SPE电极上Pt单组分及Pt-Au双组分还原态CO_2阳极剥离电化学氧化行为研究

采用循环伏安法，对ＳＰＥＰｔ电极以及ＳＰＥＡｕ－Ｐｔ电极上还原态ＣＯ２的电化学氧化行为研究表明，此类电极的电化学特性与光滑Ｐｔ电极一致：ＣＯ２在氢原子吸附电位区０～２５０ｍＶ（ｖｓ．ＲＨＥ）处，可与电极上化学吸附的氢反应，生成还原态的ＣＯ２，通过线性扫描，还原态ＣＯ２即发生一不可逆电化学氧化过程（阳极剥离）．在ＳＰＥＰｔ系列及ＳＰＥＡｕ－Ｐｔ系列上ＣＯ２的电化学行为表明，当ＳＰＥＰｔ系列上Ｐｔ的载量为２．５ｍＬ的０．０１ｍｏｌ·Ｌ－１Ｈ２ＰｔＣｌ６的Ｐｔ时，对还原态ＣＯ２的电催化活性最好，当Ｐｔ的载量相同时，在ＳＰＥＡｕ－Ｐｔ上，催化剂对还原态ＣＯ２的电化学氧化行为比ＳＰＥＰｔ电极更强，这是由于预先沉积的Ａｕ对后沉积的Ｐｔ有调制作用．     

Designed nanostructured pt film for electrocatalytic activities by underpotential deposition combined chemical replacement techniques

Multiple-deposited Pt overlayer modified Pt nanoparticle (MD-Pt overlayer/PtNPs) films were deliberately constructed on glassy carbon electrodes through alternately multiple underpotential deposition (UPD) of Ag followed redox replacement reaction by Pt (II) cations. The linear and regular growth of the films characterized by cyclic voltammetry was observed. Atomic force spectroscopy (AFM) provides the surface morphology of the nanostructured Pt films. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry demonstrate that the MD-Pt overlayer/PtNPs films can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated 0.1 M H(2)SO(4). Thus-prepared Pt films behave as novel nanostructured electrocatalysts for dioxygen reduction and hydrogen evolution reaction (HER) with enhanced electrocatalytic activities, in terms of both reduction peak potential and peak current, when compared to that of the bulk polycrystalline Pt electrode. Additionally, it is noted that after multiple replacement cycles, the electrocatalytic activities improved remarkably, although the increased amount of Pt is very low in comparison to that of pre-modified PtNPs due to the intrinsic feature of the UPD-redox replacement technique. In other words, the electrocatalytic activities could be improved markedly without using very much Pt by the technique of tailoring the catalytic surface. These features may provide an interesting way to produce Pt catalysts with a reliable catalytic performance as well as a reduction in cost.     

钴与2-[2-(5-溴苯并噻唑)偶氮]-5-二甲氨基苯甲酸显色反应的分光光度法研究

本文合成丁新试剂2-[2-(5-溴苯并噻唑)偶氮-5-二甲氨基苯甲酸(5-Br-BTAMB)。研究了在表面活性剂存在下它与钴的显色反应。发现 TritonX-100存在下,钴与5-Br-BTAMB在 pH6.0～8.5范围内形成稳定的蓝色配合物。其最大吸收峰位于660nm。表观摩尔吸光系数为1.22×10~5L·mol·cm~(-1)。配合物中钴与5-Br-BTAMB 的组成比为1:2.钴浓度在0～12μg/25ml 范围内呈良好的线性关系。在硫脲存在下,该方法具有良好的选择性,用于测定含钴分子筛和 V_(B12)中微量钴。结果令人满意。     

Bilayer rGO-Based Photothermal Evaporator for Efficient Solar-Driven Water Purification[]**

Interfacial evaporation has emerged as a promising approach to produce freshwater. However, an urgent concern is that, due to the illegal discharge of industrial wastewater, most water bodies are polluted by trace volatile organic compounds (VOCs), which are easily volatilized and enriched in the collected water during the interfacial evaporation process. Herein, a bilayer photothermal evaporator was reasonably designed for contaminated water purification. The bottom hydrophilic rGO-sodium alginate (SA) sheets purposefully disintegrate water transport channels, thus quickly removing VOCs through physical adsorption. The rGO-SA-TiO₂ upper layer sufficiently absorbs incident light and therefore persistently generates reactive oxidizing species to degrade upward VOCs. Notably, the oriented microchannels inside the evaporator allow sustained light reflections to improve the utilization of solar energy. The evaporation rate can reach 1.63 kg m⁻² h⁻¹ with a considerably high VOC removal efficiency of up to 96 %. Such an integrated bilayer evaporator provides an effective strategy to obtain clean water via solar distillation.     

Synthesis of 1,3-Bis[(3-aryl)-S-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes

1,3-bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes 2 were synthesized in high yields by the reaction of 3-aryl 4-amino-5-mercapto-1,2,4-triazole 1 with m-phthalic acid.     

