Photochemical reactions, shape-selective

Shape selectivity and orbital confinement effects are direct results of the physical dimensions of the available space in microscopic vessels and are independent of the chemical composition of nano-vessels. However, the chemical composition in many cases cannot be ignored because in contrast to traditional solution chemistry where reactions occur primarily in a dynamic solvent cage, the majority of reactions in nano-vessels occur in close proximity to a rigid surface of the container (vessel) and can be influenced by the chemical and physical properties of the vessel walls. Consequently, we begin this review with a brief examination of both the shape (structure) and chemical compositions of a unique set of nano-vessels, the zeolites, and then we will move on to examine how the outcome of photochemical reactions can be influenced and controlled in these nanospace environments. 

The generation of active coordinates for non-adiabatic dynamics is related with our interest in laser-driven control. The optimal control of photochemical reactions is based on shaped laser pulses designed to generate photoproducts selectively. 

Other properties which have contributed to the attractiveness and versatility of the sol-gel doping approach are the chemical, photochemical and electrochemical inertness as well as the thermal stability of the matrix the ability to induce electrical conductivity16 the richness of ways to modify chemically the matrix and its surface as well as the above-mentioned controllability of matrix structural properties the enhanced stability of the entrapped molecule1,17 the ability of employing the chromatographic properties of the matrix for enhanced selectivity and sensitivity of reactions with the dopant4 the simplicity of the entrapment procedure the ability to obtain the doped sol-gel material in any desired shape (powders, monoliths, films, fibers) and the ability to miniaturize it18,19. 

Carbon monoxide inhibited the 6/3-. la-, and 16a-hydroxylation of testosterone by rat liver microsomes to different extents. A C0/02 ratio of 0.5 inhibited the la-, 6/i-, and 16a-hydroxylation reactions by 14%, 25%, and 36%, respectively, and the ratio of C0/02 needed for 50% inhibition of testosterone hydroxylation in the 16a-, 6/3-, and 7a-positions was 0.93, 1.54, and 2.36, respectively (36,48). Studies on the photochemical action spectrum revealed that CO inhibition of the three hydroxylation reactions was maximally reversed by monochromatic light at 450 nm, but there were differences in the shape of the photochemical reactivation spectra for the 6/3-, la-, and 16a-hydroxylation reactions (36,48). The data from our laboratory summarized above and at the First International Symposium on Microsomes and Drug Oxidation in 1968 pointed to multiple cytochromes P450 with different catalytic activities that were under separate regulatory control (36,45,46), and we indicated that the actual number of cytochromes that participate in the multiple hydroxylation reactions must await the solubilization and purification of the microsomal system (36). The use of different inducers of liver microsomal monooxygenases caused selective increases in the concentration of specific cytochromes P450 in fiver microsomes that greatly facilitated the isolation and purification of these hemoproteins. 

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