电喷雾萃取电离质谱法检测1-羟基芘

采用电喷雾萃取电离质谱(EESI-MS)分析致癌性环境有机污染物多环芳烃(PAHs)生物标志物1-羟基芘(1-OHP),探究1-OHP在EESI源中电离的可行性,考察ESI溶剂和样品溶液组成对方法灵敏度的影响,初步建立I-OHP的EESI MS半定量分析方法.结果表明,溶液中1-OHP能够在EES1源中有效电离,生成准分子离子[M-H]- (m/z 217),并得到其二级质谱特征碎片离子[M- H- CO]- (m/z 189);水、甲醇、乙醇、正丙醇和正丁醇5种ESI溶剂中,使用甲醇时,离子峰m/z 217信噪比最大.样品溶液中甲醇含量越高,离子峰m/z 217强度越强.离子峰m/z 217强度与1-OHP浓度在10～200 μg/L内的线性相关性相对最好;相关系数(R)0.982;相对标准偏差(RSD)为3.4％～14.0％(n=5);定量下限约为10 μg/L(S/N=10);单次检测时间小于0.5 min.     

凝胶层析和离子交换层析结合法纯化高盐发酵液中谷氨酰胺转胺酶

采用凝胶层析和离子交换层析相结合的方法分离纯化高盐培养基中的谷氨酰胺转胺酶,优化的凝胶层析的条件,上样量6mL,流速为0.25 mL/min;离子交换层析的上样量50 mL,流速为3 mL/min.酶被纯化了4.22倍,比活力达17.33 U/mg蛋白,回收率为77.5％.液相色谱-串联质谱鉴定、蛋白质数据库比对结果表明,纯酶与AAN01353是同种蛋白质.     

TCM active ingredient oxoglaucine metal complexes: crystal structure, cytotoxicity, and interaction with DNA

The alkaloid oxoglaucine (OG), which is a bioactive component from traditional Chinese medicine (TCM), was synthesized by a two-step reaction and used as the ligand to react with transition metal salts to give four complexes: [OGH][AuCl(4)]·DMSO (1), [Zn(OG)(2)(H(2)O)(2)](NO(3))(2) (2), [Co(OG)(2)(H(2)O)(2)](ClO(4))(2) (3), and [Mn(OG)(2)(H(2)O)(2)](ClO(4))(2) (4). The crystal structures of the metal complexes were confirmed by single crystal X-ray diffraction. Complex 1 is an ionic compound consisting of a charged ligand [OGH](+) and a gold complex [AuCl(4)](-). Complexes 2-4 all have similar structures (inner-spheres), that is, octahedral geometry with two OG coordinating to one metal center and two aqua ligands occupying the two apical positions of the octahedron, and two NO(3)(-) or ClO(4)(-) as counteranions in the outer-sphere. The complexation of OG to metal ion was confirmed by ESI-MS, capillary electrophoresis and fluorescence polarization. The in vitro cytotoxicity of these complexes toward a various tumor cell lines was assayed by the MTT method. The results showed that most of these metal-oxoglaucine complexes exhibited enhanced cytotoxicity compared with oxoglaucine and the corresponding metal salts, with IC(50) values ranging from 1.4 to 32.7 μM for sensitive cancer cells, which clearly implied a positive synergistic effect. Moreover, these complexes appeared to be selectively active against certain cell lines. The interactions of oxoglaucine and its metal complexes with DNA and topoisomerase I were investigated by UV-vis, fluorescence, CD spectroscopy, viscosity, and agarose gel electrophoresis, and the results indicated that these OG-metal complexes interact with DNA mainly via intercalation. Complexes 2-4 are metallointercalators, but complex 1 is not. These metal complexes could effectively inhibit topoisomerase I even at low concentration. Cell cycle analysis revealed that 1-3 caused S-phase cell arrest.     

