Pyrazole-based trinuclear and mononuclear complexes: synthesis,characterization, DNA interactions and cytotoxicity studies

Transition Metal Chemistry - A new trinuclear Cu(II) complex [Cu3(μ3-OH)(μ-pz)3(Hpz)2(HCOO)(BTAO)Cl] (1) (Hpz = pyrazole, BTAO = 4,6-bis(dimethylamino)-1,3,5-triazin-2(1H)-one) and four...     

TiO2晶面依赖的Ir-TiOx相互作用对Ir/TiO2催化剂巴豆醛选择性加氢性能的影响

α,β-不饱和醇是一类重要的精细化学品,主要通过α,β-不饱和醛选择性加氢获得.由于α,β-不饱和醛分子中含有共轭的C=C键和C=O键,且后者键能更大,在热力学和动力学上均不利于C=O键的选择性加氢生成α,β-不饱和醇.因此,提高α,β-不饱和醛中C=O的加氢选择性是催化领域中一项挑战性的课题.巴豆醛属于典型的α,β-不饱和醛,研究其选择性加氢生成巴豆醇具有广泛的代表意义;Ir负载在具有还原性载体(如TiO2)上时,表现出很好的C=O加氢选择性,因此,成为近年来的研究热点.由于暴露不同晶面的TiO2具有不同的形貌和电子结构,因此研究Ir-TiO2相互作用的晶面依赖性及其对巴豆醛选择性加氢反应的影响具有重要意义.本文以分别暴露{101}、{100}和{001}晶面的锐钛矿TiO2纳米晶为载体,制备了负载型Ir/TiO2催化剂,系统研究了催化剂经过不同的预处理过程(在不同温度下H2还原和O2再氧化)后对巴豆醛的气相选择性加氢的性能.利用高分辨透射电镜、原位X射线光电子能谱和原位漫反射红外光谱及氨程序升温脱附等技术研究发现,预处理条件显著改变了Ir-TiOx的相互作用,包括Ir金属的几何、电子性质及催化剂表面酸性.这种相互作用与TiO2的暴露晶面密切相关,从而改变了不同Ir/TiO2催化剂上不同加氢反应行为.研究结果表明,经300℃预还原的Ir/TiO2-{101}催化剂催化性能最好,在80℃下初始反应速率为166.1 μmol g-Ir-1 s-1,巴豆醇的生成转化频率为0.022 s-1.与其他催化剂相比,Ir/TiO2-{101}催化剂表面Ir0浓度最高,表面酸度适中,因此表现出最佳的催化性能.同时Ir-TiOx界面在反应中的协同作用,对H2和巴豆醛分子中C=O键的吸附和活化起到了关键作用.然而当催化剂经过400℃的H2预还原后,由于产生了强的金属-载体相互作用使得TiOx对Ir粒子进行了包裹从而导致Ir-TiOx界面缺失,因而催化剂催化巴豆醛加氢性能降低.本文为理解金属-载体相互作用对巴豆醛选择性加氢反应的影响提供了新的见解,并为设计高性能α,β-不饱和醛选择性加氢催化剂提供了理论依据.     

A Triple Crosslinking Design toward Epoxy Vitrimers and Carbon Fiber Composites of High Performance and Multi-shape Memory

It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances. Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer(MSMEV), which exhibits high mechanical properties,multi-shape memory property and malleability. The triple crosslinking network is formed by reacting diglycidyl ether of bisphenol F(DGEBF) with4-aminophenyl disulfide, γ-aminopropyltriethoxysilane(APTS) and poly(propylene glycol) bis(2-aminopropyl ether)(D2000). The triple crosslinking manifests triple functions: the disulfide bonds and the silyl ether linkages enable malleability of the epoxy network; the silyl ether linkages impart the network with high heterogeneity and broaden the glass transition region, leading to multi-shape memory property; a small amount of D2000 increases the modulus difference between the glassy and rubbery states, thereby improving the shape fixity ratio. Meanwhile,the high crosslinking density and rigid structure provide the MSMEV with high tensile strength and Young's modulus. Moreover, integrating carbon fibers and MSMEV results in shape memory composites. The superior mechanical properties of the composites and the recyclability of carbon fiber derived from the dissolvability of MSMEV make the composites hold great promise as structural materials in varied applications.     

