242076 1.95 0.251 4.2239E-05 1.6567E-05 -11.00808788 1.807 0.262 4.3881 E-05 1.806E-05 -10.92182754 2.1 0.258 4.3284E-05 1.5522E-05 -11.07322719 1.9 0.271 4.5224E-05 1.6716E-05 -10.99911921 2.522 0.293 4.8507E-05 1.0299E-05 -11.48351158 2.7 0.312 5.1343E-05 1.0597E-05 -11.45493821 3.03 0.315 5.1791 E-05 7.0149E-06 -11.86747048 3.03 0.326 5.3433E-05 8.5075E-06 -11.67456682 3.617 0.335 5.4776E-05 4.0299E-06 -12.42178122 3.617 0.344 5.6119E-05 5.8209E-06 -12.05405644 4.397 0.349 5.6866E-05 1.9403E-06 -13.15266873 4.397 0.36 5.8507E-05 3.4328E-06 -12.58212387 4.985 0.354 5.7612E-05 1.194E-06 -13.63817654 5.572 0.357 5.806E-05 7.4627E-07 -14.10818017 final 0.362 5.8806E-05 0 final 0.383 6.194E-05 0 slope -0.767792473 slope -0.618305642 © © * o g O © u x ^ © — r < D Z y *0 £ ® g » Q. © *0 S ® © © ■ 5 0 5 !T ^ p C N P C OP P tn C N C N O ) C N P C D p P cn 0 5 0 p m C N tn C N C Dp 0 5 0 5 C O P cn O Ocn lO cn C O 00 tn p P m tn ▼ — O p O O 0 5 0 5 5 C N tn cn cn ■ tn cn C N00 ao P m p C O 0 in C OC O g 0 5 0 5 C OP tn 0 C O 0 5 tn 0 5 C D T f C Ncn in C N C N C O 0 5 C NID 0 5 0 5 C N C OC N • ■ N * C OC O P p cs 00 O O O 0 d c v i 0 5 C D C D0 5 0 5 0 5 0 5 t - v 1 < D < 0 O O C D « n C D o > to in tn tn tn tn tn tn tn m tn in tn tn tn C DC O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O 0 U J L U UJ UJ uj uj uj uj uj uj uj uj uj L L I uj uj m tn 0 5 tn C N C O in p p cn cn C Ncn cn C N0 5 C O G Otn 0 C N0 5 0 5 p in 0 cn C N0 5 0 0 C N0 5 m 00 0 5 m tn cn cn tn • * r N * tn C N p p C O C N0 5 tn •V0 0 p- m 0 5 C N cn tn O cd C D * cd cd in tn in tn * cn C N * —0 5 05 c ri g iL o £Si C O 0 9 C O 0 C O 0 m 0 m 0 tn 0 in 0 tn 0 tn 0 tn 0 tn 0 m 0 tn 0 tn 0 m 0 m 0 U J uj uj uj s uj uj uj uj uj UJ uj uj UJ uj uj uj uj n* 05 t —C O o o 00 05 C O05 C O CO C N cn cn C O05 05 p cn C O tn cn C O 05 p p C N C N p 0 0 N * C N p cn C N p P p p m G O C N cn C O y C O C N p C OC N p V tn 0 0 T — C NC N C Ncn ^r in cd cd P 0) a o < £ ^ — O C M © o O o o o o o C N C N C O 05 tn C N in 05 co T Z cn tn C O m C O C N cn ^ r 0 S C N C NC N cn cn N * N * o ° 0 O C 5 C 5 0 0 O d d © tn cn G O P tn M P tn tn in £ 0 0 C D . O • n * ® C N C N C N cq 0 0 0 0 O O cn N * tn p*05 © c c o o u S' £ 5 « U J , * c o c o o U J 05 « c « o S a m co cn 05 C N m C N C OG ON " N * tn in p N * cn p tn O C N in 05 N * P- cn N " N C N 0 0 p as 05 p cn P- C O C O cn C N C J tn m o o cn G O N * 05 G O V v C O 05 C O cn cn C N p p 0 C N G O P- C N C N p- O cn G O 05 05 r—C NO 05 T —P » C N 05 N * T- C D P » cn cn In 05 cn C OG O 05 05 cn C O G O C N p» 1 ^ % 1 ^ 05 cn C O cn G O t* " P » O C N cn p. G O cn tn U 7 1 n tn C O C O p P co G O O d d 0 O 05 05 C D 05 ao 0 5 *05 • 0 5 0 5 T — 1 1 T ■ * 7 m in in tn m tn m tn tn m in m tn tn m co 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 U J uj uj uj uj uj uj uj uj uj uj uj U J uj U J uj C N C N C O tn C N N * 05 p C N C O C O 05 cn p. tn tn 0 p. C O O C N 05 N * 0 5 0 •v 0 tn tn cq 0 ID C O C O p- P- P * G O cn m 05 05 c d in cn 5 cq V T “ C D O C O r- 00 C D * cd cd cd in m * in m * cn cn C N *- 05 C DC OC OC O tn in tn tn in in in tn m in m tn m 0 0 0 O 0 0 0 0 0 0 0 0 0 0 0 O 0 uj uj uj L L J uj uj uj uj L U uj uj uj uj uj uj L U U J p. P- C D 05 T —P- • * * C NC Np C Nm C O C O C OC OG Ocn • n * C N0 O C Ocn G Ocn C N0 p- C N p- p. C O tn p- C NC NP » C D C O m tn in 05 •« r cn p. p- C NC N 0 tn cq 05 C Ncn P. cn C Nm C N ■ c N * N * N * * C D 05 T “ C Ncn cn ^* tn in C D * cd P o <0 C P nr © © a o < 0 < ^ © © S T cn p 05 C N 05 C N C O C N N " 05 O 0 0 0 O C N C N cn cn cn O 0 0 0 O d O O O O 0 0 C O C O ■ * r C Nin tn oo cn tn 05 10 tn tn tn N - co N * ® . C NC NC N ® . © O O 0 d ▼ * cn N *tn p c n in o C N C N C O C O c AppendixB /OL R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. « f f l *o 5 c © o E o in © ii a . X h - © _ ■ © 2 a " O c © © ■ o *o T 3 c © © a . © ■ Q X Q. . c o O <n c co o o © C D © s to tn Ui ® C O 05 ▼ “ C N 05 C M C O C N ▼ “ C O C O C O C O 05 C O C N co rs C D 05 cn m c o r - co r- co in co m O 0 5 ts c O rs O rs a o 05 C D C O 05 m c n G O C N C N G O rs C N O 05 C O 05 C O 05 G O 00 05 05 m a> co * — m i n •*- m C O C N C D C N p O G O C N m C O C D O N C O i** I C 5 N N 05 O O C N 0 5 >05(0 ® O P m i n cn o t n cn i - eg O ^ co O co Si rs p C O C N C 2 0 I s* n co n r co < n w n . co ° ? o o o o o o j r 05 , t n m in t n m m i n tn m t n t n m t n tn m in m o cj o o o o o o o o o p p o o o o o p c UJ U i Ui UJ u i Ul Ul UJ U i u i u i U i U i u i Ui u i U i o r - C N 05 C N CO i s CO CO P r s m CN CO m o 05 p 05 r s CN G O r s m p 05 G O CO CO G O 05 CN in CO < £ > CO r s m h - CO 0 5 P r s 05 CO P ? 5 a> r s © o *— o s o CN CN G O G O 00 © CD CN to CO m CN o i f cq CN c d CO CO CN r s p p to Ui c d t n in' i n m* P p CO C N * CN o N CO CO CO co i n i n i n m m t n t n i n m t n m m ▼ — c O o o o o o o o o o p p p o o o o o O f 5 LU UJ UJ U i Ui LU u i Ui Ui U i u i U l U i UJ u!i U l u j U i o h» 05 C N p CO CO r s r*- N . CO t n m r s P p y»- CN C O o N* CO CN co CN ■O' CN m i n CO p Z _ • 05 r s C O C O r s O t s . r s . i n 05 p CO CL GO z • C O cd G O CN CN CN CO c d P P ■O ' i n CD CO r s CN t o C N in C O G O 05 G O CN G O CN C N r s CN 05 m in CO m r s 05 C N P 5 05 CN | s 05 t n CO p m CO ii 05 CN CN CN C N CN CO CO c o CO p P m i n m CO C L A < o ’ d O o ' o o o ' o d o * o ' o o ' o o o d o C O rs o C O o o d © a o M rs ^ cn I s: «* O .o < o o o C O T~ CO 05 CO CN G O CO p C N o G O CO CO o CO CN o co C D CO m m in in m p P p o ' o ‘ o* o* o o ' o o ' o ' o* d I ° o ' ^ N csi r i c s ’ o o C O C N ^ G O C O C O C O C O C N C O C O G O C N cd C O C O c C N C N C N © i n co N T Ui ©. CO G O CO r s C O i n t n C O r»» t n CN 05 G O p P f ^ C O r - i n CO m h - m CD P O CO 05 p T “ CO CN CN i n CO s T " » CN r - i n P CO G O CO r-. m CD i n 05 o C N 05 s CN o h - 05 o G O i n p i n 05 o CN CO CO 05 r*- 05 p CO p CO CO p CO G O CO d p I* * * 05 CN o 0 5 P C N O CO P CO m 05 C N m C N CO O C N CN 05 CO IS. o P C O O O CN CO m r». 05 CO CO r s rs. G O G O 05 o o o o d o o d d d d d d r - p m i n t n m t n in m in tn t n m t n m m in m in ( j o o o o o o o o p o o o o o p o o c Ui UJ U l U i UJ Ui Ui Ui L L J Ui U i L L J U i Ui UJ UJ UJ o 05 CO m C D p C N CO p CD « r — G O r s p CN o G O o i n 05 r s 05 o r s r s o 05 CO o C O C O CD p CO p CD CD » CO CO r s r s o p CO o p . CO C O C N CO 05 CO O C O o C N • C N o CO CN © p 05 CD p C O o CO p ; CN r s CO C N cq p C N 03 cd cd t n i n i n in tn p p P cd cd CN C D 0 5 r s 0) t s 0 5 C O o © a o O Ui o ^ 2 ,~ X — ' w C O 0. ^ i n c o p c o c o c o f n c o i n i r i i n t n n o r » ® n n * ? n n O O O u j u j UJ cn in p rs o o 05 P C D C N C O O W C O * C D UJ U J Ui Ui rs P . m o tn m in o in o tn in m tn in in o o o o uj p o o o UJ U J UI u i C O C D 05 Ui uj Ul ui U J C O rs ao 00 p rs 05 G O 3 p 05 05 C O C N 05 o rs G O C O C D G O C N C O 05 G O O tn in o p G O o C N C N * C N C N cd p* p P in C O r s i n .O o < 05 C N rs in p T _ 05 C N in C N C O C O cq r — C O C NC O P fs G Oo C NC Om o 05 P rs in C O in C NC NC NC N C O C O P p in m o o o d o o o d d d d o o o d d d C N C O rs C N C N C N m C O cq p C NC 5 0 0 rs C O C N o C O C O o m C N C O C OC O m tn m m m p p p C O C O o o o o o o d d d d o o o o I O 2 2 C N go co co m go in C N C O P C D rs C O ^ C O <0 C O C N C O C D C O C N C N cd C N C O C O c IS AppendixB /D l R eproduced with perm ission of the copyright owner. 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C D < • C M T T ID « - in C M O C O C M C M C O P- C M 03 C D m + — C D P» ID C O ID 03 C D ID C O p- ID p- O C M C M G O ID C O ID in C O C O C M O P-. 03 C O ID O p- C O p - ID C O P - C M 03 03 C D M * ao C D C M C M 03 O O C M V C O < 0 C O w C O C O CD C O 03 C O C O 03 03 O O O O O 0 O O 03 03 * 03 03 T — *7 O ID ID ID ID ID ID m ID in in ID ID ID ID ID ID ID ID ID O O O O O O 0 O 0 0 0 O O O O O O O O L U UJ Ui Ui Ui u i Ul Ul Ul ui Ul UJ Ul Ul UI Ul Ul u i U J P- G O G O C D O C O C D ID C O 8 ID C O ID P- in m C O m 8 ▼ — C O 03 p* ID 00 C D M * V G O ® C O in C M O M * O O C O C D 03 tn *T C D p. 03 S O C M C O 03 C D 03 03 P- ▼ — in C O 03 03 C M O p- ID C O P- P» C O 03 C D P-. C D M ” C O * C M C D O CD 03 in M * I D C M m * O m * C OC D C M ID C O C M C O O C O * M * C M O C M P - O ^ c — o s i Z C L z C M JZ ' rt 1 1 « r « ■ € CD CD CP 8 © ID ID ID ID ID ID m ID ID ID ID ID ID ID O O O O O O O ID O O O O 0 O O O O O O O UJ U I U l UJ UJ Ul Ul Ul III Ul UJ Ul Ul Ul UJ UJ L L J U l UJ UJ C M P~ ID CO CO CD 03 i n G O C D 03 ID CO C M O' CD GO j 9 i n M- C M CD ID C D C M m P-. 03 CO CO a o C M CO ID C M 0 3 CO . CO M’ ID 03 C M M * P - M * p-» 03 ID O C M O C M * ID * K 03* r - -r- T “ C M C M C M C O C O * CO M * ID ID P - m CD 03 m 0 C M CO ▼ “ T — C M C M C M 0*O O O O O O v — I D 0 3 C M tn C O C D ID C D P- C MM * 0 C MC O C O C MC MC M C O C O C O M * M - M - V O O O O 0 b 0 O O * b O ' I s - ® A o < © £ o C M M' O 03 I D C M C O C Dm 8 v— in C D p- C O p- C OO 03 P - ID M- O G O P - I D M - C O G O C O 03 C O 03 Is* P-. P^ P - P - P - C Oco co C DC OCD ID ID in M * M’ C M O * b o ' O O O o ’ 0 0 * O 0 O * O 0 0 * O 0 * O O b M » m t f i O N T r ® o o i f i o o i n o o o o ® c g “ ( D ® * - * - * -^ - * -C M C M C O ^ , ^ ' i n i O P ‘ C 0 1 £ b © £ C D 8 55 w co © £ - « <0 (jj iD e'C D CO CO CO Is- 03 C M CM 03 o r ^ 0 0 CD 03 p- ro C 3 © »• 10 0 ) 0 © 1 0 3 03 03 in C M C M c o ,<r ▼ “ 03 ID CO TT C M V ID C O ^ CD P - 0 3 03 ^ CO CD 03 c o o ^ CO CO ^ CO 03 CO P* CO 03 03 s® Si o £ JD 5 ® § ID C M ^ ID C M C M C M CO CD CO « r m * CD ID C M 03 O O C O CO O O C O P - w 03 •v C M C M CO 03 03 03 03* © O D CO • * “ 03 CO ID CO CO 03 CO 03 ID O O N O C M N O O CO C M C M * - O O S D 1 - S C M 03 03 h* © N C M CD ID C M CD O CO CO ^ P - 0 3 r - O O 0 * 0 * 0 ^ I D in ID in in m in in in in in m in I D I D m in m ID I D y O 0 O 0 0 0 0 0 0 0 0 0 0 O O 0 0 0 O O C Ul L L I L U L U UJ U J Ui UJ L L I u j U J UJ u j u j u j u j L L J Ul u j u j 0 M * P* CO M * CO 03 p - p - m M * p - CO ■ O ' C M CO C O C M I D 0 CO CD CO CO 0 3 CO 0 I D C O 03 -O' p - I D CD p - *^r S B CD O CO M * CD O 0 03 ID P - C D O CD CD co 03 03 CO C M CD p^ C M I D M * P-» in 03 C M C M 03 CO CO 03 C M 03 W © 0 03 CD CO C M G O CD M“ C M 0 C O CD C M G O T~ p- TT CD CD CD in in t h in ID m- ■ O ' C O CO C M C M U J • c 9 ° o « O D ^ f ~ ^ © 2 Q . N 2 r - C DC D C D m ID m I D ID ID ID ID ID ID ID ID ID ID O O O C D0 ID O O 0 O O O in 0 O O O O O O 0 0 uj UJ uj O UJ 1 1 1 uj UJ uj U J uj tti U J uj uj UJ Ul uj UJ uj t—C O Ul Ui C OC MG OI D V UJ C DC OG OG O P- 03 C O P-. 0 p- 03 C D 52 C O03 C OP- ID N C DC OC DC D 03 C OC OC O C MC M G OID p. C OID 03 I W /n G OC MP» M * ffi 03 P - C O co C M . C DG OO C M V lb) 03 G O 03 C M03 C O C D p ^ V- C MC MC M * C M C MC OC O * tn ib p - i C M CO C M CO C M CO 03 CO 03 C O ID C D 0 0 O C M CO y— TT CO m P - 03 O CO C O P-. C O 0 C M CO ID C M CO ID O CO ID CD (I iA T “ C M C M C M C M C M C M C O C O CO C O •o* O' in m in to .c C L A < O O b o ’ O o ’ O O* O o ’ o ' O 0 O 0 0 ’ O b b 0 O K ID ID C O P - C O G O p- P - G O CD 03 C M 03 ID ■ O ' C M C M C M 0 G O P» ID CO C M 03 G O P*. ID C M 00 CD ID C M p - p - CO p - C D C D C D C D C O CO in in m m m V -«r CO CO C M £ b O 0 O O* O* O O 0 ’ 0 0 0 0 * o ’ 0 * O o ’ 0 0 * 0 O © E o — . ^ r r t O C M M 'C D C O O D O O l D O O O O ® c M ^ r c D c o ^ ^ ^ . ^ ^ C4CNiC0^ . ^ . i n c o r ^ QOc AppendixB 21 / & R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. T O * o C o T O w 3 T O < n r* T O O O (J v ) Ui o o © U J C O o °' § o 05 D < 0. 2 5 T “ o o o o O o o o o o o o o + + + + + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C O V ID r*- G O o C N TT o C O ID o O o o O p C N C N C O 1 i 1 i t 1 1 i i i i 1 T ID ID ID ID ID ID ID ID ID C O C O C O O O O O O O o O O O o o o o o UJ UJ u j u j u j u j u j u j UJ u j u j UJ UJ + in o G O ID C N C O r*» o C O C N ID O C O C O o h- ID C O C N r^ o C N o C O C O C N C N C N ▼ — ▼ - cd ^r C N ID o C D C O ID ID ID ID ID ID ID ID ID ID ID ID o o O O O O O o O o O O O o UJ u j UJ u j uj u j LU u j u j u j u j u j u j uj C O o O ID 05 05 r*- G O o ID o C N ip p O C N •<r C O ▼ — C O C O r - G O C O T — C N C N C N C N cd cd cd cd cd C O ID ID 00 o N’ O C O ID C O ID C N 05 ID ID 05 C O 5 C N ID o C N C O C O C O N ’ ID ID C O C O C O d O O o ’ o* o o o o o d o ' d O © a o 05 © E O f N lf lO lf iO lf lO W O O O P 0 • - - - - — ' — " — ' — ■ - ' O O O O T- W C N T O TO ^ © N ID 05 U J T —T “ T “ T “ t — o o o O o o o o o o O o o o o + + + + + + + + + + + + + + + U J U J U l U J U J U J U J U J U J U J U J U J U J U J U J C N C O ID C O G OO ) * — C N ID I s - o C O C N C O O o O o O O T ~ p r — C N C N C O n; i 1 i 1 V v i i i v i T “ 1 i • ID ID ID ID ID to ID t o ID ID C O C O C O C O r — O O O O o o o o O O O o p p O uj uj uj uj uj uj U l uj uj uj uj uj uj uj uj ID G O O O C O r^ t o C O G O o ^r h- C O G O • < r c o t o C O O ID C O r- p p cd cd C N C N C N T “ " *- T “ G O * cd nr * M O c o r 0 ( O l A l / ) I O i n i A l A l A U ) U ) I O U ) ( O i n i O g o o o o o o o o o o o o o o o o OuJUJUJUJUJUJUJUJUJUJUlJUJUJUJUJIJJ O ktO lO lO lO O 5 O C O G O C O C N C O O 5 C 0 ^ ’ COCO w < - N ( O N O ^ ( O O O C M { ,) l O N O t - C N 0. ......................................................... 