油酰丝裂霉素及其脂质体的合成与抗肿瘤活性

用油酸与丝裂霉素Ｃ在缩合剂存在合成了油酰丝裂霉素Ｃ，利用元素分析，红外光谱及核磁共振等确定其结构，用改良的逆相蒸发法制成了油酰丝裂霉素Ｃ脂质体，动物实验表明该脂质体抗肿瘤效果为游离丝裂霉素Ｃ的２．２倍，而毒性仅为游离丝裂霉素的１／２０。     

一种简易液相色谱柱切换法测定血清中丝裂霉素的含量

丝裂霉素是目前广泛使用的一种抗癌药物,临床有多种给药方式,其疗效不尽相同,因此测定丝裂霉素在血中的浓度对了解某种给药方式的疗效无疑是很有意义的。目前丝裂霉素血药浓度的测定方法,一般采用Pinedo所介绍的高效液相色谱法,该法的血样前处理复杂,费时     

光谱法研究丝裂霉素、血清白蛋白以及金属离子间的相互作用

用荧光光谱法研究了抗癌药物丝裂霉素（ＭｉｔｏｍｙｃｉｎＣ）与血清白蛋白的相互作用,以及一些金属离子对丝裂霉素与牛血清白蛋白（ＢＳＡ）相互作用的影响。     

基于CdSe/ZnS量子点构建丝裂霉素荧光检测体系的研究

建立了一种基于CdSe/ZnS量子点的快速、高效的检测丝裂霉素的荧光方法。pH=7.4,反应10 min,CdSe/ZnS量子点的荧光随丝裂霉素浓度增加而猝灭,量子点的荧光强度与丝裂霉素的浓度呈良好的线性关系,适用于丝裂霉素浓度1.8~60 μmol/L,且相关系数为0.996,丝裂霉素的检测限为0.11 μmol/L,该方法相对无共存物质的干扰,并证明完全适用于丝裂霉素注射液与尿液中丝裂霉素的测定。     

单扫描极谱法测定丝裂霉素的研究

在NH3 NH4Cl(pH=10.5)底液中,用单扫描极谱法可以得到一个灵敏的丝裂霉素二阶导数还原峰,其峰电位Ep=-0.585V(vs.SCE)。峰电流与丝裂霉素浓度在9×10-7～4.5×10-5mol/L范围内呈线性关系(r=0.9992)。该法用于药物丝裂霉素的测定,结果令人满意。     

毛细管电泳-安培检测法用于7-甲基鸟苷与丝裂霉素C分离检测的研究

建立了一种同时分离检测7-甲基鸟苷与丝裂霉素C的毛细管电泳-安培检测方法。在950 mV电极(工作电极:0.3 mm微型石墨圆盘电极;参比电极:Ag/AgCl;辅助电极:Pt丝)电位下,于20 mmol/L的磷酸盐缓冲体系(pH 9.4)中,采用18 kV的分离电压进行分离。在最佳条件下,7-甲基鸟苷与丝裂霉素C在10 min内实现分离,7-甲基鸟苷与丝裂霉素C的线性范围均为0.50~50 mg/L,检测限分别为0.050 mg/L与0.025 mg/L。将该方法用于模拟尿样和模拟兔血清样的检测,7-甲基鸟苷与丝裂霉素C的回收率为93.0%～97.2%,结果令人满意。     

丝裂霉素C与牛血清蛋白结合作用的研究

结合光谱法与微量热法研究了水溶液中丝裂霉素C与牛血清白蛋白分子间的结合反应,测定了反应的结合常数K~A,结合位点数n及热力学函数△~rG~m,△~rH~m和△~rS~m,并确定了分子间作用力性质;依据Forster非辐射能量转移机制,确定了授体-受体间的结合距离和能量转移效率;采用同步荧光技术考察了丝裂霉素C对牛血清白蛋白构象的影响。     

丝裂霉素C与牛血清蛋白结合作用的研究

结合光谱法与微量热法研究了水溶液中丝裂霉素C与牛血清白蛋白分子间的结合反应,测定了反应的结合常数K~A,结合位点数n及热力学函数△~rG~m,△~rH~m和△~rS~m,并确定了分子间作用力性质;依据Forster非辐射能量转移机制,确定了授体-受体间的结合距离和能量转移效率;采用同步荧光技术考察了丝裂霉素C对牛血清白蛋白构象的影响。     

