Desorption of thiolate self-assembled monolayers (SAMs) seriously limits the fabrication of thiol-based devices. Here we demonstrate that nanoporous Au produced by dealloying Au-Ag alloys exhibits high electrochemical stability against thiolate desorption. Nanoporous Au has many defective sites, lattice strain and residual Ag on the ligament surface. First-principles calculations indicate that ...

The structure of the Au15-thiolate cluster has been elucidated using a DFT approach, and it is demonstrated to comprise a Au4-tetrahedron core protected solely by the combination of two concatenated staple motifs. The longer motif efficiently wraps the core, and threads the shorter one. The structural assignment is supported by comparison to the powder X-ray diffraction pattern and, via time de...

A series of mononuclear zinc thiolate complexes have been prepared and fully characterized. The reactions of the complexes with alkyl halides, leading to zinc halides and the corresponding thioethers, have been examined by kinetic methods. In toluene, the reactions obey a second-order rate law displaying activation parameters consistent with a S(N)2 attack of the zinc-bound thiolate on the carb...

A straightforward, versatile approach to the production of protein gradients on planar and spherical particle surfaces is described. The method is based on the spatially controlled oxidation of thiolated surfaces by Au(III) ions generated via the electrochemical oxidation of a gold electrode in a phosphate-buffered saline solution (10 mM PBS, pH 7.2, 150 mM NaCl). Because the gold electrode is ...

Synthesis protocols for colloidal nanocrystals (NCs) with narrow size and shape distributions are of particular interest for the successful implementation of these nanocrystals into devices. Moreover, the preparation of NCs with well-defined crystal phases is of key importance. In this work, we show that Sn(IV)-thiolate complexes formed in situ strongly influence the nucleation and growth rates...

The nucleophilicity of transition metal thiolates is well-documented. Biologically relevant electrophilic substrates include oxygen or oxygen-transfer agents (such as H2O2) and alkylation agents (such as CH3I). Nature makes use of the latter with Zn-containing de-alkylation proteins such as the Ada repair mechanism and the former in the case of the post-translationally modified active form of N...

Density functional theory is used to find incremental fragmentation energy, overall dissociation energy, and average monomer fragmentation energy of cyclic gold(I) thiolate clusters and anionic chain structures of gold(I) and silver(I) thiolate clusters as a measure of the relative stability of these systems. Two different functionals, BP86 and PBE, and two different basis sets, TZP and QZ4P, a...

Self-assembled monolayers of E-stilbene-4-thiolate (SAM1), E-4'-(ethoxy)stilbene-4-thiolate (SAM2), and E-4'-(dimethylamino)stilbene-4-thiolate (SAM3) on Au(111) have been obtained from reaction of ethanol solutions of the corresponding S-acetyl derivatives with gold substrates. A combination of X-ray photoelectron spectroscopy, ellipsometry, and infrared reflection absorption spectroscopy indi...

This review summarizes recent developments in the investigation of the electronic structures, spectroscopic properties, and reactivities of ferrous and ferric heme-nitrosyls and how this relates to important biological processes. Ferrous heme-nitrosyls show interesting variations in electronic structure as a function of the different types of proximal ligands, as is evident from electron parama...

A combination of spectroscopic, chromatographic and computational approaches was employed to investigate the reaction several diselenides with a thiolate nucleophile, leading breaking selenium–selenium (Se–Se) bond.