Photoprocesses of p-naphthoquinones and vitamin K(1): effects of alcohols and amines on the reactivity in solution.

The photochemistry of 1,4-naphthoquinone (NQ), the 2-methyl, 2,3-dichloro and 2-bromo derivatives, and vitamin K(1) was studied in non-aqueous solvents by time-resolved UV-vis spectroscopy after ns laser pulses at 248 and 308 nm. The triplet state of the NQs reacts with alcohols and amines, e.g. triethylamine (TEA) and DABCO, yielding semiquinone radicals (HQ(*)/Q (*)(-)). They are the major intermediates and their second-order decay kinetics depend on the properties of the additives and the medium. Transient conductivity measurements suggest the occurrence of photoinduced electron transfer from amines to the triplet state of NQs in acetonitrile. The photoconversion lambda (irr)= 254 nm) of NQs to the 1,4-dihydroxynaphthalenes (H(2)Q) was measured in the absence and presence of varying concentrations of electron and H-atom donors, and the quantum yield was found to increase with increasing electron- or proton-donor concentration. The mechanisms of photoreduction of NQs by propan-2-ol and TEA in acetonitrile exhibit a number of similarities. Oxygen quenches the triplet state, thereby forming singlet molecular oxygen. Oxygen also reacts with the semiquinone radical, thereby forming HO(2)(*)/O(2) (*) (-) radicals, and reacts with H(2)Q, thereby re-forming the quinone. A different pattern, involving intramolecular H-atom transfer, holds for vitamin K(1), where 1,3-quinone methide (1,3-QM) diradicals were observed in acetonitrile prior to formation of two 1,2-QM tautomers, but a triplet was not. The decay of the 1,3-QM intermediates becomes faster in the presence of alcohols and amines due to proton-transfer reactions.

Photo-enhanced production of the spin adduct 5,5-dimethyl-1-pyrroline-N-oxide/.OH in aqueous menadione solutions.

The production of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO)/.OH in aqueous solutions of menadione and DMPO is enhanced by fluorescent room light. The formation of DMPO/.OH requires oxygen and water, is enhanced by superoxide dismutase, and occurs to a much smaller extent for benzoquinone than for menadione. This process is assigned as photo-initiated redox cycling of the menadione, which causes oxidation of DMPO to DMPO+. and reduction of oxygen to superoxide. DMPO+. reacts with water to produce DMPO/.OH. Although DMPO/.OOH was not observed in the menadione solutions, the possibility that some of the DMPO/.OH was produced by decomposition of DMPO/.OOH cannot be ruled out. There is no evidence for participation of hydroxyl radicals. Because benzosemiquinone is less readily oxidized than the semiquinone of menadione, redox cycling is less favorable for benzoquinone than for menadione and smaller quantities of DMPO/.OH are produced by photoexcitation of benzoquinone than of menadione.

Photostabilization of menadione sodium bisulfite by glutathione.

Photodecomposition of solutions of menadione sodium bisulfite (MSB) in the presence and absence of glutathione (GSH) under artificial sunlight was investigated. In presence of 0.02% (GSH), an appreciable increase in photostability was observed when clear glass vials were used. The pH and the temperature of the solution significantly influenced the stability of MSB. Photodegradation of MSB appeared to follow first-order kinetics. Photostabilization of MSB was attributed in part to complex formation between MSB and GSH and the antioxidant property of the latter. Stability constants for the various solutions were determined at several temperatures. Thermodynamic parameters were calculated and were found to support complex formation.

Electron transfer reactions in photosystem I following vitamin K1 depletion by ultraviolet irradiation.

Photosystem I preparations were irradiated with UV to destroy vitamin K1 in situ. The depletion of vitamin K1 resulted in inactivation of NADP+ photoreduction and introduction of a approximately 220 ms component in the flash generated P700+ rereduction at room temperature. The photoreduction of the terminal FeS centers FA and FB in control and vitamin K1-depleted preparations at 7 K were comparable. The data confirm that vitamin K1 is functionally implicated in primary electron transfer reactions in PS I at physiological temperature, and that the anomalous results at cryogenic temperature may be explicable in terms of a by-pass of the vitamin K1 acceptor site or heterogeneity introduced into the photosystem by quinone removal.

[Study of the kinetics of chlorophyll photosensitized dye reduction by photopolarography]. / Izuchenie kinetiki fotosensibilizirovannogo khlorofillom vosstanovleniia krasitelei metodom fotopoliarografii.

It has been shown by photopolarographic method that under stationary illumination chlorophyll-photosensitized reduction of dyes with ascorbic acid proceeds according to the first kinetic order. Rate constants of photoreduction of vitamin K3, methelene red, safranin-T and methylviologen were found in the course of sensitization which proceeded by oxidative and reduction mechanisms. Similarity of kinetics at both sensitization mechanisms was shown. Results obtained by polarographic and spectroscopic methods were compared.

Complex formation between menadione and cetylethylmorpholinium ethosulfate: effect on UV photodegradation of menadione.

The process of menadione photodegradation can be enhanced or diminished by other compounds. The presence of the quaternary ammonium compound cetylethylmorpholinium ethosulfate (I) in solutions of minadione was found to slow the rate of photodegradation by UV light (253.7 nm). The mechanism of this effect may be due to complex formation between menadione and I. Complex formation was demonstrated by a shift in the absorption peaks of menadione from 245 and 260 nm to 251.5 and 261.5 nm, respectively. The equilibrium constant of this complex was calculated to be 1.647 M.

Action spectrum for growth delay induced in Escherichia coli B-r by far-ultraviolet radiation.

An action spectrum for growth delay induced in Escherichia coli B/r by far-ultraviolet radiation (230 to 295 nm) was obtained. It resembles the action spectrum for killing obtained in the same experiments, indicating that the chromophore for growth delay is probably the same as the chromophore for killing. Another action spectrum for killing, obtained under conditions more suitable for chromophore identification, suggests that nucleic acid, either deoxyribonucleic acid or ribonucleic acid, is the chromophore for growth delay induced by far ultraviolet. Isoprenoid quinones, which seem to be important chromophores for growth delay induced by near-ultraviolet radiation (above 300 nm), appear to play a negligible role in growth delay induced by wavelengths below 300 nm.