反相高效液相色谱法测定雷公藤提取物中雷公藤甲素含量

应用反相高效液相色谱法检测了雷公藤提取物中雷公藤甲素的含量。样品经洗脱提取后,以Ｃ１８化学键合硅胶为固定相,乙腈－水（４０∶６０,Ｖ／Ｖ）为流动相,用２１０ｎｍ波长定量检测。测定结果表明,雷公藤甲素浓度在０．２５～４．００ｍｇ／Ｌ范围内线性良好,最低进样检测浓度为０．１ｍｇ／Ｌ。批内（ｎ＝５）及批间（ｎ＝５）测定相对标准偏差分别为１．９％～６．５％和２．７％～７．８％,回收率为８９．８％～９２．０％。     

242-260nm波长区CS2分子的多光子解离电离

在242－260nm波氏范围通过CS2分子的共振增强多光子电离（REMPI）获得了母体离子CS和碎片离子的分质量激发谱．在λ＜246.4nm区间，CS激发谱上呈现出来源于CS2双光子电离的弥散谱带,碎片离子激发谱的归属强烈提示多光子过程中有中性基电子态的CS和S（经由CS2的光解离）产生：（1）CS 的谱带主要来源于中性CS碎片经由单光子跃迁产生的（1＋1）共振增强电离，（2）除了部分S 的谱峰来自CS 的光解外，多数S 的锐谱峰来自中性S原子经由3p3（2D0）4p，3p3（4S0）np（n＝6，7，8）←3p43pJ（J＝2，1,0）双光子跃迁产生的（2＋1）共振增强电离．     

有机金属衍生物α，β-［(RSn)3GeW9O37］7-的合成与性质研究

本文报道了α，β-M₄H₃［(RSn)₃GeW₉O₃₇］·nH₂O(M=Bu₄N⁺, Me₄N⁺; R=Bu, Ph)杂多配合物的合成、表征及催化性能研究、元素分析、红外光谱和紫外光谱、¹H、¹¹⁹Sn和¹⁸³W核磁共振谱、激光飞行时间(TOF)质谱和极谱数据表明，这些新化合物为三取代的Keggin结构，三个(RSn)³⁺属不同的M₃O₁₃单元并且彼此共角相连，标题杂多化合物主要以单体形式存在且对烯烃环氧化反应具有催化活性。     

纯二氧化钛介孔分子筛的合成与表征

分别用不同链长的烷基磷酸酯和脂肪胺两类不同表面活性剂为模板剂合成了纯二氧化钛介孔分子筛（Ti-TMS1，Ti-TMS2），并用溶剂法代替高温焙烧法成功地脱除了模板剂。用 XRD、TEM等测试手段对这类材料的结构进行了表征，研究了反应条件对所制备样品的结构的影响。结果表明：得到的纯二氧化钛介孔分子筛为较规则的六角堆积排列，孔径为2.7～4.4 nm, 且其纳米孔径大小可以通过改变烷基磷酸酯模板剂的烷基链长而调节。此外还发现，采用的烷基磷酸酯模板剂的烷基链越长，制得的二氧化钛介孔分子筛结构及晶型的完整性越好。进一步的研究表明，模板剂脱除之后，Ti-TMS2结构的晶体完整性和稳定性明显不如Ti-TMS1的好，且Ti-TMS1的介孔结构优于Ti-TMS2的介孔结构。     

Size-based analysis of incinerator fly ash using gravitational SPLITT fractionation, sedimentation field-flow fractionation, and inductively coupled plasma-atomic emission spectroscopy

Fly ash has been regarded as hazardous because of its high adsorption of toxic organic and/or inorganic pollutants. Fly ash is also known to have broad distributions of different chemical and physical properties, such as size and density. In this study, fly ash emitted from a solid waste incinerator was pre-fractionated into six sub-populations by use of gravitational SPLITT fractionation (GSF). The GSF fractions were then analyzed by sedimentation field-flow fractionation (SdFFF) and ICP–AES. SdFFF analysis showed the fly ash has a broad size distribution ranging from a few nanometers up to about 50 µm. SdFFF results were confirmed by electron microscopy. Inductively coupled plasma–atomic emission spectroscopy (ICP–AES) analysis of the GSF fractions showed the fly-ash particles contain a variety of inorganic elements including Ca, Si, Mg, Fe, and Pb. The most abundant in fly ash was Ca, followed by Si then Mg. No correlations were found between trace element concentration and particle size.     

