联二脲氧化生成偶氮二甲酰胺反应的钒催化机理

在钒催伦剂存在下，用氯酸钠氧化联二脲制成偶氮二甲酰胺，从钒催化剂的单晶培养和结构解析入手，通过反应动力学研究，用ＥＳＲ检测反应过程中四价钒的生成，用分光光度法（分别以钛钛试剂和硫氰酸铵为显色剂）确定了反应过程中三价钒的生成和变化情况，从而提出了可能的催化机理，还利用量化计算从热力学角度证实了所提出的包括四价钒铬离子歧化过程在内的钒催化机理的合理性。     

锰、铑原卟啉IX-二甲酯配合物共振拉曼光谱研究

合成了MnPPCl,RhPPCl,RhPPN3,RhPP(CO)Cl四种配合物 (PP =ProtophyrinIXDimethy1Ester) ,用元素分析、红外吸收光谱及紫外吸收光谱确定了配合物的组成 ,测定了它们的共振拉曼光谱 ,对特征谱带进行了归属。分析了拉曼谱带和电子吸收谱带变化的原因 ,提出了谱带频率的变化受金属离子外层d电子和轴配体的影响。     

共轭亚麻酸的制备、表征和生物活性研究进展

近年来的研究发现共轭亚麻酸(CLN)具有多种非常有益的生理功能,已成为化学家、药理学家、营养学家争相研究的热点。本文就CLN的制备、表征、分离分析以及生物活性等方面,对国内外的研究进行了综述。CLN的制备包括化学法、生物法和天然产物提取法三大类。CLN的表征方法主要有紫外光谱、红外光谱、核磁共振等方法,以及采用气相色谱法(GC)、高效液相色谱法(HPLC)和毛细管电泳法(CE)等方法对合成的CLN混合物进行分离分析。CLN的生物活性主要有抗癌、降血脂、减肥、抗致癌等。     

A microfluidic device using a green organic light emitting diode as an integrated excitation source

A simply fabricated microfluidic device using a green organic light emitting diode (OLED) and thin film interference filter as integrated excitation source is presented and applied to fluorescence detection of proteins. A layer-by-layer compact system consisting of glass/PDMS microchip, pinhole, excitation filter and OLED is designed and equipped with a coaxial optical fiber and for fluorescence detection a 300 microm thick excitation filter is employed for eliminating nearly 80% of the unwanted light emitted by OLEDs which has overlaped with the fluorescence spectrum of the dyes. The distance between OLED illuminant and microchannels is limited to approximately 1 mm for sensitive detection. The achieved fluorescence signal of 300 microM Rhodamine 6G is about 13 times as high as that without the excitation filter and 3.5 times the result of a perpendicular detection structure. This system has been used for fluorescence detection of Rhodamine 6G, Alexa 532 and BSA conjugates in 4% linear polyacrymide (LPA) buffer (in 1 x TBE, pH 8.3) and 1.4 fmol and 35 fmol mass detection limits at 0.7 nl injection volume for Alexa and Rhodamine dye have been obtained, respectively.     

西安地区成年健康人群血清中微量元素正常值研究

用随机抽样的方法对西安地区436名健康人血清中Zn、Fe、Cu、Mn、Pb、Cd、Cr、Ni、Mo和Se十种微量元素正常值进行石墨炉原子吸收光谱法测定，并用ST286型计算机进行多因素相关分析和统计处理．结果表明，血清Zn、Cu分布比较集中，其它元素变异度比较大；多数元素与年龄呈相关关系。其中Zn、Cu、Fe、Mn、Pb、Se与年龄呈正相关 而Mo则与年龄呈负相关；多数元素含量与地城环境中徽量元素的分布有明显的相似性．总之，不同地区不同性别和不同年龄段血清微量元素有显著的差异．     

吸附溶出催化伏安法测定痕量锗

利用吸附溶出伏安法、极谱催化法测定痕量锗已有报道。但将吸附溶出伏安法与极谱催化法结合进行测定,尚未见报道。我们选择适当的体系和配位体3,4-二羟基苯甲醛(DHB)及氧化剂钒(V),首先使Ge(Ⅳ)-DHB络合物在悬汞电极上于一定电位处吸附富集一定时间,然后电位向负的方向扫描。当达到Ge(Ⅳ)-DHB络合物的还原电位时,Ge(Ⅳ)还原     

Stereo- and enantioselective determination of pesticides in soil by using achiral and chiral liquid chromatography in combination with matrix solid-phase dispersion

The separation of enantiomers and diastereomers of 8 commonly used pesticides was investigated by liquid chromatography (LC) using a Chiralcel OD column (cellulose tris-3,5-dimethylphenylcarbamate as the chiral stationary phase) and a Pirkle-type Chirex 3020 column (urea derivative from the reaction of (R)-1-(alpha-naphthyl)ethylamine with (S)-tert-leucine, chemically bonded to 3-aminopropylsilanized silica as the chiral stationary phase). The pesticides studied included one organophosphorus insecticide (phenthoate), 3 triazole fungicides (uniconazole, diniconazole, and propiconazole), and 4 pyrethroids (fenpropathrin, beta-cypermethrin, beta-cyfluthrin, and alpha-fenvalerate). The enantiomers were separated within 20 min with a resolution of > or = 1.5 using a mixture of n-hexane and 2-propanol as the mobile phase for all the pesticides studied except propiconazole, for which only the 2 diastereomers were baseline separated. This method allows determination of the enantiomers or stereoisomers of the above pesticides in soil. The strategy was as follows: (1) First, the total concentration(s) of the enantiomer pair(s) of a chiral pesticide in soil was (were) determined by a newly developed matrix solid-phase dispersion (MSPD) procedure, followed by silica-based LC quantification. The recoveries ranged from 76.5 to 93.6% with relative standard deviations of 6.0%. (2) Second, the enantiomeric ratio(s) (ER(s)) of the chiral pesticide was (were) determined by LC with a chiral stationary phase after fractionation of the MSPD extract by silica-based LC. The determined ERs or stereoisomeric ratio(s) (SR(s); for propiconazole, only the SR of the 2 diastereomers was determined) in soil samples spiked with the above 8 racemic pesticides agreed with those of the corresponding standard solutions. (3) Third, based on the total concentrations and the corresponding ERs, the concentration of each enantiomer in soil was calculated. The proposed method is rapid, precise, and sensitive, and is appropriate for the investigation of the stereo- and enantioselective degradation of pesticides in environmental media.     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

耐硫催化剂上合成混合醇的研究

通过改进制备方法和添加助剂，用浸渍－热分解法制得了具有高活性和高选择性的MoS2-K-C型耐硫低碳混合醇催化剂。在8.0-11.0MPa,290-340℃，6000-12000h^-1,H2 S 浓度为100ppm 左右的条件下，在直流反应器中对催化剂进行了性能测试，结果表明，醇得率为0.14-0.47gROH(gcat·h)^-1，选择性为89-98%。同时，考察了操作条件对催化剂性能的影响。1042h的试验，证明催化剂具有很好的稳定性。     

Synthesis of polypiperazine-amide thin-film membrane on PPESK hollow fiber UF membrane

A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy.