肽类药物口服剂型材料及控制释放性能研究：Ⅰ.壳聚糖—海藻酸盐？…

应用壳聚糖－海藻酸盐微囊技术制备了一系列胰岛素微型,并研究了不同反应条件如海藻酸钠浓度,壳聚糖浓度,壳聚糖分子量及壳聚糖溶液ｐＨ值对生囊的胰岛素包封率及其释放性能的影响。结果表明,海藻酸钠浓度越高,微囊对胰岛素的包封率越高,在模拟小肠液中释放速度越低;壳聚糖浓度越大,微囊的胰岛素包封率及其在模拟胃液中释放率越高,在模拟肠液中释放达最大值所需时间越长;而随壳聚糖分子量减小,微囊在胃液中释放率增高;壳     

THE RETENTION BEHAVIOR OF ARSENIC COMPOUNDS ON PRP-X100 COLUMN UNDER ALKALINE CONDITION

系统地研究了碱性条件下（ｐＨ８～１０．８）Ａｓ３＋，Ａｓ５＋，ＭＡ，ＤＭＡ和ＡＢ等砷化合物在ＰＲＰ－Ｘ１００阴离子交换柱上的保留行为。用火焰原子吸收光谱（ＦＡＡＳ）测定从ＨＰＬＣ分离的砷化合物，即通过一根１ｍ×０．２３ｍｍｉ．ｄ．不锈钢毛细管，将ＨＰＬＣ柱出口与ＦＡＡＳ的雾化器连接起来，采用乙炔／空气火焰，在１９３．７ｎｍ处测定。具体研究了两个流动相（２０ｍｍｏｌ／ＬＮＨ４ＨＣＯ３和２．５ｍｍｏｌ／Ｌ对－羟基苯甲酸－１．０ｍｍｏｌ／Ｌ苯甲酸水溶液），并系统研究了ｐＨ值和缓冲液浓度对上述５个砷化合物的保留时间的影响，发现对于２０ｍｍｏｌ／ＬＮＨ４ＨＣＯ３体系，在ｐＨ８．７时，ＡＢ，Ａｓ３＋，ＤＭＡ可以得到完全分离，通过梯度洗提（ｐＨ８．７到９．８，流速１．６５ｍＬ／ｍｉｎ），在１５ｍｉｎ内上述５个砷化合物可以得到良好分离；对于２．５ｍｍｏｌ／Ｌ对－羟基苯甲酸－１．０ｍｍｏｌ／Ｌ苯甲酸体系，在ｐＨ９．０及流速１．５ｍＬ／ｍｉｎ时，可以在１２ｍｉｎ内将上述５个砷化合物分离。     

壳聚糖对Zn2+的吸附性能研究

本文用壳聚糖对Ｚｎ＾２＋的吸附条件进行了研究,探讨了脱乙酰度,分子量,粒度大小,溶液的ｐＨ值,温度,Ｚｎ＾２＋起始浓度和不同锌盐等方面对壳聚糖吸附性能的影响。结果表明：壳聚糖对Ｚｎ＾２＋的吸附具有Ｌａｎｇｍｕｉｒ吸附特征,其吸附最佳条件是壳聚糖脱乙酰度为１００％,锌盐为硫酸锌,Ｚｎ＾２＋溶液ｐＨ值为６．０,起始浓度４－５ｍｇ／ｍｌ。     

脱乙酰壳多糖化学修饰电极测定铂的研究

用脱乙酰壳多糖修饰电极为工作电极，阳极溶出伏安法测定痕量铂。在ｐＨ＝２￣３的ＫＣｌ－ＨＣｌ底液中，－０．３Ｖ富集２ｍｉｎ，静止１５ｓ，以０．２Ｖ／ｓ扫速阳极溶出，峰电位在－０．１６Ｖ（ｖｓ．ＳＣＥ），铂（Ⅳ）离子浓度在０．５￣５．０μｇ／ｍＬ范围内与峰高呈线性关系。富集１０ｍｉｎ后，可检测０．０２５μｇ／ｍＬ铂（Ⅳ）。该法用于贵金属矿样的测定，无需分离，结果满意。用循环伏安法、紫外光谱和拉曼光谱研     

