Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

Chemical profiling of bioactive constituents in hop cones and pellets extracts by online comprehensive two‐dimensional liquid chromatography with tandem mass spectrometry and direct infusion Fourier transform ion cyclotron resonance mass spectrometry

Humulus lupulus L. (hop) is highly interesting from a nutraceutical perspective. The hop phytocomplex contains a wide range of bioactive metabolites, and its characterization is challenging. To tackle such a task, for the first time we applied and compared a combined approach consisting of online comprehensive two‐dimensional liquid chromatography with tandem mass spectrometry and direct infusion Fourier transform ion cyclotron mass spectrometry. A reversed phase × reversed phase approach with a shifted gradient in the second dimension ensured selectivity and two‐dimensional space coverage. Hyphenation with an ion trap time‐of‐flight analyzer led to the identification of 83 compounds in 70 min, comprising a novel quercetin derivative and six unknown bitter acids. On the other hand, the direct infusion method was able to identify 40 analytes (except isomers) with high mass accuracy (≤ 0.1 ppm) in less than 1 min analysis time. The developed approach can be used in a complementary way, combining the separation capability and high informative spectra of two‐dimensional liquid chromatography tandem mass spectrometry with the ultra‐high mass accuracy of direct infusion, for potential compound discovery or the accurate profiling of bioactive compounds in different hop cultivars as well as for monitoring processing and storage of hop‐based products.     

中国出境旅游的外交效应

2000年以来，中国出境旅游高增长、高消费，影响力不断增大，成为国家外交战略的重要内容，外交效应逐渐显现。通过辨析中国出境旅游外交效应的概念、表现形式和结果，基于10个中国主要出境目的国的旅游互动数据，采用DIF-GMM计量经济模型，实证检验了中国出境旅游外交效应。结果表明，中国通过有序推进ADS协议、加强经济援助、举办“旅游年”活动、实施旅游“制裁”，并积极参与国际制度建设等旅游外交行为，促进了与世界各国的友好交往，维护了自身核心利益，提升了外交软实力和国际影响力。国际旅游反作用于国际关系，对国际关系具有显著的正向促进作用，不仅是国际关系的结果，而且是其重要动因之一。中国出境旅游与政治、经济、社会、文化等联动，多方面提升了中国的国际影响力。     

单斜ZnP2负极材料的锂化机理及性能

过渡金属磷化物电位低且比容量高, 是有发展前景的锂离子电池(LIBs)负极材料. 其中, ZnP₂属于双活性负极材料, Zn与P都能与Li⁺发生反应, 储Li⁺性能更具有竞争力. 但是, 对于ZnP₂的锂化机理及产物尚不明确. 采用第一性原理计算和电化学测试方法研究了ZnP₂的电子性质和电化学性能, 通过理论计算和实验测试相结合阐述了ZnP₂的锂化机制. 首先, 以密度泛函理论(DFT)计算揭示了ZnP₂的锂化机理、Li⁺扩散路径、势垒和理论比容量(1477 mAh/g). 其次, 通过直流电弧等离子体法及固相烧结法合成ZnP₂, 并测试其首圈放电曲线, 显示放电容量为1439 mAh/g, 与理论计算结果相近. 此外, 薄膜X射线衍射(XRD)检测最终产物成分为LiZn和Li₃P, 与DFT计算结果一致.     

两种功能化纳米金粒子固酶电极的催化性能

以合成的4-巯基苯甲酸功能化纳米金粒子和聚乙烯基吡啶包覆纳米金粒子分别作为固酶载体,制备了2种新型固酶电极,在此基础上组装了2种酶燃料电池。采用电化学方法结合紫外可见分光光度法、透射电镜技术等手段研究了固酶载体的形貌,酶-载体间相互作用对电极表面固定酶分子的光谱学性质,酶-电极间直接电子迁移能力和催化底物反应性能的影响,进一步评估和比较了两种酶燃料电池的能量输出性能。实验结果表明：4-巯基苯甲酸功能化纳米金粒子固酶基电极可以实现酶-电极间的直接电子迁移而且对葡萄糖和氧气具有良好的催化性能(催化反应起始电位分别为-0.03和0.96 V,底物转化频率分别是1.3和0.5 s^-1),其催化性能的重现性、长期使用性能、酸碱耐受性和热稳定性良好,随着自组装固酶层数的增加,催化性能随之增强直至达到极限催化电流;电池性能测试结果表明4-巯基苯甲酸功能化纳米金粒子固酶基燃料电池的开路电压为0.88 V,最大输出能量密度：864.0 μW·cm^-2,长期使用性能优异(储存3 周后仍可达到最佳能量输出的80%以上)。     

Combination of Solid‐Phase Micro‐Extraction and Direct Analysis in Real Time‐Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for Sensitive and Rapid Analysis of 15 Phthalate Plasticizers in Beverages

