C_(74)的结构、电子光谱及三阶线性光学性质的理论研究

用密度泛函（DFT）方法（BLYP/3－21G~*）研究了C_(74)的稳定几何构型。用 ZINDO及ab initio GIS两种方法对C_(74)的电子光谱进行了计算，预测C_(74)在红 外区域有光谱吸收。计算了C_(74)的三阶非线性光学系数<γ>为1.483 * 10~(-32) esu，它比C_(60)的<γ>（8.84 * 10~(-34) esu）要大得多。预测C_(74)亦将是 一种有很好应用前景的磁性材料。     

Al-Zn-Mg-Cu合金双级时效析出行为的TEM研究

Al-Zn-Mg-Cu合金是一种时效强化高强变形铝合金,长期以来广泛应用于航空航天等工业领域[1,2].其性能主要由时效过程中的时效析出相决定.研究不同时效状态下合金时效析出相的显微组织结构,对明确组织与性能的关系、确定合理的热处理工艺、改善合金的综合性能具有重要的理论意义和工程实用价值.     

Mg改性对Co/γ-Al2O3-TiO2催化燃烧丙烷性能影响

采用分步浸渍法制备了系列Mg改性的Co/γ-Al_2O_3-TiO_2催化剂,通过X射线衍射(XRD)、紫外可见漫反射光谱(DR-UV-vis)、N_2吸附-脱附(BET)、X射线光电子能谱(XPS)和H_2程序升温还原(H_2-TPR)等技术对催化剂进行表征,并考察了其对丙烷燃烧的催化性能。结果表明,Co在原始γ-Al_2O_3-TiO_2载体和Mg改性MgO/γ-Al_2O_3-TiO_2载体上均以Co_3O_4的形式存在;Mg掺入后与Al_2O_3作用形成MgAl_2O_4尖晶石,改善了载体的织构性质,提升了Co_3O_4在催化剂载体表面的暴露数量和分散程度。此外,MgAl_2O_4与Co_3O_4相互作用提升了Co_3O_4颗粒表面Co~(3+)/Co~(2+)和O_(ads)/O_(latt)的比例,并削弱了Co-O键键能,从而提升了其对丙烷的催化燃烧活性。当Mg负载量为15%(质量分数)时,在Co/MgO(15%)/γ-Al_2O_3-TiO_2催化剂上进行丙烷燃烧,丙烷90%转化率的温度比无Mg掺杂的Co/γ-Al_2O_3-TiO_2催化剂的降低了45℃,并且连续反应40 h其活性保持稳定。     

（η^2—C60）[Pt（PPh3）2]8的合成与表征

C60是高度共轭的宠状结构碳素体．分子结构中六元环间的共价碳碳双键是富电子区，其反应性能与烯键类似，以碳碳双键与中心金属形成η2配位化合物．富勒烯η2配合物的合成及性能研究是当前研究热点之一[1~7]．本文在（η2-C60）［Pt（PPh3）2］n（n=1～6）系列研究[7]的基础上制备了（η2－C60）［Pt（PPh3）2］8，并用元素分析、红外光谱和光电子能谱进行鉴定和表征．1实验部分四（三苯基膦）合铂Pt（PPh3）4按文献[8]方法制备；C60纯度为99％；其余试剂均为分析纯．元素分析在ERLA－1106型元素分析仪上进行；光电子能谱在VGESCA…     

不同构象铂(Ⅱ)配合物与G-肌动蛋白作用的光谱研究

The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).     

激发态Ti＋(3d14s2)与丙炔醇气相反应理论研究

用量子化学密度泛函(DFT)方法研究了激发态Ti^＋(3d¹4s²)与丙炔醇(PPA)气相反应的机理. 在B3LYP/DZVP水平上, 优化了反应的两个通道的反应物、中间体、过渡态和产物的几何构型, 并在MP4/[6-311＋G**(C,H,O)＋Lanl2dz (Ti)]水平上计算了各驻点的单点能量. 为了确证过渡态的真实性, 在B3LYP/DZVP水平上进行了内禀坐标(IRC)计算和频率分析, 获得了二重态反应势能面, 确定了反应机理. 研究结果表明生成产物为[C₃H₃O]^＋和Ti—H的通道是主要反应途径.     