Effect of poly(methylhydrogen)siloxane modification on adjusting mechanical properties of bamboo flour‐reinforced HDPE composites

Cellulose - Poly(methylhydrogen)siloxane (PMHS) was applied for hydrophobic modification of bamboo flour (BF) at room temperature based on the dehydrogenation between hydroxyl groups of BF and...     

Dyeing behavior and mechanism of Crocein Orange G on carboxymethyl cotton fabric

Cellulose - Traditional cotton fiber dyeing requires an abundance of salt, which leads to environmental pollution. Consequently, decreasing or eliminating the use of salt has become the primary...     

Simultaneous studies of pressure effect on charge transport and photophysical properties in organic semiconductors: A theoretical investigation

High-mobility and strong luminescent materials are essential as an important component of organic photodiodes, having received extensive attention in the field of organic optoelectronics. Beyond the conventional chemical synthesis of new molecules, pressure technology, as a flexible and efficient method, can tune the electronic and optical properties reversibly. However, the mechanism in organic materials has not been systematically revealed. Here, we theoretically predicted the pressure-depended luminescence and charge transport properties of high-performance organic optoelectronic semiconductors, 2,6-diphenylanthracene (DPA), by first-principle and multi-scale theoretical calculation methods. The dispersion-corrected density functional theory (DFT-D) and hybrid quantum mechanics/molecular mechanics (QM/MM) method were used to get the electronic structures and vibration properties under pressure. Furthermore, the charge transport and luminescence properties were calculated with the quantum tunneling method and thermal vibration correlation function. We found that the pressure could significantly improve the charge transport performance of the DPA single crystal. When the applied pressure increased to 1.86 GPa, the hole mobility could be doubled. At the same time, due to the weak exciton coupling effect and the rigid flat structure, there is neither fluorescence quenching nor obvious emission enhancement phenomenon. The DPA single crystal possesses a slightly higher fluorescence quantum yield ～ 0.47 under pressure. Our work systematically explored the pressure-dependence photoelectric properties and explained the inside mechanism. Also, we proposed that the external pressure would be an effective way to improve the photoelectric performance of organic semiconductors.     

Comparison of microbiological loads and physicochemical properties of raw milk treated with single-/multiple-cycle high hydrostatic pressure and ultraviolet-C light

The effects of ultraviolet-C radiation (UV-C, 11.8?W/m²), single-cycle and multiple-cycle high hydrostatic pressure (HHP at 200, 400 or 600?MPa) on microbial load and physicochemical quality of raw milk were evaluated. Reductions of aerobic plate count (APC) and coliform count (CC) by HHP were more than 99.9% and 98.7%, respectively. Inactivation efficiency of microorganisms increased with pressure level. At the same pressure level, two-cycle treatments caused lower APC, but did not show CC differences compared with single-cycle treatments. Reductions of APC and CC by UV-C were somewhere between 200?MPa and 400/600?MPa. Both HHP and UV-C significantly decreased lightness and increased pH, but did not change soluble solids content and thiobarbituric acid-reactive substances’ values. Two 2.5?min cycles of HHP at 600?MPa caused minimum APC and CC, and maximum conductivity. Compared with HHP, UV-C markedly increased protein oxidation and reduced darkening.     

基于Modbus/TCP的配电网自动化远方终端设计

为了提高对现代雷达系统的故障诊断能力,开发了一种融合在雷达系统内部的嵌入式测试系统;系统通过在雷达内部布设测试设备,设置故障监测点和加入测试信号,对雷达各部分的工作状态、性能进行监测,用于雷达系统的性能检测和故障诊断,缩短平均维修时间（MTTR）; 硬件选用精密的测量仪器和先进的总线通讯技术保证测试精度,软件采用先进的算法,融合了加电BIT、周期BIT和维护BIT等测试手段,保证故障隔离的准确,该系统已在多种雷达系统中得到成功的应用。