吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶化合物的合成与生物活性

应用串联氮杂Wittig反应设计合成了一系列新的2-烷氨(芳氧)基-3,8-二苯基-5-芳基-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮衍生物。通过氢核磁共振谱仪(1H NMR)、傅里叶变换红外光谱仪(FTIR)和元素分析等方法对所合成的化合物进行了结构表征,用X射线单晶衍射确证了化合物2-二正丙基氨基-3,8-二苯基-5-(4-甲基苯基)-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮(Ⅲi)晶体结构。室内的杀菌和杀虫活性测试结果表明:目标化合物具有一定的杀菌活性,其中部分化合物对黄瓜灰霉菌(Botrytis cinereapers)在50 mg/L剂量下抑制率达到90%以上,显示了优异的杀菌活性;对水稻褐飞虱无明显的杀虫活性,但发现对粘虫具有较高的杀灭效果,大多数抑制率达到90%以上。     

Development of aspartic acid ligation for peptide cyclization derived from serine/threonine ligation

Based on a mechanism analogous to the serine/threonine ligation, the aspartic acid ligation, which is facilitated by the γ-amino alcohol based ligation and oxidation, is developed and applied to the synthesis of cyclic peptides. The γ-hydroxyl group triggers the ring-chain tautomerization via a 6-endo-trig process,while the δ-hydroxyl group facilitates the oxidative cleavage of the vicinal diol to give carboxylic acid.     

Magnetic metal–organic framework MIL‐100(Fe) microspheres for the magnetic solid‐phase extraction of trace polycyclic aromatic hydrocarbons from water samples

In this work, a magnetic metal–organic framework designated as MIL‐100(Fe) was prepared and applied as a magnetic solid‐phase extraction sorbent for the determination of trace polycyclic aromatic hydrocarbons in environmental water samples by coupling with high‐performance liquid chromatography and fluorescence detection. The magnetic microspheres exhibited large surface areas and high extraction ability, making them excellent candidates as sorbents for enrichment of trace polycyclic aromatic hydrocarbons. Under the optimized experimental conditions, good sensitivity levels were achieved with low detection limits ranging from 32 to 2110 pg/mL and good linearities with correlation coefficients higher than 0.9990 for the investigated 13 polycyclic aromatic hydrocarbons. The proposed method has been validated in the analysis of real water samples with mean recoveries in the range of 81.4–126.9% at four spiked levels and the relative standard deviations in the range of 1.3–17.0%. The magnetic MIL‐100(Fe) microspheres were stable enough for 150 extractions without a significant loss of extraction performance.     

Fine-Tuning Bi2Te3-Copper Selenide Alloys Enables an Efficient n-Type Thermoelectric Conversion

Bismuth tellurides is one of the most promising thermoelectric (TE) material candidates in low-temperature application circumstances, but the n-type thermoelectric property is relatively low compared to the p-type counterpart and still needs to be improved. Herein, we incorporated different copper selenides (CuSe, Cu₃Se₂ and Cu_2−xSe) into a Bi₂Te₃ matrix to create the alloy by grinding and successive sintering to enable higher thermoelectric performance. The results demonstrated that all alloys achieved n-type TE characteristics and Bi₂Te₃-CuSe exhibited the best Seebeck coefficient and power factor among them. Along with the low thermal conductivity, the maximum dimensionless TE figure of merit (ZT) value of 1.64 at 573 K was delivered for Bi₂Te₃-CuSe alloy, which is among the best reported results in the n-type Bi₂Te₃-based TE materials to the best of our knowledge. The improved TE properties should be related to the co-doping process of Se and Cu. Our investigation shows a new method to enhance the performance of n-type TE materials by appropriate co-doping or alloying.     

PVT法钨坩埚系统中自发生长自支撑AlN单晶及其表征分析

采用物理气相传输(PVT)法在AlN原料表面自发生长出大量毫米级尺寸的AlN单晶。本文对该工艺下AlN单晶的自然形貌、极性、杂质含量等进行了分析。实验及分析结果表明,在实验工艺条件下,原料表面生长的AlN晶粒具有规则的六方外形,晶粒沿C向择优生长且具有高的生长速率(约200～250μm/h),但径向生长受限于{10-10}(m面)。不同颜色的AlN晶粒经机械切割及化学机械抛光(CMP)后,形成高表面质量的C轴取向抛光片。通过化学湿法腐蚀和SEM表征发现,淡黄色晶粒为Al极性晶体,暗棕色晶粒为N极性晶体,淡黄-暗棕混合色晶粒为Al/N混合极性晶体,其内部可以观察到清晰的两种极性分界。通过GDMS与EGA对不同颜色晶粒内部的主要杂质元素含量进行了分析,结果表明,淡黄色晶粒内氧元素的含量相比暗棕色晶粒的含量低,而碳含量则相反。     

Prediction of new vortices in single-phase nanofluid due to dipole interaction

Journal of Thermal Analysis and Calorimetry - Magnetic field effects are encountered in many engineering applications which include but are not limited to metal casting, nuclear reactor coolers,...     