A fluorescent molecular imaging probe with selectivity for soluble tau aggregated protein

Soluble forms of aggregated tau misfolded protein, generally termed oligomers, are considered to be the most toxic species of the different assembly states that are the pathological components of neurodegenerative disorders. Therefore, a critical biomedical need exists for imaging probes that can identify and quantify them. We have designed and synthesized a novel fluorescent probe, pTP-TFE for which binding and selectivity profiles towards aggregated tau and Aβ proteins were assessed. Our results have shown pTP-TFE to be selective for early forms of soluble tau aggregates, with high affinity of dissociation constants (K_d) = 66 nM, and tenfold selectivity over mature tau fibrils. Furthermore, we found that pTP-TFE is selective for tau over Aβ aggregates and had good cell permeability. This selectivity of pTP-TFE towards early forms of aggregated tau protein ex vivo was also supported with studies on human brain tissue containing tau and Aβ pathology. To the best of our knowledge, this is the first fluorescent molecule to be reported to have this form of selectivity profile, which suggests that pTP-TFE is a unique probe candidate for imaging-based detection of early stages of Alzheimer''s disease and other tauopathies.

pTP-TFE imaging probe can distinguish soluble tau aggregated proteins from other aggregated proteins enabling earlier detection of neurodegenerative diseases.     

溶胶凝胶法制氧化铝负载铜基超细粒子催化剂的研究

采用溶胶凝胶法制氧化铝负载铜基超细粒子催化剂的制备了氧化铝负载的铜基超细粒子催化剂，用ＴＧ－ＤＴＡ，ＸＲＤ，ＢＥＴ以及ＴＥＭ等技术手段，对催化剂的物相结构，表面孔结构，粒子形貌以及催化性能等进行了研究。结果表明，利用溶胶凝胶法，可以直接帛备出高比表面积，低堆积密度的纤维状纳米级负载型Ｃｕ／Ａｌ２Ｏ３超细粒子；活性组分以远低于纳米级的微晶粒子簇状态，均匀地分散在纳米级氧化铝载体表面上，而且在低于５０     

流动注射化学发光抑制法测定维生素E

实验发现,H2SO4-KMnO4-甲醛在丙酮存在下发光信号大大增强,据此建立了H2SO4-KMnO4-甲醛-丙酮新体系。同时发现维生素E(VE)对H2SO4-KMnO4-甲醛-丙酮化学发光体系有强烈的抑制作用,建立了维生素E的流动注射化学发光抑制法的新体系。化学发光信号的降低值与VE的浓度在1.0×10-5~1.0×10-3mol/L的范围内呈良好的线性关系,方法的检出限为3.0×10-6mol/L。对1.0×10-4mol/L的VE进行11次平行测定,其相对标准偏差为1.5%。该法已用于VE片剂中VE的测定。     

带功能基的全氟烷基乙烯基醚的研究——3、四氟乙烯与-7,7-二氯-3-氧杂全氟庚烯-1的共聚反应及共聚物的转化

 研究了二个新的全氟烷基乙烯基醚7,7-二氯-3-氧杂全氟庚烯-1(M_0)和10,10-二氯-3,6-二氧杂全氟5-甲基癸烯-1(M₁)-与四氟乙烯(TFE)的共聚反应,聚合物的性质,并测定了TFE-M₀竞聚率。竞聚率的测定证明M₀较其它已报道的全氟烷基乙烯基醚的聚合活性都大。TFE-M₀共聚物通过化学反应可转化成相应的全氟羧酸甲酯树脂。