The electrochemical stability of thiols on gold surfaces

In this paper we present a comparative analysis of the electrochemical stability of alkanethiols, aromatic and heterocyclic thiols on the Au(111) and Au(100) faces in relation to the theoretical energetic data. The peak potential and surface coverage are used as the key parameters to estimate the electrochemical stability while work function changes, adsorption energies and surface free energies calculated from periodic DFT, including van der Waals interactions, are used for the theoretical estimation. We find that the peak potentials do not correlate with work function changes and adsorption energies in particular for aromatic and heterocyclic thiols. In contrast, the reductive desorption potentials for the different thiols show a good correlation with the surface free energy of the SAMs estimated by density functional theory calculations. Surface coverage is a key factor that controls reductive desorption through van der Waals interactions.Fil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Carro, Pilar. Universidad de La Laguna; Españ

Thermal Stability of Self-Assembled Monolayers of n-Hexanethiol on Au(111)-(1 × 1) and Au(001)-(1 × 1)

Thermal desorption in an ultrahigh vacuum of n-hexanethiol (C6T) self-assembled monolayers (SAMs) prepared from ethanolic solutions on Au(111) and Au(001) unreconstructed surfaces was investigated by X-ray photoelectron spectroscopy. The SAMs desorption was performed from room temperature (RT) to 380 K. We report that the hexanethiolate surface saturation coverage is bigger (∼0.4 ML) for the SAM on Au(001) than on Au(111) (∼0.33 ML). We identified a greater stability for C6T SAMs on Au(001). Large amounts of physisorbed species were found on preferred oriented (111) polycrystalline Au at the low coverage regime at RT, while the SAM on the Au(001) single crystal at this conditions desorbs at a steady pace. At 340 K, both SAMs remain stable at the coverage expected for the lying-down phases that maximizes the van der Waals interactions. We observe that at higher temperatures the carbon alpha-sulfur bond breaks, producing free S on both gold surfaces.Fil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; ArgentinaFil: Ruano Sandoval, Gustavo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; ArgentinaFil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ferron, Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Materiales; Argentin

EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids), 2014. Scientific Opinion on Flavouring Group Evaluation 74, Revision 3 (FGE.74Rev3): Consideration of Simple Aliphatic Sulphides and Thiols evaluated by the JECFA (53rd and 61st meeting) Structurally related to Aliphatic and Alicyclic Mono-, Di-, Tri-, and Polysulphides with or wi thout Additional Oxygenated Functional Groups from Chemical Group 20 evaluated by EFSA in FGE.08Rev5 (2012)

The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA), and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 19 simple aliphatic sulphides and thiols evaluated by the JECFA at the 53rd meeting in 1999 and the 61st meeting in 2003. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern, and available data on metabolism and toxicity. For nine substances [FL-no: 12.088, 12.179, 12.198, 12.212, 12.238, 12.239, 12.255, 12.257 and 12.291] considered in this FGE, the Panel concluded that they would pose “No safety concern at estimated levels of intake as flavouring substances” based on the MSDI approach. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been considered for the substances evaluated through the Procedure and for all nine substances, the information is adequate. Thus, the Panel concluded that nine substances [FL-no: 12.088, 12.179, 12.198, 12.212, 12.238, 12.239, 12.255, 12.257 and 12.291] do not give rise to safety concern at their levels of dietary intake, estimated on the basis of the MSDI approach. For 10 candidate substances in FGE.74Rev3 [FL-no: 12.009, 12.013, 12.020, 12.023, 12.045, 12.074, 12.155, 12.169, 12.241 and 12.280] evaluated through the Procedure, the Panel concluded that additional toxicity data are required

EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids), 2014. Scientific Opinion on Flavouring Group Evaluation 91, Re vision 2 (FGE.91Rev2): Consid eration of simple aliphatic and aromatic sulphides and thiols evaluated by the JECFA (53rd and 68th meetings) structurally related to aliphatic and alicyclic mono-, di-, tri-, and polysulphides with or without additional oxygenated functional groups evaluated by EFSA in FGE.08Rev5 (2012).

