Synthesis,Crystal Structure and Antimicrobial Activity of a New Ternary Copper(Ⅱ) Complex with p-Chlorophenoxyacetic Acid and 2-Amino Benzothiazole

A novel ternary complex of Cu(pcpa)2(aben)2 (pcpa=p-chlorophenoxyacetic acid anion,aben=2-amino benzothiazole) was synthesized by the reaction of copper acetate,2-amino benzothiazole and p-chlorophenoxyacetic acid.Elemental analysis,IR,UV and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure.The crystal crystalli-zes in the monoclinic system,space group C2/c with a=25.795(4),b=7.384(3),c =17.741(6),β=107.47(2)°,C30H24Cl2CuN4O6S2,Mr=735.09,V=3223.2(18) 3,Z=4,Dc=1.515 Mg/m3,λ(MoKα)=0.71073 ,μ=1.022 mm-1,F(000)=1500,the final R=0.0464 and wR=0.1244.A total of 3218 unique reflections were collected,of which 2228 with I 2σ(I) were observed.The Cu(II) atom is four-coordinated with two carboxylate oxygen atoms of the two pcpa ligands and two nitrogen atoms in thiazole rings of two aben ligands.The analysis of crystal structure shows intermolecular and intramolecular hydrogen bonds between amino-nitrogen atoms of the two aben ligands and carboxylate oxygen atoms of the two pcpa ligands.The antimicrobial properties of the title complex and its two free ligands were tested against representative bacterial and fungal strains.Results show that the antibacterial activity of the complex is less than or equal to that of 2-amino benzothiazole,but for yeasts and moulds,it exhibits excellent inhibitory effect better than that of its two free ligands.     

Synthesis and Crystal Structure of 12-（2,4-Dichlorophenyl）-7,8,9,10,11,12-hexahydrobenzo[f]pyrimido [4,5-b]quinoline-9,11-dione DMF Solvate

The title compound 12-(2,4-dichlorophenyl)-7,8,9,10,11,12-hexahydrobenzo-[f]pyrimido[4,5-b]quinoline-9,11-dione DMF solvate 1(C24H20Cl2N4O3,Mr=483.34) was synthesized and crystallized.The crystal belongs to the monoclinic system,space group P21/n with a=6.4798(16),b=20.595(5),c=16.723(4),β=95.267(7)o,Z=4,V=2222.3(9)3,Dc=1.445 g/cm3,μ(MoKα)=0.328 mm-1,F(000)=1000,the final R=0.0530 and wR=0.1388 for 3484 observed reflections(I2σ(I)).X-ray analysis reveals that the central 1,4-dihydropyridine ring is slightly distorted,adopting a half-chair conformation,which is obviously different from the boat conformations of other similar compounds.In addition,the classical hydrogen bonds of N(2)-H(2A)…O(2) are presented in the crystals,and link the adjacent molecules to form dimmers.Atom O(3) in the DMF solvent forms two hydrogen bonds of O(3)…H(1H)-N(1) and O(3)…H(3H)-N(3) with a pyrimidoquinoline moiety,forming an interesting half-chair-like conformation.The hydrogen bonds link the molecules to form dimmers,while intermolecular π-π interaction connects the above-mentioned dimmers to yield a one-dimensional structure.     

高效液相色谱法测定塑胶跑道中3,3'-二氯-4,4'-二氨基二苯甲烷的残留量

将塑胶跑道样品加工粉碎至粒径在0.85～1.40mm之间,称取此样品0.500 0g,用丙酮10mL浸润并超声提取60min,收集萃取液,将其蒸发浓缩至近干,并用氮气吹干,加入甲醇1.0mL溶解残渣。溶液经0.22μm滤膜过滤后,按高效液相色谱仪的仪器条件测定滤液中3,3′-二氯-4,4′-二氨基二苯甲烷(MOCA)的含量。色谱分离中用C18反相色谱柱为固定相,以水(A)和甲醇(B)按不同比例混合作为流动相进行梯度淋洗,洗脱液中MOCA在波长245nm条件下用二极管阵列检测器检测。结果表明:MOCA的质量浓度在1.0～50.0mg·L-1内与相应的峰面积之间呈线性关系,其检出限(3S/N)为1.0mg·kg-1。在2.50,10.0,100mg·kg-1等3种浓度水平上进行加标回收试验,测得回收率在86.4%～92.3%之间,测定值的相对标准偏差(n=6)在3.2%～4.2%之间。     

8-氟-5-羟基-[1,2,4]三唑并[1,5-c]嘧啶-2-磺酰胺的合成

8-氟-5-羟基-[1,2,4]三唑并[1,5-c]嘧啶-2-磺酰胺（9）为重要的医药、农药等中间体,其合成方法暂无文献报道。以2,4-二氯-5-氟嘧啶为原料,经醚化、肼解、环合、重排、磺酰胺化、脱甲基化等反应合成了9,总收率27.2%,其结构经¹H NMR,¹³C NMR和MS（ESI）确证。     