05 < ® ^ C O c r o C L © GO T~ ■ * “ CN CN CN CN CO CO CO CO CO TT ^T CO O CO 00 CO h - ID CN 0 5 GO CD 05 ID CO o CO ID 0 5 CN ID GO 0 5 CN CN T“ CN CO CO N* ■ N * N* ID ID ID CO CO CO h* o ’ o ’ o' o o o o ’ o o ' O o' o' o o' O C N ID O o o ^ O O O IO O IT) cn cn cd cd o o o AppendixB R eproduced with perm ission of the copyright owner. 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C a * saturation data O c o o © (0 Ui o o © 0 9 UJ o o o o o o o o o o o o o o + + + + + + + + + + + + + + L U L U LU LL fU JU IlLIU JU JU ILLJlD liJLL I C N i f 0 f 0 ^ “ i n U 2 ( D N h * © 0 > ^ - C 3 ) ^ r O O O O O O O O O O t - C N C N C O o o o o o o o o o o o o o U i U J U J U J U J U J U J U J U i U J L U U J U J r ^ c o ^ r c o ^ h - T - c o c N c o t o r ^ i r } c p ^ r c M o c D c o i n c o c N O O J i n m co co’ co co* cn cvi cn cn cn oi cd d cn CD O o o U J ui S g © z O c o c D C D t D l D l D l D i n m i D t n i O l D l D l A o ° o c p o o o o o o o p o o o o o 0 O U J U J U I U J U J U I U J L I J L L I U J U J U J U J U J U J U J ° - ^ O ^ W O C M N C O t a t N O O O O l f l O '— o 0 0 5 r - T - ( 0 ^ ( p S O J O ^ ( D 0 5 0 ^ d ^ ' © o > T , , r “ r “ ,p' ,“ ^ , c N i c o c o (0 N’ C O .Q ^ J C O O N x r M O r t O ) V N ( D O C M O ( D - D y O ^ - ^ - T - W C M O J C O C O C O O © © © C L ^ O d d d d d d d d o z 0 0 0 © o .c ■ § 0 n 1 X 5 CO O © d d o ’ o t- E V - c o m c o o c o i o o o < “ C N J N C N © S T o CO c c: o c o o w © T o UJ o c o o © T o UJ o O 0. z c o n « < % s o. z 0 0 0 0 0 0 0 0 0 0 0 0 0 + + + *♦*+ + + + + + + + + U J I U U J U J U J L U L U U J U J I I J I U I U L U 2 N n 'T t D N O O O l i - C I N O N O O O O O O O O t - T - T - C S I C S I ^ r i n i n i n i n i n i n i n i o i n i o m t D N O O O O O O O O O O O O O O O u j u j u J u j u j u j u j u j u j u j u j u j L L l i M S f f l l O O O f f l N O I O O O O V O O o S B n u i i o N O M O v n v o N g o c o c v j c s i c N i c s i i ^ T - ^ e d o c r i o d j - , ' O f f l d j i n i n i o i n i n i n B i n i n i n i n i n 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ujuruju ju jiiiiu u ju iu ju iu jiiitiju j °- O t M l O O K O I O N O t t l V ' - O n i O v S o N ' r n N o n i n M s i f l N o w n co o ’ o o> *-’ cm’ cm ’ cm ’ cm csi co co ■cr M o n o n ^ o a i o o m N i o n o c i o r - T - c D r r o i o o c o r - o o o c n o T r o o ^ r - c v n n ' T ' T ' f i n i o o c o s N O o ’ o ’ o o ’ o ’ o ’ d o ’ o ’ o ’ o ’ o ’ o o ' o ’ o ' a > E o c M i n o c o o i o o t n o o o a o' 0 0 7 = AppendixB 23 /G& R eproduced with perm ission of the copyright owner. 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C D * o c o C D w o IS c o O o c o o 0) C O UJ £ d c o o © C O UJ 2 O S o O w * C D A 2 CL Z C £ o © d E H- « T “ r — *“ • o o o © o © o o © © © o © © + + + + + + + + + + + + + + Ui UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C M C O O' C O C O C O C O I s - I s- co r*- -O ' cO © p o o O o o p o o r — C M C O i T— t 1 T — 1 *7 i T — 1 1 V i • C O C O co C O to IO C O C O C O C O C O C O C O C O o o o © o o o o o o o o o o UJ L U UJ UJ UJ UJ u j L U u j u j u j u j UJ L L I C O p- 03 T — C O 03 co 03 C O G O C M 03 C O C O o ao C O C O ^r C M O) o C O C O C O * cd cd C M C M * C M C M C M C M 03 G O T* C O C O C O C O C O in C O C O C O C O C O C O co m C O o o o o O p o o o o O O o p o UJ UJ UJ UJ UJ u j LU UJ u j u j L L J u j L L J u j L U C O C O IO C O T — p — C O Is- o C O C O cn C M C O 03 03 r- o C M C O C O CD I s- p o C M C O 03 o cd G O T — T — cd cd cd cd C O o G O C O TT C O I s- G O C M 03 C O o 00 C M C O G O O C O C O 00 o C M C M C O C M I s- o o V- C M C M C M C M C O C O co C O C O C O I s- o o o d o o o o d o o o d o o C O C O G O o C O C O G O o C O C O o o o p 15 o o o C M C M C M c d o id c — - C M N C M * ■ — o o o o o o O o o o © o o o + + + + + + + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C MC O O' in C OC OC Or- r-. C OG O O o p o o p o p o o * * ■ ; C MC O I : T “ 1 t 1 T — 1 • 1 i i i 1 i 1 in C O I O C O C O co cn C O C O I O C O C O C O C O o o o o o o o o o o O o o o o o uj uj uj uj uj uj uj L U uj uj uj UJ LU u j + L U 0 3 0 3 0 3 O o in o p- C O 0 3 C M in r-- in C O T - o 00 I s - cn o C MT — C O r - 03 cn w o cd cd cd cd c m ' C MC M C MC MC M0 3 r - cd d C O C O C O I O C O C O C O C O C O C O I O lO cn in co o o o o o O o o o O O o o o o uj uj uj uj L L I uj uj uj uj uj uj uj uj uj uj Is - o T J * O ’ r- C O o C O Is - o G O a o cn 03 C O cn C O C O o C MCO C O C O p- p O C M C O G O o cd cd r - T — ▼ - cd cd cd cd o o w 0) I d UJ o u © C D LU O c o o © a C D § 5 C * ° . 5 03 03 03 G O C O C O CO Is- m o T— G O f— T — ^r r - o C O C O G O o C M C O CO CO h - 03 o T “ T- C M C M C M C M C O C O co C O C O co C O d d o o o d o o o d o d o d d S o n i n e o o n o c o o n i a o q 4J o o o d t - t -' tsi csi c n cd r ~ E i— o P 15 d cn c AppendixB w R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 03 03 ■ o c o C O (0 in C D O in Ui T ~ - o o o o o o o o o o o O o + + + + + + + + + + + + + Ui Ui UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C O CO TT • S 3 * in m CO C O r^ in o o o O o p p p p O o v- T — 1 1 7 t ( V • V 1 V i i i T in © in m m in inin in m inin CO o o o o o o o o © o o o p Ul UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ 03 C O in 03 o m CO 'O * CN o C O tn o m CO ▼ “ o CO m CO C N o co C O CO CO C O cn c s i o i csi CN CN T ” cd 00 o C N o o o o + Ui o o o' d (0 .o < CO C O co t n i n t n i n i n i n m m i n i n © i n p o o © o o o o o o o o o o o UJ UJ UJ UJ L L J UJ UJ UJ UJ Ul UJ UJ UJ UJ L L J C N C N o C O CO CN C O G O C N C O C O C O C D C O 03 s r o ▼ ”1 CO © © 03 m C D o cd G O * * “ T “ T — CN cd cd cd i n C O t n CO r*- CN C O in in ^T in T j * G O *r h*. o CN i n r ^ 03 ST C D a ) o C N CN C N C N C N C O in i n CO C D C O o o o o o d d o o o o o © o o 0 3 Q. OCMWflOOWlfiflOOrtWOOP o o o o E © *- ’ S- C M C M C N © N P C O tn e o o o o o © o o o o o o o o + + + + + + + + + + + + + + U J U J U J U J U J L U U J U J U J U J U J U J U J U J C N C O N “ •S T i n © © © h - © r ^ S T © O o p © o O o p o o r — C N C O i 1 r * t i i « 1 T “ 1 1 7 “ I i i T — i n m i n i n © © © © © © © © © © o o o o o o o o o o © O o o o o U J U J U J U J U J U J U J U J U J uj uj uj U J LLJ + 111 s t i n C D 0 3 C O C O C N o r * . © © © C N © U J i n C O © © c o © N * C N © © C O o c d c d c d c s i c s i C N c s i c s i c n C N 0 3 • s r T— d C D C D © © © © © © © © © © © © © O O o o o O o o o O © o o © o L U U J U J U J L L J U J U J U J U J U J uj U J uj U J uj C N C O 0 3 r * - r ^ - C O r * - © C N o o C D © 0 3 i n C N © C O s T © N . C D o C N © © © d c d d © T ~ T“ T “ c d c d C O C O c d o o r — C O C N _ a > C O © © © C N s T © N - o C N © © r — T” © © © O T “ C N C N C N C N C N C O © © © © © o d o d o d o o o ' o ' d o © © © C O i n 0 0 o C O © © o C O © o o o O 7 5 o o © c > i c s i c s i © o © c o u ( /} UJ o c o u _ < 0 5 uj ^ o o e tJ l l j ^ o CL ° (A tn .§ .0 © o E H - AppendixB /ozr R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. < 0 C O TJ c o C O C /3 C O O £ 2 T — T - r - ’ r - T — ▼ -* - C O O O u k _ © w Ui o o & I n Ui o c o 2 - O i § C O - < 2 * £ S CL 9 z £ o © O E r“ o o o o o O o o o o o o o o + + + + + + ■ + + + + + + + + Ui Ui UJ UJ Ul Ui UJ UJ UJ UJ UJ UJ UJ UJ CO co CO N* •O' to to CO CO N- CO o GO o O O p O p o o o O CN CN 1 ■ i r- i T- T“ 1 1 1 1 i T“ I 1 i i to to to to to to to to to to to to CO CO o p p o o o o p © o o o o o o o Ul UJ Ul LU UJ UJ UJ Ul Ul UJ Ul UJ UJ Ui + HI IO CO CN 03 00 r^. CO GO CO 00 r- I W o to CO CN o 03 oo C O to CO CN p CO c o o CO CO CO c o CN CN CN Csi CN csi T * * CO CN d CO CO CO C O C O to to to to to to to to to to o o O o o o o © o o p o o p o UJ ui Ul UJ Ul Ul ui UJ UJ Ul UJ Ul UJ UJ Ul 03 CO CN to V C O t o CO N- ■O ' to 03 C D C O r*- to CO T —CN CO to CO CO CN C O 03 IO C O ' 03 ▼ “ T“ CN CN cd cd cd CN o N. o C O CO CN o CO r«- o CN h- 03 ▼ — C O to r^- t o 03 CO C O r*» © ▼ » CN CN CN CN N’ ^r t o CO C O d o o o d o o o o o o d d o o co to oo o C O to 00 o CO t o o o o o 15 o d d T“* CN c\i CN cd d T — to' c C O h * . © Q . O C O O c o o L ~ 0) * 0 3 UJ O O © 03 Ui T — T~ o o o © © o O o o o © © o © + + + + + + + + • + + + + + + Ui Ui Ul UJ UJ Ui UJ Ul UJ UJ UJ UJ UJ Ui C O C O N * to to C O C O r^- C O N1 03 03 o o o o o o O o o o T~ T “ * C S I 1 V T " * 1 1 1 T* 1 ▼ — 1 1 *T *7 i 1 1 to to to to to to to to to to to to C O C O o o o p o o o o o o o o o o Ul UJ L U Ul UJ UJ Ul UJ Ui Ul UJ Ul Ui Ul 03 to 03 G O C N o G O r - r^. o 03 o TT C O o 03 G O N » to C O C O O IO " N * cd cd cd cd csi C N csi C N C N C N T “’ cd csi r- C O © £ o O ? S o Q-S CO CO CO CO CO to to to to to to to to to to o o o o o O o o o © o o o o o UJ Ul Ul UJ Ul Ul Ul U J Ul Ui Ul Ul Ul U J uj to 03 r*. h * - h- 03 C N C N CO 03 o T T to 03 o CO o to o T — CO - n; lO to G O C N CO G O to N » cd 03 T ” T- t— csi csi cd cd cd o > O < 1 o C O C N to C O to C O C O 03 03 r - 03 C N • N - C O C O o C N C O G O to C N r - o o T “ C N C N C N C N N’ to C O co d o o o o o o o o o d o d o o C O O C O IO p O C O I O G O O C O tO o o o o W t- V c\j c\j cvi o O Tn C O to c AppendixB A t R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Ca2‘ saturation data o c o o a i UJ a c o o ( / ) UJ CM o ° o O 0 . z cn - < r~- __ tz, 0. « ■ » *— o o o © o o o o o o o o © o o o o o o o + + + + + + + + + + + + + + + + + + + + UJ UJ UJ UJ UJ U l UJ UJ UJ U l UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ co CO C O tn tn CD CO C O r -. o o C O 00 05 05 o CO r^- tn © o p o o o O p o o o o O o O ■ r - C M T— 1 1 V* 1 i 1 i 1 1 i V 1 T — 1 1 r * i 1 i I V i tn in tn m tn tn in tn in tn tn tn in tn t n tn tn CD C O o o o o o o o o o o o o o o o o o o o O o o UJ UJ UJ LU u i UJ UJ UJ UJ UJ u j u j u j u j UJ UJ U l u j u j uj + UJ o o m C M G O tn r ^ 00 r r m C O tn o o t n tn C O TT C O C M *“ o o C O tn r r C O C M o p o o N» r^ m ; C M 05 o o o C O c o ' C O C O * C M * C M C M C M C M C M C M c s i r - r * - * C O o t o CO C O CO CO tn tn tn tn t n tn in tn tn tn m tn t n tn tn m p o o o O o o o p o o o o o o o o p o o o UJ UJ UJ U l UJ UJ UJ L L J LU UJ u j u j LU u j u j UJ u j u j u j UJ u j o o co tn o C M O 05 CO C O C M O O C M 05 C O C M C M p*. 05 p s - . CO C M C O tn 00 C M c o ■o; p r*- cq o o O o C O o 00 CO th C O hJ a i T “ T “ T — T “ C M C M C M C M C M C O C O C O h - © 0 ) o o r^- C M CO 05 C O tn 05 o C M 00 C M o p«. C O 05 o C O h - o C M tn 0 0 05 C M -o* C O P*. tn C O o C O o o T * T“ C M C M CM CM C M C M CO C O CO C O CO ■ M - tn C O C O © d o o o o O o d o o d d o o o o o d o o £ o n i f l s o f f l O n i o « n i n o o o i f l o o o o o 9 0 < d iuoooo-<-'<-cNcsicsic\icofr)cnTrTrTriricor~2 if 2 S E O C J w © o 5 LU 'c o o Q ) to UJ T — © o o O o O o o o © o © o o © O o o o o + + + + + + + + + + + + + + + + + + + + UJ UJ U l LU UJ UJ UJ UJ UJ UJ UJ U l UJ UJ UJ UJ UJ UJ UJ UJ C O C O C O ^r o* in tn C O C O r - G O 0 0 05 05 05 o C M C O C O o o o o o o o o o o o o o O o O C M 1 1 T - 1 T — 1 • • «r» i 1 i i T “ 1 1 1 v T T 1 i tn tn m in tn tn t n t n tn tn tn tn in tn tn tn tn in C O C O o o o o o o o o o o o o o o o o o o o o UJ U l UJ LU UJ U l U l U l U l U l uj uj uj UJ U l U l LU uj uj uj 05 00 C O tn C M C O C M 0 0 o C M t n 05 05 in C M tn C O C M 05 C O m C M C M o p CD P * . in C O 0 0 c q C O C O C O C O C M C M csi csi CM csi csi csi csi T “ ▼- c b C M O O O to .o % s C O C O C O C O C O tn tn t n tn tn tn tn in tn tn tn tn tn tn in tn o o o o o o o o o o o o o o o o o o o o o uj L L I UJ uj uj UJ uj uj uj U l uj uj uj uj uj U l u j UJ uj U l uj tn P^. C O C O C O C M oo tn C O O' C M r - p*- oo C M C O C O p 05 o C O C M t o tn p h - CD p O o C M m 05 00 C O th 05 ▼- y — v - y - y - y - C M C M csi C M csi co C O C O C O C O C M tn C O r»- "O' C M tn 05 C M tn oo p^ T — C O C O o in C O 00 o C M C O 05 C M P - 00 05 C O •o * in 05 C O 05 C O o o * — T — C M C M C M C M C M C M CO C O C O C O C O tn in C O o d o d o o o o o o o o o d o o o o d o o i o n i o o o o i o o n i o o n i o o o o f l o o o o P P c d ® d o’ o’ o csi csi csi csi co co ri v v m o n 2 2 = E AppendixB 27 f / C R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C a saturation data O O tn U J o o o tn U J o c , o S = Si o ^ Q_ c /3 < ° co i g — P £ L O £ o 0 o E o © © o o © o o O O O O O © o o © o o o O O + + + + + + + + + + + + + + + + + + + + + + U