配体形状对多吡啶铜(Ⅱ)配合物与DNA作用的影响

合成了一系列含有平面配体的Cu(Ⅱ)多吡啶配合物[Cu(IP)₂]²⁺、[Cu(PIP)₂]²⁺、[Cu(DPPZ)₂]²⁺和[Cu(HPIP)₂]²⁺，用吸收光谱、CD光谱和粘度等方法研究了这些配合物与小牛胸腺DNA的作用。结果表明配体上的取代基及配体的平面性对这些四面体配合物与DNA的结合强弱产生一定的影响。[Cu(DPPZ)₂]²⁺与DNA的结合较强，而[Cu(HPIP)₂]²⁺与DNA的结合较弱。CD光谱显示配合物[Cu(DPPZ)₂]²⁺、[Cu(PIP)₂]²⁺和[Cu(HPIP)₂]²⁺的加入会导致DNA的CD光谱减弱。而[Cu(IP)₂]²⁺的加入则会使DNA的CD光谱增强。同时，[Cu(IP)₂]²⁺与DNA结合后，还会引起一定程度的DNA构型转换，即DNA从B型转换成Z型。     

Tween-20与牛血清白蛋白的相互作用

通过表面张力和等温滴定量热方法，研究了非离子表面活性剂Tween-20与牛血清白蛋白(BSA)的相互作用. 结果表明，BSA与Tween-20的相互作用较弱，当Tween-20浓度增大时，能将吸附于表面上的BSA分子取代. BSA/Tween-20混合体系的性质随温度的变化趋势与单一非离子型表面活性剂相似. BSA浓度在3.7×10^-5～11.1×10^-5 kg•L^-1范围内，Tween-20的cmc不随BSA浓度的变化而变化. 当Tween-20的含量一定时，Tween-20与BSA相互作用过程的热效应也与BSA 的浓度无关. BSA/Tween-20混合体系的热力学参数表明， BSA的存在使Tween-20的cmc减小，体系的熵变增大.     

Probing the intrinsic electronic structure of the cubane [4Fe-4S] cluster: nature's favorite cluster for electron transfer and storage

The cubane [4Fe-4S] is the most common multinuclear metal center in nature for electron transfer and storage. Using electrospray, we produced a series of gaseous doubly charged cubane-type complexes, [Fe4S4L4]2- (L = -SC2H5, -SH, -Cl, -Br, -I) and the Se-analogues [Fe4Se4L4]2- (L = -SC2H5, -Cl), and probed their electronic structures with photoelectron spectroscopy and density functional calculations. The photoelectron spectral features are similar among all the seven species investigated, revealing a weak threshold feature due to the minority spins on the Fe centers and confirming the low-spin two-layer model for the [4Fe-4S](2+) core and its "inverted level scheme". The measured adiabatic detachment energies, which are sensitive to the terminal ligand substitution, provide the intrinsic oxidation potentials of the [Fe4S4L4]2- complexes. The calculations revealed a simple correlation between the electron donor property of the terminal thiolate as well as the bridging sulfide with the variation of the intrinsic redox potentials. Our data provide intrinsic electronic structure information of the [4Fe-4S] cluster and the molecular basis for understanding the protein and solvent effects on the redox properties of the [4Fe-4S] active sites.     

磷酸三乙酯改性HZSM-5沸石的活性及理论研究

采用XRD表征了水蒸气和磷联合改性的HZSM-5沸石分子筛的结构．通过NH3-TPD和N2吸附脱附研究了样品的酸性和比表面．采用正庚烷的裂化反应研究了样品的裂化活性，研究结果表明，磷改性样品与母体样品相比，经过水蒸气处理后显示出较高的酸量和正庚烷裂化活性．上述结果首次用模型簇和计算量子化学方法进行了解释．采用Gaussian94软件包和PM3半经验量子化学方法对模型簇进行了全优化和频率分析．计算结果显示磷改性后样品的脱铝补硅反应热大于母体样品脱铝补硅反应热，从而显示出磷对骨架的稳定化作用．     

A Novel Synthesis of Two-dimensional Nanopatterned TiO2 Thin Film

Recently the research on structures with an ordered two-dimensional(2D) pattern has attracted great attention due to its versatile applications in the fields of microelectronic and optoelectronic devices, displays, biochips and sensors, enzymatic immobilization, drug carriers, and photonic band gap materials. Various well-arrayed 2D structures have been made by the modern technique such as laser writing pattern fabrication, photoetching technique, micro-electromechanical systems based on scann…     

异亚硝基乙酰乙酸乙酯亚胺Pd(Ⅱ)配合物的合成、表征和tran Pd(p-CH3C6H4-IEAI)2的晶体结构

Six palladium(Ⅱ) complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R-IEAI)₂, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p-CH₃C₆H₄-IEAI)₂ (2) cry- stallizes in the monoclinic system, space group P2₁/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm^-1. The final R and wR are 0.0244 and 0.0625 for 2620 ob-served reflections with I≥2σ(I), respectively. The geometry around the Pd(Ⅱ) ions in those complexes has a distorted PdN₄ square plane, the Schiff base ligands R-IEAI^- being coordinated through their oximino-nitrogen atoms and imino-nitrogen atoms.     

微量热法研究γ-Mo2N催化剂表面氢的微分吸附热

Differential heats of H 2 adsorption on γ-Mo2N catalysts were studied by using microcalorimetry. Samples with high and medium surface areas (90 and 17 m2•g -1 ) present a homogeneous energetic distribution of surface sites, which corresponds with the preferential orientation of their (200) planes. Molybdenum nitride with low surface area (8 m2•g -1 ) displays a heterogeneous energetic distribution of H 2 adsorption sites. The higher initial differential heat of hydrogen adsorption observed for the low surface Mo nitride was attributed to species adsorbed on surface sites associated with the (111) plane.     

刚性微粒填充高聚物的宏观本构关系

用微观力学和统计方法研究了含损伤过程的刚性粒子填充高聚物的非线性本构关系．在材料的变形过程中，粒子与基体间界面的开裂引发微孔洞的成核与长大，这虽然弱化了材料的宏观力学性能，但是带来了宏观本构的非线性效应，这为材料的增韧奠定了基础．该文分析了刚性粒子对材料的强化作用和微孔洞演化对材料的弱化作用，以及这两种竞争机制的耦合效应对宏观本构关系的影响，并从理论上给出了界面强度，粒径分散度，平均粒径等参量对材料宏观力学行为影响的定量分析结果．     

The Role of Acetylcholine in the Cognitive Function of Frontal Neurons in Monkeys

To study the role of acetylcholine(ACh) in the cognitive function of frontal lobes, ACh and atropine were applied iontophoretically to the task-related neurons recorded from an area around the superior ramus of arcuate sulcus in the frontal cortex of 4 rhesus monkeys during the performance of two tasks. The spontaneous discharges and taskrelated responses of most of the neurons which increased their discharge rate in the delay and differentiation periods of the discrimination response go/no-go task and in the cue and delay periods of the delayed discrimination go/no-go task, were further increased during the application of ACh and suppressed during atropine. These results suggest that ACh may be involved in the excitatory process of the activity of the neurons in the above-mentioned area of frontal cortex to play an important role in the cognitive functions of attention, discrimination and short-term memory.     

金属有机导体、半导体和超导体

本文综述了三类金属有机固体化合物的合成、结构与导电性能。这三类化合物是金属有机电荷转移盐,金属酞菁和会属卟啉络合物,以及金属有机夹层化合物。