中性蛋白酶对壳聚糖的降解

用粘度测定法和还原糖测定法,研究了中性蛋白酶非专一性降解壳聚过程中温度,ｐＨ值,反应时间,酶浓度,底物浓度,金属离子及壳聚糖的脱乙酰度对中性蛋白酶降解壳聚糖反应速度的影响,确定了以壳聚糖为底物的中性蛋白酶的一些催化特性：最适温度为５０℃;最适ｐＨ值为６．０;米氏常数Ｋｍ值为１．１×１０＾－２ｇ／ｍＬ;一定浓度的Ｃｕ６２＋,Ｂａ＾２＋,Ｍｎ＾２＋抑制该酶的活性;     

毛细管区带电泳电化学检测法测定药物及果汁中芦丁和L— …

用毛细管区带电泳－电化学检支同时测定复方芦丁片及果汁中芦丁和Ｌ－抗坏血酸的含量。研究了电极电位、电解液浓度和酸度、电泳电压及进样时间等对电泳的影响,得到了较为优化的测定条件。以直径为３００ｕｍ的碳圆盘电极为检测电极,电极电位为１．０Ｖ（υｓ．ＳＣＥ）,在２５０ｍｍｏｌ／Ｌ硼砂－５０ｍｍｏｌ／Ｌ ＮａＨ２ＰＯ４（ｐＨ ８．０）运行缓冲液中,上述两组分在１２ｍｉｎ内完全分离。芦丁和Ｌ－抗坏血酸浓度分别     

高效离子交换液相色谱法分离绿脓杆菌外膜蛋白

利用高效ＤＥＡＥ离子交换液相色谱法分离纯化了绿脓杆菌标准菌株ＰＡＯ１外膜蛋白。流动相为ｐＨ８．０Ｔｒｉｓ－ＨＣｌ缓冲液,色谱柱为ＴＳＫｇｅｌ－ＤＥＡＥ－５ＰＷ（０．７５ｃｍ×７．５ｃｍｉ．ｄ．）。通过纯化外膜蛋白,可以为研究绿脓杆菌外膜通透性与抗生素耐药性之间的关系及缩短研究周期提供有效的方法。     

基体溶液pH值对基体辅助激光解吸电离质谱法测定结果的影响

研究了基体溶液的ｐＨ值对基体辅助激光解吸电离（ＭＡＬＤＩ）的影响，测定了从强酸至强碱不同ｐＨ值的α－氰基，４－羟基肉桂酸水溶液的紫外吸收谱，并分别用作基体测定细胞色素Ｃ的相对分子质量。结果显示除按常规配制的基体溶液（ｐＨ＝２．５）在激光波长３５５ｎｍ处有强紫外吸收外，其他ｐＨ＝１．０、ｐＨ＝８．０、ｐＨ＝１０．０的溶液皆没有吸收，而相对分子质量测量结果是ｐＨ＝１．０和ｐＨ＝２．５两种溶液可得到质量     

高效毛细管电泳,激光干涉检测快速分离二糖研究

首次报道一种高效毛细管电泳、激光干涉折射检测快速分离二糖的新方法。详细研究了四硼酸钠溶液中，ｐＨ值、四硼酸钠浓度及有机添加剂对二糖－硼酸络离子迁移行为的影响，发现在ｐＨ为９．７的０．１ｍｏｌ／Ｌ四硼酸钠溶液中，１０ｍｉｎ内４种二糖得到基线分离。采用自制激光干涉型折射指数检测器，不需对二糖衍生化处理，可直接进行在柱检测。     

金在脱乙酰壳多糖学修饰电极上的电化学行为及分析应用

用脱乙酰壳多糖化学修饰电极为工作电极，阳极溶出伏安法测定痕量金。在ｐＨ１￣２的ＫＣｌ－ＨＣｌ底液中，超始电位０．２０Ｖ，终止电位１．３０Ｖ，富集时间５ｍｉｎ，以－０．１／ｓ扫速阳极溶出，峰电位在１．００Ｖ（ｖｓ．ＳＣＥ），Ａｕ（Ⅲ）浓度在０．１０ｍｇ／Ｌ￣１０ｍｇ／Ｌ范围内与峰高呈线性关系。在富集１０ｍｉｎ时，可检测０．２５ｍｉｇ／ＬＡｕ，大大提高了测定灵敏度，用于矿样测定，无需分离，结果满意。用     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.