A search for radical intermediates in the photocycle of LOV domains

LOV domains are the photoactive part of many biological sensors for blue light. The primary photochemical reaction leads to formation of a covalent adduct between the cofactor flavin and a cysteine residue of the protein. The reaction starts from the flavin triplet state. Does this reaction proceed in a single step, or are other intermediates involved?

High efficiency photoresist-free lithography of UO3 patterns from amorphous films of uranyl complexes

The solid state photochemistry of uranyl carboxylate complexes is presented with the purpose of developing methods for optical lithography of uranium oxide films. These complexes of the general formula, UO2(OOCR)2 (R = i-C3H7, C5H11, CH2C6H5, CH2OC2H5, C2H4OC2H5), were all photosensitive as thin amorphous films. The primary photochemical reaction for each of these complexes was the extrusion of a CO2 from the ligand and the production of radicals which initiated a chain reaction. The nature of this chain reaction was dependent upon the identity of the organic substituents, R. In some cases the chain reaction required a photochemical step while others were entirely thermal in nature. Of importance are the potentially high quantum yields which can be associated with thermal chain reactions. Some of the systems presented here exhibit quantum yields in excess of 1. This process was shown to be compatible with optical lithography by the patterning of the uranium oxide product on silicon surfaces.

Paraquat (Methylviologen): Its Interference with Primary Photochemical Reactions

Paraquat(methylviologen), a widely used nonspecific herbicide, is ptoreduced in the primary photochemical reaction of photosystemI. Using two types of the photosystem I reaction center preparations, i.e. one with FeSA/FeSB and the other without, the immediate electron donor to methylviologen was determined to be FeSx (P430) rather than FeSA/FeSB.

Wavelength controlled production of SO4- radicals in the ultraviolet photolysis of ceric sulfate solutions

Solutions of cerium(III)/(IV) and formic acid in 0.4 M sulfuric acid have been photolysed under 254 nm and 365 nm light. Marked differences in the reaction kinetics and quantum yields are observed at the two different wavelengths. At 365 nm, the reactions leading to cerium(IV) reduction are caused almost exclusively by the SO4- radical. The ratio of rate constants, k(SO4- + CeIII)/ k(SO4- + HCOOH), is 116 � 11 and the quantum yield of sulfate radicals, ф(SO4-), is 0.023 � 0.002. At 254 nm, the reactions leading to cerium(IV) reduction are caused mainly by the OH radical, but approximately 35% of the oxidizing radicals formed in the primary photochemical reaction are SO4-. Cerium(III) species, excited at 254 nm, transfer energy to cerium(IV) and this results in an additional yield of OH and SO4- radicals. Fluorescence measurements confirmed the efficiency of the energy transfer reaction. The ratio of rate constants, k(OH+CeIII)/k(OH+HCOOH), is 2.22 � 0.18 and ф(CeIV*) and ф(CelIII*) giving oxidizing radicals are 0.116 � 0.010 and 0.0083 � 0.0008 respectively. Thus about 5 times more total oxidizing radicals are produced from excited cerium(IV) species at 254 nm than at 365 nm.