J UJ UJ UJ UJ UJ UJ U l U l UJ UJ U J UJ UJ UJ UJ U J UJ U J LU LU U J CO CO CO •*T TT ID ID ID CD CD r - I s- h - CO GO 0 3 0 3 ■ < T O CO o p o O © o O p O O O © o o o O O O T - T— CM CM 1 t 1 t 1 1 i * 7 i t i i 1 t 1 V T* 1 "V * 7 • i i i d ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID CO CO o o O o O O O O o O O O O o O o O O o O O o o o U I U J U J U J UJ UJ u j U J u j u j UJ u j UJ UJ UJ u j u j UJ UJ U l LU U J + LLJ o> o o CM C M ID h - CO CM ID GO CM CO ID GO CM CO CO 0 3 CO CO CO CM O 0 3 GO r - CD ID CO CM O p 0 3 r - ID O o CO o C O * CO CO CO CO cm ' C M * CM CM csi CM CM CM C M cm T — ' r“ d C O * d CD CD CO CD CD CD CD CD ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID o o O o O O O O O O O O O O o O O O O O p O o UJ UJ U J U J UJ UJ UJ u j u j UJ LU u j U I L L J LU L L J u j UJ UJ UJ U J LLJ UJ CD CO CM T — CO ID O CO ID O GO GO o p - CO CO CM 0 3 C M CO C M CM o o p - ID CM m ; p p CD p T— CO CO N - CO ID CD r - CO 0 3 <— T — T — <r" CM CM CO c d c d GO CO O M- CO CO CO o CO ID CM CD CO 0 3 o 0 3 CO 0 0 ID CM ID p - 0 3 O CM CO TT CD 0 3 o ID CO GO o ▼ » CO r - ID CO CO O o O C M CM C M CM C M C M CO CO CO CO TT ID ID CD o o o d o o o d d o o o o o o o d d d o o d d CO tD CO o c o ID c o o ID GO o ID GO o ID oo o o o o o o 1 5 d o o CM CM csi CO CO CO •<T ID c d r -i d ID d CM c T * “ o © © o © o o © © o o © o o o O o o o o O o + + + + + ♦ + + + + + + + + +• + + • + ■ + + +■ + UJ UJ UJ UJ UJ UJ UJ U J LU U J U J UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ CM CO CO CO CO ID ID ID CO CO CO r - r - f - GO 03 CO GO co O o o o o o o o O o O p o o o o o O O t - T — CM i 1 1 r— 1 1 1 • 1 i 1 1 1 t i T * 1 i i i T ” 1 i ID CD ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID ID CO CO o O o © o O o O o O o © O o o O O O O O O p o o UJ U l U l UJ UJ UJ L L J UJ U J U l L U u j UJ UJ UJ UJ UJ LU u j u j L U UJ + L L I CO 0 0 O CM CO ID GO 0 3 CD 0 3 N» CO C M ID r - r - GO M 1 p - ID CO C M O 0 3 G O P - p ID TT C M C M P N» CM p o CO CO CO C O * CO C O * C O * CM C M C M * C M csi csi C M csi CM c s i t— o o o k_ 0) V ) U J o o S a ? U J O C o o C O C O C O C O C O C O C O C O I D I D I D ID ID ID ID ID ID I D D ID ID I D ID o o o o o o p o o o p O o O o o O O o o o O o u j U J L L J U J U J U l U J U J u j u j U J u j U J u j LLJ u j U J U J U J U J U J u j u j C O I D C O r - O ’ ID ID C M C O G O ID o p - 0 3 C O 0 3 O O GO C O 0 3 o ID p C O M - C M 0 3 C O ID o O T - C O CO p p p C O O ID o -O ’ G O CM* c d i d c d c d P ^ G O T — T— CM c s i c d c d c d o C O C O r ^ - C O o C M r - G O h - 0 3 I D r - 0 0 r t T * C M O ’ GO CM C O C O C O o o * C D 1 ^ - 0 3 o CM C O ^ r P— C O 0 3 C M CO M - P — C O 0 3 C M ID O ’ C O 0 0 C O o o o o o ▼ — r — C M CM CM CM C M C M C O C O I D I D C O d d d d d d d o o o d o o o o o o o o o o o d o < /) c § . O N i f l a o o n i f l s o i D a o o K i o o o o o o o o ®oo'ddr-<-r-T-'(\icsirgnnriTi:'ir'fifl(Ds E o o o C O o ID d c CM AppendixB 28 / / / R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 3 « j x j c o m w 3 IS C O < 0 o o o 3 In L U o o o o o o o o o o o o o o o o o o + + + + + + + + + + + ■ + + + + + + + L U U JU JU JL L JL U U JL IJL U L L IL L IU JL L IL U L L JL IJL U U J W^WU)tf)(DO(DSNN05^0®COr* O O O O O O O O O O O O O t - > * - ^ “ «-CM G O U ) o c o o 3 'tn L U o o o o CL z i n i n i n i n i n i n i f l i f l i n i n i n i n i n i n i n t o m c D o o o o o o c p o o o o o o o o o o o L L J L L I L L J Llll L L J L ill till Llll L L J Lilt L L J L L I L L I L L J UJ L L J Llll L lll O O O N t N O I N ' T I D O M I l ^ B n O O qo) 0)oqN(oww^nfo^-o^(M(OCM^ CO 04 04 CM* cm' CM CM CM CM CM CM CM CM *-* 05 f-» IO O O + UJ o o (O(D(O(O(O0(O(O(O(O(OiniAinininu5toio o o o o o o o o o o o o o o o o o o o U J l U U J U J U J L U l U L U L U U J l U L U U J U J U J L L i U J U J U J OVO)0(D^SOCOO)«C4^U)OONU)0) 0)r-CDNM;CNI05Cq^;040)0^005CM^qr- CM* 04 CO M* to U5 CO N CO CO ▼- *-* CM* CM CM CM CO 0 3 a c > tn < n X 2 o>< * = ii a. o n N O v N o n in o in ^ fflN 'T O 'tfflN O gnniniosoiot-cMvinsfliiocMootMiom o o o o o o o - ^ - t — r— r - T - T - - ^ c o c o < T 2 T r ' r m o o o o o o o o o o o o o o o o o o o o a> E o n i n o w o i f l o w o t D o o o 0 0 0 0 0 m o' o o* C O c m c m cd cd ^ ^ m cd r ^ * 2 !2 ^ ^ ^ c CM CM CO C C3 c o o tn UJ o o 3 'tn U J o o ^ T “ T ” o O o o o o o o o o o o O o o o O O o + + + + + + + + + + + + + + + + + + + U J U J U J U J U J U J U J U J U J U J U J L U U J U J U J L U L U L U U J m m m m m C O CO CO CD h- N - G O © o CO CO 05 C M p o o o o o o o O o O O O o CM • > i T *7 1 1 1 ■*7 t TT i \ 1 T “ 1 *7 t i m m m m m m m m m m m m m m m m C O CO C O o o o o o o o o o o o o o o o o o o o uj uj uj L U uj uj uj U J U l uj Ul uj uj uj uj U l L U U J U J r* - CO o o- 05 CM o * o CO m GO r* - CO CM 05 GO GO GO r^» CO CO m CO CM o 05 p CM r — h- C M CM CM C M * CM C M CM CM csi C M C M CM CM * — T- 05 cd m a IO © o o + U J o o o' C O C O C O C O C O C O C O C O C O C O C O C O m m m m m m m m o o o p o o o o o o o o o o o p o o o o u j u j u j u j u j L L J u j u j u j u j u j u j u j u j u j L L J u j u j UJ u j 00 CO CO CM h - CO CQ CO CO CO CO CD © CO o * m N - m CO m CO o r * - m C M 05 h- © m 0 5 C M M * C O C M * cd cd cd m cd cd r^ 00 cd 0 5 T “ T ~ c m ' c m ' CM c d o © m C O 05 C M m r * - o C M m CO C O C O CM C O C O m C O o < « Tm C O C Or*- 05 o CO m C O CO O 5 CO CO C Mm o o o o o o o CM CM C O CO t o o o ' o ' © o o © o o'o © d o' d o'o o'o o’o o a> % c § o CO IO CO 0) o o o o E mom ▼- cm cm o m o m o o o o o o o CO o'm d m o c CMCMCO AppendixB //2 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. ro 7 5 ■o c o C D < 0 C O o o c o o I — 0) 7 5 UJ o c o a o > C /5 LU * — T— 1 T “ o o o o o O o o o o O o o + + + + + + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C N r r IO C O o CO 00 o o O p o o o *— V C N CO tT T — t i 1 ( 1 1 T V 1 ▼ — 1 i 1 ▼ — i CO IO m i n i n i n IO IO IO CO CO CO r - o o o o o o o o o o o o p Ul L L I UJ UJ UJ UJ Ui L L J UJ U J Ul UJ UJ CN r - o> t o 03 o C N 03 00 o o CO o o> m o CO CN o r - C V I CN * r CN 00 cd c n CO CN CN CN v v - IO CN lO o > C N O o + U i o o p * - o C D C O in IO IO IO m IO in m in m in in o o o o o O o o o o o p © o L L I L U U J U l UJ UJ Ul L U u j L U u j u j U J UJ 00 C N C O C O C N o C O o 00 03 C O C N 03 IO C O r - N 1 r-. 03 r - 00 C O cd T“ C N CN C N CN cd cd cd C O < £ <0 CM Z o m * fc 2~ “ C O r*- o in oo 0 0 IO in 00 03 C O CN 00 o - CO o C O C O o TT CO CO CN m o r “ CN CO CO T f o in CO CO Is- Is- o o o d o o o o o o o o o S o CN lO O © o ' o * o t - E l o o i q o i c o o o CN CN CO C O CO I s- P C D IO C O O w 0) T o UJ o c o o © T o UJ T “ o o o o o © o o o © © o O + + + + + + + + + + + + + U J U J UJ U J U J L U UJ Ul Ul UJ UJ U J U J C O T T t n C O G O 03 C N 03 C N T ” r r p o o o O O C N c n V T * “ t 1 • 1 *— i i 1 i V t • i 1 in in i n m i n i n m in in C O C O C O I s* o o o o o o o o o o p o o u j Ul U J u j Ul LLI u j Ul uj u j u j Ul Ui 00 r- C O 00 00 00 C D r - r-. i n m o 5T C O o co i n C O C O o T- G O cd cd C N C N C N r - d th CN in o o + UJ o o O C o a C O C O m m m i n in in in in m in in in o o o o o o o o o o o o o o U l U l U l UJ u j U l U l Ul Ul u j U I UJ u j UJ © C N C O C O C O in i n m o C O C N T T in p C O in p-. C N Is- G O 03 I s- T~ CN C N C N C N cd cd cd cd cd C O 3 oo CN < § * S 2 S T 9 C D 00 o < 3* CO CO CO o O' o 00 00 in m r*- CN o CO T— CO o o- Is- CO ao CO CO h - o CN CN CO CO ’O' o m m CO CO co d o o o o o o o o o d d o o SOMOO © d o d ^ E o m o in o o o CN CN CO CO cd p^ o o o in AppendixB U3 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. JS 05 TD C o < 0 C O o 5 u + w UJ a > cn c o °- u j r 2 in B 9 a uj ©> o S' (O © < o co L U o o o o o o o o o o o o o o + + + + + + + + + + + + + + m i l l h i t if h i m m |i f i n i f i m m m q i P ) V 0 S C O O ^ r t ^ ( O O ) M C M N O O O O © * - * —*-*— C S I C O C D UJ O i C O N * in in in in m m in in m c o c o c o c o c o o O O O O O O O O O O O O O O O UJUJUJUJUJUJLUUJUJUJUJUJLJJUJm C M O J ( D W ( D O ^ U ) N ^ O ) 0) O O J ! ; c n c n co m c d o ( * ) D IO M O) N C O C N C s i C N in r- C N O o > o > o o N © CO CD q O) (O N* ^ *0 q r i D i D u i i n i n i o i n m i D i n i n i n i n i o i n i n q O O O O O O O O O O O O O O O O (jj Ou!ju!iLuu!imLuiumujaiujmujuju!jLU o. - ' - < f O T ! D I D ' - N < O V O n ' - n O T - 2 ^ ^ Irt I k . H A > A H A H ™ k H ™ N J M Q. z C O C D N O P ) i n s d ) r { O i n c D O O ^ c n c n c n c n c n c o c o c o c o - o '- ^ t co . q ctfrCONO)^ncOO(OSlC t W O O ^ g ^ N rO ^ O in O f S O W N O C O O D ®DO^*T-cNco<oco^;^tf)inic®©(p<0 o o o o o o o o o d o o o o o o o C D C O co 0 ^ 0 1 ° t- •o _ m • C N • C O ■ t- C N C O C O ^ ^ in to s V o m © o o u _ a> to U J O O O O O O O O O O O O O O O + + + + + + + + + + + + + + + LUUJUJUJUJUJUJUJUJLLJUJUJLUUJUJ CNCO^TCOr*-COO^-COO*CDCOOCOO O O O O O O ^ - t - ^ - ^ - t - t - C N C N ^ T 9 U J *■» ao C N © i n § 9 O L U s < ° © n to UJ l o i o c n i o t n t n i o i n i o c o c o c o c o r ^ o O O O O O O O O O O O O O O O UJUJLUUJUJLUUJLIJUJujuJLIJUJUJm CODCNOOWOOrCNncDCOOo ( O O ) ( p C M O ) N l O ( * ) r l O 0 O ) S N Q cncsicNCN^; ^-^“^“T -:oir^ihcNaDC 5 c < o c o i n i n i n i n m c D i n i n i n i n i n m i n c n O p p p p p p p p p p p p O p p p (jj O l u l u u j u j u j u j u j u j u j u j l j j u j l i j u j u j l j j & d S S n “ " ( o S S S “ o n ( d ® n I o O '-^'coN: o^r^ocoinN-o)*-CN^r"-a50 c o ^ C O C D ^- ’ T- T- C N C N C N C N C N C O C O * C O C O O N * O JS <<CD(ON, GOin{DO’-inNlO^CDCNN'0) >'©^-®N’OinON, NOD«OCDir)CO© DOt-T-CN{OCO^^^lOiOU)iflCD®<D a. d o' d o o’ o’ o o o o’ o o * d o d o < § C M I O O 0) d o E C D O in o m ^ C N C N C O C O O c o O O o ^ v irj 0 n °. C O c n c AppendixB / r R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 3 C D ■o c o 1 5 w 3 1 5 C fl O) 5 o e o a © to U J cT o o 0 5 UJ o o o o o o o o o o o o o o o + + + +’ +• + + + + + + + + + + U J t i l U J U J U J U J U J U J U J U J U J U J U J U J U J (no^cMnvwNcooJonwcMV 0 5 0 5 0 0 0 0 0 0 0 0 ^ ^ — T - c m n O) 05 t— r- r- ^ r- r- ^ r- r- ^ r— UJ o i ir)u}u)ioioioioioio«oinu)(0 ( 0 o o o p o o o o o o o o o o U J U J U I U J U J U J U J U J U J U J I J J U J U J U J 0>0(OCOfO)iOCMU)^OCOCOCM oqCp^NOO)(D(OOQO(ONa)CO ^ co o’ c m cm c m c m r-* o> rr CO o o o it r O f f l m i o i f i i f l i n i f l i n i o i n i n i n i n i n m m o ^ p p p p p o p p p p p p p o p o Om u! lL L Il U u j u j u ! ll U l U u j u j u ! l u j u j u !l u j u j C 'o n n ioeo N n offlo O N v c'in N '- w ’ o N f ^ i o f f l n i o o i N i o N o n c o ^ n ^ o ^ ^ ^ cm cn cm ’ t*j co co rr rr tfi iri m r f- t“ (O C5 O ) CO ? s i 2 0 N C M O ) S , « . . . ^ ^ ^ w _ -•CkoOT-t-f\)nir^’U)U)©(0 (Dscocoo> n d o o’ o’ d o’ o o’ o’ o’ d o o’ o’ o’ © o' O ^ 0 5 C O C M rr O in T- C O o CO 05 ^ C O C O C O 05 T- r - C O C O . CO CO S o E s c E 0) ^ ^ ^ 10 — . ^ O If) • C M - o - ^ - w c o h - z i z : ^ C M C O ^ ^ ^ o o © © UJ o c o o © U 5 UJ O O O O O O O O O O O O O O O + + + + + + + + + + + + + + + UJUJUJUJUJLUUJUJUJLUUJUJUJUJUJ N « M , t f ) © N 0 5 0 ' “ «OM, NO ) N C M O O O O O O O ^ - ' T —V T — T — CM^* < n in tf)io u )ir)ir)u )ir)ir)tn c o c 0 co 00000000000000 U J U J U J U J L L JU J L IJ U IU J U JL U U L JL L J U J CDCOO 5 l f ) ^ C O C M 0 0 r ^ O 5 CO l f ) O 5 CM c p ^ ’ O r ^ ^ x - o ) C D ' ^ C M ^ - c o r s- o CO CO CO CM CM CM ▼ "• r - T- ^r- od (O CO r- o O O i s P © < 0 o c 2 <ocDcototf)tnif)tr)ir)if)mif)if)mmtr) o O p o o p o p o o o o o o o p o o ^ OojUJLiJUJUJUJLLJUJLiJLLJUJujujLULiJUJLU Q. S ' o N O C M ^ N W O C O C O ^ O ^ ^ N C M W C O O C O I O S ^ n d co co t- CDr-tON o* 0 5 o C M C M C M C M C M C O C O C O C O ^T 0) St-OOONt-OOCVJNCONCM^OiOr- OJX 0(OOIOt-Nt-OOCO(DCJM-NCON05 '^ 0 ‘OOr»^-CNCMntO^^^M, U)in©(D(0 of o o' o' o' o’ o’ d d o’ o’ o’ d d o’ o’ d o' o CM If) o d o’ d •* -* O if) o if) o C M C M C O C O O ’ if) o o p if) cd P © 15 If) c AppendixB / / S R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C D * o c o C O 3 ra cn u c o C J 1 0 UJ o c o o 0) o 5 UJ C O g o ® a C L z (0 n eo< % CL z a > E o o o O o O O o o o © O T~ o o + + + + + + + + + ♦ + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C O in C O GO o> o C N * < T C O C N C O © o o o o o o C N C O 1 i • V 1 i 1 1 1 *T i 1 T "* 1 in m in in in m in in in m m C O C O cp o o o o o p o o o o o o o p UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ o C O C O CO C O o C N C D C N ▼ — r^. C O GO in C O p r*- in C O *“■ GO r*. C O * C O C M * C N C N C N T-’ ■ * — o> * < r ▼ — U i 0 0 <- T - T -' C N O O 0 ( D ( O l A t A i n i O ( n i O U ) I O l A ( f l l O U ) l O ^ O O O O O O O O O O O O O O O UjUJUJUJUJUJUJUJUJUJUJUJUJUJUjUJ — O O ^^Sr(0^(O O N C M (O O N ^5 O U ) r * r r t ( p C O O N ^ ; U ) C O O V N O ) C O O i f i c d r * ^ c n c n cm cm c n CO CO CO CO Su5OM(OCO(DCNJtf^COSCO0OO g®^a<ONi-IOCOr-^*COCMO)«)CO °. Ot-t-CMNCOCOrt^^^WlOCOCO © © d o o’ © d o o' d o d d d o © CO CO CO _ in T“ © © o o © o © o o o o o o o o + + + + + + + + + + + + + + + UJ UJ U i UJ UJ U i UJ UJ UJ UJ U J UJ UJ UJ UJ CN CN CO r r in co G O 05 o CO in CN O o o o o q q O O CN CO i 1 i 1 T — 1 ■ < T “ 1 T - 1 1 1 1 T T“* i in m in in in in in in in in i n in in CO CD o o o o o o o o o o o o o o o O o • UJ • UJ UJ UJ UJ UJ UJ UJ i UJ UJ UJ • UJ UJ UJ UJ + UJ o* in CO T *- r*- CO o 05 05 CN i n CO CO Q r - in CN o r*. in co O C D i n CN o CO p o CO CO CO CO CN CN C N C N in r— d CD CO CO CO in in in in m in i n i n in in in m O o o o o o o o o o o o o o o p UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ CO o* o C N CO 05 o 05 r*. N* CO CO CN 05 05 ’ C * CO o G O CN p p o CN •o- h - 05 N- r*- 05 cvi d 'r“ f T- CN CN CN CN CN CO CO CO CN in o> o T “ ^ V o o TT r*. CN CO m o> C N CO 05 CN h - T “ 05 in G O o o CN CN C N C O CO CO ’ O' in in CO CO o o d d o o o o o o d d d d o d o u k . 