La1-xCaxCrO3体系复合氧化物的甘氨酸-硝酸盐法合成与表征

采用甘氨酸-硝酸盐法(GNP)合成了La1-xCaxCrO3 (x=0～0.3)体系复合氧化物粉料,对合成产物的粉体结构和性能进行了表征,研究了体系组成及合成方法对材料烧结性能和导电性能的影响.实验结果表明,在La1-xCaxCrO3体系中Ca2 离子的引入促进了材料的烧结,随着Ca2 离子含量的增加,材料的烧结致密度和导电性能明显提高.与常规固相法相比,GNP法合成的粉料颗粒细小均匀(100～200 nm),烧结活性高,其烧结体在1400 ℃以下即可达到较高的烧结致密度和良好的电性能.     

K/Ru(10ī0)表面上的CO-4a1轨道对称性确定

用同步辐射角分辨偏振紫外光电子谱对Ｋ／Ｒｕ（１０１０）面上吸附分子轨道的对称性测量发现：结合能在１１、．２ｅＶ的ＣＯ－４ａ１（４σ）分子轨道对ｓ偏振光（在沿〈１２１０〉的人射面）是禁戒的。结果表明由于Ｋ的强烈影响,ＣＯ的分子轨道重新排列（ｓＰ＾２杂化）。依据选择定则和分子轨道的对称性６说明,ｓｐ＾２再杂化的ＣＯ分子吸附的桥位取向是〈１２１０〉晶向。     

不同分子筛载体对CO加氢产物分布的影响

研究了几种小孔分子筛ＺＳＭ－５，ＨＹ，ＮａＹ及β担载ＺｒＯ２对Ｃ加氢反应的催化作用，并就产物的分布情况与担载ＺｒＯ２的硅铝中孔分子筛进行了对比研究。其中中孔分子筛分别用季铵盐和一级胺为模板剂，在水热条件和常温常压下合成；并用ＢＥＴ，ＸＲＤ，ＳＥＭ等手段表征了它们的孔道和骨架结构。另外，考察了碱金属Ｋ＾２＋，Ｎａ＾２＋对催化剂催化性能的影响。     

煤焦在燃烧过程中孔隙结构变化的模拟

煤焦在燃烧过程中的物理特性，如比表面积和孔径分布会发生连续变化，直接测量煤焦在燃烧过程中的孔隙结构变化很困难，但可以通过合适的数学模型来观察，二维的圆柱孔模型已大量用来对煤焦气化与燃烧过程中表面积和孔隙结构的变化进行模拟，这个模型把孔隙分成两大部分－－大孔与小孔，因为小孔构成比表面的绝大部分，所以在反应过程中比表面积的变化可以由单一小孔模型来拟合，本文采用了用Ｔｓｅｎｇ和Ｅｄｇａｒ提出的孔模型对几     

Ultrasensitive small molecule fluorogenic probe for human heparanase

Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.

Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal.     

Synthesis of comb‐shaped poly(methyl methacrylate)‐b‐poly(polytetrahydrofuran acrylate) under 60Co γ‐ray irradiation

Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under ⁶⁰Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under ⁶⁰Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]₀/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002     

Cinnamolid‐3β‐ol hemihydrate and 3β‐hydroxycinnamolide acetate,two drimanolide‐class sesquiterpene lactones from Warburgia ugandensis

3β‐Hydr­oxy‐7‐drimen‐12,11‐olide hemihydrate, C₁₅H₂₂O₃·0.5H₂O, (I), has two sesquiterpene mol­ecules and one water mol­ecule in the asymmetric unit. The OH groups of both mol­ecules and both H atoms of the water mol­ecule are involved in near‐linear inter­molecular hydrogen bonds, having O⋯O distances in the range 2.632 (3)–2.791 (2) Å. 3β‐Acet­oxy‐7‐drimen‐12,11‐olide, C₁₇H₂₄O₄, (II), has its ring system in very nearly the same conformation as the two mol­ecules of (I).     

High-performance liquid chromatography of some basic drugs on a n-octadecylphosphonic acid modified magnesia-zirconia stationary phase

The high-performance liquid chromatographic behavior of some basic drugs was studied on a n-octadecylphosphonic acid modified magnesia-zirconia (C18PZM) stationary phase. The effect of mobile phase variables such as methanol content, ionic strength, and pH on their chromatographic behavior was investigated. The retention mechanism of basic drugs on the stationary phase was elucidated. The results indicate that both hydrophobic and cation-exchange interactions contribute to solute retention under most chromatographic conditions. The inherent Br?nsted-acid sites and also the adsorbed Lewis base anionic buffer constituents on accessible ZM surface Lewis acid sites play a role in the retention of ionized solutes by cation-exchange interaction. However, especially at high mobile phase pH, the retention of basic drugs depends mainly on hydrophobic interactions between solutes and support. Separations of the basic drugs on the C18PZM phase by a predominantly reversed-phase retention mode were very promising. The mixed-mode retention feature on this phase, as a result of the adsorbed Lewis base anionic buffer constituents acting as sites for cation-exchange, could also be very useful, e.g. for enhancing the chromatographic selectivity of such analytes. The C18PZM seems to be an excellent alternative to silica-based reversed-phase stationary phase for the separation of strongly basic solutes.     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

雪松烯的光氧化反应研究

以次甲基兰为光敏剂, 甲醇为溶剂, 用通氧光照产生的单重态氧与雪松烯反应,产物只有一种。用元素分析、红外光谱。核磁共振谱、质谱以及高压液相色谱等方法测定了产物的分子结构。并讨论了光氧化反应的动力学控制和立体效应。