The kinetics of CO pathway in methanol oxidation at Pt electrodes, a quantitative study by ATR-FTIR spectroscopy

Methanol (MeOH) oxidation reaction (MOR) at Pt electrodes under potentiostatic conditions has been investigated by electrochemical in situ FTIR spectroscopy (FTIRS) in attenuated-total-reflection configuration under controlled flow conditions in 0.1 M HClO(4) with 2 M MeOH, where the mass transport effects are largely eliminated using a flow cell. Our results reveal that (i) at constant potentials, the methanol dehydrogenation rate decreases while the CO(ad) oxidation rate increases with the accumulation of CO(ad) until the maximum CO(ad) coverage (ca. 0.5 ML i.e., the steady state) is reached; (ii) at fixed CO(ad) coverage, the rates for MeOH decomposition to CO(ad) and CO(ad) oxidation increases with potential from 0.3 to 0.7 V (vs. RHE), with Tafel slopes for MeOH dehydrogenation of ca. 440 ± 30 mV/dec, which is independent of CO(ad) coverage; (iii) the current efficiency of the CO pathway in MOR at 0.6 and 0.7 V is below 20% and it decreases toward higher potentials. The mechanisms as well as the potential induced change in the kinetics of different pathways involved in MOR are briefly discussed.     

A new correlation between the characteristics temperature and glass-forming ability for bulk metallic glasses

Journal of Thermal Analysis and Calorimetry - A new criterion or parameter χ given by $$\left( {\frac{{T_{\text{x}} - T_{\text{g}} }}{{T_{\text{l}} - T_{\text{x}} }}} \right) \times \left(...     

Effect of Arylmethylene Substitutions on Molecular Structure,Optoelectronic Properties and Photovoltaic Performance of Dithienocyclopentafluorene-Based Small-Molecule Acceptors

Two dithienocyclopentafluorene-based small-molecule acceptors (SMAs) were developed that feature methylene-functionalized conjugated side chains, to study the effect of arylmethylene substitution and its number on structure, optoelectronic properties and device performance. Results showed that two SMAs have better absorption properties and planarity, lower bandgaps and higher LUMOs compared with the control SMA without conjugated side chains. The synthesized SMAs were tested in polymer solar cells for examples of their applicability. This work argues that the introduction of methylene-functionalized conjugated side chains has great potential in tuning molecular structure, optoelectronic properties, device physics and photovoltaic performance of SMAs.     

Synthesis and Biological Activities of Diosgenin-Triazole Conjugates with a 1,3-Dipolar Cycloaddition Reaction

Chemistry of Natural Compounds - A novel series of diosgenin-triazole conjugates (10a–d, 11a–c, 12a–c, 13a–c) was designed and synthesized as antifungal agents by using a...     

The Investigation of Interaction Competition Between ATP and DIPP-Ala,Boc-Ala,or Ala by ESI-MS/MS and Theoretical Calculation

The interactions between ATP and N-(O,O-diisopropyl) phosphoryl-L-alanine (DIPP-Ala), N-(tert-butoxycarbonyl)-L-alanine (Boc-Ala), or L-alanine (Ala) were investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The non-covalent complexes between ATP and Boc-Ala or DIPP-Ala were observed, while the complex between ATP and Ala was not found in the mass spectra. The affinity of DIPP-Ala for ATP was confirmed to be stronger than that of Boc-Ala by competition experiment. Through molecular modeling calculations, it was found that the non-covalent complexes were stabilized by intermolecular hydrogen bonds, and the affinity sequence for ATP was DIPP-Ala > Boc-Ala > Ala by comparing their binding energy, ?35.407 kcal/mol, ?15.634 kcal/mol, ?6.555 kcal/mol, respectively. The results implied that a phosphoryl group was a very important functional group to provide an interaction site between amino acids and ATP, and that N-phosphoryl amino acids can be used as a good model of protein in the studies of molecular recognition of ATP.     