0) CO UJ o u 0) o 5 UJ C O d to « 5.S * = s S oT 9 5 . 0 CM 0 3 d o' E O O l f l O I O O I D O ci ^ c\i c m ’ co ci to o o o O O T S AppendixB //6 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Mg2* saturation data d c o o o o o o o o o o O o + ♦ + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ o 04 CO in CO r ^ CO o> 0) o © o o o o o o o o UJ T* T— T— 1 1 * i 1 • i 1 c f o i n tn m in in m m in tn in c o o o o o o o o o o o o UJ UJ UJ UJ UJ UJ UJ U I UJ UJ — * . 04 c o ^r CM CM co o CD in GO ^r CD lO C O o 00 ® CO CO co’ C M * cm' 04 04 G O UJ a c o CO CO CO m in in in in in in o o o o o o o o o o o o o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ o o- a> CD C O in o h» o 04 o o- m CO q q CM o- O) C L Z o ' CO id o> T~ cm CM CM cm’ + + + + C M C O U i o o o o r- o- co o > v- t— t— m co o o o tii £| « o ^ o 0 4 o o o o o o o « D 0 0)10 r — CO ( O M O ( O 2 r i f l N V) (0 .Q ^000100)^10010(0(07100)0^^ «-'20COO(OC\JCOfOCOC4CDOCDCOCM »-COOJ ^ D O O r - (M W (*) O ^ ^ I O l O I O ( O N N C O qT d o o o o o d © o © o’d © d © © © c ^ ♦ § co E < o ■ 3 - _ C D C O l O l O ^ U ) o 0 • r* * C M * C O ® g o 04 E ^ co £ lO < D (- O « § o o o o o o o o o o o o o o o o o + + + + + + ■++•+ + + + + + + w U J L U U J U J U J U J L L I U J l i J U J U J U J U J U J U J fn rvj «m m ift rft iw m m >r\ r r \ m © W UJ cf o c o o © U i o c o O N N W ^ l f l O N C O W O r W l O Q O ) O O O O O O O O O ^ - ’t-^-T-T-CM iOtOiOlOlOlO(OU)iO(OlOlOlOCD0O o o o o o o o o o o o o o o o o U J U J U J U J U J U J L U U J U J U J U J U J U J U J U J m COtOCOOJCDCNflOSCDOJr-COlOO’ Tn Sl004a)NlOC40CO(OiONOlO^Q cocococicNcvicsioi^^^^^cboiQ O ( O 0 0 l O ( O l O l O l A t O l O i O l O i O i O l O l O O O O O O O O O O O O O O O O O O Q UJUJUJUJUJUJLIJUJUJUJLLIUJUJUJUJIJJUJ a. 0(DWODNrlOO)OOCDlOO)CN(NWNO O O ^ C D O rtlO N O C M W lO N O ^ rC O O V) © « u) r^’ r“ *— *-* C M 04 C M * 04 04 C O C O C O V ^ r* 00 9) (D IA O lO C O C O C O “ o o ( O S C O I A O O O ’" 0 (3 5 0) r c M c o o ^ c o ^ - ^ r c o c M c o i n o ^ - < M C M ( O c o n v v ^ i n u ) ( O N o o c l © d o o' o' o’ d o o' o *o o o o o o o 3 C £ o N i f l o i a o n o i o e d d d ' - ' - p i N n n E O O O O . . (0 AppendixB 34 //? R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. 03 * 5 5 ■ D c o C O < /) o _ o O w H i a) C M 0 3 ® UJ T o o o o o o o o o o o o o o o + + + + + + + + + + + + + + + U J L U L L ilL iL U L L i U J U J U J U J U J U J U J L iJ U J M 0 J C * ) ^ l f l l / ) ( D S C D 0 ) O M ( 0 0 ) N O O O O O O O O O O ^- t - ^— *“ CM ioiAU)ioioir}ir)iAu3(oiflinio(o o o o o o o o o o o o o o o U J U J U J U J L U U J U J U J U J U J U J U J U J U J O l O ^ O ) 5 r f O i - t - r - ^ N T - C O ^ s l f l n O C D ( 0 ^ ( \ O C D ( 0 ^ t-T- C O C O C O co’ C M C M C M * C M C M t- N .* CO o o o £ L U p g n o © m £ o O i O UJ o ^ © C O * 0 9 UJ r ( O t o i O D © i n i n i n i n i n i n i n u ) i n i n m i f l c j o o o o o o o o o o o o o o o o o OaimiiiujLuiiJLULLJUiajujujujujujujuj O ( O Q O O ) V C O C O O ) ^ ^ ^ © W r - ^ ^ r * C M ^oOT-©ocn^-coco©o^c»)(0®coNO ^ c m co v' cb oi ^ ^ c m c m c m c m c m tr> to 05 U I .Q t f f f l i D i - B i - n os N O f f l i o o o oo n 2 'fffleoi-tDO^Nt-vsomaisu-oi gqoor-T-cMCMCMnnnM^^ioffiffl o f o o o o o o o o o o o o . 2 in o o o o o " c ^ — co E ®t jg in in - b ~ ^ E ? t- o' 0 ) C M W © o to m m • C M _ : C O • ^ C M C O in (O N o to 2 o o C O m c o c o u C O UJ o o o o o o o o o o o o o o o + + + +* + + + + + + + + + + + U J U J U J U J I U U J U J U J U J U J U J U J U J U J U J UJ WWOIflU)0N©O)OffM^OGO ® O O O O O O O O O ^ -T -T -^ -C M C M ® o m t n t n i n i o t n m i n i o i n i n i o i n c o c o o o o o o o o o o o o o o o o U J U i U i U i U J L U U J U J U i U i L U U J U J U J u j rCM(OtWCMOO)OW©CMO)NOJ M O C M N S l O W O O M O r t O C M N rtrtCOCMCMCMCMCM r- t- 0 C M o o + Ui o o o ’ o c o o _ s ° o c o c o c o i n i o m i n t n t n m i n i n i n t n t n i n o o o o o o o o o o o o o o o o o ^ UjUJUJUJUJUJUJUJUJUJUJUJUJUIUJUiUJ a O ^ U 3 ( O i n t D N O ) 0 0 ) ( O ^ N O ( D ^ O ) 5 o ® s c n w n M ; < p O ) o w ^ © c»3 n © co o W M * N r- C N | C N I C4 CV <vi CO CO CO C O . . . _r^^CMN.^“ OOOOOOGO i ^ 0 0 C M r t - « 3 0 ) ( M © 0) ( M ( D O O ^ C 0 OHOO^-CM CM CM CM COCOCOM 'M 'tOtOCOCO o o d o ' o o d o ’ o ’ o o d o d o ’ d o ’ £ o cm m © o d d E O 03 o m o tn C M C M C O C O °. 03 cn c AppendixB //F R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Mg2' saturation data O e o C J w © to Ui o o U i M l CO d T — 0 0 0 0 0 0 O 0 O O O 0 0 0 O + + + + + + + + + + + + + + + U J U J U J UJ U J U J U J UJ UJ U J UJ U J UJ U J U J CM CM CO CO o* m m CO N . G O GO 0 CO CO O O 0 0 q 0 0 q q q q C M • * 7 7 1 1 1 t * 7 1 *7 1 * 7 * 7 1 1 in m in in m in in in in 1 0 in in in CO CO 0 0 p 0 0 0 0 0 q q 0 0 q 0 q q 0 U J U J UJ UJ UJ UJ U J UJ U J UJ U J U J U J UJ UJ U J T“ c o r ^ CO in o* m CO GO m GO m GO r - 0 CO CO M’ C M 0 GO CO C M t— q q CM 0 CO co CO CO C O * C M CM CM C M C M 0 5 0 U i « o O ? O ui 2 o & § CO CO CD CO m m in m in in m m m tn in m 0 q O q q 0 0 0 0 0 0 p 0 q q 0 UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ GO C M CO CM 0 GO m GO CO CO GO 05 0 q CM q r«~ a> s— CO CO CO 0 C M * CO tn a o T - ▼- r - C M * CM CM C O * CO C O 5 00 & i § 3 fe • CO CO C M 05 m O' CO r*- C O 0 0 0 CO 0 CO 0 CO r - O" r*- 0 CO CO in O’ C M 0 O 0 T“ C M C M CM CO CO CO in CO r*» d d O o d d O d O 0 d d d d d d • p - o £ co E ® ® E t- co m co co o T - w in _ in C M ; CO - C M PO % ( O S ° ? o u £ t o U i u c o O C O Ui O o " z O O 0 O O O O 0 O O 0 O O O 0 + + + + + + + + + + + + + + + Ui UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C M CM CO CO O’ in CO CO h- G O 05 O C M CO CO q O © O q q 0 q 0 q q C M 1 1 *7 V T— 1 1 1 1 *7 • 1 1 1 i in in in in in in in in in m m in m CD CO h- 0 0 0 0 0 q 0 0 0 0 q 0 q O 0 0 UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ 0 5 0 0 0 5 0 0 0 CO CO 0 CO CO in CO CO ^r C M 0 5 GO CO C M 0 q CO T- CO q c d C O * C O * CO CM C M C M * C M C M C M T — 0 5 1 CO C O CD CD in m m in in in in tn m in m in 0 0 0 O 0 0 0 0 0 0 0 q 0 0 q 0 UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ CO O 0 5 M* CO CO CO 0 h - CO r* * 0 y — 0 CO CO CM C M O C M q CD q T— CO CO y — C O 0 CM C O C O y— -r-* <-■ CM CM CM CO c d ■ O ’ ’ UJ 05 © a o 5 w i O N C O O ) C O N t - i - O S O ) © O ^ N O ^ N r - ^ © t - ^ 0 O ^ ' O O t - t - t — C M C M C N C O C O C O ^ 'O ’ d O O ' d O 0 0 0 0 0 0 0 0 S O 1 0 © M O ) tn co co o d d * o o © E C M CO O o ' o ' ^ q o m o i n o m o o o *— cm cm c d co M’ ^ r m co r— P C D m c AppendixB 36 //? R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C D * o c o 1 5 k. o 1 5 V) o c o u © « 5 o o 0 3 to UJ T — T — T * * o o o o o © o o o O o o o o © + + + + + + + + ■ + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C M C M CO CO *r to lO CD r^» f-» G O o CO o © O o o o o o o O O o O C M i T“* 1 1 1 1 1 i i 1 i 1 1 1 to to to to to to to to to to to to to to C D o o o o o o o o © o o p o o o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ C M o CO to r-» o C M CD o •M * o N- T* CO 00 p- to CO o G O CD to CO C M P r - C M CO C O CO CO CO CO co C M C M C M * C M C M cd U i N S o C M c o ' O o CL Z 0 ( D ( D O ( 0 ( O U ) U ) t O i r } i A l O l A l O l A l O t n O O O O O O O O O O O O O O O O O U jU J U J U J U J L U U J U J U iL L iL L iL I J L L J U J U J U J L L i O N C O N S r © C O O © t - ( 0 0 ) t - ^ C N l O O ^ l f l W O C D O C N ^ l O S C O O C O C D ^ O o ' cm « i o n © i - » - i " W o i o j cm c n C O 5 03 ^ < ° ^ S - O #T © C M C M C M C O 05 to o o 05 o 05 0) * CD © C M to G O <* CO 05 C M CO 05 05 G O 05 o o © C M C M C M C M C O C O CO ^r to C D d d d O o ' o* d o o o o d o o o o co C D _ C D lO O o E 2 E © o *- to ID ^ L O - C M * C O C M C O o o C O UJ o c o o © to UJ T “ o o o o o o O O O O O o o o o + + + + + + + + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ C M C M CO CO ^ r to to CD p^ I s- CD o CO 05 o O o o p o O o O o o O T— T* 1 i T— i t 1 t i ▼ — 1 i T— 1 1 T— 1 r— 1 T~ 1 i to to to to to to to to to to to to to to CD Is- o o o o o o o © o o o o p o O O UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ G O p- o TT o p*. CO C O CD CO 00 Is- co to CO 05 G O CD M’ CO x— • p Is- C M CD O' cd cd cd cd cd C M C M * C M * C M C M * C M * T “ C D cd CD CD CO CO CO to to to to to to to to to to t o O O o o o O o o o o o o o O o o UJ UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ UJ UJ UJ CO CO p ^ G O G O C M 05 lO o p^ 05 T — CO CO to C M G O O C M C O to I s - G O o C M G O CO © C M * cd id G O * - T-' C M C M * C M * cd Is- _ S CL Z c o 5 00 < o o C M ■ * T C M p - 05 G O C O C D I s- to to o C D 05 C M to G O C O C O 05 to 05 G O G O 05 o O O C M C M C M C M <o C O C O to C O o o o o o o d o o o d d o d o b O C M to © O O E H O to o ’ T- O C O O to o C M C M C O C O CO O O O t o co 5- ic 9 9 1 5 to c AppendixB /3b R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C D * o c o C D 3 to c o 0 5 5 o o © to LU c o c o o 0) to Ui o O o o o o o O o o o O o O o © + + + + + + + + + + + + + 4* + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ o T ~ C M C M C O C O C O TT CD CO 0 5 C O GO o o o © © o © o o © O O O O 1 1 1 T— 1 i t 1 T * 1 1 v i i 1 “ T i i CD CD CD CD CD CD CD CD ID ID CD ID ID CD CD CO o O O o O O © O © O o O O O O O o o U i UJ U i UJ UI UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ + UJ O 5T CO C O r - r - r * - C M 0 5 CO GO o CO Q ^ r co o CO CO CD C O C M o O) CO CO C M CO o rr TT C O C O CO C O C O C O C M csi C M • » “ ■ < “ o N o U i o> O ) 00 g o § 5 £ o 0- S CO CD CO CO CO CD CD ID CD ID CD ID CD CD CD ID ID o O o o o o O O O O O O O O © o o UJ UJ UJ U I UJ UJ UJ UJ UJ UJ Ui U I UJ UJ UJ UJ UJ CO CD 0 5 CM ID CD T* CO r — ID GO C M o h - GO CD CO CO CO 0 5 c n p p C M CO 0 5 P C M * C O * ID co’ G O * 0 5 *-* CM CM co CO a o c o 5 00 ^ ^ $ ^ o * ^ CD CO CO CO TT y ~ CO CO C M r - CM CM CM CM 0 5 TT CO M 1 CD 0 5 T“ f"- 0 5 C M CD r ^ O CO CO 0 5 h - o O O O ▼ — t— C M C M CM CO CO CO <T CD CO G O o ’ © o ’ o o ’ o ' o ’ O O o ’ o ’ o ' o ' o ’ O o ’ o’ *c ^ . E CD E <o < 3 . ^ CD c o flj ° < o E *° o *- * D C D ^ C D C M _ : C O * C M C O lO (O N O C D O < 0 C M C o u © to U J o o © t o U i o f S 1 ° o o o © o O o o o o o o o O o + + + + + + + + + + + + + + + UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ C O TT CD CD C O C O C O CM CO N - ID o O o o O p o o o p o T — * — T ~CM t i T * “ 1 1 i ▼ — 1 *T 1 1 T ” 1 V 1 1 1 • CD CD CD ID C D CD ID CD CD ID CD ID CD C O C O o O O O O C o o o O O O O O o o o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ U I UJ + UJ h - CD M 1 CO CM o 0 5 Is*. CO ID CM CD M ’ o Q TT T“ O CD G O C O C O C M T — ^T CM C M C O o CO CO CO csi csi csi csi csi csi C M C M r " G O c d d r ^ C O C O C O C O CO C O CO ID C D CD CD ID ID CD ID p o o o O o o o O O O O O O o o UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ o o G O C M C M G O ID ID CO 00 G O CM 0 5 r - CO 00 C O G O p o CO * r O C S I O T— C O o csi cm’ C O cd cd 05 T* c i csi csi c d c d C M e ■ U i r* . o » cb © a o C O S i Q l O ^ N C O ^ ^ V D D n r - a O S O O CDH S o ^ C O © O C M ^ © C O O W ^ M D D C p O O O O r T - f - r r M M C o n ^ W S T 9 o o o o o o o o o o ' o o o’ o o’ C M 0 5 CD O 5 . 