Synthesis,electrochemical and an e.s.r study of heterodinuclear MIIZnII (M = Cu,Ni, and VO) complexes of asymmetric macrocyclic ligands made from 2,6-diacetyl-4-methylphenol

A series of heterodinuclear complexes, [MZnL][ClO4)2· nH2O (M = Cu, Ni, and VO) where L is a dinucleating Schiff base ligand derived from the condensation of 2,6-diacetyl-4-methylphenol (1mole), with ethylenediamine (1mole), 1,2-diaminopropane (1mole), or 1,3-diaminopropane (1mole) have been synthesized and evaluated. The complexes exhibit a single one-electron redox couple as anticipated. The e.s.r spectra for the CuZn complex shows an isotropic signal and the frozen glass spectra of VOZn complex is characterized by two sets of eight lines.     

基于表面增强拉曼光谱检测技术的肺癌早期诊断研究

表面增强拉曼光谱技术是近年来快速发展的一种痕量特征标记性物质检测技术,以提高检测灵敏度为目的的表面增强拉曼光谱技术非常适合于生命科学研究。本文利用表面增强拉曼光谱技术对肺癌患者及正常人的唾液样本进行检测,并进行光谱分析,建立了肺癌患者唾液样本的实验模型,对该模型系统分析可为肺癌诊断提供辅助依据。统计学分析效果良好,并发现了分类比较明确的特异性波段1015cm-1～1070cm-1和1250cm-1～1280cm-1。在找出的12个特征峰的基础上应用K-均值方法验证了其判别准确性,结果提示提取的12个特征峰有一定的代表性,能够代表近2000个波数的拉曼光谱图,灵敏度较特异度高,说明该方法适合预防性筛查工作。     

AFM Observation of Phospholipid Molecules Absorbed on Mica

An atomic force microscope was used to observe the adsorption of phospholipid molecules(phospha-tidylcholine, PC) on the mica substrate.The film-formation by PC molecules adsorption spontaneously on the specific substrate has been proved. It is revealed that the evident differences of morphology exist among different sampler with different concentrations of PC/decane solutions. different adsorption times, etc.The effect of tip-induced change in size of domains formed by adsorption of PC molecules on the substrate during the AFM scanning was observed.     

Synthesis,electrochemical and magnetic properties of new macrocyclic copper(II) complexes derived from 2,6-diacetyl-4-4-methylphenol

A series of binuclear macrocyclic copper(II) complexes [Cu2Lm,n](ClO4)2·xH2O have been prepared in which the two copper(II) ions are placed in two geometrically distinct co-ordination environments. The macrocycles with two 2,6-bis(iminomethyl)-4-methylphenol entities combined through two different lateral chains, –(–CH2–)–m and –(–CH2–)–n (m = 2 or 3, n = 2 to 5) were synthesized by stepwise cyclization. Cyclic voltammetry shows the presence of two reduction couples: CuIICuII CuICuII and CuIICuI CuICuI. The comproportionation constants, Kcom, for the mixed valence CuICuII complexes have been determined electrochemically. The Kcom value increases in the order of the macrocycles: (L2,2)^2–<(L2,3)^2–<(L2,4)^2–<(L2,5)^2– and (L3,3)^2–<(L3,4)^2–<(L3,5)^2–. Cryomagnetic investigations (80–300K) reveal a moderately strong antiferromagnetic spin exchange between the copper(II) ions within each complex (J = –210 to –390 cm–1).     

含FEC电解液的锂离子电池低温性能研究

研究含FEC溶剂电解液(FEC+EMC,EC,PC)的低温性能及其与磷酸铁锂正极或中间相碳微球(MCMB)负极的匹配.该电解液具有较高的低温电导率,FEC可在1.6 V与负极反应成膜,有效地提高负极稳定性.红外测试发现,FEC可抑制其它电解液溶剂在负极成膜过程中的分解,在常温(20℃)和低温(-20℃)下形成的SEI膜阻抗均较低.电化学测试表明,以该电解液装配的锂离子电池(电极)具有较高的低温放电容量和倍率性能.     

水岩化学作用对黑色页岩的化学损伤及力学劣化试验研究

为模拟黑色页岩化学风化中酸性水-页岩化学作用过程,本文对其进行氧化条件下的不同pH值H2SO4溶液的非平衡流动态腐蚀性试验,获得了黑色页岩化学腐蚀前后矿物变化、相对质量损失、次生孔隙率、纵波波速变化及微观结构特征的变化。通过单轴压缩试验,获得黑色页岩在不同浸泡时段的变形和强度特性规律,探讨了酸性水对黑色页岩化学作用的化学损伤和力学劣化的腐蚀效应及机制。研究表明,页岩试件在化学腐蚀后,易溶性矿物成分减小,黏土矿物增加,同时矿物胶结变得松散,矿物边缘变得模糊;页岩试件的相对质量损失与次生孔隙率随pH值减小和浸泡时间的增长而增大,而纵波波速则减小;其力学特性有从脆性破坏向延性破坏转化的趋势,单轴抗压强度和弹性模量有随pH值减小和浸泡时间的增长而减小的趋势。基于次生孔隙率,构建化学损伤变量来描述试件化学-力学损伤演化过程。分析酸性水-页岩化学作用的机理主要为:溶解作用、氧化作用、水解作用及离子交换吸附作用。     

基于唾液的拉曼光谱检测进行肝癌诊断的研究

表面增强拉曼光谱技术是近年来快速发展的一种痕量特征标记性物质检测技术, 达到了分子识别水平, 具有很高的灵敏度, 能够精确地分析和了解物质结构和成分。人体唾液中含有大量体征相关的特异性蛋白质和分泌物质。唾液检测具有无创、获取方便、适合开展大规模普查等优点。表面增强拉曼光谱检测技术可以快速地对唾液进行检测, 二者的结合, 有可能成为一种癌症诊断的新方法。本文利用表面增强光谱技术对肝癌患者进行实验研究, 通过对肝癌患者唾液的采集、样品的处理、光谱的采集及光谱分析, 肝癌特异性标记物AFP(alpha fetoprotein)的检测及分析等过程得到肝癌相关特征信息, 表明肝癌患者与正常人的唾液样本分类良好, 灵敏度及特异性较好; 进一步验证了AFP抗原的分子组成, 且AFP抗原的拉曼强度基本随浓度的递增呈递减趋势; 对肝癌患者的唾液样本及AFP抗原的拉曼光谱进行比对分析, 提示利用表面增强拉曼光谱检测唾液有可能诊断早期癌症。     

压缩载荷作用下岩石类材料的断裂模式研究

为了解岩石类材料在压缩条件下的裂纹扩展规律,本文对含有内部倾斜裂纹的石膏板试件进行了双轴压缩实验. 研究表明:在通常情况下岩石裂纹按I 型张拉模式扩展,但随着裂纹表面摩擦系数μ和围压与纵向荷载比值λ的提高,翼裂纹扩展的偏转角随之减少.当裂纹表面摩擦系数和围压与纵向荷载比值足够大时,例如,μ=0.83和λ=0.315,岩石裂纹按Ⅱ型剪切模式扩展.然而,当裂纹表面摩擦系数和围压与纵向荷载比值进一步增加时,石膏板试件将发生强度破坏.本文提出了一个理论模型用以解释和描述这一实验现象.     

Silica Coating of Water-Soluble CdTe/CdS Core-Shell Nanocrystals by Microemulsion Method

"Using Te powder as a tellurium source and Na2S as a sulfur source, core-shell CdTe/CdS NPs were synthesized at 50 oC. UV-visible and photoluminescence (PL) spectra were used to probe the effect of CdS passivation on the CdTe quantum dots. As the thickness of CdS shell increases, there is a red-shift in the optical absorption spectra, as well as the PL spectra. The broadening absorption peaks and PL spectra indicate that the size distributions of CdTe/CdS NPs widen increasingly with the increase of CdS coverage. The PL spectra also show that the fluorescence intensity of CdTe QDs will increase when the particles are covered with CdS shell with ratio of S/Te less than 1.0, otherwise it will decrease if the ratio of S/Te is larger than 1.0. Furthermore, the (CdTe/CdS)@SiO2 particles were prepared using a water-in-oil microemulsion method at room temperature in which hydrolysis of tetraethyl orthosilicate leads to the formation of monodispersed silica nanospheres. The obtained (CdTe/CdS)@SiO2 particles show bright photoluminescence with their fluorescence intensity being enhanced 18.5% compared with that of CdTe NPs. TEM imaging shows that the diameter of these composite particles is 50 nm. These nanoparticles are suitable for biomarker applications since they are much smaller than cellular dimensions."     

爆炸荷载作用下配筋砌体结构的动力响应

基于大型非线性动力有限元软件LS-DYNA,通过改变墙体的约束情况、砌体材料的强度等级、纵向配筋率、高宽比、荷载峰值、墙体距爆心点距离、墙体开洞以及粘贴玻璃纤维复合材料等,得到配筋砌体墙在爆炸荷载作用下的变形规律、破坏情况以及结构墙体中砌体材料、钢筋的应力和位移随时间的变化规律。同时对各种不同工况下配筋砌体墙的防爆性能进行比较,找出了影响结构响应最为重要的因素,给配筋砌体墙防爆设计提供参考。