Experimental Evidence for a Triboluminescent Antiperovskite Ferroelectric: Tris(trimethylammonium) catena‐Tri‐μ‐chloro‐manganate(II) Tetrachloromanganate(II)

The perovskite structure is rich in ferroelectricity. In contrast, ferroelectric antiperovskites have been scarcely confirmed experimentally since the discovery of M₃AB‐type antiperovskites in the 1930s. Ferroelectricity is now revealed in an organic–inorganic hybrid X₃AB antiperovskite structure, which exhibits a clear ferroelectric phase transition 6/mmmF6mm with a high Curie point of 480 K. The physical properties across the phase transition are obviously changed along with the symmetry requirements, providing solid experimental evidence for the ferroelectric phase transition. More interestingly, the discovered antiperovskite shows intense photoluminescence and triboluminescence properties. The confirmation of the triboluminescent ferroelectric antiperovskite will open new avenues to explore excellent optoelectronic properties in the antiperovskite family.     

Determination of Enantiomeric Purity of GSK962040 Based on Liquid Chromatography Using Chiral Stationary Phase Combined with a Pre-column Derivatization Procedure

A sensitive and accurate LC method was developed and further validated for the determination of enantiomeric purity of GSK962040. Before separation, a pre-column derivatization procedure was performed. Baseline separation with a resolution higher than 1.9 was accomplished within 15 min using a Chiralpak AD-H (250 × 4.6 mm; particle size 5 μm) column, with n-hexane: 2-propanol (85:15 v/v) as mobile phase at a flow rate of 1 mL min^?1. The eluted analytes were subsequently detected with a UV detector at 260 nm. The effects of mobile phase components and temperature on enantiomeric selectivity as well as resolution of enantiomers were thoroughly investigated. The calibration curves were plotted within the concentration range between 4 and 200 μg mL^?1 (n = 8), and recoveries between 98.15 and 101.48% were obtained, with relative standard deviation (RSD) lower than 1.42%. The LOD and LOQ for the Boc-GSK962040 were 1.23 and 4.15 μg mL^?1 and for its enantiomer were 1.38 and 4.76 μg mL^?1, respectively. The developed method was also evaluated and validated by analyzing bulk samples with different enantiomeric ratios of GSK962040. It was demonstrated that the method was accurate, robust and sensitive, and also had practical utilities for real analysis.     

Microwave-accelerated derivatization processes for the determination of phenolic acids by gas chromatography-mass spectrometry

A rapid method for the derivatization of phenolic antioxidants using microwave irradiation has been developed. Six antioxidatively active phenolic components of wines and fruits, namely gallic acid, gentisic acid, vanillic acid, caffeic acid, ferulic acid and p-coumaric acid were used in the model study. The solution of phenolic acids was evaporated to dryness on a rotary evaporator followed by further drying under microwave irradiation (600 W, 30 s). The resultant residue was dissolved in pyridene and treated with bis(trimethylsilyl)acetamide while irradiated by microwave using high power for 30 s. Controlled reaction was carried out employing bis(trimethylsilyl)trifluoroacetamide under conventional heating for 30 min. The trimethylsilyl derivatives were identified and quantified on a gas chromatography/mass selective detector. The mass spectral fragmentation patterns of the derivatives obtained by microwave irradiation were identical to those prepared by heating. The yields of microwave-assisted silylation were comparable to those from conventional heating. The rsd were less than 8% for six replicates. The linearity in wine matrix was nearly perfect. This method is a useful protocol to examine the phenolic constituents in wines and agricultural products.     

铜镍和铜钴合金电极在碱性介质中的光电化学

用动电位伏安法对含镍量10％、30％和50％的铜镍合金以及含钴量5.1％、9.7％、15 ％、25％和40％的铜钴合金电极在硼砂-硼酸缓冲溶液（pH 8.5）中的光电化学行为进行了 研究.铜镍合金和铜钴合金均显示p-型光响应,铜镍合金的光响应来自Cu2O,铜钴合金的光 响应来自Cu2O和氧化钴.含镍量10％和30％的铜镍合金电极以及含钴量5.1％铜钴合金电极的 最大光电流iph,max均大于纯铜电极,含钴量15％、25％和40％的铜钴合金电极以及含镍量 50％的铜镍合金电极由于电极表面相当一部分面积分别被氧化钴和氧化镍所占有,iph,max 小于纯铜电极.铜镍合金电极的φv值（电位负向扫描过程中电极表面完全还原为Cu时的电位 ）负于纯铜电极,而铜钴合金电极的φv值与纯铜电极大致相等, NiO的存在致使铜镍合金 表面Cu2O膜具有更大的稳定性.从光电化学角度通过φv和iph,max反映铜合金的耐腐蚀性能 与交流阻抗法测得的结果相符.