0 C M © O o ' E C D O O ^ C D OCD OC DOC DOO O O O O -s CMCMCOCn^^CDC0^2!?S5 AppendixB & R eproduced with perm ission of the copyright o w n e r Further reproduction prohibited without perm ission T O “ O c o 2 3 T O C O ♦ N O ) S o u tn Ui o o T O "tn U J o c o o 0- Z T O X ) < o o o o o o o o o o o o o o o o o + + + + + • + '♦ » + + + + + + + * ♦ • + + UiUiliiUJUiUJUJUiUiUJUJUJUJLUUJUiUi ^ w i o i n i o t o a t o s N s o o r t i f l T - 0 0 0 0 0 0 0 0 0 0 0 0 0 ^ * t-*-CM ifllOtOlO(OlAU)U)lAlfltniOiniAlA(D(00 o o o o o o o o o o o o o o o o o o U JL U U JL U U J U J L IJ U J U J L L J L L J U J U J L L J U J U J L L J m o o o o N ^ N a i w ' K o o f f l s n a o i u j S q f f l o i i o N O i q i o v n n t - O N c i i D V g C O csi Csi csi C M CM cm’ cm' cm' C M C M C M C M ^ t - 05 LO f-j S ( S I B ( 0 < 0 ( O C O I S C D ( 0 ( S C D I O I C I O I f l U 5 I O I O “ O O O O O O O O O O O O O O O O O O U jaJujlUlUUiaJlUuIllUULJlJLJUJLULLiUiLLJlLiUJ o 0 7 0 i o ( D < ~ M o c o a n o n i D o c \ i M O > O f f l r - f f l N M C N I O K p ' f C M O l O ' - V W N O T - d'"f'i(Nic3,tlrilritdls -njo6r-T-^r-CMCJ(>5 I S n N O ' r s o n i n a n M n i T - s n i D o PjCOCOir5CDI^OJO'«-CM^-lOr^O>COCMCOl01f> H O O O O O O ' < - - > - - r - i - i - T - T - C M C 0 0 1 T T lf) 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 c £ ® E I- m o C M o c? c o u w ( 0 U i o c o o T O 0 3 UJ o o o o o o o o o o o o o o o o o o + + + + + + + + + + + + + + + + + + UJUJUiUJUJUJUJUiUJUJUJUiUJUJUJUJUJUJ t0 l0 t n i / ) U ) ( 0 ( D ( 0 (0 N - N S G 0 G 0 O n ( D ( V 0 0 0 0 0 0 0 0 0 0 0 0 0 0 * - T - T - C M i A i n i o m i f l i n i r ) i A i o i o i A i o u ) i n u ) i A 0 0 o o o o o o o o o o o o o o o o o o o o UJUJUJUJUJUJLUUJLLiliJUJLLiUJUJlJLlLLJLLiLLJm NnONffiCM'ffNOniOOCOfflM-CM'-t-Si c q o o N f f l f f l i r i ' C M O C M ' - o a i O N ' - t - g CM C MC MC M CM CM CM CM CM CM CM CM CM -i- T- '^ -d dQ xO(0(oco(Dcococo<ococococou5inintninmm Q O o o o o O O O O O O O O O O O O O C p C p „ OmUJujujujujaJLULUlijLUlillXJLljLUljjLUIlJLUuj O . S-ococoocMr>.cocococooco!3ri^a5"SiMr5¥S31 ^ ' p ^ ’^wcqtfjcooi^tocMwr^o^-iooscMCD'*- to o c m co co o’ ic i co o' n eo eo oi ^ ^ r-' pi c m ' ri O < g ©• 9 00 w r “ C O 03 C M m r ^ o C M in C O m in o C M C O tn C O to C O C O 1"- 03 o T* C O in C O 00 o C O C O C O tn o o O o O o T — C M C M CO CO tn d o o o' o o' d o' o' o' o' o o o o o o' o o' c o n n a o i a o i o o n o i o o o o p o p p ■ = # O O O O r i - N ( M C O n ^ ^ W ( D N ° l<1 5 ^ CD _ _ C C M C O C AppendixB R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. © o o o o o o O o o o o o o OOp OO 3 CD b 05 b © CO © 4k 4 k 4k 05 r o N5 fO A t 1a © S . 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CO GO 0 3 C M CO GO CM m CM p * CO CO CO r - CO C M C O C O i n O p~ V GO P - p - CM CO i n CO X GO CO CO GO CO 03 T “ M * 0 3 r*- © m* CM p » P * 0 3 03 C M CO m o CO T ~ CO CO CO i n m o P - i n m CO a o 0 3 o < n a o p ~ CM i n V CO © CM P - m CM CO I D o 0 3 O 03 C M CO CM CO GO i n 0 3 CO i n p - p - CO c n O a o CO p * CM CM CO CO CO CO i n i n o CO © 0 3 i n 0 3 r - * * CO i n CO m CO p » 03 o c n 0 3 i n p - CO CO p* tn 0 3 m CO TT 0 3 o i n o o O CM CM CM O' © CO p - CM c q p * * CO GO GO 0 3 0 3 0 3 o o © o o d d o o o o o o o ▼ - T — in o i 0) 1 0 3 0 3 1 0 3 i • i t t T“ 1 i T— 1 i • • i i i i 1 ■ © o c o ^ o o ^ p 'sr d ,2 — ' to UJ o c o O © in in to in © in in in m m in in in in in in in in in in CO CO o o © o o o o © o o o o o o o o o o o o o o o UJ UJ UJ U J UJ UJ UJ UJ UJ UJ Ui U J UJ UJ UJ U i U I U I UJ LU UJ LU U J G O C O CO CM CO C M p . 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CN CO i n CO CO b - co 0 0 03 CN CO •O ' m c o b - b* CO 0 3 o T * d d o o o d o d d o d o d o y f— T *“ V r - CN C O 1 T- T ~ T - T“ 1 *“ m b- o > " 5 5 L ii o c . - o s g g-s: U i - < 03 C N . t — *=-o in m tn tn tn tn tn tn m m in m tn in tn tn in C O C O C O C O C O C O C O 0 9 o p o o o o o o p o o o o o o o o o O o o O o o O UiUJuiuiliiUJUJliiUiliiLUliiUJliiliiliiUJliiliiUJliiU J liiL LJlii m C O C N 03 O' T- C O C N C O C O C N 03 C O 03 b- tn C N 03 C O in C N C O 03 m b-• < 3 *03 C D C O C N 03 03 03 b . C O o b - tn 03 C Ob- o C O 03 b- 03 ® O 03 b- C O C O C N b - C N tn b* o 03 C ON* C O V o C O b. C O o 00 m C O 03 b- m C O C N o co b- C N C O C D C N m b. b» 0 3 C O * C O C O * C N c v i csi C N C N C N csi r - T—03 03 cd G O b » d tn m t n m m t n i n i n t n m i n i n i n i n i n i n m i n m i n t n m t n p o o t n o o m o o o i n o o o o o o o o o o o O o o o o o l i il i il i i i in l i i • in UJ l i i in U i L i i U J l i iL i iUi U J l i il i il i iu i l i iUJUiUJ UJ Y “ “ CN m rn CO CN t n CN CN CO CO m TT CO GO m t n CO 00 o •O’ b - CO 03 m b - CN o •O' 0 3 s r N - i n i n •sr CO GO 03 03 i n O i n CO b - m vU m CO w CN CN CO oo CO CO b - CN b - GO CO b - N “ N ” co CO N» W J T ~ CO t n b - CO o n;i n CO b - 00 CO 03 03 o o r - b - ▼- T “ c s i CN c s i c s i c d c d c d c d c d c d N * T T d N* s r i n i n t h t n CO CO 0 0 CN CN T — ' CO b * b - CN b - CN CO b * 03 CO CN CO C O c o GO b - CO ao ▼ — b - b - CO o CO 03 b - G O 03 CN CO N* S f C O b . G O C N CN c o CO N ’ tn tn tn in CO CO CO CO b - b - b- oo 00 GO G O CO 00 GO o d o d o o o o d d o d o d o o o d o o d d o o o 0 3 0 3 © 4 > co E o o ^ o CO b * CO CO CN CN CN i n t n b * t n CO CO CO b - CO CO GO b» CN b - CD b - 0 0 CO CO b » 0 3 CN GO CO CO o O ' GO b - o CO CO t n 0 0 t n co o CN o CO CO CO •O' O ' m i n GO GO GO 0 3 o o o T-* CN c o o o o d d d o d o d o o o o o T-' T — T ” T — T - o o J 2 03 UJ o o U i UJ 03 CO O ' m CN CO CO CO m 0 3 GO CO m CO GO CN CO m b - b - 0 3 CN CO 2 CO i n O ' CO b* b * GO GO /f t CO CO o CO G O CO GO 03 CO o CO b - CN V * J rt CO CO GO 0 3 O 0 0 CN u t n 0 3 CN CO t n O CO CO CO CO O ' CO CN CO i n r t 0 3 CO i n 0 3 0 0 CO o CO >4 f t CO O ' CO b - CN CO N CN CO o o o 0 0 03 0 3 w O CO CO o CO CO CN CO U l o CO t n t n o b - CO b - o o o O ' 03 CO m 0 3 CO GO O ' CO O ' b . 2 CN 0 3 o * G O CN CO GO GO 0 3 CN CN CO >4 m t n co CO b* GO 0 3 CN . o ; i n CO t o b - b - 03 03 0 3 d o o O o d d o o o o d o T“ T— T - r — T— p i ■ i t T*“ i • T “ 1 1 r* 1 1 i 1 V **7 T— 1 i 1 i t 1 i n t n i n m t n i n t n m i n t n m t n i n m i n m i n CO CO CO CO CO CO CO CO o o o o o o o o o o o o o o o o o o o o o o p o o o lii UJ UJ lii Ul UJ lii L U UJ lii UJ lii UJ UJ lii UJ lii UJ Ul lii U J lii L U U J U J 03 CO O ' CO O ' 03 CN CO 03 GO b - i n 03 b* CO CN GO CO CO CO i n 03 m i n b - CO i n CN co O’ 03 o CD i n CO CO T“ CN CN CO 00 b * O ' O ' co b - CO 03 o 03 O ' CO b» CO 03 CN CO CN o o b» CO m q 03 CO co o GO s O ' O ' CN T“ 03 b - CN o CN T“ CO b* CO CN O ’ O ' c o ’ CO CO CO CN csi CN cn CN CN ▼ ” < — v- v- 03 00 g o ’ GO b .’ CO cd _ o R 8 g g S'Q. z z m in o o UJ UJ m 03 O m b ^ co S S g s n N ® ® & C N b - o c s i UJ ^ £ g g § C N C N i n i n i n i n o © © © UJ UJ Ui UJ m cn co CD 0 0 r - i n N ^ N ' N ' *- C N C O N * <o‘ co co co lO to to to to o o o o o UJ UJ UJ UJ UJ to C O N N 03 C O 00 C O C N «- O ) C M S N T - lO G O 03 ^ C O C O C O C O N“ ^ U i C N 5 - g ~ 00 C O 03 C O tn C O C N C O C O C O in in 03 in in 03 03 in C N oo C O C O o C O b - 03 G O b» 03 o C O C O T T tn C O b - G O C N C O tn m in in C O b - G O C O G O C O G O G O C D C O C O d o d o o o d d d o o o o o o o d o o o d d d d t o i o t o t o t o t o t o t o t o t o p q q q o q q q q q UJUJUJUJUJUJLIJUJUJUJ ® N C O C N t - t - O O ^ - S ^ 9- C O O S C N t - O ^ - C O C O f O O tn ( D C C ) C 0 0 3 0 3 0 0 0 ^ N ^•^^•^^^totoidto 03 o - ^ O C S J N M W C O O C O C D C O N W C N N O t - t O ^ ^ C O C O O C O C O t O O J - 2 o { N 0 3 C N N ^ C 0 C N ( D 0 3 C M U > 0 J N f ^ t “ C 0 l 0 N ( N U ) O ^ N W C O E o O O ^ T - M C M C O c n O ^ ^ ^ l f i t O Q O O O O O ^ ^ N N N t O C o o ’ o o* d o o o d o* o o o o o o* o o* t-' t- *•" AppendixB 43 M-b R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. N i saturation data o c p - 8 x £ o U ) LU 0 5 0 5 O CO c o 05 0 5 t o to O ’ T— O p^ O ' o* CO CO CO CO CO O ' CN O to CO CO T“ G O O ' CN 00 G O 05 CN CO N 1 o CO N * to h * O O C O r— r^. 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C O P*- GO C N C N 05 T “ C N r - C O C O O’ C O to 05 to oo o CN co CN C O 00 05 N- C O r - Ul co C O C N C O 05 C N to P* 05 05 C O to C O CO Ul C N C O 05 o C O ty h- o csi o i csi csi csi C O C O co' C O C O O o : ’ O' to to to to CD CO < 00 ^ m 0. o © E o N - to CN p - CN t o C O t o C O cp G O to t o G O N “ r * - p - •O' G O GO C O CO p - o t o o CN p - CN "VI J S , ^ to CO CN h - 05 CN CN CO CO TT t o t o C O CO co G O 0 5 05 05 o o d o o d d o d d o d d d o o o d o d d d C N C O CO Y — to to G O CN 00 to CO C O P - CN p- CN C O o o 00 CO to p - 05 o to G O p - CN CN O T * CN CN C D o r - CN CN to to to h * G O G O 05 05 CN C O o i to f^ - c o o o o d o d o o o o o o o CN csi **“ o c ^ 8 £ * - co ’UJ . o i s CN JL o O o t r o © .'sr' c o — UJ 05 CN 0 5 C O 05 CO O 0 5 C O C O 05 05 05* 05* O C N 05 C O t T V C O G O P w C O to G O C O C N 05 P- C O G O O' C O to T “ C O C O C O m C O C O sr N * p^ to O • O ' / < S 05 C N p^ C O C O 00 C N p^ C O Ul p^ C O p* C O p- C O o C N O' n K C O 05 C O C N C O G O C O ^r r * » lA to C O C N C O o C O o 1 ^ Q C N C O o C N G O t T O to Ul G O o C O T - “ to O' C O to p^ C N O C N to p * C O T “ G O G O C O w u o C N o to C O G O P- C N O’ C N ID G O O' to 05 o V ■ C N C O C O " O ' to C O C O P w P- 05 05 o •o q O' C O o o o o o o d d d o o o o d d T — T- C N C N o 1 i ^7 *7 i T ^ " 1 1 ■ * 7 * \ i 1 1 i 1 ’ T T 1 1 1 40 to to to to to to to to to to to to to to to C O C O C O C O o o o o o o o o o o o o o o o o o o o o o Ul UJ Ul Ul 1 1 1 UJ U J UJ UJ UJ U J UJ Ul UJ Ul UJ UJ UJ UJ UJ C N 05 G O Tf 05 C O r r " O ’ 05 to C N p^ p- to C N C O p . C O 05 o G O 05 C O p- 00 C O p- to C N -o * C O C N C O to C O to P « - G O 05 G O C O P- p- G O C N p^ C N C O O’ 05 C O o C O • O ' C N o o C O C O T “ o p- ( D o 05 C N 05 y — T T Tr C O C O C O C O csi oi csi csi csi t - 05 c d c d c d O c o O 0. z co < (O N * S - ^ Q. o o z t o lO ID to ID t o t o to to to ID t o t o to t o ID to to t o t o IA t o t o o o o o o o o o o q o o o o o o o o o o *41 o o o UJ U l U J U l UJ U l U l U i U l UJ U l U l U l U i UJ UJ U l U l UJ U l 1 III U l UJ t o CO O ' t o p ^ CN CD C O O ’ T — CD CO G O C O CO 05 U l O ’ t o C O t o r r CO O ’ O ' C O C O t o o CD Pw CN G O o C O U l rr> O ' C O CO 0 0 O ’ CN G O O ' C O t o C O to C O CN o CO O ’ o I’l #o CO T— CN t o O i CN C O p ^ 05 o C O to C O C O 05 CN c n O ' 05 o O ' v y p . o r - t - ’ T~ csi cn csi CN cd cd c d c d c d C O O'’ O' o ; o 1 to* t o to t o cd C M CN p ^ CN G O G O C N to to C N CN to C O C O t o co t o 05 CN CN t o GO O ' G O t o o p» ▼ — C O CO G O CN O' t o CO C O r * . C O CN CO C O O ' o to to C O C O C O CO p - 00 G O 05 05 0 5 o d d d d o d o o o o d d d o d d d o d <D O c o .E o H - © 5“ CN GO p - o o t o CN o C O C O CN C O O ' O ’ O ' r - t o 05 CN t o _ _ CO o o p ^ co to CD 05 05 O ' C O p . o CD 00 p ^ o 05 C D o CN CN C O O ’ t o t o to p ^ p - G O 05 05 CN C O q o to CD c o o o d o o d o o o o d o o y - •«- csi csi csi AppendixB 44 /<*n R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. C O ffl c o « b . 3 C O r^- CD CO CM p - CN CM CO CO 0 5 o * CM CM t n CO CO TT CO c o t n CO o CD p ^ CD O CO H i o CO CM ■ M S GO 0 5 CO o GO TT O o o i n 0 5 o GO S GO 0 5 fO CO GO 0 0 C M CO t n CO © GO CD 0 5 © CM CD o - O CD o GO CO CO CD «ki o5 CM CO CO m * t n t n CD CD CD P - GO % ^ ID m O* d o o d d d o O o o c T ' • i i i v T i i 1 ■ i Q t n c n i n t n t n i n t n t n t n i n m t n o c O o o © © o o o © o o o Z o LU U J UJ UJ U J U J L L J UJ UJ U i U i LU CM o CO CD CD m CD CD GO O © CM 0 5 O o P ^ TT p - o CD © CO © CO CO i n p - P - GO 05 r^- 0 5 ■ O ’ ■ i CD CO CO p*. t n CO C M y ^ o II ” © CO CO CO o i o i o i o i o i o i o i T — Z UJ Q m t n t n t n t n t n t n i n i n i n i n i n t n c o © o o o o o o o o o o o o UJ LU U l UJ U J LU l i i UJ LU LU UJ U i UJ © o © a> CD CD CD p ~ t n CM GO CM CL GO 0 5 CM 05 O o CO CD CO CO O GO GO GO o - t n N* CO C M i n t n r ^ CM © CL i n 0 5 O CO CO O - GO 0 5 o CM ▼ — CM Z T~ ■ * ” o i o i o i o i o i o i o i CO CO i n C O CM r t t— 0 5 CM CD p . CO 0 5 TT CD o> CO t n O I t o p ^ GO O CM CD 0 5 S T o CM O CO d CO d o d N* o d N* o t n d t n d t n d d o F». z % © p - i n GO p * CO t n t n GO c cO CM ^ r © 0 5 m GO CM CO i n © c o o CM CM O I CO CO CO CO c H - o o o o o O d o o o o d o GO GO CD CO y - CD y - GO GO ID c GO 0 5 t n P - 0 5 CM o CM GO h * o GO CM CM CD TT CM CD p - t n 2 t n CO o CD 0 5 GO CD CD O GO 0 5 CD t n n r*- ID N* i n m CM CD O m t n w CO o ID © 0 5 CM t n p - GO C M CO o CM CD C M t n CD CD p . GO CD 0 5 h - 0 0 © U J o d d o o o o d o d T ” CO i i ' ■ i 1 • i * 1 t o t n t n t n t n i n t n t n t n i n i n CO o c o o o o o © o o o o o o z o U J LU U J U J U J UJ U J U J U J U J UJ LU C M o C M CM GO C M CM CO CD CM CO O T " “ 0 5 p*. CO © CD P* o T ~ o - CO © ■ « — « * 1 * - m GO m CD CD CD O 0 5 GO o CM ii £ CO 0 5 o i t n M - CM o 0 5 CD II © CO o i o i o i o i o i CM v - GO z UJ i n t o t n •a t n m t n t n t n i n t n t n m c o o o U J o o o o o o o o o o o U J UJ U J i i 1 1 1 UJ U J U J U J U J U J U J U l © o Q 0 5 0 0 U J GO 0 5 GO GO o - GO h - T"* Q . 