Description
| Abstract: | Adenosinetriphosphate (ATP), bis-p-nitrophenyl phenylphoshonate (bis-PNPP) and tris-p-nitro-phenylphosphate were studied in bile salt systems. ATP showed essentially no solvolysis in dimethyl sulfoxide (DMSO) or water systems with sodium cholate (NaC). Rate constants for the solvolysis of bis-PNPP in DMSO in the presence of aggregated NaC are enhanced by factors of more than 5 million fold and 1.89x10⁻⁵ fold with respect to those in the pure bulk solvent and in water systems. The observed rate constant for the formation of p-nitrophenoxide ion exibits a sigmoidal dependence with increasing NaC concentrations reaching a plateau at high NaC concentrations. No kinetic deuterium solvent isotope effects were observed and no reaction occurs in the presence of methyl cholate. A mechanism for the bile salt catalysis is proposed and discussed in terms of both physical and chemical interactions for bis-PNPP. Tris-PNP showed the same trends as bis-PNPP but data was not analyzed completely for this paper. |
| Item Description: | Undergraduate thesis written for Program year: 1977-1978 |
| Physical Description: | 1 online resource (44 pages). Digitized from print version held at Pickle Center High Density Storage, HDR barcode A14850693772 |