The photocatalytic destruction of cinnamic acid and cinnamyl alcohol: Mechanism and the effect of aqueous ions.

Cinnamic acid was chosen as an exemplar molecule to study the effect of potential contaminants on the kinetics and mechanism of the photocatalytic destruction of hydrocarbons in aqueous solutions. We identify the principal intermediates in the photocatalytic reaction of the acid and corresponding alcohol, and propose a mechanism that explains the presence of these species. The impact of two likely contaminants of aqueous systems, sulfate and chloride ions were also studied. Whereas sulfate ions inhibit the degradation reaction at all concentrations, chloride ions, up to a concentration of 0.5 M, accelerate the removal of cinnamic acid from solution by a factor of 1.6. However, although cinnamic acid is removed, the pathway to complete oxidation is blocked by the chloride, with the acid being converted (in the presence of oxygen) into new products including acetophenone, 2-chloroacetophenone, 1-(2-chlorophenyl)ethenone and 1,2-dibenzoylethane. We speculate that the formation of these products involves chlorine radicals formed from the reaction of chloride ions with the photoinduced holes at the catalyst surface. Interestingly, we have shown that the 1-(2-chlorophenyl)ethenone and 1,2-dibenzoylethane products form from 2-chloroacetophenone when irradiated with 365 nm light in the absence of the catalyst. The formation of potentially dangerous side products in this reaction suggest that the practical implementation of the photocatalytic purification of contaminated water needs to considered very carefully if chlorides are likely to be present.

Molecular recognition of chiral conformers: a rotational study of the dimers of glycidol.

Two homochiral dimers of glycidol, deriving from two different conformers, have been characterized by rotational spectroscopy in a supersonic expansion.

Light induces phenylpropanoid metabolism in Arabidopsis roots.

Experiments have shown that many phenylpropanoid genes are highly expressed in light-grown Arabidopsis roots. Studies employing reporter gene constructs have indicated that the expression of these genes is localized not only to the lignifying root vasculature, but also to non-lignifying tissues, such as the root cortex, suggesting that the proteins encoded by these genes may be involved in aspects of phenylpropanoid metabolism other than lignification. Consistent with this hypothesis, roots of etiolated and soil-grown plants contain almost no soluble phenylpropanoids, but exposure to light leads to the accumulation of flavonoids, as well as high levels of coniferin and syringin (coniferyl and sinapyl-4-O-glycosides), compounds not previously reported to be accumulated in Arabidopsis. To elucidate the mechanism by which light induces root secondary metabolism, extracts of mutants defective in light perception and light responses were analyzed for phenylpropanoid content. The results of these assays showed that phytochrome (PHY)B and cryptochrome (CRY)2 are the primary photoreceptors involved in light-dependent phenylpropanoid accumulation, and that the hypocotyl elongated (HY5) transcription factor is also required for this response. The presence of phenylpropanoids in etiolated roots of cop (constitutively photomorphogenic)1, cop9, and det (de-etiolated)1 mutants indicate that the corresponding wild-type genes are required to repress root phenylpropanoid biosynthesis in the absence of light. Biochemical analysis of root cell walls and analysis of phenylpropanoid gene expression suggest that coniferin and syringin accumulation may be the result of both increased biosynthesis and decreased conversion of these compounds into other phenylpropanoid end products. Finally, our data suggest that the accumulation of coniferin, syringin, and flavonoids in Arabidopsis roots is a high-irradiance response (HIR), and suggest that comparative analysis of light- and dark-grown Arabidopsis roots may provide new insights into both phenylpropanoid biosynthesis and light signaling in plants.