0 0 o CM p*» 0 5 CO t n CM 0 5 GO CM o o CD o CO u 0 5 p - 0 5 m CD t n CD © CL i n o o N* CD p - 0 5 0 5 CO 0 5 z o i o i CM o i o i o i o i O I C O * CO © CM t n 0 5 t n CM 0 5 CM GO GO m m 05 Is* t n CO CD GO o h * m 2 * T - CM CO CO O ' n •o* t n i n i n t n CD qT o o o o o d o d o d d d o o #7 Z © o p - o m o p* T “ GO o t n o c o c o C M ^T CM O ’ 0 5 t n CD CO GO o 15 c o o CM C M C M CO CO CO ' N' GO e ( — o o o o o d d d o d o o o i f f AppendixB R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Mg2 t io n effects o n th e hydrolysis of P-nitrophenyl acetate § 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O+ + + + + + + + + + + + + + + t_LULLlLULULULlJUJLUUJlULiILLl(UUJLU < D C N J c s jc s jc o c o c o c o c o c o ^ rs rif > < o r'-* a o ^ o o o o o o o o o o o o o o o CO UJ C O 8 9 LU O- C T ) 2 1 0 I n UJ loioinminmioioioioininioioo o o o o o o o o o o o o o o o L L J UJ L L J L L J UJ L l l l UJ L L J L i l t L L J L L J L L J L L J L lll I X J r o ^ c M O c o N c o M D n m ^ i D O o i f l i n i n i n ^ ^ n n T - o s i n c M ^ o co co co co co co co co co co csi csi csi csi o o a ( — r— 0 0 0 s s 0 0 < D f f l ( O ( O ( D i o i f l i n i n O O O O O O O Q O O O O O O C J U O C J U C J U O U O O O O O O O .................... 1 1 1 (D O u J U J U J U J U J U J U J U J L U U J U J U J U J L U U J U J Q- C i D i D O ' f o o m o i T f r ^ o o o m n o o O o o r— t— t— n t- co co cd o co lo <0 in ^ ^ ■ ^ i r i N o j ^ ^ o g ' o i s r ' i c i o d ^ t-' 1— ’ co in s.3 < < ( M N O C O B O i - S O l O O O i n C M O O O O ^ O O r - t - ^ - t M n c O ^ N f f l ' J ’ f f l l Oi nt NI O O ' O O O O O O O O O O O s — t-CMCMCO 0 1 0 0 0 0 0 0 o 0 o o’ 0 o o’ 0 o’ o’ § w if lin m in in. t o in o 0 Q O O ro <0 O E C S ) O _ O o a > c m « 9 UJ v 0 0 0 0 0 0 0 0 0 0 0 0 0 0 + + + + + + + + + + + + + + U J U J U J U J U J U J liJ U J U J U J U J U J U J U J C M c o i o c o n n n n s r ^ - i n t o s o o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 CO o 1 Ul o T “ CO o o 10 8 9 — UJ o a > 10 n i n i o i o u i i n i n i n i o i n i n i n i o i n o o o o o o o o o o o o o o o o I I t I I I I I I I I I t I + LU LU LLJ LLJ LU LU LU LU L X J LLJ LLI LU LU LU LLJ N ( O C N O C O t- O ) N ( O W I O O ( O 0 o i f l i q U ) U ) ^ t ( 0 ( O t - O N i O ( M O o co co co co co co co co co co csi csi csi csi o LU r OO N N N N o o o o o o X 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 C J U J U J U J U J U I U J U J U J U J U J U J U J U J U J U J U J _ — — — i n r T - o n i o o c o t o C D C O C D C O C O C O C O l D i n i D i D o o o o o o o o o o o C 'O ) O O O (D O ' S o q c ' i i n n c s i o o T - n ' T N M - ■sr cm co r-’ oi cm cm " 10 00’ CO ID CD CO tn jo < r <f T - i n T - c o ( D ’- c M N O ( D c i ) ( o o i o i n o S O O r - T - i - c s i c o n ^ N o i s r o i n c D C M P O - o O O O O p o O O O O s - r - C M C M C D o n o’ o’ o’ o’ o’ d o’ o’ o d o’ o’ ci 0 ci o’ ^ . ididcoioid9 P P P P P P o o < L > O E M* CD CO AppendixB 46 129 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission. Mg2’ ion effects on the hydrolysis of P-nitrophenyl acetate 0.2M(Mg) 0.2 M(Mg) Time (min) NP(t) Abs NP (t)Conc Ester(t) conc. ln(Ester conc.) Time (min) NP(t) Abs NP (t)Conc Ester(t) conc. ln(Ester conc.) 6.5 0.062 3.59E-06 2.43E-05 -1.06E+01 6.5 0.068 3.94E-06 2.51 E-05 -1.06E+01 11.5 0.069 3.99E-06 2.38E-05 -1.06E+01 11.5 0.073 4.23E-06 2.48E-05 -1.06E+01 16.0 0.079 4.57E-06 2.33E-05 -1.07E+01 16.0 0.079 4.57E-06 2.44E-05 -1.06E+01 18.0 0.081 4.69E-06 2.32E-05 -1.07E+01 18.0 0.081 4.69E-06 2.43E-05 -1.06E+01 20.0 0.085 4.92E-06 2.29E-05 -1.07E+01 20.0 0.086 4.98E-06 2.40E-05 -1.06E+01 45.0 0.120 6.95E-06 2.09E-05 -1.08E+01 45.0 0.125 7.24E-06 2.18E-05 -1.07E+01 60.0 0.140 8.11E-06 1.97E-05 -1.08E+01 60.0 0.142 8.23E-06 2.08E-05 -1.08E+01 90.0 0.170 9.85E-06 1.80E-05 -1.09E+01 90.0 0.172 9.97E-06 1.90E-05 -1.09E+01 120.0 0.200 1.16E-05 1.62E-05 -1.10E+01 120.0 0.210 1.22E-05 1.68E-05 -1.10E+01 150.0 0.230 1.33E-05 1.45E-05 -1.11E+01 150.0 0.240 1.39E-05 1.51 E-05 -1.11E+01 180.0 0.250 1.45E-05 1.33E-05 -1.12E+01 180.0 0.260 1.51E-05 1.39E-05 -1.12E+01 final 0.480 2.78E-05 slope 0.00E+00 -3.47E-03 final 0.500 2.90E-05 slope 0.Q0E+00 -3.48E-03 > *0 £ a ° & X z < Ui OD CL 2T a o o O o o © cl 05 > 3 © £ 3 O P © P = < T3 . O (J < 8 E » = C M to “ Ui i < b © ©IO 5 CM S t < 2 X z *-■ z CL < r o e n n < 0 o 5 0 o rt rt O N N o n © © © © T N S O O n n , N © © ^ T- (ft IO i © © © n o © © ^ r - r > « » ^ m t o © i n © o cd © n n N N T V ® O 0 0 0 0 0 0 0 0 ' CM N CM CM r-. r * . o o o » ® CD CO 03 03 m in m m o o © CM CM 1 © < 33 I CD <0 • n c o N I— c o e o CM CM CO < 0 - 0 5 o o o t n co o o o o 0 o CD CD M ’ M* o o c n c n o o b 0 s s b b tn m o o o o to to p> h* o o f? m * > S N ® I S ' .w • O o 0*2 £ > © u © o t CM • 1 1 1 a o c E 2 0 0 5 © X ■= o « « S h t E f f l O Z t 3 ci o p - 0 ) o 1 in t e r c e p t 1 *r o c n b m b o CM o i n t n t n Q CM CM c n CD CO CD CO CD £ E 6 c R m O 2 0 | SO 1 I 3 CD O A p p en d ixB *8 fr ! R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Reproduced w ith permission o f th e copyright owner. Further reproduction prohibited without permission p-nltrophenol standard curve for UV spectroscopy Conditions temp(bath) C* Temp(cuvet)C pH(borate buffer) mixture Borate buffer MgCI2.6H20(M) NaCI(M) 253 25.1 8.5 10mM 0.1 1 p-nltrophenol(mM) Abs(4002NHM) T=25.1 Average Abs T=25.1C* Estimated Abs T=25.1C* 0 0 0 0 0.01 0.171 0172 0.171638073 0.01 0.173 0.171838073 002 0.343 0.3395 0.338769266 0.02 0.336 0.336769266 0.03 0.518 0.509 0.505900459 0.03 0.502 0.505900459 0.04 0.696 0.8795 0.673031651 0.04 0.663 0.673031651 005 0.825 0.6365 0.640162844 0.05 0.848 0.840162844 0.075 1.268 1 2555 1.257990826 0.075 1.243 1.257990826 0.1 1.688 1.672 1.675818807 0.1 1.856 1.675818807 Slope slope 18.81808917 18.71311927 Intercept Intercept 000285138 0.004506881 i 0 9 OS IS 7 STD curve2 p-nltroP(PH°8.5)Mg i i i 0 02 0 04 0 08 p*nitroph«nol conc.(mM) 0 08 0 1 Effect of Mfl2* Ion on p-nltrophenol STD curve Mn2+ ion conc.(Ml slope intercept 0 1664 0.0041 0.01 16.65 0 0044 0.05 16.71 0.0065 0.1 1671 0.0045 0.025 16.75 0.0035 0.5 16.65 0.0052 0.75 1664 0.0051 ID Etf«ct ol borate buffer conc. on p-nltroph«nol STD curv«(Mfl2**0.1M ) Butter conc (mM) •lope intercept 1 1662 0 0041 5 1641 0 0031 10 16 71 0 0065 20 1672 0 0041 50 16 65 0 0051 p - n i t r o p h e n o l ( P N P ) STD p H = 5 .8 , 6.3 4 / 1 1 1 9 7 5 E o C N ' a > ■ol 8 O o o o X , a E c e o < CO CO t n tn (O t n CN CN © o 09 d o d o o © cn m it X a w £ 3 A m m _ o o p p p o . . o o o o ° ° * o 8 c o LI oo E c ■ * r co 09 .o < CN CN r*- r*- CO ao CO O O CO CO o o o b d b o o cd it £ £ 3 A. © •o o u C O L I o c o «- m tn _ _ © o o o o o o o o o o o o oo O ) o cn c n o C O o AppendixB 50 i R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. p-nltrophenol(PNP) S T D curve for solvent Isotope effect 4/11/97 2 e T— o 2 E o o ^ co 0 m csj v co co oo cd r r- Ifi in r - r- o d o o ^ o o © cr c 2 6 c t 3 A © m © r - »• m in _ o O O O O O W d o o o ° Abs.(317.4nm) 0.108 0 108 0 561 0 561 1 129 1.128 CO C M T T • O ' C O O i C O C O I -0.005598361 n © & 3 a X J c o t - m i n ^ ^ © O o o o o o o - - 5 0- d o d o 0 0 , . © 2 Q. o © CL © © U d a o © < 0 C AppendixB 51 m R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. o c ® t i; IE o L a o o CO 2 o ® a. CD > 3 © e a Q ■ 2 « •e c 5 CD O c © x: a o c a o c © ! c C L 1 1 2 uT n in 0 H < h - I d a n \ 2 uT Si© 0 m j d u < H » 5 o £0 ZuT •6 E • c © £ © ® S u l SO <0 r» g o ° l o © c o io 0 A r - r t I * - < * 5 * ^ r> o in 0 1 to ao p- cn 0 ® d < = > o o c m cn < o co C M C M oi c n CO CO CM CM f « - » N f * > S N N N N S C M C M C M C M C M C M C M C M C M C M O O C 0 ( D ( O I D ( D O C O CO cntncncncncncncn cn cn o a a a o o f f i a o o o o o o o o o o o o 6 6 6 6 0 6 6 0 6 0 C M S S 5 © 0 o © o o m in CM CM © o © d m m , lO © o © m ini r*. rv o o cn cn l»- C M a at © © u £ > !<rJ o sy 2 uT '<d o 5 1 suit ! d © ^ O 2 u j o a ZuT 0 O ' a H Eo < 0 | ® a o I a! Ssi m l cn " a. 2 j o ? lo O) O i © p ..1 I co m eo cn P-. ~ C O V C M A C O ♦ O ♦ r- A f - © O C M *-■ 6 0 0 3 1 C M C M 0 0 ' C M C M j O O C M C M 0 C D cn cn C M C M © © a > © © o P - P — ^ ^ C M C M © © © © P ^ P - ^ ^ O © o®cn cn0 0cn en ©©CMCMP-p-cntn ^ ^ 0 0 0 0 0 0 S C T T ’T ▼ V T 0 C M C M A © 0 0 0 0 0 0 0 ® ^ * “ W C V T T O O O ® 0 6 0 6 0 6 6 0 £ © ^ C M O O o © i0 p- 0 0 C M C M 0 0 C M C M o o o © m « s n © 0 r * . 0 . p-. © © I o o - 0 0 , O © o © Id o| 0 0 P>- |S» o © d d J onI® g « t § o C M • 0 3 ^ o 0 0 ® £ 1 -8 = ■ 3 S a — e S S s s a , a. 2 a sr E E £ - ® u © ® X o * K »- O . « Z ~ - i « o O 0 C ^ 0 0 © 0 C M O c a t a . © • 0 ? O s*flD w £■ § ® *= o o « 3 S 5 2 5 e s g f z 2S © © Q. <2 2 -r C c E E - 2 U • o © « X o « Q. O H H Q . C D Z AppendixB 52 s^r R eproduced with perm ission o f the copyright owner. Further reproduction prohibited without perm ission Reproduced with permission o f th e copyright owner. Further reproduction prohibited without permission Effect of buffer base catalysis on rate constants for hydrolysis of MFJII-11A Borate Buffer (NaCI=1.0M,T=25 °C) pH=8.5 pH=10,3 Buffer conc.(mM) Ave Kobsd (1/min) Ave Kobsd (1/min) 1 0.0578 2.06 5 0.0575 1.98 10 0.0585 2.04 50 0.0591 2.14 100 0.0592 1.99 N -ethylmorpholine (NaCI=0.SM, T=50 °C) pH=7.2 pH=6.7 Buffer conc.(mM) Ave Kobsd (1/min) Ave Kobsd (1/min) 1 0.012 0.0085 10 0.0118 0.0087 20 0.0119 0.0086 50 0.0119 0.0088 100 0.0121 0.0087 Cacodylate (NaCI=0.SM, T=S0 °C) pH=6.3 pH=5.8 Buffer conc.(mM) Ave Kobsd (1/min) Ave Kobsd (1/min) 1 0.0098 0.01 10 0.0095 0.0099 20 0.0099 0.0104 50 0.0099 0.011 100 0.0095 0.0105 Acetate (NaCI=0.5M T=50 °C) pH=5.3 pH=4.2 Buffer conc.(mM) Ave Kobsd (1/min) Ave Kobsd (1/min) 1 0.0108 0.0067 10 0.0118 0.0066 20 0.0119 0.0069 50 0.0125 0.0071 100 0.0121 0.0072 Nonlinear regression cnrv. O t^g for pH depende.ee ..penmen. (N o mend T= 25 "Ci (Program—Mathcad(PZKS6.0) 1 0 ' 10 -3 " 2.04 1 0 9-8 0.662 vx - 1 0 ’ 9-5 »y = 0.345 1 0 9 0 0.10436 . 10 '8-7 . _ 0.0534 i =0 .. 4 VX —logvx. i * i VYj =!ogvy. vx '10.3' ' 0.31 I 9.8 -0.179 10.3 9.8 v = 9.5 Y - -0.462 9.5 9 -0.981 9 8.7 8.7 1.272 AppendixB R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression curve fitting for pH dependence experiment (No metal T= 25 °C) (Program—Mathcad(P£ US6.0) i m e r c e p c l Y.V) - 9 . 9 8 1 10 -9.981 ‘ •O H 1.-10 14 K q h - 1 . 0 4 5 * 1 0 *i =logiKOH- " w r 2 vV 8i 2 i - 0 K =1.0-10 -14 G. =K OH~ VY. 1 *y, G. i 0.31 0.319 2.04 2.084 -0.179 -0.181 0.662 0.659 -0.462 -0.481 0.345 0.33 -0.981 -0.981 0.104 0.104 -1.272 -1.281 0.053 0.052 e r r o r —5 . 1 8 6 " 1 0 -4 V Y . 0 9.5 V X . 10.5 AppendixB 55 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression carve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(P£ US6.0) F(z.u) =: =10 -14 V V 2 - u oV U 4K »-(u)qV * u5 z 3 - U o z 2 - u 0 u1- z- u o ui u 2 U j-z2 - u1 U4 K w - u , -z-U g. u0 'u3 '*2 - V U1 -U4 K w - ( u) 0 U1-Z'u 5 7 2----------------------------------------------- 0— ~"z ~u i'z~ ‘u i‘u2 z - v - » 0 u 1 z - u 0 u 1-u2 z3 - v 2 _ v ^ _ Uo.U i.U 2 2 u0 u 4 K » ~U 5 U 0^' .“o'V*~ V i U 4'K » -< U ,0 U 1 zu5 ,z3 -u 0 z2 -u 0 u ,z - u oU lv2 3 2 3 V * V 2 0 0 1 0 1 2 ■ z ~“ g * * •U g U ^ -Z — U g - U ^ U ^ _V3z 2"u Ouiu 4kw-(u)oui'zu5 10 10 53 2 “O U1 Z - U 0 -Z - U q U ^ - U q - U ^ ^ z2 U 0 3 2 z - u Q z -U 0 U1Z-U0 U1U2 0 “1 3 z - u 0 -z - u Ql, 1- z - Uou1 u2 0 “1 3 2 z - u 0 -z - V l -z-V l ^ lo 87 10-8.2 ‘ 0.178 7 2 0.0614 10 0.012 1 0 0 . 0 0 8 6 10’6’3 ^ z 0.0099 5.8 0.0104 0.011 0.0106 10 5 0 0.00685 10 4-2 Append ixB 56 m R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression curve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(PZf756.0) 0.1 3.3-10 6 »g = 4.1-10 11 0.0073 34455 0.0082 p -genfitfYX.vy.vg.F) ' 0.0959334 0.00000349 4.15094151 ‘ 10' 11 " 0.00730023 34453.1866579 0.00830026 AppendixB 57 i t - Reproduced with p e rm issio n ^ the copyright owner. Further reproduction prohibited without permission Nonlinear regression curve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(PZ. £756.0) i =0.. 8 g(»x) -Iog'F(vx.p)Q vp. =kJogrvx. i » j pH ~ log i vx. i i Y =log'vy 8 p a Y. t I-**. 8.7 -0.74958 -0.74942915 8.2 -1.21183163 -1.21017377 7.2 -1.92081875 -1.84819811 6.7 -2.06550155 -1.97457963 6.3 -2.00436481 -2.01743417 5.8 -1.98296666 -2.03828969 5.3 -1.95860731 -2.04508594 S -1.97469413 -2.04665209 4.2 -2.16430943 -2.04778392 - ‘10 g ' V X . g ' V X . 