Intramolecular stacking interaction in mixed-ligand complexes containing ATP4- and aromatic N-heterocyclic ligands

The stability constants of the binary ML2+ and ternary M(ATP)L2- complexes,where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+,have been determined by poten-tiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4),T=25℃.The stability of the ternary complexes characterized by corresponding to the equilibrium M(ATP)2-+ML2+=M(ATP)L2-+M2+ is higher than what would be expected on statistical grounds.The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP4- 1H NMR studies of Zn2+/ATP4-/L confirm the presence of stacking in the ternary complexes.It is concluded that the strength of the intramolecular stacking interaction is dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge.Possible implications are discussed briefly.     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

配合物[Cu(L-Ile)(TATP)(H2O)]ClO4的结构、表征及与DNA之间的相互作用

Ternary complex [Cu(L-Ile)(TATP)(H₂O)](ClO₄)] was synthesized and characterized by molar conductivity, rotational analysis, spectroscopic (IR and UV-Vis) and X-ray diffraction methods, where L-Ile=L-Isoleucine, and TATP=1,4,8,9-tetraazatriphenylene. The complex crystallizes in triclinic space group P1 with two molecules in a unit cell of dimensions a=8.240 3(9) nm, b=11.914 9(13) nm, c=13.436 0(15) nm, α=109.136(2)°, β=101.101(2)°, γ=106.302(2)°. V=1.209 2(5) nm³, Z=2, D_c=1.589 Mg·m^-3, μ=1.132 mm^-1，R₁=0.036 9, wR₂=0.098 0. The crystal contains two independent [Cu(L-Ile)(TATP)(H₂O)]⁺ complexes for Cu₁ and Cu₂, respectively, having essentially the same distorted square-pyramidal structure, where each Cu(Ⅱ) ion is coordinated with two nitrogen atoms of TATP and the amino nitrogen atom and one carboxylate oxygen atom of L-Ile in the equatorial positions and one water oxygen atom at an axial position. Furthermore, the primary studies on the interaction between the complex and calf thymus DNA were also performed by electronic absorption spectroscopy and viscosity methods. CCDC: 244231.     

聚乙烯燃烧和阻燃的热分析研究

<正> 聚乙烯是一种极易燃烧的高分子材料,氧指数仅17.6,随着其应用面的拓宽和现代社会对防火要求的提高,聚乙烯的阻燃成了越来越重要的课题。目前,聚乙烯及其共混物的阻燃配方已不计其数,理论探讨也有一些报道,但由于对阻燃效果与阻燃剂的性质之间的内在联系尚缺乏足够的认识,所以阻燃剂的选择仍主要依赖于经验及大量的配方试验,缺少系统有效地选择阻燃剂的方法。     

Double folding model calculation applied to fusion reactions

The interaction potential between a spherical and a deformed nucleus is calculated within the double-folding model for deformed nuclei.We solve the double folding potential numerically by using the truncated multipole expansion method.The shape,separation and orientation dependence of the interaction potential,fusion cross section and barrier distribution of the system 16O+154Sm are investigated by considering the quadrupole and hexadecapole deformations of 154Sm.It is shown that the height and the position of the barrier depend strongly on the deformation and the orientation angles of the deformed nucleus.These are quite important quantities for heavy-ion fusion reactions,and hence produce great effects on the fusion cross section and barrier distribution.     

HPLC-ELSD法测定绞股蓝中绞股蓝皂苷A的含量

采用HPLC-ELSD法测定绞股蓝中绞股蓝皂苷A的含量。色谱柱为HibarC18(250×4.6mm,5μm),流动相为乙腈-水梯度洗脱,流速0.5mL/min,柱温为20℃,绞股蓝皂苷A在0.0425—1.995mg/mL范围内线性关系良好(r2=0.9962),并通过正交法优化其提取工艺。该方法简便、有效,为绞股蓝的质量控制提供一种准确可行的检测方法。     

用激光加工硅钢片降低铁损残余变形的云纹干涉法测量研究

应用双镀层高温高频光栅和云纹干涉法对激光加工硅钢片降低铁损的残余变形进行了测量研究。分别对采用ＣＯ２连续激光和ＹＡＧ脉冲激光不同参数处理后硅钢片表面的残余变形进行了测量，对双镀层Ｃｒ－Ｃｒ光栅的制作方法、云纹干涉法测量残余变形的原理进行了讨论。实验结果表明，硅钢片在激光加工后，试件表面产生负性残余应变是细化磁畴，降低铁损的直接原因     

数学实验课的教学模式研究

本文主要探讨工科数学教学中数学实验课的多个层次和开设数学实验课的几种方式 ,并且介绍我们的一些具体做法和面临的一些问题     

气相色谱－三重四极杆质谱法测定动物源性食品中砜吡草唑残留量

建立了动物源性食品中砜吡草唑残留量的气相色谱－三重四极杆质谱检测方法。猪肉、猪肝、鸡肉、鸡肝、牛奶和鸡蛋中的砜吡草唑用乙腈提取,经乙二胺-N-丙基硅烷化硅胶、十八烷基键合硅胶和无水硫酸镁去除杂质,离心后取上清液氮吹至干,加入丙酮复溶、过滤后经气相色谱－三重四极杆质谱检测,外标法定量。通过对仪器条件、提取溶剂和净化方式等进行优化,确定最合适的前处理方法和仪器条件。对样品的基质效应进行考察,发现6种基质中砜吡草唑的基质效应均小于20%,为弱基质效应,无需采取补偿措施。在优化实验条件下,砜吡草唑在0.5 ~ 100 μg/L范围内线性关系良好,相关系数为0.999 5。空白样品在4个加标水平下的平均回收率为85.8% ~ 106%,相对标准偏差（n = 6）为3.1% ~ 6.8%,方法定量下限为0.001 mg/kg。采用该方法对50个动物源性食品进行测定,在1个牛肉样品和1个羊肉样品中检出砜吡草唑。该方法操作简单、灵敏度高、准确性好,适用于动物源性食品中砜吡草唑的检测,可为砜吡草唑在动物源性食品中的风险监控提供技术支撑。     

二氧化铅修饰玻碳电极的镀膜/循环伏安法制备及电催化性能

采用镀膜/循环伏安法制备了PbO2修饰玻碳电极.在Pb(NO3)2溶液中,在-0.7 V 将Pb膜沉积在玻碳电极表面,然后在5 mol/L NaOH溶液中以100 mV/s速度在-1.0～1.0 V循环伏安扫描20次,PbO2膜均匀沉积在玻碳电极表面.采用交流阻抗法监控电极修饰每一过程,环境扫描电镜表征电极表面形貌.探讨了PbO2膜的沉积机理及其电化学行为,表面活性位点覆盖量为7.5×10-10 mol/cm2.PbO2修饰电极对H2O2电氧化表现出较高催化活性,起始氧化电位低至0.1 V,考察了影响催化活性的因素.计时电流法测定H2O2 (工作电位0.40 V),响应时间小于2 s; 线性范围为5.0 ×10-6 ～ 5.5×10-4 mol/L;检出限1.1×10-6 mol/L (信噪比为3).在实际水样中H2O2测定结果满意.电极在室温环境下储存30 d,其催化活性基本不变.该修饰电极制备工艺简单、重现性良好、稳定性高.