PHOTOCHEMISTRY OF MELANIN PRECURSORS: DOPA, 5-S-CYSTEINYLDOPA AND 2,5-S,S'-DICYSTEINYLDOPA

The photochemistries of the melanin precursors dopa, 5-S-cysteinyldopa (5-SCD) and 2.5-S,S'-dicysteinyldopa (2.5-SCD) were investigated by 265-nm laser flash photolysis. The quantum yield of hydrated electron following flash photolysis of dopa (9.1%) was half the yield of dopasemiquinone (19.6%), implying that dopasemiquinone is formed via two primary photochemical mechanisms: photionisation (giving e) or photohomolysis (giving H^˙). Dopasemiquinone rapidly disproportionates to form dopaquinone and re-form dopa. Dopaquinone in turn decays via a base-catalysed unimolecular cyclisation eventually to form dopachrome. Assignment of the transient species was confirmed by previous pulse radiolysis studies of the one-electron oxidation of dopa. In contrast, flash photolysis of the cysteinyldopas, 5-SCD and 2,5-SCD results in lower photoionisation quantum yields and the production of initial transient species whose absorption spectra were markedly different from their semiquinone absorption spectra previously determined pulse radiolytically. These observations indicate that the primary cysteinyldopa photochemical species is not such a semiquinone, but rather results from S-CH₂ bond photohomolysis. Absorption spectra and rate constants for the formation and decay of various transient species are reported.     

SINGLET OXYGEN GENERATION BY FUROCOUMARIN TRIPLET STATES—I. LINEAR FUROCOUMARINS (PSORALENS)

Abstract— Triplet extinction coefficients and hence singlet → triplet intersystem crossing quantum yields have been measured in benzene for a number of linear furocoumarins including pseudopsoralen, 5, 8-dimethoxypsoralen, 4, 5', 8-trimethylpsoralen and 3-carbethoxypseudopsoralen. These triplet yields were then used in conjunction with the corresponding quantum yields of singlet oxygen formation, measured in oxygenated solution, to estimate the fractions of furocoumarin triplets which when quenched by ground state oxygen produce singlet excited oxygen, similar data being obtained for psoralen, 5-methoxypsoralen, 8-methoxypsoralen and 3-carbethoxypsoralen. The superoxide anion radical was not detected from these oxygen quenching reactions, nor was a contribution to the singlet oxygen yield found from furocoumarin excited singlet state quenching by oxygen. The fraction of furocoumarin-oxygen quenching interactions leading to singlet oxygen varied between 0.13 (for 5, 8-dimethoxypsoralen) and unity (for 3-carbethoxypsoralen), and thus needs to be taken into account, as well as the triplet quantum yields, in assessing photobiological processes involving singlet oxygen.     

EXCITED STATES OF BILIRUBIN

Abstract— The excited states of bilirubin (BR) in a variety of environments have been studied by 347 nm laser flash photolysis. Quantum yields of formation of triplet BR have been shown to be less than 0.005 in solution in water ( p H 9–11), methanolic ammonia, 10% aqueous mulgofen and in cetyl trimethyl-ammonium bromide. In benzene the quantum yield was 0.01 although this diminished to less than 0.005 on addition of triethylamine. Permanent products are formed with benzene and with 1% methanolic ammonia. With BR in HSA a transient decaying with k = 3.5 × 10⁵ s^-1 is formed by a monophotonic process together with a permanent product. Neither species is affected by oxygen or by iodide ion. Both originate from BR molecules in the strongest binding site in the HSA. The yields of both species are unaffected by salt but are temperature dependent. The decay of the transient is strongly temperature dependent corresponding to an activation energy of about 50–60 kj mol^-1. If this transient is a triplet it is formed with a quantum yield of 0.13 ± 0.01. The relevance of these results to an understanding of the photo therapeutic process is discussed.     

A high flux,liquid-helium cooled source of metastable rare gas atoms

We have developed a novel, high flux source of metastable rare gas atoms (helium, neon and argon) that uses liquid helium cooling to reduce the initial atomic velocity. Fluxes exceeding 10¹⁴ atoms/ster/s with He and Ne were obtained. With average velocities of 600 m/s for He and 300 m/s for Ne and Ar, this source will enable simpler, more compact beam lines for loading magneto-optical traps. PACS 34.80.Dp; 39.10.+j; 39.25.+k     

SOME PHOTOPHYSICAL PROPERTIES OF 3-CARBETHOXYPSORALEN, 8-METHOXYPSORALEN and 5-METHOXYPSORALEN TRIPLET STATES

Abstract Triplet absorption spectra, extinction coefficients (ɛ_T), decay rates ( K ₁), oxygen quenching rates (k_q) and intersystem crossing yields (φ_T) for 3-carbethoxypsoralen (3-CPs). 8-methoxypsoralcn (8-MOP) and 5-methoxypsoralen (5-MOP) in methanol are reported. For 8-MOP and 3-CPs corresponding values are also reported with water as the solvent. Some photophysical data are also reported for 5-MOP in water, but ɛ_T and φ_T were not obtained.
The phosphorescence spectra for these furocoumarin derivatives in ethanol at 77 K are reported together with the corresponding lowest triplet energy and lifetime. The values of the various photophysical properties obtained are compared with values reported by previous workers.