0 1 2 •3 6 8 10 4 P * error -0 .0 0 0 0 2 1 4 8 AppendixB ‘ ’'0 - R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression curve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(PZ £#6.0) d — fc3-Kt f x , ,2 dk l! x2 —K ,2'* x2 — K j j x , d fc| »(2)-fc2 Ka2K w-lC3 K a2x d ‘ 1 dk3 . •x< 2 > - k 2 K a2'K w*'"k 3’K a2'x X — K - y X k , x(2 > - k 2 K l2 K w- k 3 K a2 x' k 2'Kw~ '[ 3'x k I’ * ^ a 2 J dK , ■ x2 - K l2-x x 2 - K „ , x x 2 - K . , x K. =10- 1 4 (2 ) U q - x , - b 1-u3- K w - u 2 -«3 -x x2 - u 3 -x 10' 8 -7 ' 2 '* -U3'X 10 -8.2 0.1785 7 2 0.0614 10 x2 - u, x " 2 2 1 0 '4 2 3 x - u 3 x. 0.012 , n 6.7 Kw 10 00086 F(x.u) = “3 2 n ~ 10 6 3 *7 ' 0.0099 x-uyx 3 -5.8 0.0104 u3 2 -5 3 0012 x t-u-'x: 10 . d ,u 0.0106 ly K ^ - u ^ x u0-x(2 ) - u 1-u3-Kw- u 2-u3-x 10 5'° 0.00685 AppendixB 59 IV - R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression curve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(P£KS6.0) 0.001 30000 vg = ■ 0.09 0.0000020001 . ' 0 .0 0 9 9 8 3382 3 .1 3 0 7 8 geofitfvx.vy.vg.F) - 0.0 0 8 9 8 3.4906-10”6 AppendixB .60 Reproduced with p e rm is s io n ! the copyright owner. Further reproduction prohibited without permission Nonlinear regression carve fitting for pH dependence experiment (No metal T= 50 °C) (Program—Mathcad(PZ. US6.0) i =0.8 vp; - lo g vx. vk. =log/vy. i p =genfit(vx.vy .vg.F) * < «) =log/F(vx.p)0 ’ 'Pi i t . i 8.7 -0.748 -0.749 8.2 -1.212 -1.204 7.2 -1.921 -1.84 6.7 -2.066 -1.966 6.3 -2.004 -2.009 5.8 -1.983 -2.032 5J -1.921 -2.043 5 -1.975 -2.052 4.2 -2.164 -2.134 0 ■ 1 •2 ■ 3 vpi gvx. 2 vy. - 10 error -2 .5 6 2 -1 0 "5 AppendixB 61 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear regression curve fitting for pH dependence experiment (Added Ni ion T= 50 °C) (Program—Mathcad(PZ. US6.0) k ,x(2)-t y 2'K j j K w - k j-K ji-x dk ■ x2 -Ka2X x2 - K j2X dk- k,<(2t-k 2Kl2-K»-k3-Kj2x : * 2 - K j2 ‘ x x — K ^ x k,x(2)-k 2Ka 2Kw-k 3Ka2x 2 x — K -yx x — K x d ‘ I dK jj k , x( 2) - k 2'K ,2'K w - k j-K jj x x2 - K l2 x . k 2’ K w — k yx k , x £-k yK „yK „-k r K ,yx 2 a2 w 3 a2"J x 2-K,yx x2 - K j2X K„ =10 14 (0\ V 2 x -u^x F(x.u) = x 2- “ 3x x 2- U 3 - x 3 2 10 71 ' 2.150 10 6-6 0.693 -1 0 59 vy = 0.161 10 53 0.0402 0.0158 10 42 / 2 ^ u1 Kw - u2 x “o' ui u3 K w - u 2'u3'x x2- V x 2- “ 3x AppendixB 62 •u. I • R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. u s Nonlinear regression curve fitting for pH dependence experiment (Added Ni ion T= 50 °Q (Program—Mathcad(PZ. US6.0) 0.02 10000000 0.02 0 .0 0 0 0 0 4 0 genfit(vx.vy.vg,F) 0.012 2 - 107 0.06 3 .1 6 2 2 8 -1 0 -6 AppendixB 63 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Nonlinear n^ressio. carve d tto j for pH dependence eaperinen, (Added Ni ion T - 50 «0 (Program—Mathcad(/> Z .£/S’ 6.0) i = 0 . 4 vp. = log vx. vfc =log'vy. p =genfit(»x.vy,vg,F) g(vx) =log/F(vx,p)p ''Pi » t i g'vx. 7.1 0.332 0.332 6 .6 -0.159| -0.157 5.9 -0.793 -0.812 5.3 -1.396 -1.318 4.2 -1.801 -1.905 I - v ’° ,-0 g vx. -2 ’ T ’ i error -1 .3 1 5 * 1 0 * AppendixB 64 \V) . ' I R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. APPENDIX C R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Estimation of pKa’s for MFJ13-11A Since pKa’s of MFJII-11A can not be directly determined by titration due to its hydrolysis, pKa’s were estimated by using the electrostatic potential. The magnitude of the electrostatic potential (the energy of interaction of a point positive charge) at the acidic hydrogen relates to the pKa of a molecule. The more positive the potential, the greater the charge on hydrogen and the greater the acidity. The program MacSPARTAN (Wavefunction, Inc.) determine the electrostatic potential of each acidic group of MFJH- 11A by using semi-empirical and ab initio molecular orbital methods V lcvel 3-21G*, geometry optimization). The calculation shows that the most acidic group is the first phosphonic group POH and the oxime group NOH is more acidic than the second phosphonic group POH in the monoanion of MFJII-11A (elpot for POH -9.71, elpot for NOH 9.74 kcal/mol). To estimate the range of pKa’s of MFJII-11 A, the C-methyl ester of troika acid was used as standard compound whose linear relation of pKa’s and the electrostatic potential were already known. The pKa’s of the C-methyl ester of troika acid were determined by Professor A. Haegele using titration and 3 1 P NMR in a sample prepared by Dr. B. A. Kashemirov (McKenna laboratory). The pKai, pKa2 and pKa3 values of the C- methyl ester were 0.35, 5.31, and 10.83, respectively. The electrostatic potential for the second phosphonic group POH and oxime group NOH for the monoanion were -28.84 and -24.86 kkal/mol, respectively. m R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. MacSPARTAN ab initio program: Release 1.0 PAAN02PH Geometry Optimization B-21GC*) Number of basis functions: 195 Number of electrons: 148 Total molecular charge: 0 Multiplicity: 1 Point group: Cl Number of independent degrees of freedom: 72 No useable symmetry or symmetry intentionally disabled Cartesian Coordinates (Angstroms) Atom X Y Z C 1 -0.3267137 -2.4039445 1.0438971 P 2 0.5794517 -3.9704459 1.0116632 0 3 0.7537796 -4.5049821 -0.3271009 0 4 1.9144547 -3.6297789 1.7671996 0 5 -0.2317174 -4.8119817 2.0495288 H 6 -1.0922581 -4.5043498 2.3719079 H 7 2.7438339 -3.6146253 1.2698887 N 8 -1.4496690 -2.4292876 1.6304576 C 9 0.3427365 -1.2661296 0.3658649 0 10 -2.2850142 -1.3164307 1.7028047 0 11 1.4743938 -1.3078231 -0.0233785 0 12 -0.4646201 -0.1656635 0.2462968 C 13 -0.1750702 1.0339257 -0.4241184 C 14 0.1508706 3.4161383 -1.7085580 C 15 -1.2780317 1.8338262 -0.6655626 C 16 1.0929207 1.4160642 -0.8151697 C 17 1.2469601 2.6230685 -1.4669106 C 18 -1.1137537 3.0370767 -1.3116238 H 19 -2.2487210 1.5072498 -0.3570197 H 20 1.9322003 0.7887611 -0.6337172 H 21 2.2091316 2.9537706 -1.7890900 H 22 -1.9442919 3.6724441 -1.5183231 N 23 0.3253141 4.6767157 -2.3966833 0 24 -0.6933633 5.3603917 -2.5949242 0 25 1.4778812 4.9850844 -2.7419689 H 26 -1.8844450 -0.5812475 1.2033289 Hessian will be taken from archive file Guess wave function from archive file Cycle no: 1 Energy = -1348.1557063 rmsG - 0.0006 rmsD = Cycle no: 2 Energy = -1348.1557372 rmsG m s 0.0005 rmsD = Cycle no: 3 Energy = -1348.1557807 rmsG - 0.0006 rmsD = Cycle no: 4 Energy = -1348-. 1558055 rmsG - 0.0005 rmsD * Cycle no: 5 Energy = -1348.1558322 rmsG 0.0006 rmsD = rw « m i n t 1 0.0065 0.0126 0.0044 0.0091 0.0089 16? R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Cycle no: 6 Energy = -1348.1558570 rmsG s 0.0004 rmsD 0.0026 Cycle no: 7 Energy = -1348.1558702 rmsG = 0.0004 rmsD 0.0090 Cycle no: 8 Energy = -1348.1558860 rmsG = 0.0004 rmsD = 0.0031 Cycle no: 9 Energy = -1348.1558984 rmsG = 0.0003 rmsD = 0.0032 Cycle no: 10 Energy = -1348.1559046 rmsG * 0.0002 rmsD = 0.0023 Cycle no: 11 Energy = -1348.1559088 rmsG = 0.0002 rmsD = 0.0042 Cycle no: 12 Energy = -1348.1559132 rmsG = 0.0002 rmsD - 0.0023 Cycle no: 13 Energy = ■ -1348.1559178 rmsG = 0.0002 rmsD a s 0.0042 Cycle no: 14 Energy = -1348.1559235 rmsG = 0.0002 rmsD = 0.0037 Cycle no: 15 Energy = -1348.1559305 rmsG « 0.0002 rmsD 0.0032 Cycle no: 16 Energy = -1348.1559365 rmsG s 0.0002 rmsD = 0.0046 Cycle no: 17 Energy = -1348.1559409 rmsG a t 0.0002 rmsD = 0.0033 Cycle no: 18 Energy = -1348.1559460 rmsG s 0.0002 rmsD = 0.0055 Cycle no: 19 Energy = -1348.1559512 rmsG 38 0.0002 rmsD = 0.0046 Cycle no: 20 Energy = -1348.1559568 rmsG = 0.0002 rmsD = 0.0062 Cycle no: 21 Energy = -1348.1559606 rmsG as 0.0002 rmsD SB 0.0027 Cycle no: 22 Energy = -1348.1559651 rmsG = 0.0002 rmsD s 0.0032 Cycle no: 23 Energy = -1348.1559683 rmsG as 0.0001 rmsD = 0.0025 Cycle no: 24 Energy = -1348.1559700 rmsG s : 0.0001 rmsD = 0.0012 Cycle no: 25 Energy = -1348.1559713 rmsG = 0.0001 rmsD = 0.0037 Cycle no: 26 Energy = -1348.1559725 rmsG K 0.0001 rmsD = 0.0028 Cycle no: 27 Energy * -1348.1559735 rmsG = 0.0001 rmsD s 0.0023 Cycle no: 28 Energy = -1348.1559742 rmsG = 0.0001 rmsD = 0.0015 Cycle no: 29 Energy «= -1348.1559748 rmsG S 0.0001 rmsD = 0.0016 Cycle no: 30 Energy = -1348.1559753 rmsG = 0.0001 rmsD * 0.0015 Cycle no: 31 Energy * -1348.1559760 rmsG = 0.0001 rmsD 0.0023 Cycle no: 32 Energy = -1348.1559769 rmsG = 0.0001 rmsD = 0.0021 Cycle no: 3 3 Energy * -1348.1559779 rmsG s 0.0001 rmsO a s 0.0024 Cycle no: 34 Energy = -1348.1559788 rmsG = 0.0001 rmsD * 0.0010 151 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Cycle no: 35 Energy = -1348.1559794 rmsG 0.0001 rmsO 0.0029 Cycle no: 36 Energy * = -1348.1559800 rmsG X 0.0001 rmsD 0.0012 Cycle no: 37 Energy = -1348.1559806 rmsG = 0.0001 rmsD = 0.0031 Cycle no: 38 Energy = -1348.1559814 rmsG x 0.0001 rmsD = 0.0028 Cycle no: 39 Energy = -1348.1559821 rmsG = 0.0001 rmsD X 0.0034 Cycle no: 40 Energy = -1348.1559829 rmsG = 0.0001 rmsD = 0.0030 Cycle no: 41 Energy = -1348.1559839 rmsG = 0.0001 rmsD = 0.0028 Cycle no: 42 Energy = -1348.1559850 rmsG x 0.0001 rmsD = 0.0022 Cycle no: 43 Energy = -1348.1559865 rmsG = 0.0001 rmsD = 0.0021 Cycle no: 44 Energy = -1348.1559878 rmsG = 0.0001 rmsD 0.0031 Cycle no: 45 Energy = -1348.1559886 rmsG = 0.0001 rmsD = 0.0012 Cycle no: 46 Energy = -1348.1559889 rmsG - 0.0001 rmsD - 0.0015 Cycle no: 47 Energy = -1348.1559892 rmsG = 0.0000 rmsD = 0.0004 Cycle no: 48 Energy = -1348.1559893 rmsG s 0.0000 rmsD = 0.0002 Cycle no: 49 Energy = -1348.1559894 rmsG = 0.0000 rmsD X 0.0002 Cycle no: 50 Energy = -1348.1559895 rmsG x 0 •0000 rmsD X 0.0001 Cycle no: 51 Energy = -1348.1559895 rmsG - 0.0000 rmsD = 0.0002 Cycle no: 52 Energy = -1348.1559896 rmsG X 0.0000 rmsD = 0.0004 Cycle no: 53 Energy = -1348.1559896 rmsG X 0.0000 rmsD = 0.0006 Cycle no: 54 Energy = -1348.1559898 rmsG X 0.0000 rmsD K 0.0006 Cycle no: 55 Energy = -1348.1559899 rmsG X 0.0000 rmsD = 0.0003 Cycle no: 56 Energy « = -1348.1559899 rmsG = 0.0000 rmsD X 0.0002 Cycle no: 57 Energy = -1348.1559900 rmsG = 0.0000 rmsD = 0.0004 Cycle no: 58 Energy = -1348.1559901 rmsG = 0.0000 rmsD - 0.0004 Cycle no: 59 Energy = -1348.1559902 rmsG X 0.0000 rmsD X 0.0003 Cycle no: 60 Energy = -1348.1559903 rmsG - 0.0000 rmsD = 0.0001 Cycle no: 61 Energy = -1348.1559903 rmsG = 0.0000 rmsD = 0.0001 Cycle no: 62 Energy * -1348.1559903 rmsG X 0.0000 rmsD = 0.0002 Cycle no: 63 Energy ■ > -1348.1559904 rmsG c 0.0000 rmsD 0.0002 1 5 2 . R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Cycle no: 64 Energy = -1348.1559904 rmsG = 0.0000 rmsD = 0.0002 Cycle no: 65 Energy = -1348.1559905 rmsG = 0.0000 rmsD E 0.0003 Cycle no: 66 Energy = -1348.1559905 rmsG = 0.0000 rmsD = 0.0003 Cycle no: 67 Energy = -1348.1559906 rmsG s 0.0000 rmsD K 0.0003 Cycle no: 68 Energy = -1348.1559907 rmsG * 0.0000 rmsD E 0.0003 Cycle no: 69 Energy = -1348.1559907 rmsG = 0.0000 rmsD E 0.0004 Cycle no: 70 Energy = -1348.1559908 rmsG = 0.0000 rmsD = 0.0005 Cycle no: 71 Energy * -1348.1559909 rmsG s 0.0000 rmsD S 0.0005 Cycle no: 72 Energy = -1348.1559910 rmsG = 0.0000 rmsD S 0.0004 Cycle no: 73 Energy = -1348.1559911 rmsG = 0.0000 rmsD - 0.0003 Cycle no: 74 Energy = -1348.1559911 rmsG = 0.0000 rmsD = 0.0003 Cycle no: 75 Energy = -1348.1559912 rmsG s 0.0000 rmsD S 0.0005 Cycle no: 76 Energy = -1348.1559913 rmsG = 0.0000 rmsD s 0.0006 Cycle no: 77 Energy = -1348.1559913 rmsG = 0.0000 rmsD = 0.0004 Cycle no: 78 Energy * -1348.1559913 rmsG S 0.0000 rmsD = 0.0002 Cycle no: PAAN02PH 79 Energy « -1348.1559913 rmsG s 0.0000 rmsD s 0.0000 Cartesian Coordinates (Angstroms) Atom X Y Z C 1 -0.3368244 -2.4314663 0.9916030 P 2 0.6525492 -3.9388192 1.1355656 0 3 0.9884878 -4.5453972 -0.1404408 0 4 1.8835786 -3.4709089 1.9932027 0 5 -0.2058604 -4.7734971 2.1407806 H 6 -1.1284368 -4.5405147 2.3198670 H 7 2.7602616 -3.4450521 1.5881331 N 8 -1.5088617 -2.4938576 1.4686123 C 9 0.3342605 -1.2939350 0.3124496 0 10 -2.4024795 -1.4274057 1.4056774 0 11 1.4816249 -1.3226571 -0.0282916 0 12 -0.4900186 -0.2188298 0.1275663 C 13 -0.1899944 0.9991104 -0.5035177 C 14 0.1576948 3.4331298 -1.6809598 C 15 -1.2453031 1.8941591 -0.5413092 C 16 1.0400804 1.3080874 -1.0503800 C 17 1.2058183 2.5443505 -1.6452687 C 18 -1.0701181 3.1219807 -1.1349062 H 19 -2.1862162 1.6243204 -0.1117705 H 20 1.8422472 0.6106785 -1.0158126 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. H 21 H 22 N 23 0 24 0 25 H 26 Energy 2.1402199 -1.8611477 0.3441950 -0.6298005 1.4638624 -1.9835601 1348.155991 2.8218795 3.8364990 4.7247609 5.4981074 4.9710643 -0.6879604 -2.0800209 -1.1823710 -2.3054017 -2.3167906 -2.7857550 0.9282281 Mulliken and electrostatic fit charges (electrons) atom Mulliken electro fit C 1 -0.179415 -0.274101 P 2 1.645102 1.478885 0 3 -0.600835 -0.778996 0 4 -0.741823 -0.807551 0 5 -0.747592 -0.682745 H 6 0.461426 0.402580 H 7 0.452899 0.531890 N 8 -0.219198 0.017404 C 9 0.929524 0.959432 0 10 -0.523159 -0.555025 0 11 -0.568409 -0.594551 0 12 -0.841941 -0.456640 C 13 0.404055 0.389006 C 14 0.269941 -0.120160 C 15 -0.269196 -0.339617 C 16 -0.265483 -0.290261 C 17 -0.180562 -0.096312 C 18 -0.178832 -0.042361 H 19 0.285108 0.199947 H 20 0.336762 0.240914 H 21 0.327207 0.199316 H 22 0.326087 0.193711 N 23 0.180916 0.862822 0 24 -0.379405 -0.481002 0 25 -0.377871 -0.473711 H 26 0.454692 0.517124 Dipole moments from Mulliken and electrostatic fit charges and from wavefunction (debyes) comp Mulliken electro fit actual X 2.0650 -0.9497 -0.9138 Y -4.4254 1.2124 1.1956 Z 1.8777 2.1307 2.1145 Total 5.2321 2.6290 2.5953 Time for Ab Initio