Low-dimensional hybrid copper halides with novel D6R Cu(6)I(6) cores

Two low-dimensional hybrid copper halides, (2,2'-bipy)Cu(3)I(3) (1) and (2,2'-bipy)Cu(4)I(4) (2) (2,2'-bipy = 2,2'-bipyridine), with novel D6R (double six-membered rings) Cu(6)I(6) cores were synthesized by hydro(solvo)thermal reactions and characterized by single-crystal X-ray diffraction.     

Ligand binding properties of myoglobin reconstituted with iron porphycene: unusual O2 binding selectivity against CO binding

Sperm whale myoglobin, an oxygen storage hemoprotein, was successfully reconstituted with the iron porphycene having two propionates, 2,7-diethyl-3,6,12,17-tetramethyl-13,16-bis(carboxyethyl)porphycenatoiron. The physicochemical properties and ligand bindings of the reconstituted myoglobin were investigated. The ferric reconstituted myoglobin shows the remarkable stability against acid denaturation and only a low-spin characteristic in its EPR spectrum. The Fe(III)/Fe(II) redox potential (-190 mV vs NHE) determined by the spectroelectrochemical measurements was much lower than that of the wild-type. These results can be attributed to the strong coordination of His93 to the porphycene iron, which is induced by the nature of the porphycene ring symmetry. The O2 affinity of the ferrous reconstituted myoglobin is 2600-fold higher than that of the wild-type, mainly due to the decrease in the O2 dissociation rate, whereas the CO affinity is not so significantly enhanced. As a result, the O2 affinity of the reconstituted myoglobin exceeds its CO affinity (M' = K(CO)/K(O2) < 1). The ligand binding studies on H64A mutants support the fact that the slow O2 dissociation of the reconstituted myoglobin is primarily caused by the stabilization of the Fe-O2 sigma-bonding. The IR spectra for the carbon monoxide (CO) complex of the reconstituted myoglobin suggest several structural and/or electrostatic conformations of the Fe-C-O bond, but this is not directly correlated with the CO dissociation rate. The high O2 affinity and the unique characteristics of the myoglobin with the iron porphycene indicate that reconstitution with a synthesized heme is a useful method not only to understand the physiological function of myoglobin but also to create a tailor-made function on the protein.     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.     

Covalent attachment of phospholipid analogous polymers to modify a polymeric membrane surface: a novel approach

A novel method for the surface modification of a microporous polypropylene membrane by tethering phospholipid analogous polymers (PAPs) is given, which includes the photoinduced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) and the ring-opening reaction of grafted poly-(DMAEMA) with 2-alkyloxy-2-oxo-1,3,2-dioxaphospholanes. Five 2-alkyloxy-2-oxo-1,3,2-dioxaphospholanes, containing octyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, and octadecyloxy groups in the molecular structure, were used to fabricate the PAP-modified polypropylene membranes. The attenuated total reflectance FT-IR spectra of the original, poly(DMAEMA)-grafted, and PAP-modified membranes confirmed the chemical changes on the membrane surface. Scanning electron microscope pictures showed that, compared with the original membrane, the surface porosities ofpoly(DMAEMA)-grafted and PAP-modified membranes were somewhat reduced. Water contact angles measured by the sessile drop method on PAP-modified membranes were slightly lower than that on the original polypropylene membrane, but higher than those on poly(DMAEMA)-grafted membranes with the exception of octyloxy-containing PAP-modified membranes. However, BSA adsorption experiments indicated that the five PAP-modified membranes had a much better protein-resistant property than the original polypropylene membrane and the poly(DMAEMA)-grafted membranes. For hexadecyloxy- and octadecyloxy-containing PAP-modified membranes, almost no protein adsorption was observed when the grafting degree was above 6 wt %. It was also found that the platelet adhesion was remarkably suppressed on the PAP-modified membranes. All these results demonstrate that the described approach is an effective way to improve the surface biocompatibility for polymeric membranes.     

含CexZr1-xO2三效催化剂设计的神经网络仿真与优化

提出一种含CexZr1-xO2的三效催化剂的设计方法,即利用人工神经网络来进行辅助设计.首先考察了影响三效催化剂性能的一些重要因素,确定了所研究的三效催化剂模型.然后采用共沉淀方法制备了一系列铈锆固溶体,并将它们作为三效催化剂的助催化剂.采用传统的催化剂制备方法制备了一系列负载贵金属的三效催化剂,所制备的催化剂在模拟尾气中进行评价,得到的数据作为神经网络的训练样本和测试样本,建立了神经网络模型,并初步进行了预测和优化.