酚醛冠醚共缩聚物的合成与性能

用2,6-二羟甲基-4-苯基苯酚分别与二苯并-18-冠-6(2B18C6)、二苯并-24-冠-8(2B24C8)、二苯并-30冠-10(2B30C10)、苯并-15-冠-5(B15C5)、苯并-18-冠-6(B18C6)缩聚合成了五种酚醛型冠醚共聚物。我们用聚冠醚的氯仿溶液萃取苦味酸碱金属盐水溶液,研究了它们对金属离子的络合性能。结果表明,聚冠醚(PB15C5)和(PB18C6)的萃取能力和选择性显著优于相应的单冠醚。     

甲氧基苯基偶氮衍生物电子结构与二阶NLO性质的HF/FF方法研究

采用量子化学HF方法在6-31G水平上优化6个甲氧基苯基偶氮衍生物分子的几何构型，利用HF／6-31G。方法计算它们的偶极矩、电荷分布、前线分子轨道能级并结合有限场(FF)方法计算二阶非线性光学系数．结果表明，偶氮苯衍生物分子具有很好的共轭性，在给吸电子基团作用下，电荷转移明显，展现示出较强的极性．偶氮苯衍生物分子与苯乙烯、Schiff碱类衍生物相似，也具有很好二阶非线性光学活性，同时六元杂环取代的偶氮苯衍生物分子二阶非线性光学系数比未取代的大，五元杂环取代结果相反．     

4,4′-二(硬脂酰胺基)二苯甲烷在乙烯基类单体中的分子组装及其结构形态研究

4,4′-二(硬脂酰胺基)二苯甲烷(BSDM)能在乙烯基类单体中进行聚集、自组装,并可使苯乙烯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸-2-羟基乙酯等凝胶化,形成相应的分子凝胶.凝胶/溶胶相变温度(TGS)与BSDM浓度有关,BSDM质量分数越大,凝胶体系中分子间氢键和π-π键越多,要破坏它们所需要的能量越高,TGS因而也就越高.透射电镜表明,BSDM在各种可聚合溶剂中通过分子间相互作用形成类似纤维状的聚集体结构.BSDM在可聚合溶剂聚合前后的偏光显微照片表明,BSDM在体系中的晶型结构是球晶.     

氢原子在Ru(0001)表面的化学吸附

用密度泛函理论研究了氢原子的污染对于Ru(0001)表面结构的影响. 通过PAW(projector-augmented wave)总能计算研究了p(1×1)、p(1×2)、(3^(1/2)×3^(1/2))R30°和p(2×2)等几种氢原子覆盖度下的吸附结构, 以及在上述结构下Ru(0001)面fcc(面心立方)格点和hcp(六方密堆)格点的氢原子吸附. 所得结果表明, 在p(1×1)-H、p(1×2)-H、(3^(1/2)×3^(1/2))R30°-H和p(2×2)-H几种H原子覆盖度下, 以p(1×1)-H结构单个氢原子吸附能为最大. 在p(1×1)-H吸附结构下,由于氢原子吸附导致的Ru(0001) 表面第一层Ru 原子收缩的理论计算数值分别为-1.11%(hcp 吸附)和-1.55%(fcc 吸附), 因此实际上最有可能的情况是两种吸附方式都有一定的几率. 而实验中观察到的“清洁”Ru(0001)表面实际上是有少量氢原子污染的表面. 不同覆盖度和氢分压下氢原子吸附的污染对Ru(0001)表面结构有极大的影响,其表面的各种特性都会随覆盖度的不同而产生相应的变化.     

Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.     

Thermochemistry on the Complex of Erbium Perchlorate with L-α-Glutamic Acid [Er2（L-Glu）2（H2O）6]（ClO4）4·6H2O（s）

