Lignin peroxidase (LiP) is a fungal haemoprotein similar to the lignin-synthesizing plant peroxidases, but it has a higher oxidation potential and oxidizes dimethoxylated aromatic compounds to radical cations. It catalyses the degradation of lignin models but in vitro the outcome is net lignin polymerization. LiP oxidizes veratryl alcohol to radical cations which are proposed to act by charge t...

Erythrocytes (RBCs) loaded with alcohol dehydrogenase (ADH) and aldehyde dehydrogenase (ALD) can metabolize plasma ethanol and acetaldehyde but with low efficiency. We investigated the rate-limiting factors in ethanol oxidation by these enzymes loaded into RBCs. Mathematical modeling and in vitro experiments on human RBCs loaded simultaneously with ADH and ALD (by hypoosmotic dialysis) were per...

A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-spar...

The basidiomycete Pleurotus sajor-caju mineralizes ring-14C-labelled lignin (dehydrogenative polymer) when grown in mycological broth. Under these conditions, two veratryl alcohol oxidase (VAO) enzymes were found in the culture medium. They oxidized a number of aromatic alcohols to aldehydes and reduced O2 to H2O2. The enzymes were purified by ion-exchange and gel-permeation chromatography. The...

Eugenol oxidase (EUGO) from Rhodococcus jostii RHA1 had previously been shown to convert only a limited set of phenolic compounds. In this study, we have explored the biocatalytic potential of this flavoprotein oxidase, resulting in a broadened substrate scope and a deeper insight into its structural properties. In addition to the oxidation of vanillyl alcohol and the hydroxylation of eugenol, ...

Density functional theory calculations were performed to investigate the reaction mechanism of aerobic oxidation benzyl alcohol benzaldehyde catalyzed by Au and Au–Pd clusters. Two consecutive mechanisms examined with Au8 Au6Pd2 clusters: (1) dissociated O atoms on metal clusters generating H2O; (2) adsorbed oxygen molecules H2O2. The show that energetically prefers proceed in former mechanism,...

in the urine, and the kidney must have a considerable power of concentrating formate. The inhibition of the appearance of formate during the administration ofethanol is in accordance with Zatman's (1946) interpretation of the earlier experiments, namely, that a primary oxidation of methanol to formaldehyde through the agency of alcohol dehydrogenase is competitively inhibited by ethanol. More r...

Monolignol binding to the peroxidase active site is the first step in lignin polymerization in plant cell walls. Using molecular dynamics, docking, and free energy perturbation calculations, we investigate the binding of monolignols to horseradish peroxidase C. Our results suggest that p-coumaryl alcohol has the strongest binding affinity followed by sinapyl and coniferyl alcohol. Stacking inte...

The trichloromethylsulfonyl-, dichloromethylsulfonyl-, chlorosulfonyl-, and fluorosulfonyl esters of a neopentyl-type alcohol have been prepared via sulfonylation or sulfinylation followed by oxidation. The preparative usefulness and potential of the transformations are discussed.

The results of a mechanistic study using ab initio theoretical methods are used to outline plausible mechanistic sequences for alkane, alcohol, and alkene oxidation by chromyl and molybdyl chlorides. We suggest that the second oxo group is intimately involved in the reaction sequence. This spectator oxo group is suggested to play a central role in stabilizing critical intermediates in these rea...