Engine CPU: 014:48:04.20 Wall: 015:39:14.10 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Time for Properties Engine CPU: 000:00:57.04 Wall 000:01:06.30 Time for PAAN02Ph2 CPU: 014:49:01.24 Wall 015:40:20.40 Graphics requests: surface-elpot value--10.00 resolution-med pending Graphics files written: surface-elpot value--10.00 resolution-med completed Time for Graphics Engine CPU: 000:05:40.42 Wall 000:06:06.30 Time for PAAN02Ph2 CPU: 000:05:40.42 Wall 000:06:06.30 Graphics requests: surface-elpot value=-10.00 resolution-med completed surface-density value-0.002 property-elpot resolution-med Graphics files written: surface-density value-0.002 property«elpot resolution-med Time for Graphics Engine 000:01:29.14 Time for PAAN02Ph2 000:01:29.14 CPU: 000:01:18.57 Wall: CPU: 000:01:18.57 Wall: pending completed R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Time for Ortroikal- CPU: 002:22:55.57 Wall 002:26:03.32 Graphics requests: surface-density value-0.002 property-elpot resolution=med Graphics files written: surface-density value-0.002 property-elpot resolution-med Time for Graphics Engine 000:00:34.14 Time for Ortroikal- 000:00:34.14 CPU: 000:00:26.41 Wall CPU: 000:00:26.41 Wall: pending completed R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. I5H Cycle no: 41 Energy = -955.8613569 rmsG * 0.0000 rmsD = 0.0000 0RTR0IKA1- Cartesian Coordinates (Angstroms) Atom X Y Z 0 1 0.4380485 -2.5754844 -0.8743745 p 2 1.1430516 -1.2855681 -0.9014718 0 3 1.2885706 -0.4401753 -2.0987614 c 4 0.3285068 -0.2454327 0.4047460 0 5 2.5701584 -1.4539232 -0.1604889 H 6 2.9902905 -0.6275094 0.1085668 H 7 -3.4050780 0.1484406 2.7485446 N 8 1.0616683 0.4013308 1.2117885 C 9 -1.1628860 -0.2458213 0.3876042 0 10 0.4724220 1.2248480 2.2222423 H 11 -0.4646680 0.9720507 2.3090187 0 12 -1.8677135 -0.4707507 -0.5524979 0 13 -1.7298705 0.0382560 1.6175449 C 14 -3.1744523 -0.0530816 1.7157720 H 15 -3.5006586 -1.0419466 1.4340701 H 16 -3.6419758 0.6720900 1.0674688 Energy -955.861357 hartrees Mulliken and electrostatic fit charges (electrons) atom Mulliken electro fit 0 1 -0.726594 -0.883816 P 2 1.505328 1.484018 0 3 -0.725173 -0.876806 c 4 -0.147568 -0.241564 0 5 -0.784542 -0.784306 H 6 0.389636 0.394199 H 7 0.206467 0.112344 N 8 -0.264465 -0.142904 C 9 0.844976 1.046093 0 10 -0.588285 -0.571421 H 11 0.431059 0.446867 0 12 -0.577774 -0.632697 0 13 -0.738349 -0.453416 C 14 -0.271092 -0.167939 H 15 0.230283 0.139068 H 16 0.216095 0.132281 Time for Ab Initio Engine CPU: 002:22:37.46 002:25:42.02 Time for Properties Engine CPU: 000:00:18.11 000:00:21.30 Wall: Wall: I # R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Cycle no: 12 Energy = -955.8591299 rmsG s 0.0074 rmsD : 0.0162 Cycle no: 13 Energy = -955.8609267 rmsG = 0.0013 rmsD = 0.0229 Cycle no: 14 Energy = -955.8608367 rmsG = 0.0016 rmsD = 0.0171 Cycle no: 15 Energy * -955.8610053 rmsG c 0.0009 rmsD = 0.0048 Cycle no: 16 Energy = -955.8610400 rmsG = 0.0009 rmsD = 0.0049 Cycle no: 17 Energy = -955.8610824 rmsG = 0.0008 rmsD = 0.0051 Cycle no: 18 Energy = -955.8611274 rmsG = 0.0009 rmsD e 0.0104 Cycle no: 19 Energy = -955.8611962 rmsG - 0.0008 rmsD = 0.0091 Cycle no: 20 Energy = -955.8612380 rmsG = 0.0007 rmsD = 0.0060 Cycle no: 21 Energy = -955.8612642 rmsG s 0.0005 rmsD 3 0.0048 Cycle no: 22 Energy = -955.8612811 rmsG = 0.0004 rmsD S 0.0051 Cycle no: 23 Energy = -955.8612941 rmsG = 0.0004 rmsD = 0.0081 Cycle no: 24 Energy = -955.8613107 rmsG - 0.0004 rmsD = 0.0079 Cycle no: 25 Energy = -955.8613248 rmsG = 0.0004 rmsD = 0.0059 Cycle no: 26 Energy = -955.8613359 rmsG = 0.0004 rmsD = 0.0028 Cycle no: 27 Energy = -955.8613430 rmsG = 0.0003 rmsD 3 0.0028 Cycle no: 28 Energy = -955.8613465 rmsG = 0.0002 rmsD = 0.0024 Cycle no: 29 Energy = -955.8613488 rmsG = 0.0002 rmsD = 0.0024 Cycle no: 30 Energy = -955.8613505 rmsG = 0.0002 rmsD = 0.0028 Cycle no: 31 Energy = -955.8613524 rmsG = 0.0002 rmsD = 0.0022 Cycle no: 32 Energy = -955.8613537 rmsG = 0.0001 rmsD = 0.0015 Cycle no: 33 Energy = -955.8613545 rmsG = 0.0001 rmsD = 0.0013 Cycle no: 34 Energy = -955.8613551 rmsG = 0.0001 rmsD = 0.0014 Cycle no: 35 Energy = -955.8613557 rmsG 3 0.0001 rmsD = 0.0014 Cycle no: 36 Energy « -955.8613563 rmsG = 0.0001 rmsD = 0.0010 Cycle no: 37 Energy = -955.8613566 rmsG s 0.0001 rmsD = 0.0004 Cycle no: 38 Energy = -955.8613568 rmsG = 0.0000 rmsD = 0.0002 Cycle no: 39 Energy = -955.8613568 rmsG s 0.0000 rmsD = 0.0002 Cycle no: 40 Energy = -955.8613569 rmsG s 0.0000 rmsD S 0.0002 1 5 * 1 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. MacSPARTAN ab Initio program: Release 1.0 0RTR0IKA1- Geometry Optimization 3-21GC*) Number of basis functions: 119 Number of electrons: 94 Total molecular charge: -1 Multiplicity: 1 Point group: Cl Number of independent degrees of freedom: 42 No useable symmetry or symmetry intentionally disabled Cartesian Coordinates (Angstroms) Atom X Y Z 0 1 0.4249506 -2.5713880 -0.8667364 P 2 1.1411044 -1.2879286 -0.8985209 0 3 1.2971799 -0.4497960 -2.0996700 C 4 0.3294904 -0.2377141 0.4016515 0 5 2.5644189 -1.4635419 -0.1517301 H 6 2.9900366 -0.6386389 0.1137920 H 7 -3.3999334 0.1127942 2.7553815 N 8 1.0624718 0.4098384 1.2081632 C 9 -1.1623626 -0.2353532 0.3837998 0 10 0.4708888 1.2374667 2.2143117 H 11 -0.4650973 0.9806370 2.3035347 0 12 -1.8675945 -0.4510428 -0.5581930 0 13 -1.7279194 0.0362984 1.6170898 C 14 -3.1721386 -0.0610493 1.7170336 H 15 -3.4965414 -1.0430847 1.4103628 H 16 -3.6435403 0.6798255 1.0895021 Hessian calculated using X forcefield Cycle no: 1 Energy = -955.8613581 rmsG = 0.0001 rmsD = 0.0229 Cycle no: 2 Energy = -955.8597800 rmsG c 0.0038 rmsD = 0.0229 Cycle no: 3 Energy = -955.8537669 rmsG = 0.0104 rmsD S K 0.0229 Cycle no: 4 Energy - -955.8496961 rmsG * 0.0126 rmsD = 0.0229 Cycle no: 5 Energy = -955.8503404 rmsG = 0.0119 rmsD = 0.0229 Cycle no: 6 Energy = -955.8483508 rmsG = 0.0134 rmsD S5 0.0229 Cycle no: 7 Energy = -955.8487961 rmsG - 0.0139 rmsD 8 0.0229 Cycle no: 8 Energy - -955.8580939 rmsG s 0.0052 rmsD 8 0.0229 Cycle no: 9 Energy = -955.8588625 rmsG - 0.0042 rmsD = 0.0229 Cycle no: 10 Energy = -955.8594435 rmsG = 0.0041 rmsD = 0.0229 Cycle no: 11 Energy = -955.8604458 rmsG - 0.0025 rmsD 8 0.0229 Ifc# f W * i 1 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission c 17 -0.187570 -0.054404 c 18 -0.187737 -0.034926 H 19 0.288154 0.235863 H 20 0.326967 0.264842 H 21 0.298190 0.182454 H 22 0.296734 0.180128 N 23 0.166679 0.916916 0 24 -0.406143 -0.520843 0 25 -0.405555 -0.517912 Time for Ab Initio Engine CPU: 005:56:34.37 Wall 006:36:01.36 Time for Properties Engine CPU: 000:00:55.32 Wall 000:01:03.06 Time for PAAN02Ph2-2 CPU: 005:57:30.09 Wall 006:37:04.42 Graphics requests: surface-density value-0.00Z property=elpot resolution-med Graphics files written: surface-density value-0.002 property-elpot resolution-med Time for Graphics Engine 000:02:39.10 Time for PAAN02Ph2-2 000:02:39.10 CPU: 000:01:15.42 Wall: CPU: 000:01:15.42 Wall: pending completed Ib ^ R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. PAAN02PH2- Atom Cartesian X Coordinates i Y (Angstroms) Z C 1 -0.2485258 -2.2052418 1.4068923 P 2 0.1516764 -3.4983730 0.1542387 0 3 0.9410673 -2.6965592 -0.8071599 0 4 1.1964618 -4.3954871 1.0035947 0 5 -1.0455422 -4.2762914 -0.1720026 H 6 -1.7031362 -1.2933764 3.8614316 H 7 2.1180042 -4.2356051 0.7634196 N 8 -0.9985835 -2.3449691 2.4027235 C 9 0.4167064 -0.9100740 1.0828660 0 10 -1.0967641 -1.0852597 3.1392392 0 11 1.4826342 -0.5034245 1.4429332 0 12 -0.4145191 -0.2042059 0.2416346 C 13 -0.1328694 0.9331821 -0.4602551 C 14 0.1766960 3.2173918 -1.9539684 C 15 -1.1479036 1.3507663 -1.3145004 C 16 1.0436947 1.6629151 -0.3618219 C 17 1.1909789 2.8063165 -1.1157517 C 18 -0.9957555 2.4906585 -2.0604765 H 19 -2.0322594 0.7544849 -1.3736156 H 20 1.8156287 1.3295226 0.2892506 H 21 2.0853861 3.3861884 -1.0609166 H 22 -1.7604386 2.8286668 -2.7235342 N 23 0.3378328 4.4160191 -2.7287092 0 24 -0.6031409 4.7612298 -3.4739824 0 25 1.4073723 5.0498664 -2.6127071 Energy -1347.624205 hartrees Mutliken and electrostatic fit charges (electrons) atom Mulliken electro fit C 1 -0.088817 -0.020448 P 2 1.530336 1.445987 0 3 -0.765110 -0.895439 0 4 -0.773326 -0.837637 0 5 -0.689821 -0.840593 H 6 0.398349 0.439760 H 7 0.388610 0.466764 N 8 -0.271961 -0.282111 C 9 0.853372 1.108822 0 10 -0.565826 -0.517953 0 11 -0.600385 -0.679548 0 12 -0.785581 -0.628051 C 13 0.463836 0.693609 C 14 0.255026 -0.213263 C 15 -0.266784 -0.445932 C 16 -0.271636 -0.446085 R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. MacSPARTAN ab initio program: Release 1.0 PAAN02PH2- Geometry Optimization 3-21GC*) Number of basis functions: 193 Number of electrons: 148 Total molecular charge: -1 Multiplicity: 1 Point group: Cl Number of independent degrees of freedom: 69 No useable symmetry or symmetry intentionally disabled Cartesian Coordinates (Angstroms) Atom X Y Z C 1 -0.2551846 -2.2190030 1.3874639 P 2 0.1495175 -3.5710632 0.2009478 0 3 0.8766931 -2.8072637 -0.8370591 0 4 1.2560211 -4.3707741 1.0698323 0 5 -1.0273625 -4.4116896 -0.0298109 H 6 -1.7419316 -1.1837824 3.7724884 H 7 2.1619694 -4.2004953 0.7827827 N 8 -1.0275754 -2.3069476 2.3724640 C 9 0.4311148 -0.9443811 1.0289754 0 10 -1.1163433 -1.0167361 3.0559477 0 11 1.5186693 -0.5646677 1.3528357 0 12 -0.4040782 -0.2241262 0.2049844 C 13 -0.1266100 0.9255438 -0.4786212 C 14 0.1724742 3.2368582 -1.9322553 C 15 -1.1484143 1.3596756 -1.3163560 C 16 1.0515025 1.6524768 -0.3770319 C 17 1.1926978 2.8105232 -1.1095847 C 18 -1.0013657 2.5130836 -2.0426919 H 19 -2.0349177 0.7667093 -1.3774565 H 20 1.8297711 1.3052199 0.2589980 H 21 2.0880432 3.3885303 -1.0508891 H 22 -1.7716011 2.8639389 -2.6926317 N 23 0.3289188 4.4491908 -2.6873037 0 24 -0.6122686 4.8011525 -3.4286412 0 25 1.3949614 5.0863680 -2.5585649 Hessian will be taken from archive file Guess wavefunction from archive file Cycle no: 1 Energy = -1347.6241740 rmsG = 0.0001 rmsD = 0.0015 Cycle no: 2 Energy = -1347.6241752 rmsG as 0.0001 rmsD = 0.0017 Cycle no: 3 Energy = -1347.6241765 rmsG - 0.0001 rmsD = 0.0019 Cycle no: 4 Energy = -1347.6241780 rmsG c 0.0001 rmsD = 0.0026 Cycle no: 5 Energy « -1347.6241800 rmsG = 0.0001 rmsD 0.0032 Cycle no: 6 Energy = -1347.6241825 rmsG • 0.0002 rmsD = 0.0032 i b f R eproduced with perm ission of the copyright owner. Further reproduction prohibited without perm ission. Cycle no: 7 Energy = -1347.6241849 rmsG - 0.0002 rmsD a 0.0019 Cycle no: 8 Energy = -1347.6241865 rmsG = 0.0001 rmsD a 0.0009 Cycle no: 9 Energy = -1347.6241874 rmsG = 0.0001 rmsD = 0.0006 Cycle no: 10 Energy * -1347.6241880 rmsG * 0.0001 rmsD = 0.0008 Cycle no: 11 Energy = -1347.6241886 rmsG = 0.0001 rmsD = 0.0010 Cycle no: 12 Energy = -1347.6241893 rmsG a 0.0001 rmsD a 0.0011 Cycle no: 13 Energy = -1347.6241899 rmsG = 0.0001 rmsD = 0.0007 Cycle no: 14 Energy * -1347.6241902 rmsG - 0.0001 rmsD 0.0007 Cycle no: 15 Energy = -1347.6241905 rmsG = 0.0001 rmsD = 0.0006 Cycle no: 16 Energy = -1347.6241908 rmsG 3 = 0.0001 rmsD = 0.0011 Cycle no: 17 Energy = -1347.6241912 rmsG - 0.0001 rmsD = 0.0016 Cycle no: 18 Energy = -1347.6241919 rmsG - 0.0001 rmsD 0.0026 Cycle no: 19 Energy = -1347.6241928 rmsG a 0.0001 rmsD = 0.0023 Cycle no: 20 Energy < = -1347.6241938 rmsG a 0.0001 rmsD = 0.0025 Cycle no: 21 Energy = -1347.6241947 rmsG = 0.0001 rmsD = 0.0016 Cycle no: 22 Energy - -1347.6241956 rmsG K 0.0001 rmsD = 0.0024 Cycle no: 23 Energy = -1347.6241968 rmsG s 0.0001 rmsD 0.0018 Cycle no: 24 Energy = -1347.6241983 rmsG a 0.0001 rmsD = 0.0033 Cycle no: 25 Energy * -1347.6241997 rmsG = 0.0001 rmsD = 0.0014 Cycle no: 26 Energy = -1347.6242009 rmsG a 0.0001 rmsD = 0.0020 Cycle no: 27 Energy = -1347.6242018 rmsG = 0.0001 rmsD = 0.0014 Cycle no: 28 Energy * -1347.6242029 rmsG a 0.0001 rmsD = 0.0016 Cycle no: 29 Energy = -1347.6242036 rmsG * 0.0001 rmsD = 0.0009 Cycle no: 30 Energy = -1347.6242042 rmsG a 0.0001 rmsD = 0.0009 Cycle no: 31 Energy = -1347.6242044 rmsG a 0.0001 rmsD = 0.0005 Cycle no: 32 Energy = -1347.6242046 rmsG * 0.0000 rmsD - 0.0006 Cycle no: 33 Energy = -1347.6242048 rmsG a 0.0000 rmsD = 0.0002 Cycle no: 34 Energy « -1347.6242049 rmsG - 0.0000 rmsD 0.0004 Cycle no: 35 Energy * -1347.6242049 rmsG a 0.0000 rmsD — 0.0001 R eproduced with perm ission of the copyright owner. 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Asset Metadata

Creator Fujimoto, Mari (author)

Core Title Synthesis and metal cation-promoted hydrolysis of (hydroxyimino)phosphonoacetic acid derivatives

School Graduate School

Degree Master of Science

Degree Program Chemistry

Degree Conferral Date 1997-05

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c16-19002

Unique identifier UC11337118

Identifier 1389987.pdf (filename),usctheses-c16-19002 (legacy record id)

Legacy Identifier 1389987.pdf

Dmrecord 19002

Document Type Thesis

Rights Fujimoto, Mari

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA