1-(2-羟甲基-1,3-氧硫杂环戊基)吡啶酮类化合物的合成

研究了1,3-氧硫杂环戊烷核苷类似物的合成. 以吡啶酮为碱基, 利用三甲基硅基三氟甲磺酸酯(TMSOTf)催化, 与1,3-氧硫杂环戊烷发生Vorbruggen缩合反应, 合成了一系列的保护的核苷类似物, 经过进一步脱保护或者还原得到目标产物. 并测试了合成化合物的抗菌活性, 发现该类化合物对革兰氏阳性菌具有中等抑制活性.     

N-[5-(2-氯苯基)-2-呋喃甲酰氨基硫羰基]-L-α-氨基酸乙酯的合成与生物活性测定

设计并合成了9种未见文献报道的N-(5-邻氯苯基-2-呋喃甲酰氨基硫羰基)-L-α-氨基酸乙酯衍生物,其结构经IR,1H NMR,MS和元素分析测试确证.MTT法测试结果表明大部分目标化合物对白血病K562细胞系的增殖具有明显的抑制作用.     

高效液相色谱-串联质谱联用测定脂肪中乙酰孕激素残留

建立了脂肪中5种乙酰孕激素,包括醋酸甲羟孕酮(MPA)、醋酸氯地孕酮(CMA)、醋酸甲地孕酮(MEGA)、甲烯雌醇醋酸酯(MLA)及17α-羟基孕酮醋酸酯(HPA)的液相色谱-串联质谱(LC-MS/MS)检测方法。考察了脂肪样品溶剂提取、固相萃取净化对样品分析的影响,确定样品各前处理过程的条件。采用电喷雾(ESI)阳离子,在选择反应监测模式(SRM)下,本方法对5种乙酰孕激素的检出限为0.2～0.3μg/kg,定量限为0.5μg/kg。在空白猪脂肪样品中以0.5、1.0和5.0μg/kg3个水平添加时,5种乙酰孕激素的回收率范围在60.5%～84.1%,RSD为8.9%～16.8%。     

金的化学状态对Au／CoCeOx催化剂CO氧化性能的影响

以CoCeOx复合氧化物为载体,采用沉积沉淀法制备了负载型的金催化剂,并通过不同温度的预处理控制Au的化学状态. 使用粉末X射线衍射、高分辨透射电子显微镜、程序升温还原和X射线光电子能谱对催化剂进行了表征,考察了在室温条件下该系列催化剂的一氧化碳氧化性能. 结果表明, Au/CoCeOx催化剂的CO氧化性能与催化剂表面Au 的含量成正比, Au 可能是反应的主要活性物种. 添加水汽对反应有一定的促进作用,但由于Au 不能稳定存在,特别是当催化剂表面Au 的含量过高时,在水汽的作用下Au 迅速发生歧化反应,使得催化剂的性能下降.     

含四硫富瓦烯结构单元的酞菁和四氮杂卟啉衍生物的研究概况

综述了含四硫富瓦烯(TTF)结构单元的酞菁和四氮杂卟啉衍生物的合成、光物理和电化学性质以及聚集和自组装性能的研究概况.     

环糊精-杯芳烃偶合体系研究进展及前景展望

综述了环糊精-杯芳烃偶合体系(cyclodextrin-calix[n]arene)的合成及性质研究的进展, 并对其开发前景进行了展望. 环糊精-杯芳烃偶合体系可以应用于分子识别、主客体化学、水相有机反应、分子催化反应等领域.     

Synthesis and Crystal Structure of 5-（p-Toly1）-4- [2-（2,4-dichlorophenoxy）acetamido]-l,2,4- triazole-3-thione Ethyl Acetate Solvate

A novel compound 5-（p-tolyl）-4-[2-（2,4-dichlorophenoxy）acetamido]-1,2,4-tria zole- 3-thione 2a has been synthesized by the reaction of 5-（p-tolyl）-4-amino-1,2,4-triazole-3-thione 1 with 2-（2,4-dich/orophenoxy）acetyl ch/oride. Interestingly, the title compound 2 was obtained when 2a crystallizes from a mixed solution of petroleum ether and ethyl acetate, and it has been characterized by elemental analysis, IR, ^1H NMR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.780（5）, b = 10.876（6）, c = 11.615（6） /A, a = 104.822（7）, β= 94.105（6）, ）, = 94.305（6）°, V= 1185.7（11）/A3, Z = 2,μ = 0.397 mm^-1, Mr= 497.39, Dx= 1.393 g/cm^3, F（000） = 516, S = 1.097, the final R = 0.0730 and wR = 0.2133 for 4111 unique reflections （Rint = 0.0525） with 3212 observed ones. The dihedral angles made by the triazole ring with the methyl- and chloro-substituted benzene rings are 43.5（7） and 50.2（9）°, respectively. Some intra- and intermolecular hydrogen bonds together with C-H…π interactions existing in the lattice stabilize the crystal structure.     

