A study in the applications of flash photolysis : 1. a.b- unsaturated nitro compounds : 2. tryptophan degradation by singlet oxygen
A study in the applications of flash photolysis : 1. a.b- unsaturated nitro compounds : 2. tryptophan degradation by singlet oxygen
This thesis reports on the aspects of microsecond flash photolysis, from the construction and design of the apparatus to its application in two photochemical fields of interest aa-unsaturated nitro compounds and tryptophan degradation. The generation of 511s light pulses from a 200 Joule discharge source is described in detail. The optimisation of the lamp design is specifically considered within the given working parameters. A system for obtaining an improved signal to noise ratio is developed using a second synchronised pulsed source for the analysis of the transients.E-1-(9-phenanthryl)-2-nitroprop-l-ene on irradiation in solution undergoes isomerisation to the Z isomer. The Z isomer on photolysis behaves differently and yields 2-methylphenanthro-9,10-b furan and phenanthrene-9-aldehyde, via intermediate transients. Flash photolysis and low temperature NMR studies were used to demonstrate the presence and character of this transient. A probable structure for this transient is suggested.A model peptide, N-acetyl-tryptophan methyl amide was prepared to investigate photo-degradation of tryptophan amino acids. Evidence for the participation of singlet oxygen in the direct sensitisation by the model using the deuterium enhancement method of the singlet oxygen lifetime is presented.
University of Southampton
1979
Humphry-Baker, Robin
(1979)
A study in the applications of flash photolysis : 1. a.b- unsaturated nitro compounds : 2. tryptophan degradation by singlet oxygen.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
This thesis reports on the aspects of microsecond flash photolysis, from the construction and design of the apparatus to its application in two photochemical fields of interest aa-unsaturated nitro compounds and tryptophan degradation. The generation of 511s light pulses from a 200 Joule discharge source is described in detail. The optimisation of the lamp design is specifically considered within the given working parameters. A system for obtaining an improved signal to noise ratio is developed using a second synchronised pulsed source for the analysis of the transients.E-1-(9-phenanthryl)-2-nitroprop-l-ene on irradiation in solution undergoes isomerisation to the Z isomer. The Z isomer on photolysis behaves differently and yields 2-methylphenanthro-9,10-b furan and phenanthrene-9-aldehyde, via intermediate transients. Flash photolysis and low temperature NMR studies were used to demonstrate the presence and character of this transient. A probable structure for this transient is suggested.A model peptide, N-acetyl-tryptophan methyl amide was prepared to investigate photo-degradation of tryptophan amino acids. Evidence for the participation of singlet oxygen in the direct sensitisation by the model using the deuterium enhancement method of the singlet oxygen lifetime is presented.
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Published date: 1979
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Local EPrints ID: 462709
URI: http://eprints.soton.ac.uk/id/eprint/462709
PURE UUID: a06141fe-a4be-4def-bea4-32fbedbbc212
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Date deposited: 04 Jul 2022 19:43
Last modified: 04 Jul 2022 19:43
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Author:
Robin Humphry-Baker
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