Theoretical modeling of pK_a's of thiol compounds in aqueous solution

Abstract

The pKa's of different kinds of thiols (R-SH) were investigated by using the M06-2X method with a SMDsSAS model.

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

“…Fluorescence quenching experiments showed that 4-fluorothiophenol strongly quenches the excited state of the CdSe/CdS QDs. The researchers noted the oleylamine ligands decorating the QDs are able to deprotonate the thiol (e.g., for 4-fluorothiophenol, p K a (calc) = 8.0 in H 2 O) 910 to form the thiolate anion and that this thiolate anion likely plays an important role in quenching the hole within the VB. Additional experiments using stoichiometric amounts of TEMPO yielded the TEMPO-thiophenol adduct, suggesting that thiyl radicals are generated over the course of the reaction.…”

Probing the interactions between air bubbles and (bio)interfaces at the nanoscale using FluidFM technology

“…While EDL and VDW interactions are likely to stabilize this film, the strong attraction resulting from the hydrophobic interaction will lead to the film breakage and the further bubble attachment to the surface by the formation of a three-phase contact line (TPC, three phases are surface, water, air) [46,47]. In our case, bubbles are negatively charged [48], the gold surfaces produced are neutral at the pH considered (7.4 [49]), thus the electrostatic interactions are not attractive. Regarding the VDW forces, although not known for our system, the Hamaker constant of the interactions air-water-hydrocarbon is negative [50].…”

Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods

“…The methodology consists of using three explicit molecules of water in addition to a continuum solvent model. After some experiments and benchmarking of levels of theory (see Supporting Information), the model was applied to α‐ d ‐Glc‐2Ac_H and α‐ d ‐Glc‐3Ac_H using m062x/6‐31+G(d,p)/SMD=water as level of theory for the optimization of the structures which has shown excellent results with thiols [33] . After some benchmarking, m062x/cc‐pvtz/SMD=water level of theory was used for energy calculations.…”