The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA), and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 44 simple aliphatic and aromatic sulphides and thiols evaluated by the JECFA at the 53rd and the 68th meeting. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern, and available data on metabolism and toxicity. For 36 substances considered in this FGE the Panel concluded that they would pose “No safety concern at estimated levels of intake as flavouring substances” based on the MSDI approach For seven substances [FL-no: 12.038, 12.085, 12.137, 12.138, 12.145, 12.252 and 12.259] the Panel decided, contrary to the JECFA that these substances could not be evaluated due to absence of a NOAEL from either one of these substances or from a structurally related substance. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been considered and for all 44 substances, the information is adequate. For candidate substance 3-(methylthio)heptenal [FL-no: 12.273], which contains 5 to7 % of an α,β-unsaturated aldehyde, 2-(E)-heptenal, with a possible genotoxic potential, the Panel cannot conclude that the material of commerce for this candidate substance is not of safety concern, until either this component is cleared with respect to a concern for genotoxicity, or this component is removed from the commercial product

Opening new gates for the modification of PVC or other PVC derivatives: Synthetic strategies for the covalent binding of molecules to PVC

Several synthetic strategies based on the use of substituted aromatic and hetero-aromatic thiols for the covalent binding of modifier compounds to PVC are described. A variety of aliphatic alcohols and amines are linked to the aromatic or heteroaromatic rings via highly active functionalities as the isocyanate, acidchloride, or chlorosulfonyl group, and the three chlorine atoms of trichlorotriazine. The first three pathways lead to protected aromatic disulfides obtaining the substituted aromatic thiols by reduction as a final step of an unprecedented synthetic route. The second approach, in a novel, extremely efficient, and scalable process, uses the particular selectivity of trichlorotriazine to connect aliphatic amines, alcohols, and thiols to the ring and creates the thiol via nucleophilic substitution of a heteroaromatic halogen by thiourea and subsequent hydrolysis. Most of the modifier compounds were linked to the polymer chains with high degrees of anchorage. The presented approaches are highly versatile as different activations of aromatic and heteroaromatic rings are used. Therefore, many types of tailored functional nucleophiles may be anchored to PVC providing non-migrating materials with a broad range of applications and properties.The authors gratefully acknowledge support from Grant MAT 2013-42957-R. Rodrigo Navarro gratefully acknowledges funding from the Spanish Research Council (CSIC) and European Social Fund (ESF) through the JAE-doc program.Peer Reviewe

The X-ray photoelectron spectroscopy of surface films formed during the ASTM D-130/ISO 2160 copper corrosion test

This is an Author’s Accepted Manuscript of an article published in Petroleum Science & Technology [Volume 32, Issue 4, 2014 ], available online: http://www.tandfonline.com/10.1080/10916466.2011.588635The surfaces of ISO 2160 copper strips tested in iso-octane with elemental sulfur, aliphatic, cyclic and aromatic thiols, diphenyl sulfide, and diphenyl disulfide individually or in combination were studied using XPS. Aliphatic thiols bonded through the sulfur, whereas elemental sulfur formed a cuprous sulfide layer. Aromatics bonded partially through the sulfur with the rings oriented horizontally due to π orbital interactions, accounting in part for their inhibitory effects in the test. The test rating was not directly related to the sulfur concentration in solution or on the surface, and certain combinations of species resulted in higher levels of sulfur at the surface than found individually

Active site voltage clamp fluorometry of the sodium glucose cotransporter hSGLT1.

In the human sodium glucose cotransporter (hSGLT1) cycle, the protein undergoes conformational changes where the sugar-binding site alternatively faces the external and internal surfaces. Functional site-directed fluorometry was used to probe the conformational changes at the sugar-binding site. Residues (Y290, T287, H83, and N78) were mutated to cysteines. The mutants were expressed in Xenopus laevis oocytes and tagged with environmentally sensitive fluorescent rhodamines [e.g., tetramethylrhodamine (TMR)-thiols]. The fluorescence intensity was recorded as the mutants were driven into different conformations using voltage jumps. Sugar binding and transport by the fluorophore-tagged mutants were blocked, but Na+ binding and the voltage-dependent conformational transitions were unaffected. Structural models indicated that external Na+ binding opened a large aqueous vestibule (600 Å3) leading to the sugar-binding site. The fluorescence of TMR covalently linked to Y290C, T287C, and H83C decreased as the mutant proteins were driven from the inward to the outward open Na+-bound conformation. The time courses of fluorescence changes (milliseconds) were close to the SGLT1 capacitive charge movements. The quench in rhodamine fluorescence indicated that the environment of the chromophores became more polar with opening of the external gates as the protein transitioned from the inward to outward facing state. Structural analyses showed an increase in polar side chains and a decrease in hydrophobic side chains lining the vestibule, and this was reflected in solvation of the chromophore. The results demonstrate the opening and closing of external gates in real time, with the accompanying changes of polarity of the sugar vestibule