三种基于2，4，6-三(3-吡啶基)-1，3，5-苯配体的Ni(Ⅱ)基配位聚合物的合成、结构及催化性能

通过调变溶剂热的反应条件,我们合成了3种Ni (Ⅱ)基的配位聚合物(CPs)[Ni (CH₃-BDC)(3-TBT)(H₂O)₂]·EtOH·2H₂O (CP1)、[Ni₃(CH₃-BDC)₃(3-TBT)₂(H₂O)₅]·2DMF·2H₂O (CP2)和[Ni₃(CH₃-BDC)₃(3-TBT)₂(H₂O)₆]·2DMF·4H₂O (CP3),其中CH₃-H₂BDC=5-methylisophthalic acid,3-TBT=2,4,6-tris (3-pyridyl)-1,3,5-benzene。X射线单晶衍射分析表明,3个CPs都是由相似的Ni₂(CH₃-BDC)₂的双核单元构建的,并分别呈现出从零维(0D)、2D到3D结构的网络骨架。反应条件的微小调变,导致了不同结构的配位聚合物。同时,催化实验表明,3在无溶剂的温和反应条件下,CP3对苄醇及其衍生物与苯胺的氧化-偶联反应表现出极好的催化活性和循环稳定性。     

Catalytic activity of chiral chelating N-heterocyclic carbene palladium complexes towards asymmetric allylic alkylation

Abstract

The catalytic activity of a series of chiral heteroaryl coordinated chelating N-heterocyclic carbene (NHC) palladium complexes towards asymmetric allylic alkylation (AAA) were presented here. The effects of different N-substituents, NHC backbones and chelate rings on the catalytic activity and the enantioselectivity of the alkylation of (E)-1,3-diarylallyl acetates with dialkyl malonate were investigated. The results showed that, under the optimized conditions, complexes 3a, 3b, and 3i carrying the pyridinyl-coordinated five-membered chelate ring showed high catalytic activity and chiral induction efficiency. The corresponding alkylated products were obtained in high yields with moderate ee. Furthermore, it was found that the substituents of (E)-1,3-diarylallyl acetates and the type of the nucleophile affect the results as well.     

淀粉功能化Fe_3O_4纳米簇球的制备与表征

以淀粉为表面活性剂,利用乙二醇溶剂热法一步制备了Fe3O4纳米簇球.采用X射线衍射仪、傅立叶变换红外光谱仪、扫描电镜等分析了产物的结构;采用热重分析仪测定了其热稳定性.结果表明:所得产物为直径约为230nm的簇球结构,构成簇球的纳米粒子直径约为10nm;引入淀粉成功地改善了产物的纳米结构和表面性能.合成的Fe3O4纳米簇球具有独特的结构和表面性能,在生物领域具有潜在的应用前景.     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Synthesis and the effect of alkyl chain length on photochromic properties of diarylethene derivatives

A new class of photochromic diarylethenes bearing pyrrole and thiophene units with different length of alkyl chains at 2-position of thiophene rings have been synthesized. Their characteristics, including photochromism and fatigue resistance were investigated systematically, and each diarylethene derivative showed good photochromic properties whether in solution or in PMMA films. The alkyl group moiety was connected directly to the central cyclopentene ring as a heteroaryl unit and availably participated in photoisomerization reaction. And some properties, for example, the conversion ratio in the photostationary state(PSS) and the absorption coefficient of the ring-closed isomers in acetonitrile were significantly affected by the alkyl chain length. The results revealed that substituents of alkyl chain played an important role in the photoisomerization process of diarylethenes.     

Theoretical Study on the Kinetics of Electron Transfer for Bond—breaking Reaction

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Catalytic effect analysis of metallic additives on light crude oil by TG and DSC tests

This research aimed at the investigation of the effect of different metallic additive on the combustion and kinetic behavior of crude oil. For this purpose, the thermal behavior of the oil-only and oil–metallic salts mixtures were studies by the thermogravimetry (TG)/derivative thermogravimetry and differential scanning calorimetry (DSC) on heating rate at 10 °C min^?1. The result shows that Dagang crude oil exhibited apparent low temperature oxidation (LTO), fuel deposition, and high temperature oxidation processes. With the addition of metallic salts, the LTO process has been shortened and samples added CuSO₄, CrCl₃·6H₂O, and AlCl₃·6H₂O achieved a much lower peak temperature than that of oil. Based on the Arrhenius model, metallic additives were proven to have obvious influence on the combustion activation energy. And, by comprehensive analysis of TG/DSC profile and activation energy, ZnSO₄ exhibited a positive influence on light crude oil combustion during the high pressure air injection process.     

Mo-V-Nb多组元氧化物催化乳酸氧化脱氢反应制备丙酮酸

丙酮酸是一种重要的有机合成和药物合成中间体,本文采用成本低廉的乳酸为原料,以Mo-V-Nb多组元氧化物为催化剂,在较低的反应温度下催化氧化脱氢合成了具有高附加值的丙酮酸。应用X射线衍射（XRD）和扫描电子显微镜（SEM）表征了Mo-V-Nb多组元氧化物的物相组成和微观结构,采用气相色谱质谱联用（GC-MS）分析了反应产物,研究了乳酸氧化脱氢可能的反应路径,并深入探讨了关键反应参数反应温度、氧气分压和质量空速对催化选择性和乳酸转化率的影响。     

多孔软硬磁Ni0.5Zn0.5Fe2O4/SrFe12O19复合纤维制备及吸波性能

通过静电纺丝技术制备了多孔软硬磁Ni_0.5Zn_0.5Fe₂O₄/SrFe₁₂O₁₉复合纤维,利用综合热重分析仪（TG-DSC）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线能谱仪（EDS）和矢量网络分析仪（VNA）等对复合纤维的晶体结构、微观形貌和电磁性能进行了表征,研究了不同软硬磁质量比对纤维结构和性能的影响。结果表明：900℃下制备的复合纤维具有立体多孔结构,软硬磁质量比为1∶3时,复合纤维的比表面积达到55 m²·g^-1。吸波性能测试结果显示,当吸波剂涂层厚度为3.5 mm时,复合纤维在10.6 GHz处反射损失（R_L）值达到-31.9 dB,在2~18 GHz频率范围内,R_L值小于-10 dB的吸收带宽达到10.5 GHz,覆盖了整个X波段（8.2~12.4 GHz）和Ku波段（12.4~18 GHz）,显示出优异的宽波段吸收性能。     

聚-γ-N-(β-丁硫基乙基)胺丙基硅氧烷钯络合物的合成及其催化性能的研究

报导了聚－γ－Ｎ－（β－丁硫基乙基）胺丙基硅氧烷和氯化钯的反应，得到固载在二氧化硅上的聚－γ－Ｎ－（β－丁硫基乙基）胺丙基硅氧烷钯络合物，并用ＸＰＳ研究其结构．选用硝基苯、烯丙基环氧丙基醚、烯丙基苯基醚、丙烯腈、烯丙基苯、苯乙烯、环己烯及丁烯等８种底物进行催化加氢，以评价其催化活性．结果表明，该催化剂催化效果良好，并且有很好的稳定性．