电感耦合等离子体质谱法测定土壤中有效态镉

建立电感耦合等离子体质谱(ICP–MS)仪测量土壤样品中有效态镉的方法。为了提高ICP–MS法测量的稳定性和准确度,优化样品粒度、称样量、振荡时间等条件,以二乙三胺五乙酸–三乙醇胺–氯化钙混合溶液(DTPA)为提取剂(固液比为1∶12.5),元素铑为内标,ICP–MS仪测定有效态镉的含量。有效态镉的线性范围为0～0.200 mg/L,线性相关系数为0.999 8,检出限为0.000 9mg/kg。测定结果的相对标准偏差为1.56%～3.16%(n=6)。用该法测定国家标准物质土壤中的有效态镉,测定值与标准值基本一致,相对误差为–2.92%～3.13%。该方法减少了样品的浪费,提高了工作效率,增加了测量稳定性,测定结果准确可靠,在检测大批量土壤有效态镉时更具有优越性。     

反式羰基铑碘络合物催化甲醇制乙酸反应的动力学研究

本文运用密度泛函理论, 选取 B3LYP/6-311+G(2d,p)//B3LYP/SDD方法基组,对反式羰基铑碘络合物催化甲醇羰基化制乙酸反应进行了计算研究, 对势能面上各稳定点进行了全几何参数优化, 通过频率分析确认了过渡态, 并采用内禀反应坐标(IRC)进行了验证, 确定了反应路径. 运用Kozuch撰写的能量跨度模型获得循环反应的动力学信息, 并利用转化频率评估了催化性能与温度的变化关系.     

反式羰基铑碘络合物催化甲醇制乙酸反应的动力学研究

本文运用密度泛函理论, 选取 B3LYP/6-311+G(2d,p)//B3LYP/SDD方法基组,对反式羰基铑碘络合物催化甲醇羰基化制乙酸反应进行了计算研究, 对势能面上各稳定点进行了全几何参数优化, 通过频率分析确认了过渡态, 并采用内禀反应坐标(IRC)进行了验证, 确定了反应路径. 运用Kozuch撰写的能量跨度模型获得循环反应的动力学信息, 并利用转化频率评估了催化性能与温度的变化关系.     

2-（3,5-二氯-2-吡啶偶氮）-5-二乙氨基酚分光光度法测定啤酒中微量铬的研究

在0.09—0.16mol·L-1硫酸介质中,Cr2O72-与2-（3,5-二氯-2-吡啶偶氮）-5-二乙氨基酚作用,形成二离子缔合物,最大吸收波长533nm,表观摩尔吸光系数为为4.51×104L·mol-1·cm-1,铬含量在0—3.3μg·mL-1内符合比耳定律,用于啤酒样品中微量铬的测定,结果满意。     

2,4-D对血清体系中性激素干扰机理研究

为了进一步了解环境内分泌干扰物对人体内性激素平衡的影响,实验选择2,4-D这种已被确认为环境内分泌干扰物的农药,研究了2,4-D、天然性激素（雌二醇、睾酮）加入人血清后体系紫外吸收光谱以及荧光光谱的变化,并通过温度与体系荧光强度的关系、计算扩散碰撞猝灭常数Kp等方法确定了2,4-D、天然性激素对血清组分的荧光猝灭机理,认为2,4-D可发生类似天然性激素和血清组分间的基态络合,并可能与天然性激素竞争占据血清蛋白的结合位点,由此干扰了生物体内正常的性激素水平。     

铕及其掺杂稀土噻吩乙酸、邻菲哕啉配合物的合成、表征及荧光性能

合成了十种以2-噻吩乙酸（TPAC）、邻菲哕啉（Phen）为配体,单一稀土Eu^3＋配合物、Eu^3＋掺杂La^3＋、Gd^3＋、Y^3＋、Er^3＋以及不同比例的Eu^3＋掺杂La^3＋异核配合物。进行了元素分析、摩尔电导、热谱、红外光谱、核磁共振及荧光性能研究。配合物的组成分别为EuL3L’,Eu0.5L3L＇,Eu0.5La0.5L3L＇,Eu0．5,Gd0.5L3L＇,Eu0.5Er0.5L3L＇和EuxLa1-xL3L＇（其中L=TPAC,L’=Phen）。羧酸的氧原子和邻菲哕啉的氮原子与稀土离子配位,配合物为非电解质。荧光光谱的测试表明荧光惰性离子La^3＋、Gd^3＋、Y^3＋对Eu^3＋的荧光有增强作用,顺序为La^3＋〉Gd^3＋〉Y^3＋;Er^3＋对Eu^3＋的荧光有猝灭作用。不同比例Eu^3＋掺杂口’异核配合物中,当Eu^3＋：La^3＋=0．50：0．50时敏化作用最强,荧光强度值最大。