Properties of Aqueous Polyurethane Dispersion Modified by Epoxide Resin and Their Use as Adhesive

The aqueous polyurethane hybrid dispersion modified by the epoxy resin were synthesized using 1,4-butanediol ( BDO ) and dimethylolpropionic(DMPA) as chain extenders. A kind of automobile interior decoration adhesive was made by the modified hybrid dispersions. Effects of the content and the kinds of epoxide resin on the properties of dispersions and dispersion-cast films such as appearance, pot life, viscosity, particle size, molecular mass, hardness, swelling in water, contact angle, strength of stress, elongation at break, and other mechanical properties were studied. At the same time the effect of the E20 content on the peel strength of the adhesive for several automobile interior decoration substrates such as rubber/wood, poly(vinyl chloride)/wood; leather/wood, sponge/wood was investigated. The experimental results show that when the epoxy resin E20 content was 8%, the modified polyurethane hybrid dispersions possess better properties and the adhesive made by the modified dispersions posses better adhesion for automobile interior decoration substrates. The stress-strain curve of the modified aqueous polyurethane hybrid dispersions films shows the modified aqueous cast films possess better rigidity and toughness.     

Biomonitoring of infant exposure to phenolic endocrine disruptors using urine expressed from disposable gel diapers

Infant exposure to endocrine disruptors (EDs) may cause adverse health effects because of their fast growth and development during this life stage. However, collecting urine from infants for exposure assessment using biological monitoring is not an easy task. For this purpose, we evaluated the feasibility of using urine expressed from disposable gel absorbent diapers (GADs) as a matrix for biomonitoring selected phenolic EDs. GADs urine was expressed with the assistance of CaCl₂ and was collected using a device fabricated in our laboratory. The analytes were extracted and concentrated using a liquid-liquid method and their hydroxyl groups were modified by dansyl chloride to enhance their chromatography and detection. Finally, the analytes were measured by high-performance liquid chromatography (HPLC) coupled with electrospray ionization (ESI) tandem mass spectrometry (MS/MS). The target chemicals were bisphenol A, triclosan, 17 α-ethynylestradiol, the natural hormone estrone, and 17 β-estradiol. The ratio of the CaCl₂ to the urine-wetted gel absorbent, variation of the inter-urination volume, and analyte deposition bias in the diaper were assessed. Analyte blank values in the diapers, the sample storage stabilities, and recoveries of the analytes were also evaluated. The results showed that 70–80 % of the urine could be expressed from the diaper with the assistance of CaCl₂ and 70.5–124 % of the spiked analytes can be recovered in the expressed urine. The limits of detections (LODs) were 0.02–0.27 ng/mL, well within the range for detection in human populations. Our pilot data suggest that infants are widely exposed to the selected EDs.     

Determination of sphingosine kinase activity in biological samples by liquid chromatography–tandem mass spectrometry

Sphingosine kinase (SphK) is a key enzyme in modulating the levels of sphingosine 1‐phosphate (S1P) as well as an important enzyme in numerous biological responses. Using C17‐sphingosine as a substrate, we established a rapid, sensitive and highly efficient method for determination of SphK activity by analyzing the product C17‐sphingosine 1‐phosphate (C17‐S1P) using liquid chromatography–tandem mass spectrometry. The standard curve for C17‐S1P was linear over a wide range (10–1000 ng/mL) with correlation coefficient (r²) greater than 0.999. The lower limit of quantification for C17‐S1P was 10 ng/mL. The K_m values for C17‐sphingosine and ATP were determined to be 28.17 and 188.5 mM, respectively. More importantly, the SphK activity dramatically increased in cultured HEK 293 cells expressing wild‐type SphK1 as well as cells treated with tumor necrosis factor‐a, a sphingosine kinase activator. In contrast, the SphK activity decreased in cultured HEK 293 cells treated with dimethylsphngosine, a sphingosine kinase inhibitor. In conclusion, this method was sensitive and rapid in the determination of SphK acitivity, providing striking utilities in exploring the sphingosine kinase signaling pathway and screening active compounds targeting SphK activity. Copyright © 2010 John Wiley & Sons, Ltd.     

在无机盐和阴离子表面活性剂存在下2-(5-溴-2-噻唑偶氮)-5-二乙氨基苯甲酸与镍显色反应的研究

本文合成了新显色剂2-(5-溴-2-噻唑偶氮)-5-二乙氨基苯甲酸(简称5-Br-TAEB),利用光度法测定了试剂的三级质子化常数,研究了它与镍显色反应的最佳条件,同时对表面活性剂及无机盐的作用机理进行了初步探讨。实验结果表明,在NaCl和NaDS存在下,pH=5.0～8.0范围内,5-Br-TAEB与镍形成稳定的蓝色络合物,络合比为Ni~(2+):5-Br-TAEB=1:2,摩尔吸光系数ε_(642)=1.23×10~5 SL·mol~(-1)·cm~(-1)。镍浓度在0～10μg/25ml范围内服从比尔定律,方法用于铝合金中镍的测定,结果满意。