Full Text Available
Note: Clicking the button above will open the full text document at the original institutional repository in a new window.
Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution
The role of metal ions as catalysts for numerous biochemical reactions has been the subject of many investigations. One of the most important classes of ligands are phosphate esters. In this thesis I describe the investigation of some phosphate ester-metal ion equilibria. Formation constants for the...
Saved in:
| Main Author: | |
|---|---|
| Other Authors: | |
| Format: | Thesis |
| Language: | English |
| Published: |
Department of Chemistry
2016
|
| Subjects: | |
| Tags: |
No Tags, Be the first to tag this record!
|
| _version_ | 1867613307534311424 |
|---|---|
| access_status_str | Open Access |
| author | Kramer, Ulrike |
| author2 | Linder, Peter W |
| author_browse | Kramer, Ulrike Linder, Peter W |
| author_facet | Linder, Peter W Kramer, Ulrike |
| author_sort | Kramer, Ulrike |
| collection | Thesis |
| description | The role of metal ions as catalysts for numerous biochemical reactions has been the subject of many investigations. One of the most important classes of ligands are phosphate esters. In this thesis I describe the investigation of some phosphate ester-metal ion equilibria. Formation constants for the complexation of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate, methyl phosphate, 8-quinolyl phosphate, 8-quinolyl methyl phosphate, triphosphate and fluorotriphosphate with protons, copper, zinc and calcium ions were determined by potentiometry. In addition, the complexation of 1-naphthyl phosphate, 8-quinolyl phosphate and 8-quinolyl methyl phosphate with nickel and cobalt ions was also studied. Protonation enthalpies and copper complexation enthalpies of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate and methyl phosphate were determined by calorimetry. A correlation between the nucleophilicity of the ester group and the magnitude of the stability constants of the proton, copper and zinc complexes of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate and methyl phosphate is found and explained in terms of electronic induction effects, i.e. by polarisation of the phosphate oxygens by the ester group. The calorimetric results show that the desolvation of ligand and metal ion during the complexation plays an important role. The possibility of similar correlations for complexes of triphosphates is also discussed. |
| format | Thesis |
| id | oai:open.uct.ac.za:11427/17083 |
| institution | University of Cape Town (South Africa) |
| language | eng |
| last_indexed | 2026-06-10T12:34:03.682Z |
| license_str | Not specified — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository |
| publishDate | 2016 |
| publishDateRange | 2016 |
| publishDateSort | 2016 |
| publisher | Department of Chemistry |
| publisherStr | Department of Chemistry |
| record_format | dspace |
| source_str | UCTD — University of Cape Town Open Access Repository |
| spelling | oai:open.uct.ac.za:11427/17083 Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution Kramer, Ulrike Linder, Peter W Chemistry Esters Ligands Complex compounds The role of metal ions as catalysts for numerous biochemical reactions has been the subject of many investigations. One of the most important classes of ligands are phosphate esters. In this thesis I describe the investigation of some phosphate ester-metal ion equilibria. Formation constants for the complexation of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate, methyl phosphate, 8-quinolyl phosphate, 8-quinolyl methyl phosphate, triphosphate and fluorotriphosphate with protons, copper, zinc and calcium ions were determined by potentiometry. In addition, the complexation of 1-naphthyl phosphate, 8-quinolyl phosphate and 8-quinolyl methyl phosphate with nickel and cobalt ions was also studied. Protonation enthalpies and copper complexation enthalpies of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate and methyl phosphate were determined by calorimetry. A correlation between the nucleophilicity of the ester group and the magnitude of the stability constants of the proton, copper and zinc complexes of p-nitrophenyl phosphate, phenyl phosphate, 1-naphthyl phosphate, α-D-glucose-1'-phosphate, glycerol-2-phosphate and methyl phosphate is found and explained in terms of electronic induction effects, i.e. by polarisation of the phosphate oxygens by the ester group. The calorimetric results show that the desolvation of ligand and metal ion during the complexation plays an important role. The possibility of similar correlations for complexes of triphosphates is also discussed. 2016-02-17T07:16:30Z 2016-02-17T07:16:30Z 1988 Doctoral Thesis Doctoral PhD http://hdl.handle.net/11427/17083 eng application/pdf Department of Chemistry Faculty of Science University of Cape Town |
| spellingShingle | Chemistry Esters Ligands Complex compounds Kramer, Ulrike Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| thesis_degree_str | Doctoral |
| title | Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| title_full | Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| title_fullStr | Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| title_full_unstemmed | Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| title_short | Complexation of divalent copper, zinc and calcium ions by phosphate esters in aqueous solution |
| title_sort | complexation of divalent copper zinc and calcium ions by phosphate esters in aqueous solution |
| topic | Chemistry Esters Ligands Complex compounds |
| url | http://hdl.handle.net/11427/17083 |
| work_keys_str_mv | AT kramerulrike complexationofdivalentcopperzincandcalciumionsbyphosphateestersinaqueoussolution |