超高效液相色谱-串联质谱法测定兔血浆中的丝裂霉素C

建立了采用超高效液相色谱-串联质谱测定兔血浆中丝裂霉素C的方法。以兔空白血浆为基质,通过添加标准溶液的方法配制含丝裂霉素C和内标物曲安奈德的样品,选用乙酸乙酯为提取溶剂,液-液萃取法处理血浆样品。采用Hypersil Gold C18分析柱(50 mm×2.1 mm, 1.9 μm),流动相为甲醇-0.1%甲酸水溶液(90:10, v/v),等度洗脱,流速0.2 mL/min,柱温35 ℃,在3 min内实现了快速分离。采用电喷雾正离子(ESI+)模式电离,选择反应监测(SRM)模式检测,以曲安奈德作为内标物进行定量。用于监测的定量离子对分别为丝裂霉素C m/z 335.2→242.2和曲安奈德m/z 435.2→397.3/415.2,用基质匹配标准溶液法进行定量。结果表明: 兔血浆中丝裂霉素C的质量浓度在1～1000 μg/L范围内线性关系良好(r=0.9978,权重系数(weighting): 1/x2);血浆中丝裂霉素C的检出限(信噪比为3)为0.2 μg/L;其平均回收率为85%～ 115%;日内及日间的相对标准偏差(RSDs)均小于15%,满足生物样品检测的要求。该方法可用于兔气管外壁给药后的血浆样品中丝裂霉素C的检测。本方法选择性强、灵敏度高、操作简便快速、重现性好,适用于丝裂霉素C药代动力学等方面的研究。     

丝裂霉素C还原代谢机理研究

采用光谱电化学方法,结合循环伏安法、紫外-可见光谱、圆二色光谱等多种手段,提出了丝裂霉素C(MMC)的还原代谢机制。其还原活化为MMC首先从电极上得到一个电子,形成半醌自由基,随后脱去甲氧基形成吲哚半醌自由基,接着环乙亚胺基水解开环,最后吲哚半醌自由基歧化得到吲哚醌和吲哚氢醌。     

DTAB-月桂酸钠体系表面活性剂双水相研究

绘制和分析了十二烷基三甲基溴化铵（DTAB） 月桂酸钠（SL）组成的表面活性剂混合体系相图,系统研究了温度和无机盐等因素对该体系表面活性剂双水相 (ASTP) 影响的规律性.结果表明:与富含负离子表面活性剂双水相 (ASTP A) 相比较,富含正离子表面活性剂双水相(ASTP C)区域更大、更稳定;温度升高,无机盐(NaBr)的浓度增大,都引起 ASTP 体系上相体积的减小和下相体积的增加;囊泡普遍存在于ASTP的上下相之中.     

Aqueous surfactant two-phase systems in a mixture of cationic gemini and anionic surfactants

The phase behavior as well as the microstructures of the cationic gemini surfactant and anionic conventional surfactant aqueous two-phase system (ASTP) have been studied. The ASTP formation can be attributed to the coexistence of different kinds of aggregates in the upper and lower phases. The effects of temperature, shearing, surfactant concentration and mixing molar ratio on the phase separation of the ASTP-forming systems are systematically investigated. The ASTP can be destroyed by applying shear and increasing temperature. In this process, the lamellar structures (flat bilayers) in the ASTP are transformed into vesicles. Variation of surfactant structure also affects the phase behavior and the aggregates transformation. Appropriate molecular packing is crucial for the formation of ASTP.     

正、负离子混合表面活性剂双水相系统相图及微观 结构研究

研究了水/十二烷基硫酸钠(SDS)/十六烷基三甲基溴化胺(CTAB)三元相图上的双水相区及其相关性质,研究发现：该系统在两个非常狭窄的区域能够形成双水相,SDS过量的双水相区具有类似浊点的性质,上相有明显的偏光现象,而CTAB过量的双水相区则具有Krafft点性质,上相偏光现象较弱。冷冻蚀刻显微镜观察双水相的微观结构表明,上相为层状结构,下相一般为球状结构。双水相的体积比对正、负离子表面活性剂比例的微小变化非常敏感。     

SDS/CTAB/H2O的双水相性质及萃取作用

正负离子表面活性混合物;牛血清蛋白质;色氨酸;SDS/CTAB/H2O的双水相性质及萃取作用     

Contribution of sulfonyl-aromatic and sulfonic acid-aromatic interactions in novel sulfonyl/sulfonic acid-embedded reversed phase materials

Two novel sulfonyl-embedded reversed phase materials with sulfonic acid moieties (SO(X)-RP) were prepared by a simple oxidation of two silica-based sulfur-embedded RP-phases (S-RP). The chromatographic behavior of the resultant sulfonyl/sulfonic acid-embedded phase C3-SO(2)-C18/SO(3)H and the sulfonyl-embedded phase C3-SO(2)-C14 e.c. (silanol endcapped) was extensively elucidated with a number of well-established as well as self-assembled column tests. These SO(X)-RP phases were also compared with their corresponding S-RP phases as well as with two commercial carbonyl-containing RP phases (CO-RP) with amide- and urea-embedding. The SO(X)-RP phases were found to exhibit exceptionally high planar recognition ability for polyaromatic analytes at comparable retention times to the investigated CO-RP phases and highly reduced retention compared to the parent, non-oxidized S-RP-materials. The results of this study suggest that the selectivity enhancement observed with the S-oxidized phases is due to sulfonyl-pi and sulfonic acid-pi interactions. Furthermore these novel SO(X)-RP phases proved to be fully applicable under 100% aqueous mobile-phase conditions making them a useful alternative to conventional RP as well as polar-embedded CO-RP phases.     