Synthesis, Crystal Structure and DNA Binding Studies of α,α'-Bis(3,5-bismethyl-1-pyrozolyl)- carbene-acetyl-isopropenyl Hydrazine

The title compound α,α'-bis(3,5-bismethyl-pyrozole-N-yl)-carbene-acetyl-isopro-penyl hydrazine (C16H22N6O, Mr = 314.40) has been prepared. It was characterized by elemental analysis as well as IR, MS, 1H-NMR and 13C-NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction, getting the following data: triclinic, space group P1 with a = 6.9734(16), b = 10.773(3), c = 12.001(3) A, α = 75.311(4), β = 82.695(4), γ = 77.143(4)°, Z = 2, V = 847.9(3) A3, Dc : 1.231 g/cm3, F(000) = 336 and μ(MoKα) = 0.082 mm-1 (λ = 0.71073 A). The results of crystal structure determination show that there exist intermolecular and intramolecular hydrogen bonds, resulting in a two-dimensional supramolecular framework of the title compound. The binding of the title compound to DNA was investigated by absorption, emission, and viscosity measurements. The title compound shows absorption hyperchromicity accompanied by a blue shift at about 254 nm. The binding constant Kb for the title compound has been determined to be 1.89 × 104 M-1 from absorption measurements. The addition of the title compound to DNA pretreated with EB causes appreciable reduction in the emission intensity, indicating that the DNA-bound EB fluorophore is partially replaced by the title compound. The value of K is 3.093 × 104 M-1. The relative viscosity of DNA decreased with the addition of the title compound. Results suggest that the title compound binds to DNA with a non-classical intercalative or groove interaction mode. The observed efficient nuclease activity of the title compound is interesting and may have further influences on the chemistry of DNA minor groove binders.     

CoO纳米颗粒/石墨烯纳米纤维复合材料的制备及电化学性能

用石墨烯和Co(CH₃COO)₂·4H₂O作为原料,利用超声辅助法合成了锂离子电池的负极材料CoO纳米颗粒/中空石墨烯纳米纤维复合物.采用X射线衍射(XRD)确定材料的物相组成,采用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察材料的表面形貌和微观结构,采用X射线光电子能谱(XPS)确定材料的价态结构.采用循环伏安、恒电流充放电和交流阻抗谱表征材料的电化学性能.结果显示,在100 mA/g的电流密度下,循环了160次后,可逆容量仍超过800 mA/g,库仑效率保持在99%以上.该材料优异的电化学性能主要归因于石墨烯的中空纤维结构,中空内部可以容纳电解液,能直接将离子输送到颗粒表面,实现了离子的快速传输;二维中空纤维搭建成三维网络结构,实现了三维电子传导网络.     

IM-5分子筛在Ni-Cu催化剂甲烷热裂解制氢反应中的作用研究

甲烷热裂解制氢并生成高附加值的纳米碳材料,被认为是极具发展前景的氢气生产途径,但高性能催化剂的研发仍存在诸多挑战.我们选择多种载体(TS-1、 IM-5、 Y、介孔SiO₂、 γ-Al₂O₃、 CNTs),采用浸渍法制备Ni-Cu负载催化剂,通过低温N2吸附-脱附、 XRD、 SEM和H₂-TPR等系列表征方法对样品进行分析,考察不同载体对催化剂甲烷裂解制氢和纳米碳材料的影响.实验结果发现,分子筛载体独特的孔道结构有利于金属颗粒的分散,能有效避免反应中界面效应导致的催化剂失活,可提高催化剂反应活性并延长反应寿命,也显著提高了其碳产率.其中以IM-5分子筛为载体的催化剂表现最佳,在反应温度为700℃时, NiCu/IM-5催化剂甲烷转化率高达80%,氢气选择性达100%,反应400 min后活性未见明显降低. NiCu/IM-5催化剂碳产率高达1 446 g_C/g_cat,是NiCu/SiO₂催化剂的5.7倍, NiCu/γ-Al