TEMPO/NaBr/NaClO体系催化氧化法合成α-D-葡萄糖醛酸

以α-D-葡萄糖为起始物,用TEMPO/NaBr/NaClO体系催化氧化法合成α-D-葡萄糖醛酸。合成过程为:首先对α-D-葡萄糖上的C1位进行甲基化保护,然后用TEMPO/NaBr/NaClO体系对伯醇羟基进行催化氧化转化为羧基,最后脱甲基。对第三步稀盐酸水解法脱甲基的条件作了优化,分别水解15h、30h、45h、58h、65h,高效液相色谱(HPLC)结果显示,在水解58h时甲基葡萄糖醛酸钠基本水解完毕,葡萄糖醛酸水解得率最高,水解得率为64.9%。经过高效液相色谱提纯后的葡萄糖醛酸熔点为164.3～165.2℃(m.p.165℃),得率(基于α-D-葡萄糖)为45.2%。     

La3+提高拟南芥耐旱能力研究

稀土元素有着广泛的生物学效应,稀土作为微肥在我国农业广泛使用.然而,稀土对植物抗旱性影响的研究很少.以模式植物拟南芥为材料,研究了不同浓度的镧(La3+)对植物根生长以及对植物耐旱能力的影响.结果表明,10和100 μmol ·L-1的La3能显著促进根生长,提高植物耐旱能力;1μmol·L-1La3+没有明显促进根生长,但显著提高了植物耐旱能力;1和10 mmol·L-1的La3+不能促进根生长,同时还降低了植物耐旱能力.该结果提示,稀土农用过程中要重视剂量的使用,同时避免带来生态环境问题.     

3－苯氧甲基－6－（2，4－二氟苯基）－7H-1,2,4-三唑并[3,4-b][1,3,4]噻二嗪的合成与晶体结构研究

由苯氧乙酸出发，经多步反应，制得3-苯氧甲基－4－氨基－5－巯基－1，2， 4－三唑，它与2-氯－2'，4'－二氟苯乙酮进行环化反应，生成3-苯氧甲基－6－（ 2,4-二氟苯基）－7H-1,2,4-三唑并[3,4-b][1,3,4]噻二嗪，通过元素分析、红外 光谱、核磁共振氢谱与碳谱、质谱进行表征，并利用单晶X射线衍射法测定其结构 。晶体属单斜晶系、P2_(1/c)空间群，a = 1.339(3) nm, b = 1.4683(4) nm, c = 0.8606(2) nm, β = 108.49(2)°, Z = 4, F(000) = 736, R_1 = 0.0509。还 对均三唑并噻二唑两类稠杂环的晶体结构作了比较。     

氟烷基化C_(60)与四（N，N-二甲基）氨基乙烯电荷转移复合物磁性的EPR研究

变温ERP研究揭示氟烷基化富勒烯C_(60)(R_f)_n与四(N,N-二甲基)氨基乙烯 (TDAE)间稳定的电荷转移络合物TDAE-C_(60)(R_f)_n的居里温度高达190K[R_f = C_3F_7，H（CF_2）_4]。而非氟烷基化络合物TDAE-C_(60)的相应值仅为16.1K。 这种铁磁性可能是络合物分子中氟烷基化富勒烯多价阴离子基在相应居里温度下具 有某种有序排列的缘故。     

Structural Study of Inclusion Complex of Andrographolide with β-Cyclodextrin Prepared under Microwave Irradiation

Andrographolide (Andro) (Figure 1) is a diterpene lactone isolated from Andrographis paniculate Nees1. It has showed several biological activities including analgesic, antipyretic and anti-inflammatory effects2. However, its poor water solubility and unstability towards oxygen restrained its application. In pharmaceutics, b-CD is used to increase solubility and stability3. We have prepared the inclusion compound of Andro/b-CD (Figure 2) under microwave irradiation4. It has been found…     

α-杂环硫代苯乙酮衍生物的合成

以5-氨基-3-巯基-(1H）-1，2，4-三唑和2-巯基苯并噻唑为主要原料在碱性条件下与α-氯代苯乙酮反应合成了10个新的标题化合物。其结构经元素分析、IR，^1H NMR和MS确证。     

溶胶凝胶法合成LiCuVO4及其电化学性能研究

以CH3COOLi.2H2O、Cu(NO3)2.3H2O、V2O5和双氧水(30%)为原料,采用溶胶凝胶法合成了LiCuVO4,其结构、组成和形貌经XRD和SEM确认。结果表明,本文所合成的LiCuVO4具有隧道结构的形貌,颗粒粒径为0.2～6μm。将LiCuVO4作为锂离子电池正极材料,首次循环的放电比容量达到160mAh/g;而作为负极材料,其最大放电比容量达到481mAh/g。在两种电化学测试中,LiCuVO4都显示了良好的循环性能。