Adsorption configuration and local ordering of silicotungstate anions on Ag(100) electrode surfaces

X-ray reflectivity, cyclic voltammetry, and scanning tunneling microscopy (STM) are used to examine the structure of alpha-SiW12O4(4-) or silicotungstic acid (STA) adsorbed on Ag(100) in acid solution. The voltammetry shows that STA passivates the Ag surface relative to electron transfer to a solution redox species. STM images reveal the formation of a series of lattice structures, one of which can be associated with a commensurate ( radical13x radical13)R33.69 degrees structural model. X-ray reflectivity measurements show uniquely that STA orients with its four-fold axis perpendicular to the Ag(100) surface and that the center of the STA molecule is 4.90 A above the top layer of the Ag substrate. Analysis of bond lengths leads to a footprint of STA on Ag(100), in which the four terminal O atoms are located near the hollow sites and have a Ag-O bond length of 2.06 A. This bond length is consistent with a strong covalent interaction between STA and the Ag surface.     

Coating of Tetraethylorthosilicate (TEOS)/Vinyltriethoxysilane (VTES) Hybrid Solution on Polymer Films

Tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) hybrid materials were prepared and the hydrolysis and condensation reactions during processing were investigated by means of 29Si NMR solution spectroscopy. The variation of drying characteristics of the coating films was examined with respect to the tetraethylorthosilicate (TEOS)/vinyltriethoxysilane (VTES) ratio, as well as drying temperature, by FT-IR spectroscopy. It is shown that the TO mode of Si–O–Si stretching absorption was enhanced with increasing tetraethylorthosilicate (TEOS) content and drying temperature. Also, the wettability of the coating films on polymer films was independent of the solution composition but enhanced by the precoating of poly(4-hydroxystrene) (PHS) as a wetting agent. The adhesion between the coating and the films was also enhanced when the vinyltriethoxysilane (VTES) content in the coating solution was increased.     

Difference in Conversions Between Dimethyl Sulfide and Methanethiol in a Cold Plasma Environment

This study compared the conversion of two malodorous substances, dimethyl sulfide (CH₃SCH₃, DMS) and methanethiol (CH₃SH) in a cold plasma reactor. The DMS and CH₃SH were successfully destroyed at room temperature. DMS decomposed less than CH₃SH at the same conditions. In oxygen-free condition, CS₂ and hydrocarbons were the major products, while SO₂ and CO_x were main compounds in oxygen-rich environments. The DMS/Ar plasma yielded more hydrocarbons and less CS₂ than that of CH₃SH/Ar plasma. In the CH₃SH/O₂/Ar plasma, rapid formation of SO and CO resulted in the yields much more amounts of SO₂ and CO₂ than those in the DMS/O₂/Ar plasma; and remained only a trace of total hydrocarbons, CH₂O, CH₃OH, CS₂, and OCS. The major differences between the reaction mechanisms of DMS and CH₃SH were also proposed and discussed.     

Tuning chirality of single-wall carbon nanotubes by selective etching with carbon dioxide

CO2 molecule chemisorbs selectively on the zigzag tube edge without an activation barrier, whereas it physisorbs on the armchair edge of nanotubes. In addition, carbon nanotubes can be etched by an adsorbed oxygen atom of CO2 molecule. From our results, we suggest a selective etching mechanism for tuning the chirality of the mass-produced carbon nanotubes.     

Computational study on the electrocyclic reactions of [16]annulene

The electrocyclic reactions of [16]annulene have been investigated by ab initio and DFT calculations. Among the six conformers of [16]annulene identified, 3, with Cs symmetry, is taken as the starting reactant for the cyclization reactions of [16]annulene, even though it is 31.4 kJ mol(-1) less stable than the most stable conformer, 1. The pathways of the electrocyclic reactions from reactant 3 to two tricyclic products, 5 and 6, have been found. All pathways identified are stepwise, i.e., the two ring closure processes occur one after the other. Among the pathways found, the ones with the lowest overall barrier for reactions 3 --> 5 and 3 --> 6 have the same rate-determining step and hence the same overall barrier, 131.0 kJ mol(-1). Thus, based on the barriers calculated, it is not possible to determine whether 5 or 6 is the dominant product in the cyclization reaction of 3.     

