一种含噻吩环酰腙及其Cu(Ⅱ)配合物的合成、晶体结构和抗氧化活性及量化计算

合成了一种酰腙类含硫Schiff碱4-(二乙胺基)水杨醛缩2-噻吩甲酰腙一水合物(H₂L·H₂O,1),采用扩散法制备了它的铜配合物[Cu(phen)L](2,phen=菲咯啉),通过元素分析、红外光谱、紫外光谱和X射线单晶衍射对它们进行了表征。1的晶体属正交晶系,P2₁2₁2空间群;2的晶体属单斜晶系,P2₁/c空间群。在2中H₂L以烯醇式脱除羟基质子与铜配位,中心离子的配位环境为畸变的四方锥构型。应用Gaussian09程序,采用密度泛函方法(DFT),分别在B3LYP/6-31G(d)和UB3LYP/6-31G(d)水平对1和2进行了量化计算,对分子的前线分子轨道的能量和组成以及电子光谱进行了分析讨论。测试、分析了化合物的抗氧化活性。     

Theoretical Study on the Reaction of Thymine with Iodomehane in the Water Phase

The reaction mechanisms of carcinogenic methylating agent iodomethane (MeI) with keto and enol tautomers of thymine (K- and E-thymine) were studied by using the B3LYP/6-311+G (d, p) method in water phase. The solvent effects were examined using the polarizable continuum model (PCM). Specifically, PCM single-point calculations at the same level of theory were performed in acetone and CCl4 that represent a range in nonpolarity. The calculated results show that the reaction of K-thymine with MeI is a two-step mechanism, whereas that of E-thymine is a one-step mechanism. Our calculations reveal that K-thymine is appreciably more stable than the enol form in the water phase or in the two solvents. The K- and E-form reaction barriers are 135.6 and 222.1 kJ/mol, respectively in water phase. These findings indicate that the reactions mentioned above could not occur efficiently in biological media in the absence of catalyst. Our conclusions are in agreement with the previous studies on the reactions of guanine with methyl chloride and methyl bromide.     

SiNP分子结构及稳定性的理论研究

采用B3LYP/6-311G(d),QCISD和CCSD(T)方法,对单重态和三重态SiNP体系的异构化进行了研究.在QCISD/6-311G(d)水平下,得到了7个稳定的异构体,它们由4个过渡态所连接,其中三重态线型异构体SiNP(31,3Σ1),单重态环状异构体SiNP(14,1A')和单重态线型异构体SiNP(11,1Σ)都具有较大的热力学及动力学稳定性.     

2,4-二羟基苯乙酮缩异烟酰腙的实验和DFT理论研究:合成、晶体结构和性质及量化计算

合成了一种酰腙类Schiff碱2,4-二羟基苯乙酮缩异烟酰腙(C₁₄H₁₃N₃O₃,H₂L),经元素分析、红外光谱、紫外光谱、荧光光谱和热重分析等技术手段进行了表征。 用X射线单晶衍射测定了它的晶体结构,该晶体属单斜晶系,C2/c空间群,晶胞参数a=2.0102(2) nm,b=0.75891(8) nm,c=1.9530(2) nm,α= 90°,β=111.481(12)°,γ=90°,V=2.7725(5) nm³,Z=4,D_c=1.4292 g/cm³,R₁=0.0422,wR₂=0.1113,F(000)=1256。 同时进行了量子化学计算研究。 使用Gaussian09量子化学程序包, 在密度泛函理论(DFT)的B3LYP/6-31G(d)水平,对化合物的分子结构进行全参数优化计算,获得了热力学参数和几何结构参数,对分子的总能量及前线分子轨道、Mulliken电荷分布进行了分析讨论;同时,用TD-DEF方法计算了化合物的电子吸收光谱和荧光发射光谱。     

高中化学“烃的衍生物”的教学法(下)

第九课酯类本课目的:使学生认识酯和脂化反应教师可重点讲解:酯的结构式和通式,酯化的意义及酯类的主要用途。检查学生知识:怎样由焦炭、石灰等无机原料制乙酸?有机酸中有什么特殊的官能团?由何类物质氧化可生成有机酸?何类物质氧化可生成醛?醇有什么官能团? 讲授新教材:从乙醇和乙酸的结构式或示性式说明酯的生成,指出这个反应和中和不同,叫作酯化,结合课本上的反应式说明酯化反应是醯基取代醇的羟基中的氢而生成酯的反应,然后写出通式。     

Epitaxial evolution on buried cracks in a strain-controlled AlN/GaN superlattice interlayer between AlGaN/GaN multiple quantum wells and a GaN template

Epitaxial evolution of buried cracks in a strain-controlled AlN/GaN superlattice interlayer(IL) grown on GaN template, resulting in crack-free AlGaN/GaN multiple quantum wells(MQW), was investigated. The processes of filling the buried cracks include crack formation in the IL, coalescence from both side walls of the crack, build-up of an MQW-layer hump above the cracks, lateral expansion and merging with the surrounding MQW, and two-dimensional step flow growth.It was confirmed that the filling content in the buried cracks is pure GaN, originating from the deposition of the GaN thin layer directly after the IL. Migration of Ga adatoms into the cracks plays a key role in the filling the buried cracks.     

Induced Nucleation of Diamond Films on ZnS Substrates Precoated with Ceramic Interlayer

We attempt to coat a multi-spectrum chemical-vapour-deposition ZnS substrate with smooth crystalline diamond films on the top of properly designed ceramic interlayer,which provides protection for ZnS against corrosion by the H2-CH4 microwave plasma and mitigates the thermal expansion coefficient mismatching between diamond and ZnS.However,difficulties in the homogeneous diamond nucleation on a ceramic interlayer were encountered.It was found that high rate nucleation of diamond could be induced by a metal or semiconductor mask placed on the top of ZnS.     

聚酰亚胺柔性基底上磁控溅射金属铜膜的电学性能研究

为了制备用于挠性电路板中的挠性覆铜板,在聚酰亚胺上使用中频磁控溅射方法制备金属Cu膜.实验中,通过改变制备温度、衬底偏压、制备时间等工艺参数,制备出导电性符合要求的Cu薄膜.用X射线衍射仪(XRD)、扫描电镜(SEM)研究薄膜的成分、结构以及表面形貌,用触针式台阶仪、四探针电阻测量仪测量薄膜的膜厚以及电阻,并计算薄膜的电阻率.最终得到制备导电性符合工业应用标准的Cu膜的最佳工艺条件:制备温度100℃,直流偏压50 V,无脉冲偏压.     

具有单分子磁行为的二维Dy(Ⅲ)-配合物

在水热条件下,利用刚性配体Hapca（3-氨基吡嗪-2-羧酸）合成了一例基于双核镝结构基元的二维网格配合物[Dy₂（apca）₄（OH）₂（H₂O）₂]_n （1）。磁性研究表明：该配合物显示铁磁耦合,并具有典型的慢弛豫行为,其弛豫时间τ₀=9.47×10^-7 s,各向异性能垒U_eff/k_B=73.7 K,是一例少见的具有单分子磁行为的镧系二维网格配合物。