花菁-脱氧核糖核酸的共振光散射光谱及其分析应用

研究了一种苯并噻唑阳离子花菁与脱氧核糖核酸(DNA)作用的共振光散射光谱,在pH 6.0的六次甲基四胺-HCl缓冲介质中,痕量DNA的加入使花菁在590nm的共振光散射强度显著增强。在最佳实验条件下,增强的共振光散射强度与DNA浓度具有良好的线性关系,据此建立了一种测定DNA的共振光散射光谱法。方法的线性范围为:小牛胸腺DNA(CT DNA),0～20μg/mL,鱼精子DNA(FS DNA),0～15μg/mL;检出限分别为0.005μg/mL和0.008μg/mL。该方法已用于合成样品中DNA的测定。     

吖啶橙共振光散射法测定痕量脱氧核糖核酸

研究了三环杂芳香类染料吖啶橙(AO)与DNA作用的共振光散射光谱,在pH11．5～12．5的范围内,加入DNA导致吖啶橙共振光散射增强,在339nm处,存在一共振光散射增强峰,其强度与DNA浓度呈线性关系,据此建立了一种测定DNA的共振光散射新方法?对于ctDNA,方法的线性范围为14．3～1000μg／L,检出限为2．86μg／L,RSD为3．6％;对于fsDNA,方法的线性范围为24．0～1250μg／L,检出限为4．78μg／L,RSD为6．0％。已用于合成样品中DNA的测定。     

溴代十六烷基三甲基铵敏化吡罗红B-核酸作用的共振光散射增强法测定核酸

基于表面活性剂溴代十六烷基三甲基铵（CTMAB）对吡罗红B-核酸作用的共振光散射增强效应有敏化作用,建立了一种高灵敏测定核酸的新方法。在pH7．4时,吡罗红B在328nm处的共振光散射的增强与核酸浓度有良好的线性关系。在最佳实验条件下,对小牛胸腺DNA（ct-DNA）、鲱鱼精DNA（fs-DNA）、酵母RNA（yeast—RNA）测定的线性范围分别为0．0～1．2mg／L、0．0～0．8mg／L和0．04～1．4mg／L。检出限分别为6．1μg／L、11．2μg／L和8．6μg／L。该法简便、快捷、重现性好,对合成样品进行了测定,结果令人满意。     

甲基紫6B共振光散射法测定脱氧核糖核酸

基于甲基紫6B与脱氧核糖核酸在酸性条件下共振光散射的增强效应，建立了测定DNA的共振光散射法。在pH值为2．0～3．0的三羟甲基氨基甲烷一盐酸缓冲溶液中，甲基紫6B与fsDNA、ctDNA分子作用后共振光散射增强，其强度增加值与DNA的浓度呈线性关系，线性范围分别为0～1．0、0～1．5mg／L，相关系数分别为0．9993、0．9997，检出限分别为15．3、12．2ug／L，用于DNA合成样品的测定，测定结果的精密度、准确度较高。     

天青Ⅰ共振光散射法测定DNA

基于脱氧核糖核酸(DNA)对混合有机染料天青Ⅰ的共振光散射增强效应,拟定了一种测定DNA的共振光散射法。在pH9.5～10.5的范围内,天青Ⅰ在299、355、400、570、630nm附近均有较弱的共振光散射信号,随着DNA的加入,共振光散射信号大大增强。在355nm处,其散射光增强强度与DNA质量浓度呈线性关系。其线性回归方程为ΔI=-96.62 606.6ρ,线性范围为0 20～0.60μg mL,相关系数r=0.9998,检出限为11.2μg L。该方法可应用于合成样品中DNA的测定。     

荧光素共振光散射法测定脱氧核糖核酸

研究了咕吨类染料荧光素Fluorescein(FL)与DNA作用的共振光散射光谱。加入DNA后,在pH6～8的范围内,荧光素在DNA分子表面发生长距离自组装,在400nm处产生了增强的共振光散射峰,其发光强度与DNA的浓度呈线性关系,线性范围为0．04～3．1mg／L;检出限为16μg／L。考察了影响因素和最佳反应条件,建立了用RLS光谱测定ng级DNA的新方法。     

溴化十六烷基吡啶的双波长共振光散射比率法测定

应用双波长共振光散射（DW—RLS）比率法研究了溴百里酚蓝（BTB）与阳离子表面活性剂溴化十六烷基吡啶（CPB）的相互作用。在pH1．5的乙酸钠-HCl缓冲溶液中,CPB本身的共振光散射很弱,BTB有一定的共振光强度,加入CPB后BTB的共振光信号显著增强,最大散射峰位于523nm,且散射光强度与CPB的浓度呈线性关系,可以通过单波长共振光散射法检测CPB,CPB质量浓度的线性范围和检出限分别为0．05—0．60mg／L和42μg／L。使用248nm和424nm两波长处散射强度比值（I248／I424）代替单波长处的共振光散射强度测定CPB,其线性范围和检出限分别为0．03～1．0mg／L和3μg／L。与共振光散射法相比较,DW—RLS比率法受酸度、离子强度等环境条件影响较小,并且有更宽的线性范围和更低的检出限,应用于合成和实际水样中CPB的测定,获得较好的结果。     

两性离子表面活性剂作为共振光散射探针测定脱氧核糖核酸

将两性离子表面活性剂用于DNA的共振光散射测定。在pH值为7．96～9．40较宽的范围内,DNA与椰油酰胺丙基-2-羟基-3-磺基丙基甜菜碱(HSB)在392nm处有稳定的共振光散射增强,其强度与DNA浓度呈线性关系,建立了一种测定DNA的新方法。线性范围为0．02—4．25mg／L;检出限达1．5μg／L。该法简便、快速,用于合成样品中DNA的测定,重现性好,结果满意。同时探讨了有关机理。     

罗丹明S与热变性DNA作用的共振光散射光谱研究及其应用

研究了小分子染料罗丹明S与热变性脱氧核糖核酸(DNA)在弱酸性条件下共振光散射光谱的特征.考察了各种影响因素,在优化条件下确立了共振光散射强度与鱼精DNA和小牛胸腺DNA浓度之间的线性关系,相应的线性范围分别为0.024～3.00,0.018～3.50 mg·L-1;相关系数为0.998 6,0.999 0;检出限为24.0,18.3μg·L-1;基于共振光散射的增强,建立了一种测定DNA的方法.     

同多酸和染料探针共振光散射法测定蛋白质

在酸性条件下,铬黑T、钼酸铵与蛋白质形成聚合物,使体系的共振光散射明显增强。据此建立了利用共振光散射技术测定总蛋白含量的新方法。在最佳条件下,体系的最大散射峰位于555nm处。共振光散射增强的程度与蛋白质的浓度呈良好的线性关系。牛血清白蛋白和人血清白蛋白的线性范围分别为0.20～10.0μg/mL和0.10～8.0μg/mL,检出限为0.050μg/mL和0.039μg/mL。方法已用于人血清样品的分析,并与考马斯亮蓝的测定结果进行了比较,两者无显著性差异。     

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.