Mechanisms of acid decomposition of dithiocarbamates. 3. Aryldithiocarbamates and the torsional effect

The acid decomposition of some p-substituted aryldithiocarbamates (arylDTCs) was observed in 20% aqueous ethanol at 25 degrees C, mu = 1.0 (KCl, for pH > 0). The pH-rate profiles showed a dumbell shape with a plateau where the observed first-order rate constant k(obs) was equal to k(o), the rate constant of the decomposition of the dithiocarbamic acid species. The acid dissociation constants of the dithiocarbamic acids (pK(a)) and their conjugate acids (pK(+)) were calculated from the pH-rate profiles. Comparatively, k(o) was more than 10(4)-fold faster than alkyldithiocarbamates (alkDTCs) with similar pK(N) (the acid dissociation constant of the parent amine). It was observed that the values of pK(a) and pK(+)were 5 and 8 units of pK, respectively, higher than the expected values from the pK(N) of alkylDTCs. The higher values were attributed to the inhibition of the delocalization of the nitrogen electron pair into the benzene ring because of the strong electron withdrawal effect of the thiocarbonyl group. Comparison of the activation parameters showed that the rate acceleration was due to a decrease in the enthalpy of activation. Proton inventory indicated the existence of a multiproton transition state, and it was consistent with an S to N proton transfer through a water molecule. There are two hydrogens contributing to a secondary SIE, and there are also two protons that are being transferred at the transition state to form a zwitterion followed by fast C-N bond cleavage. The mechanism could also be a concerted asynchronic process where the N-protonation is more advanced than the C-N bond breakdown. The kinetic barrier is similar to the torsional barrier of thioamides, suggesting that the driving force to reach the transition state is the needed torsion of the C-N bond that inhibits the resonance with the thiocarbonyl group and the aromatic moiety, increasing the basicity of the nitrogen and making the proton transfer thermodynamically favorable.     

Reversible replication between ordered mesoporous silica and mesoporous carbon

Highly ordered mesoporous silica can be regenerated from a mesoporous carbon CMK-3 that is a negative replica of mesoporous silica SBA-15, indicating reversible replication between carbon and inorganic materials.     

Synthesis and properties of the Co7Se8−xSx and Ni7Se8−xSx solid solutions

We report the synthesis and elementary properties of the Co₇Se_8−xS_x (x=0-8) and Ni₇Se_8−xS_x (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni₇Se_8−xS_x system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co₇Se_8−xS_x system, as well as Ni₇Se₈ and Ni₇SeS₇, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/mol_CoK² and ∼7 mJ/mol_NiK² for Co₇Se_8−xS_x and Ni₇Se_8−xS_x, respectively.     

High-Throughput Analysis of Sofalcone in Human Plasma by Use of Automated 96-Well Protein Precipitation and LC-MS-MS

A sensitive and selective method for the determination of sofalcone in human plasma was established by use of protein precipitation and liquid chromatography-tandem mass spectrometry. Plasma samples were transferred into 96-well plate using an automated sample handling system and spiked with 10 L of 2 g mL^–1 internal standard solution (d₃-sofalcone). 0.5 mL of acetonitrile was added to the 96-well plate and the plasma samples were then vortexed for 30 sec. After centrifugation, the supernatant was transferred into another 96-well plate and completely evaporated at 40 °C under a stream of nitrogen. The dry residue was reconstituted with mobile phase. All sample transfer and protein precipitation was automated through the application of both the PerkinElmer MultiPROBE II HT and TOMTEC Quadra 96 workstation. The limit of quantitation of sofalcone was 2 ng mL^–1 using a sample volume of 0.2 mL for the analysis. The reproducibility of the method was evaluated by analyzing five samples at nine quality control (QC) levels over the nominal concentration range from 2 ng mL^–1 to 1000 ng mL^–1. Validation of the method showed that the assay has good precision and accuracy. Sofalcone and internal standard produced a protonated precursor ion ([M+H]⁺) at m/z 451 and 454, and both gave a corresponding product ion at m/z 315. The high sample throughput of the method has been successfully applied to a pharmacokinetic study of sofalcone in human plasma.     

Discovery of a small molecule that inhibits the interaction of anthrax edema factor with its cellular activator, calmodulin

The catalytic efficiency of adenylyl cyclase activity of edema factor (EF) from Bacillus anthracis is enhanced by approximately 1000-fold upon its binding to mammalian protein calmodulin (CaM). A tandem cell-based and protein binding-based screen of a 10,000 member library identified a molecule that inhibits the EF-CaM interaction and therefore the adenylyl cyclase activity. A combination of fluorescence spectroscopy and photolabeling studies showed that the molecule targets the CaM binding region of EF. A series of related compounds were synthesized and evaluated to identify one compound, 4-[4-(4-nitrophenyl)-thiazolylamino]-benzenesulfonamide, that maintained activity against EF but showed minimal toxicity to two cultured cell lines. This compound represents an important reagent to study the role of EF in anthrax pathology and may represent a drug lead against anthrax infection.