A method for rapid identification and quantification of phthalate plasticizers in beverages was developed. A number of 15 phthalate plasticizers which covered all the phthalates concerned in the US Consumer Product Safety Improvement Act (CPSIA), European Union legislations and Chinese national standards (GB) were analyzed. By a combined solid‐phase micro‐extraction (SPME) and direct analysis in real time mass spectrometry (DART‐MS) approach, phthalates at sub‐ng·mL^?1 levels can be qualitatively and quantitatively analyzed in a short time. The use of ultrahigh‐resolving power and the accurate mass measurement capacity naturally provided by Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS) minimizes the matrix interferences and thus enables the evaluation of phthalates in a complex matrix without extensive sample handlings or preparations. The limits of quantification (LOQs) were estimated to be at 0.3–5.0 ng·mL^?1, lower than the Maximum Residue Limit (MRL) regulated by the European Union legislations (2007/19/EC) in foods, beverages, food packaging and toys (0.3–30 ng·mL^?1). This rapid and easy‐to‐use SPME‐DART‐FT‐ICR‐MS method provided a relatively high‐throughput and powerful analytical approach for quick testing and screening phthalates in beverages and water samples to ensure food safety.     

Highly Enantioselective Direct Asymmetric Aldol Reaction Catalyzed by 4,5‐Methano‐L‐proline

The 4,5‐methano‐L‐proline was used as chiral organocatalysts in direct asymmetric aldol reactions. Under the optimal conditions, excellent enantioselectivities (up to 99% ee) were obtained with high chemical yields (up to 95%) for a series of aldehydes using only 5 mol% catalyst loading. To show the practicality of the method, the reaction was tested at a large scale. The reaction was complete in 16 h, and the aldol product was obtained in 86% yield and 93% ee.     

三维有序结构的金掺杂纳米TiO_2修饰电极用于H_2O_2的测定

在ITO玻璃表面构建了三维有序多孔结构的金掺杂纳米Ti O2薄膜(3DOM GTD/ITO),同时制备了一种细胞色素c(Cyt c)酶生物传感器(Cyt c/3DOM GTD/ITO)。通过透射电镜(TEM)、扫描电镜(SEM)对修饰电极进行表征。紫外-可见光谱实验表明吸附在GTD上的Cyt c能够保持其生物活性,二级结构未被破坏。同时研究了Cyt c在3DOM GTD/ITO修饰电极表面的直接电化学及对H2O2的电催化行为。结果显示,Cyt c在3DOM GTD/ITO修饰电极上有显著的直接电化学响应,峰电流与扫描速度呈线性关系,说明该电极过程是表面电化学控制过程。Cyt c/3DOM GTD/ITO修饰电极对H2O2具有良好的催化性能,线性范围为3.0×10-7~1.70×10-5mol/L,检出限为3.6×10-8mol/L(S/N=3),响应时间为5 s,且该修饰电极具有较好的重现性和稳定性。     

Direct chemical profiling of olive (Olea europaea) fruit epicuticular waxes by direct electrospray‐ultrahigh resolution mass spectrometry

In the present paper, an electrospray ionization (ESI)‐Orbitrap method is proposed for the direct chemical profiling of epicuticular wax (EW) from Olea europaea fruit. It constitutes a rapid and efficient tool suitable for a wide‐ranging screening of a large number of samples. In a few minutes, the method provides a comprehensive characterization of total EW extracts, based on the molecular formula of their components. Accurate mass measurements are obtained by ultrahigh resolution mass spectrometry, and compositional restrictions are set on the basis of the information available from previous studies of olive EW. By alternating positive and negative ESI modes within the same analysis, complementary results are obtained and a wide range of chemical species is covered. This provides a detailed compositional overview that otherwise would only be available by applying multiple analytical techniques. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and thermal characterization of poly(2‐vinylpyridine) copolymers coordinated to Cr nanoparticles

In this study, polystyrene‐block‐poly(2‐vinylpyridine), PS‐b‐P2VP, polyisoprene‐block‐poly(2‐vinylpyridne), PI‐b‐P2VP and poly(methyl metacrylate)‐block‐poly(2‐vinylpyridine), PMMA‐b‐P2VP, coordinated to Cr metal were synthesized and characterized by Fourier transform infrared, transmission electron microscopy and direct pyrolysis mass spectrometry techniques. Both thermal degradation mechanism and thermal stability of P2VP blocks were affected by the coordination of Cr nanoparticles to nitrogen of pyridine rings. Thermal decomposition of P2VP blocks was started by loss of pyridine units leaving an unsaturated and/or crosslinked polymer backbone that degraded at relatively high temperatures. Incorporation of Cr metal did not noticeably influence thermal behavior of PS and PI blocks. However, increase in thermal stability of PMMA block was detected and associated with inhibition of the interactions between carbonyl groups of MMA chains with nitrogen atom of pyridine ring as a consequence of coordination to metal. Copyright © 2015 John Wiley & Sons, Ltd.