Visible light photopolymerization of nitro‐stilbenzene photosensitive initiating systems

In this paper, we presented four novel visible light photoinitiating systems, which employed nitro‐stilbenzene derivatives as photoinitiators. Visible light photopolymerization of these systems was studied completely. The results showed that the chemical structures of the photoinitiators, photoinduced electron transfer approach, solvent polarity, and monomers played significant effects on the visible light photopolymerization. The electrochemistry of nitro‐stilbenzene was dramatically influenced by the linking benzophenone moiety. The cyclic voltammograms of four photoinitiators were determined and discussed. We further estimated the thermodriving force for electron transfer between nitro‐stilbenzene and benzophenone. Thermal stabilities of new photoinitators were determined by the analysis of differential scanning calorimetry (DSC) and thermogravimetry (TG) in this paper. Copyright © 2009 John Wiley & Sons, Ltd.     

A Projected Extrapolated Gradient Method with Larger Step Size for Monotone Variational Inequalities

Journal of Optimization Theory and Applications - A projected extrapolated gradient method is designed for solving monotone variational inequality in Hilbert space. Requiring local Lipschitz...     

Nickel(II)-α-diimine complexes containing naphthyl substituents for ethylene polymerization under low ethylene pressure

Two new α-diimine containing Ni(II) complexes, {bis[N,N′-(2,6-dimethyl-4-naphthylphenyl)imino]-1,2-dimethylethane}dibromonickel 3a and {bis[N,N′-(2-methyl-4-naphthylphenyl)imino]-1,2-dimethylethane}dibromonickel 3b were synthesized and characterized. The crystal structures of representative ligand 2a and its complex 3a were determined by X-ray crystallography. Complex 3a bearing 2,6-dimethyl and 4-naphthyl groups, activated by diethylaluminum chloride (DEAC), shows high catalytic activity for the polymerization of ethylene [4.43 × 10⁶ g PE/(mol Ni h bar)]. Interestingly, complexes 3a and 3b bearing the naphthyl substituent in the para-aryl position produced dendritic polyethylenes (branching degree, 3a: 112, 118, and 147; 3b: 113, 127, and 151 branches/1,000 C at 20, 40, and 60 °C, respectively). The dendritic polyethylene particle size obtained by 3a and 3b/DEAC can be controlled in the 1–20 nm range under low ethylene pressure (diameter, 3a: 18.31, 14.44, and 11.09; 3b: 12.29, 8.98 and 6.27 nm at 20, 40, and 60 °C, respectively) and could be expected to produce a nano-targeted drug carrier after modification with water-soluble oligo(ethylene glycol).     

New chiral α‐diimine nickel(II) complexes bearing ortho‐sec‐phenethyl groups for ethylene polymerization

A series of new α‐diimine nickel(II) catalysts bearing bulky chiral sec‐phenethyl groups have been synthesized and characterized. The molecular structure of representative chiral ligand, bis[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane rac‐1c and chiral complexes, {bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dibromidonickel rac‐2a and bis{bis[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐2,3‐butadiene}dibromidonickel rac‐2b, were confirmed by X‐ray crystallographic analysis. Complex rac‐2c bearing two chiral sec‐phenethyl groups in the ortho‐aryl position and a methyl group in the para‐aryl position, activated by diethylaluminum chloride (DEAC), showed highly catalytic activity for the polymerization of ethylene [4.12 × 10⁶ g PE (mol Ni.h.bar)^?1], and produced highly branched polyethylenes under low ethylene pressure (branching degree: 104, 118 and 126 branches/1000 C at 20, 40 and 60°C, respectively). Chiral 20‐electron bis‐α‐diimine Ni(II) complex rac‐2b also exhibited high activity toward ethylene polymerization [1.71 × 10⁶ g PE (mol Ni · h · bar)^?1]. The type and amount of branches of the polyethylenes obtained were determined by ¹H and ¹³C NMR. Copyright © 2013 John Wiley & Sons, Ltd.