The synergistic effect of nitric oxide toward dephosphorylation reactions involving phosphate esters was the subject of investigation in this research. Sodium nitroprusside under UV irradiations at 254nm, 365nm and white light was utilized as nitric oxide donor in solutions. The effects of cobalt trimethylenediamine and nitroprusside towards dephosphorylation of nitrophenylphosphate and pyrophosphate which were modeled as organophosphate ester substrates were also investigated. The activated substrate models showed more rate enhancement than the unactivated models in all cases. The direct interaction of nitric oxide with the phosphorus centre is presumed to be the reason for enhanced hydrolysis. This study demonstrates the possible role of nitric oxide in decontamination reactions of poorly biodegradable phosphate esters in the biosphere. / Chemistry / M. Sc. (Chemistry)

The synergistic effect of nitric oxide toward dephosphorylation reactions involving phosphate esters was the subject of investigation in this research. Sodium nitroprusside under UV irradiations at 254nm, 365nm and white light was utilized as nitric oxide donor in solutions. The effects of cobalt trimethylenediamine and nitroprusside towards dephosphorylation of nitrophenylphosphate and pyrophosphate which were modeled as organophosphate ester substrates were also investigated. The activated substrate models showed more rate enhancement than the unactivated models in all cases. The direct interaction of nitric oxide with the phosphorus centre is presumed to be the reason for enhanced hydrolysis. This study demonstrates the possible role of nitric oxide in decontamination reactions of poorly biodegradable phosphate esters in the biosphere. / Chemistry / M. Sc. (Chemistry)

Highly selective and sensitive phosphate sensors have been fabricated by constructing a solid membrane disk consisting of variable mixtures of aluminium powder (Al), aluminium phosphate (AlPO4) and powdered copper (Cu). Both binary and ternary electrode systems are produced depending on their composition. The ternary membranes exhibit greater selectivity over a wide range of concentrations. The ternary electrode with the composition 25% AlPO4, 25% Cu and 50% Al was selected as our preferred electrode. The newly fabricated ternary membrane phosphate selective electrodes exhibited linear potential response in the concentration range of 1.0 × 10−6 to 1.0 × 10−1 mol L−1. The electrodes also exhibit a fast response time of <60 s. Their detection limit is 1.0 × 10−6 mol L−1. The unique feature of the described electrodes is their ability to maintain a steady and reproducible response in the absence of an ionic strength control. The electrodes have a long lifetime and can be stored in air when not in use. The selectivity of the new phosphate selective electrodes with respect to other common ions is excellent. The results obtained provide further insight into the working principles of the newly fabricated phosphate selective electrodes. Dephosphorylation and phosphorylation reactions were monitored using the preferred phosphate selective electrode. The following reactions were studied and inferences drawn; (a) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[OH(PO2O)]2- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[OH(PO2O)]2- ratios.(b) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[O2NC6H4PO2(O)(OH)]- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[O2NC6H4PO2(O)(OH)]- ratios. (c) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)2O]2- for 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)2O]2- ratios, and (d) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)3O2]3- for the 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)3O2]3- ratios. Further insight into dephosphorylation and phosphorylation reactions is unravelled by the novel phosphate selective electrode monitoring. *For clarity of the complexes utilized, see chapter 4, table 4.1. KEY WORDS; Dephosphorylation, phosphorylation, ion selective electrodes, phosphate ion selective electrode, decontamination, electromotive force, potential difference, activity, concentration, selectivity coefficient, calibration, ionic strength, hydrolysis, inorganic phosphates, nitrophenylphosphate, pyrophosphate, tripolyphosphate, organophosphate esters. / Chemistry / D.Phil (Chemistry)

The FT-Raman techniques were developed to quantify reactions that follow on mixing aqueous solutions of bis-(1,3-diaminopropane)diaquacobalt( III) ion ([Co(tn)2(0H)(H20)]2+) and p-nitrophenylphosphate (PNPP). For the development and validation of the kinetic modelling technique, the well-studied inversion of sucrose was utilized. Rate constants and concentrations could be estimated using calibration solutions and modelling methods. It was found that the results obtained are comparable to literature values. Hence this technique could be further used for the [Co(tn)2(0H)(H20)]2+ assisted hydrolysis of PNPP. It was found that rate constants where the pH is maintained at 7.30 give results which differ from those where the pH is started at 7.30 and allowed to change during the reaction. The average rate constant for 2:1 ([Co(tn)2(0H)(H20)]2+:PNPP reactions was found to be approximately 3 x 104 times the unassisted PNPP hydrolysis rate. / Chemistry / M. Sc. (Chemistry)

Highly selective and sensitive phosphate sensors have been fabricated by constructing a solid membrane disk consisting of variable mixtures of aluminium powder (Al), aluminium phosphate (AlPO4) and powdered copper (Cu). Both binary and ternary electrode systems are produced depending on their composition. The ternary membranes exhibit greater selectivity over a wide range of concentrations. The ternary electrode with the composition 25% AlPO4, 25% Cu and 50% Al was selected as our preferred electrode. The newly fabricated ternary membrane phosphate selective electrodes exhibited linear potential response in the concentration range of 1.0 × 10−6 to 1.0 × 10−1 mol L−1. The electrodes also exhibit a fast response time of <60 s. Their detection limit is 1.0 × 10−6 mol L−1. The unique feature of the described electrodes is their ability to maintain a steady and reproducible response in the absence of an ionic strength control. The electrodes have a long lifetime and can be stored in air when not in use. The selectivity of the new phosphate selective electrodes with respect to other common ions is excellent. The results obtained provide further insight into the working principles of the newly fabricated phosphate selective electrodes. Dephosphorylation and phosphorylation reactions were monitored using the preferred phosphate selective electrode. The following reactions were studied and inferences drawn; (a) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[OH(PO2O)]2- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[OH(PO2O)]2- ratios.(b) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[O2NC6H4PO2(O)(OH)]- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[O2NC6H4PO2(O)(OH)]- ratios. (c) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)2O]2- for 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)2O]2- ratios, and (d) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)3O2]3- for the 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)3O2]3- ratios. Further insight into dephosphorylation and phosphorylation reactions is unravelled by the novel phosphate selective electrode monitoring. *For clarity of the complexes utilized, see chapter 4, table 4.1. KEY WORDS; Dephosphorylation, phosphorylation, ion selective electrodes, phosphate ion selective electrode, decontamination, electromotive force, potential difference, activity, concentration, selectivity coefficient, calibration, ionic strength, hydrolysis, inorganic phosphates, nitrophenylphosphate, pyrophosphate, tripolyphosphate, organophosphate esters. / Chemistry / D. Phil (Chemistry)