两相催化体系中烯烃氢甲酰化的高区域选择性

采用水溶性铑膦配合物催化剂在两相(水/有机物)体系中进行长链烯烃氢甲酰化反应合成高碳醛,具有反应条件缓和、催化剂与产物容易分离的优点,而且用水作溶剂既便宜、又安全,有利于环境保护,因此引起国内外化学家重视,进行了大量研究[1,2].     

The significant effects of linear medium chain fatty alcohols on phase behavior of aqueous solution of mixed cationic–anionic surfactant

The effect of 1-hexanol on the phase behavior of aqueous solutions of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) has been systematically studied. The phase ranges of vesicle and liquid crystal (LC) can be greatly extended with the addition of 1-hexanol. These specific structures distributed symmetrically on the two sides of the SDS/CTAB equimolar line in the pseudo ternary phase diagram. The aqueous two phase system (ATPS) contained vesicles that would transform into lamellar LC with the change of ratio of SDS/CTAB. The phase behaviors of SDS/CTAB system with addition of different alcohols (C₅OH–C₈OH) showed similar trends in structural transition except for phase span, demonstrating that the obstruction of electrostatic interaction between surfactant polar heads was affected by the insertion depth of the added alcohols.     

甲基丙烯酸3-磺酸丙酯钾盐苯乙烯共聚物负离子与N,N,N-三甲基十六烷基溴化铵相互作用研究

聚电解质与表面活性剂相互作用研究已有很多报道[1～4],由于在很多方面与生物膜中脂质体-蛋白质间相互作用相似,从而近年来备受关注[5～6].作为带电荷的水溶性高分子,聚电解质与带相反电荷的表面活性剂分子可以形成规整性非常好的聚电解质表面活性剂复合物.Ａｎｔｏｎｉｅｔｔｔｉ等报道聚丙烯酸与十六烷基三甲基溴化铵(ＣＴＡＢ)形成规整的介规相(Ｍｅｓｏｐｈａｓｅ)聚电解质表面活性剂复合物结构[7],漆宗能等在同一体系既观察到了热致液晶也观察到了溶致液晶[8].在研究甲基丙烯酸3磺酸丙酯钾盐(ＳＰＭＳ)的苯乙烯(Ｓｔ)共聚物(Ｐ(ＳＰＭ…     

Investigation of interfacial and structural properties of CTAB at the oil/water interface using dissipative particle dynamics simulations

We have used dissipative particle dynamics (DPD) to simulate the system of cetyltrimethylammonium bromide (CTAB) monolayer at the oil/water interface. The interfacial properties (interfacial density, interfacial thickness, and interfacial tension), structural properties (area compressibility modulus, end to end distance, and order parameter), and their dependence on the oil/water ratio and the surfactant concentration were investigated. Three different microstructures, spherical oil in water (o/w), interfacial phase, and water in oil (w/o), can be clearly observed with the oil/water ratio increasing. Both the snapshots and the density profiles of the simulation show that a well defined interface exists between the oil and water phases. The interface thickens with CTAB concentration and oil/water ratio. The area compressibility modulus decreases with an increase in the oil/water ratio. The CTAB molecules are more highly packed at the interface and more upright with both concentration and oil/water ratio. The root mean square end-to-end distance and order parameter have a very weak dependence on the oil/water ratio. But both of them show an increase with CTAB concentration, indicating that the surfactant molecules at the interface become more stretched and more ordered at high concentration. As CTAB concentration increases further, the order parameter decreases instead because the bending of the interface. At the same time, it is shown that CTAB has a high interfacial efficiency at the oil/water interface.     

两相体系中钌膦配合物催化4—苯基—3—丁烯—2—酮加氢反应的研究

研究了水和有机物组成的两相催化体系中,由ＲｕＣｌ３－ＴＰＰＴＳ（ＴＰＰＴＳ：Ｐ（ｍ－Ｃ６Ｈ４ＳＯ３Ｎａ）３）原位反应生成的催化活性物种对４－苯基－３－丁烯－２－酮（又名苄叉丙酮）的催化加氢反应．考察了钌浓度（１．０×１０－３～６．０×１０－３ｍｏｌ／Ｌ）、氢压（１．０～６．０ＭＰａ）、反应温度（３０～７０℃）、配体浓度（１．２～７．２×１０－２ｍｏｌ／Ｌ）、阳离子表面活性剂（ＣＴＡＢ：十六烷基三甲基溴化铵）及反应时间等对加氢反应活性和选择性的影响,并与以配合物ＲｕＣｌ２（ＴＰＰＴＳ）３为催化剂前体生成的催化活性物种对加氢反应的活性及选择性进行了比较．结果表明,分别由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３及ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种,都只催化４－苯基－３－丁烯－２－酮的Ｃ＝Ｃ键选择加氢．由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３形成的催化体系的加氢活性及选择性均优于ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种．阳离子表面活性剂的加入,使加氢反应活性下降,选择性略有提高