The SmtB/ArsR family of prokaryotic metalloregulatory transcriptional repressors represses the expression of operons linked to stress-inducing concentrations of di- and multivalent heavy metal ions. Derepression results from direct binding of metal ions by these homodimeric "metal sensor" proteins. An evolutionary analysis, coupled with comparative structural and spectroscopic studies of six Sm...

L-Cvsteine-S-conjugates are responsible for the mutagenic and c\ totoxic consequences which occur following exposure to certain xenobioticsl I I Following enLyme mediated C-S lysis of the cc steine conjugate. equimolar amounts of pyruvate, ammonia and a thiolate species are formed (Fig 1 ) It has now been established that one of the physiological rdles of C-S lyase enzymes is that of transamina...

The local adsorption structure of methylthiolate in the ordered Au(111)-(sqrt[3]xsqrt[3])R30 degrees phase has been investigated using core-level-shift measurements of the surface and bulk components of the Au 4f(7/2) photoelectron binding energy. The amplitude ratio of the core-level-shift components associated with surface Au atoms that are, and are not, bonded to the thiolate is found to be ...

An increasing number of reactions of sulfenic acid anions are being demonstrated in the literature. As such, mild, general and reliable means for the generation of sulfenates are due. In the current paper, an addition/elimination of 2-sulfinyl acrylates using various nucleophiles is demonstrated and evaluated as a protocol for alkane- and arenesulfenate generation. Cyclohexanethiolate, methoxid...

Cytochrome P450 (CYP) enzymes are the primary proteins of drug metabolism and steroid biosynthesis. These crucial proteins have long been known to harbor a cysteine thiolate bound to the heme iron. Recent advances in the field have illuminated the nature of reactive intermediates in the reaction cycle. Similar intermediates have been observed and characterized in novel heme-thiolate proteins of...

The nature of the thiolate/Au 111 interface is a long-standing puzzle. It has been suggested that thiolates drive surface reconstruction, however, a consensus regarding the adsorption configuration is missing. Herein, the density-functional theory is used to evaluate surface core-level shifts SCLSs for methyl thiolates on Au 111 assuming a representative set of different surface reconstructions...

An organic thiolate/disulfide redox couple with low absorption in the visible region was developed for use in fabricating novel dye-sensitized photovoltaic wires with an aligned carbon nanotube (CNT) fiber as the counter electrode. These flexible wire devices achieved a maximal energy conversion efficiency of 7.33%, much higher than the value of 5.97% for the conventional I(-)/I3(-) redox coupl...

Cysteine plays structural roles in proteins and can also participate in electron transfer reactions, when some structural folds provide appropriated environments for stabilization of its sulfhydryl group in the anionic form, called thiolate (RS(-)). In contrast, sulfhydryl group of free cysteine has a relatively high pK(a) (8,5) and as a consequence is relatively inert for redox reaction in phy...

Nitric oxide synthase (NOS) catalyzes the production of nitric oxide from L-arginine and dioxygen at a thiolate-ligated heme active site. Although many of the reaction intermediates are as yet unidentified, it is well established that the catalytic cycle begins with substrate binding and rate-limiting electron transfer to the heme. Here we show that Ru(II)-diimine and Re(I)-diimine electron tun...