A computational study on the thermochemistry of several simple sulfenic acids (RSOH) and esters (RSOR′) is reported. The enthalpies of R-S, S-O, and O-R′ homolytic cleavage are calculated at the G2 level of theory and compared to related peroxides and disulfides. Less expensive B3LYP calculations were unsatisfactory. When R and R′ are both alkyl, the O-C bond is expected to be the weakest in th...

The majority of protein disulfides in cells is considered an important inert structural, rather than a dynamic regulatory, determinant of protein function. Here, we show that some disulfides in proteins also are regulated by cell redox status with functional consequences. We find that reactive oxygen species (ROS) produced by mitochondria are actively used by cells to facilitate cell-surface pr...

The synthesis of a new series of tetrathiafulvalene (TTF) and pi-extended TTF (exTTF) disulfides and the electrochemical properties of self-assembled monolayers derived from these compounds are described. When the intermediate bromides 3 and 7 were reacted with thiourea, followed by basic hydrolysis, the expected thiol formation was not observed and only disulfides were obtained. A mechanism is...

Infusion of cystamine into the isolated, perfused rat liver resulted in tissue damage preceded by the formation of cystamine-protein mixed disulfides which were mainly detected in the plasma membrane fraction. Hepatotoxicity was prevented when dithiothreitol was infused after cystamine or when the calcium antagonist, verapamil, was co-infused with the disulfide. In isolated hepatocytes, the for...

A selected group of aromatic disulfides, thiuram disulfides and thiosulfones, provided by the National Cancer Institute, were evaluated in vitro for their inhibitory activity against Junin virus (JUNV), the causative agent of Argentine hemorrhagic fever. The aromatic disulfides NSC4492 and NSC71033 and the thiuram disulfide NSC14560 were, respectively, the more potent virucidal and antiviral ag...

The C-terminal cystine knot (CK) (CTCK) domain in von Willebrand factor (VWF) mediates dimerization of proVWF in the endoplasmic reticulum and is essential for long multimers required for hemostatic function. The CTCK dimer crystal structure reveals highly elongated monomers with 2 β-ribbons and 4 intra-chain disulfides, including 3 in the CK. Dimerization buries an extensive interface of 1500 ...

Zinc chlorochromate nonahydrate is easily prepared from the aqueous solution of chromium trioxide and zinc chloride in quantitative yield. This oxidant, in methylene chloride and at room temperature, oxidizes thiols to their disulfides. Acetals and thioacetals are deprotected to their corresponding carbonyl compounds. Sulfides are selectively converted to ther sulfoxides or sulfones. Arylox...