吖啶类衍生物的荧光性质

用比较法测得23种啶类衍生物的荧光量子效率（Φf)，以评估这些化合物的荧光性质，结果表明，N－烃基吖啶酮类化合物的荧光量子效率要比9－取代苯基吖啶类和9－取代苯亚甲基－10－甲基－9，10－二氢吖啶类化合物的荧光量子效率大，在非极性溶剂中，9－聚代苯亚甲基－9，10二氢吖啶分子内的强吸电子基NO2增强荧光量子效率，强推电子基OCH3降低荧光量子效率，这些测量结果与取代基的电子作用经验规律不相符，这种现象可以用分子内电荷转移理论进行解释。     

On lower bounds of number of perfect matchings in fullerene graphs

Couting perfect matchings in graphs is a very difficult problem. Some recently developed decomposition techniques allowed us to estimate the lower bound of the number of perfect matchings in certain classes of graphs. By applying these techniques, it will be shown that every fullerene graph with p vertices contains at least p/2+1 perfect matchings. It is a significant improvement over a previously published estimate, which claimed at least three perfect matchings in every fullerene graph. As an interesting chemical consequence, it is noted that every bisubstituted derivative of a fullerene still permits a Kekulé structure.     

气相色谱法测定溴己新血药浓度及药代动力学研究

建立了人血浆中溴己新的气相色谱 电子捕获测定法 ,对溴己新胶囊在健康人体内的药代动力学进行了研究。色谱柱为 5 %SE 30 (2m× 3mmi.d .)硅烷化玻璃柱。 5 氯 2 氨基二苯甲酮为内标 ,血浆样品加入磷酸盐缓冲液 (pH 6 0 )后用正己烷 二氯甲烷 (体积比为 9∶1)提取。线性范围为 1 0 μg/L～ 5 0 0 μg/L ,r =0 9994。人血浆中最小检测质量浓度为 0 5 μg/L。方法重现性好 ,日内、日间RSD分别小于 4 5 6 %和 7 11% ,平均回收率 97 5 %。 8名健康志愿者口服 8mg溴己新胶囊后 ,其体内代谢过程符合一房室模型。方法可用于体内血药浓度测定 ,简单、快速 ,灵敏度高 ,数据准确可靠     

Study of the effect of Wuzhi tablet (Schisandra sphenanthera extract) on tacrolimus tissue distribution in rat by liquid chromatography tandem mass spectrometry method

A liquid chromatography/tandem mass spectrometry (LC‐MS/MS) method was developed and validated for determining tacrolimus (FK506) in rat tissues to study the effect of Schisandra sphenanthera extract on FK506 tissue distribution. After a liquid–liquid extraction with ethyl acetate, FK506 and ascomycin (IS) were subjected to LC‐MS/MS analysis using positive electrospray ionization under multiple reactions monitoring mode. Chromatographic separation of FK506 and ascomycin was achieved on a Hypersil BDS C₁₈ column with a mobile phase consisting of methanol‐water (containing 2 mM ammonium acetate, 95 : 5, v/v). The intra‐ and inter‐batch precision of the method were less than 8.8 and 9.8%, respectively. The intra‐ and inter‐batch accuracies ranged from 97.5 to 104.0%. The lowest limit of quantification for FK506 was 0.5 ng/mL. The method was applied to a FK506 tissue distribution study with or without a dose of Wuzhi (WZ) tablet. Most of the FK506 tissue concentrations were slightly increased after a concomitant WZ tablet dose, but the whole blood concentration of FK506 was dramatically increased 3‐fold after a concomitant WZ tablet dose. These results indicated that the LC‐MS/MS method was rapid and sensitive enough to quantify FK506 in different rat tissues, and strict drug monitoring is recommended when co‐administering WZ tablet in clinical use. Copyright © 2009 John Wiley & Sons, Ltd.     

Reducibly degradable hydrogels of PNIPAM and PDMAEMA: Synthesis,stimulus‐response and drug release

Reducibly degradable hydrogels of poly(N‐isopropylacrylamide) (PNIPAM) and poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) were synthesized by the combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and click chemistry. The alkyne‐pending copolymer of PNIPAM or PDMAEMA was obtained through RAFT copolymerization of propargyl acrylate with NIPAM or DMAEMA. Bis‐2‐azidyl‐isobutyrylamide of cystamine (AIBCy) was used as the crosslinking reagent to prepare reducibly degradable hydrogels by click chemistry. The hydrogels exhibited temperature or pH stimulus‐responsive behavior in water, with rapid response, high swelling ratio, and reproducible swelling/shrinkage cycles. The loading and release of ceftriaxone sodium proved the feasibility of the hydrogels as the stimulus‐responsive drug delivery system. Furthermore, the presence of disulfide linkage in AIBCy favored the degradation of hydrogels in the reductive environment. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3604–3612, 2010     

Diterpenoid Alkaloids of Delphinium buschianum Grossh.

From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of ¹H‐, ¹³C‐, DEPT, ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.     

基于Fe3O4@Ag壳核结构磁性纳米复合物的对杀螟硫磷的电化学传感

制备一种壳核结构的Fe3O4@Ag磁性纳米粒子,将该纳米粒子通过壳聚糖（CS）修饰在玻碳电极（GCE）表面,制备了对杀螟硫磷有灵敏电化学传感的Fe3O4@Ag/CS/GCE。应用透射电镜（TEM）和紫外可见光谱（UV-VIS）,对Fe3O4@Ag纳米粒子进行表征。运用电化学交流阻抗（EIS）、循环伏安法（CV）和时间电流法（I-T）来研究杀螟硫磷电化学特性。研究发现,在1.74×10-7～3.27×10–4 mol/L浓度范围内,该传感器可以实现对杀螟硫磷的快速检测,检测限为5.7×10-8 mol/L（S/N=3）     

N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑的合成方法及表征

以2,7-二溴咔唑为原料经过N-烷基化、Suzuki偶联反应、Buchwald-Hartwig偶联反应合成了有机发光二极管(OLED)空穴传输材料N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑,利用NMR、IR和熔点等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了物质的热稳定性和光学性能。     

石墨消解-电感耦合等离子体质谱(ICP-MS)法测定铜精矿中汞的含量

称取0.2g样品于50mL样品管中,以5mL硝酸-盐酸(1∶1)混合溶液为溶剂,采用石墨消解仪对样品进行前处理。以159 Tb作内标元素补偿基体效应,用电感耦合等离子体质谱(ICP-MS)法对铜精矿中的202 Hg进行测定。结果显示,在0～50μg/L的浓度范围内,校准曲线线性相关系数在0.999 9以上,方法检出限0.019μg/L。对铜精矿标准样品的检测结果与标准值相符。铜精矿中汞的浓度在0.94～15.06μg/g时,与直接测汞仪检测结果对比基本一致。