A coordination compound of erbium perchlorate with L-α-glutamic acid, [Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）, was synthesized. By chemical analysis, elemental analysis, FTIR, TG/DTG, and comparison with relevant literatures, its chemical composition and structure were established. The mechanism of thermal decomposition of the complex was deduced on the basis of the TG/DTG analysis. Low-temperature heat capacities were measured by a precision automated adiabatic calorimeter from 78 to 318 K. An endothermic peak in the heat capacity curve was observed over the temperature region of 290-318 K, which was ascribed to a solid-to-solid phase transition. The temperature Ttrans, the enthalpy △transHm and the entropy △transSm of the phase transition for the compound were determined to be： （308.73±0.45） K, （10.49±0.05） kJ·mol^-1 and （33.9±0.2） J·K^-1·mol^-1. Polynomial equation of heat capacities as a function of the temperature in the region of 78-290 K was fitted by the least square method. Standard molar enthalpies of dissolution of the mixture [2ErCl3·6H2O（s）＋2L-Glu（s）＋6NaClO4·H2O（s）] and the mixture {[Er2（Glu）2（H2O）6]（ClO4）4·6H2O（s）＋6NaCl（s）} in 100 mL of 2 mol·dm^-3 HClO4 as calorimetric solvent, and {2HClO4（1）} in the solution A＇ at T=298.15 K were measured to be, △dHm,1=（31.552±0.026） kJ·mol^-1, △dHm,2 = （41.302±0.034） kJ·mol^-1, and △dHm,3 = （ 14.986 ± 0.064） kJ·mol^-1, respectively. In accordance with Hess law, the standard molar enthalpy of formation of the complex was determined as △fHm-=-（7551.0±2.4） kJ·mol^-1 by using an isoperibol solution-reaction calorimeter and designing a thermochemical cycle.     

片状LiV3O8软模板辅助溶胶-凝胶法制备及其在水系锂离子电池中的性能研究

负极材料是目前制约水溶液锂离子电池的关键.采用十二烷基苯磺酸钠软模板辅助的溶胶凝胶法制备了片状LiV3O8材料.XRD和SEM测试表明,目标材料为纯相的片状结构LiV3O8,属单斜晶系,P21/m点群.组装LiMn2O4//Li2SO4//LiV3O8水溶液锂离子电池,测试发现片状LiV3O8具有较高的倍率性能和较好的循环寿命.在0.1C下,LiV3O8的放电比容量为154 mAh·g-1.在1C、5C和10C时,放电容量分别为134 mAh·g-1、78 mAh·g-1和54 mAh·g-1.1C前170周循环的容量保持率约60%.     

Microwave Assistant Synthesis and Dimeric Crystal Structure of 2-(((6-Chloropyridin-3-yl)-methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole

The title compound 2-(((6-chloropyridin-3-yl)methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole 5(C26H18Cl2N8S4) was synthesized, and its structure was confirmed by 1H NMR, MS and elemental analyses and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 9.452(4), b = 12.335(4), c = 13.017(5) A, α = 90.624(5), β = 110.541(5), γ =104.879(4)°, Dc = 1.561 g/cm3, Z = 2, V = 1364.9(9) A3, F(000) = 656, the final R = 0.0300 and w R = 0.0635 for 4206 observed reflections with I 2σ(I). The preliminary biological test showed that the title compound has activities against Stemphylium lycopersici(Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory activities to be 9.82%, 44.44% and 20.00%, respectively.     

6×n阶矩形网络等效电阻猜想的证明

任意k×n阶电阻网络等效电阻的公式研究属于科学难题,到目前为止已经获得了当k=1,2,…,5时的5种情形下的等效电阻公式,但对k≥6时的等效电阻的普适公式仅仅作为猜想给出.本文根据建立的任意k×n阶电阻网络等效电阻研究的方法,证明了k=6时的等效电阻公式的正确性,并且给出了其无穷网络的等效电阻公式,在对比验证时得到了一些新的三角恒等式.     

新型N-(取代芳氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲及其环合产物的合成及其杀虫活性

采用亚结构拼接法,将苯氧乙酸类结构引入酰基硫脲中,设计并合成了8个新型的硫脲类化合物——N-(取代苯氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲(5a~5h);5a~5h在酸性条件下关环形成8个新型的含1,3,4-噻二唑的酰胺类化合物——1-甲基-N-(5-取代基-1,3,4-噻二唑-2-基)环氧甲酰胺(6a~6h),其结构经1H NMR和ESI-MS表征。初步的生物活性测试结果表明,在用药量为500mg·L-1时,N-(2,4-二氯苯氧乙酰胺基)-N'-(1-甲基环己基酰基)硫脲对粘虫的抑制率为80%。