腙类配合物的研究——Ⅱ.二茂铁芳酰基腙和它们的一些过渡金属螯合物

通过甲酰基二茂铁与相应芳酰基肼的缩合反应合成了二茂铁基的苯甲酰基、对-甲氧基苯甲酰基和间-硝基苯甲酰基腙,并制备了它们与Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Mn(Ⅱ)醋酸盐的十种整合物。元素分析、IR和PMR谱的测定结果表明,这些金属有机配体是以烯醇式进行配位的。     

卟啉超分子化合物在分子器件中的应用

分子电子器件已成为近年来的一个研究热点，卟啉类化合物因为光敏性好、性能稳定、易于修饰等优点成为分子器件研究的理想模型化合物。本文着重介绍了它在分子器件中的最新应用进展。     

富勒烯四甲氧基衍生物的合成与表征

富勒烯四甲氧基衍生物的合成与表征甘良兵，周胜，姜剑峰，黄春辉（北京大学化学与分子工程学院，北京，１００８７１）武轶，吕木坚，潘景歧（北京微量化学研究所）（北京大学分析测试中心）关键词Ｃ＿６０衍生物，甲氧基，四氮杂环十二烷富勒烯化学是目前人们研究的热门...     

Determination of pefloxacin in serum and pharmaceutical forms by derivative spectrophotometry

A method for the direct determination of pefloxacin in serum and pharmaceutical forms (tablets and ampoules) has been developed, based on the use of second-order derivative ultraviolet spectra. Spectrophotometric assay of pefloxacin in tablets and ampoules was carried out in 0.1 mol/L NaOH, while in serum it was performed in 0.1 mol/L NaOH with the addition of sodium dodecylsulfate, in 337–347 nm wavelength range. Linear calibration curves were obtained in the concentration ranges 2–30g/mL pefloxacin for tablets and ampoules and 0.12–5 g/ mL for serum samples. Relative error of determination, as criterion for accuracy, was less than 1%, while the precision was better than 4 ng/ml. The minimum detectable concentration of pefloxacin in serum was 15 ng/mL.     

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade^?1 in the concentration range of 10^?1–10^?5 mole L^?1, a detection limit of 1×10^?5 mole L^?1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. , benzoate, I^?, SCN^?). Selectivity was confirmed by calculating the formation constant (K_β) using sandwich membrane method, where K_β for TUD1‐salicylate is 10^0.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (β_HRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of β_HRS, and the shortest lengths of the four N?H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®.     

手性环丙烷类衍生物双水解转换的研究

具有四个新手性中心的螺环／环丙烷类化合物4在丙酮－12％HCl溶液中50℃下 发生双手性辅基－双水解转换反应，得到了手性环丙烷／双半缩醛类化合物，螺 [1-溴－4－羟基－5－氧杂－6－氧代双环[3.1.0]己烷－2，2′-(3′-亲核氧基－ 4′－羟基丁内酯）]（5），化学产率65％－79％，光学纯度ee≥98。通过元素分 析，[a]D^20,UV,IR,^1H NMR,^13C NMR,MS以及X射线四圆衍射测定，确认了它们的 化学结构、立体化学和绝对构型。该双半缩醛类化合物的合成方法学研究可为官能 团的转换，为某些复杂结构的手性化合物提供新的合成方法和途径。     

Design and Synthesis of Glycosylated Aromatic Nitrogen Mustard Derivatives

Antibody-directed enzyme prodrug therapy(ADEPT) is a new strategy for the treatment of cancer that has arisen in recent twenty years, the main merits of which are that it can improve the selectivity of anticancer drugs and reduce the side effects in remote tissue. In the present study, two prodrugs-glycosylated aromatic nitrogen mustard derivatives were synthesized. Glucose and lactose were converted into glycosyl donors-trichloroacetimidate; the obtained glycosyl donors were glycosylated with p-nitrophenol(glycosyl donors) to form β-glucosyl p-nitrobenzene and β-lactosyl p-nitrobenzene that were protected by acetyl in a stereoselective manner; the two products were reduced by zinc dust and then treated with ethylene oxide, afforded two glycosylated nitrogen mustard derivatives that were protected by acetyl; the last step was to deacetylate and then afforded the two target compounds that could be used as prodrugs of ADEPT for further Anti-tumor research.     

弱酸树脂D113对S-腺苷-L-蛋氨酸的交换行为及分离应用研究

考察了S-腺苷-L-蛋氨酸 (S-adenosyl-L-methionine, SAM) 在弱酸树脂争光D113上的静态吸附及分离行为,利用Langmuir等温式对平衡等温线进行了拟合,实验表明,随着pH的提高,平衡交换量增加,提高温度和SAM的初始浓度在一定程度上能促进内扩散过程,利用D113树脂在f 1.7×30.0cm小型柱上从酵母提取液中分离SAM的得率为90%以上,纯度达87%以上。     

Enantioseparation in capillary electrophoresis using 2-O-(2-hydroxybutyl)-beta-CD as a chiral selector

The resolving ability of 2-O-(2-hydroxybutyl)-beta-CD (HB-beta-CD) with different degrees of substitution (DS = 2.9 and 4.0) as a chiral selector in CZE is reported in this work. Fourteen chiral drugs belonging to different classes of compounds of pharmaceutical interest such as beta-agonists, antifungal agents, ageneric agents, etc., were resolved. The effects of the DS of HB-beta-CD on separations were also investigated. The chiral resolution (R(s)) was strongly influenced by the concentrations of the CD derivative, the BGE, and the pH of the BGE. Under the conditions of 50 mmol/L Tris-phosphate buffer at pH 2.5 containing 5 mmol/L HB-beta-CD, all 14 analytes were separated. The very low concentration necessary to obtain separation was particularly impressive. The DS had a significant effect on the resolution of the chiral drugs and the ionic strength of the separation media; hence, the use of a well-characterized CD derivative is crucial.