对乙酰基偶氮氯膦-钡(Ⅱ)-乳化剂OP分光光度法测定蛋白质

提出了借对乙酰基偶氮氯膦(CPApA)-钡(Ⅱ)-乳化剂OP与蛋白质显色反应分光光度法测定蛋白质的高灵敏方法。在pH2.5Britton-Robinson缓冲介质中,蛋白质可与CPApA-钡(Ⅱ)-乳化剂OP形成蓝色复合物,蛋白质的加入可使Ba(Ⅱ)-CPApA配合物溶液增色且增色程度与蛋白质的质量浓度成正比。体系的最大吸收波长位于362nm,测定白蛋白(BSA)表观摩尔吸光系数3ε62nm=6.11×105L.moL-1.cm-1,BSA在0~20mg/L浓度范围内遵守比耳定律。加入乙醇可提高体系的稳定性和灵敏度。表面活性剂OP的加入,显著地提高体系的稳定性。血清中常见组分不干扰蛋白质的测定。所提出的方法可用于人血清样品中蛋白质总量的测定。     

二苯氨基脲-乳化剂OP分光光度法测定钢中微量钒

测定钒的胶束增溶分光光度法绝大多数是阳离子表面活性剂体系,非离子表面活性剂体系则很少被研究。本文研究了在非离子表面活性剂乳化剂OP存在下,二苯氨基脲(DPC)和钒的显色反应和光度特性,拟定了用该体系测定微量钒的条件和方法。试验表明,络合物最大吸收位于544 nm处,0—30μg/50mL钒符合比尔定律,摩尔吸光系数为7.6×10~4,络合物组成比为V:DPC=1:2,室温下5min显色完全.     

共振光散射测定蛋白质的新方法

在非离子表面活性剂OP存在下,姜黄素能与蛋白质发生作用。研究表明,蛋白质与非离子表面活性剂OP可协同增强姜黄素的共振光散射强度,其增强程度与蛋白质的浓度在一定范围内呈良好的线性关系。在8×10-5mol.L-1姜黄素和3∶10 000的非离子表面活性剂OP存在下,该法测定牛血清白蛋白(BSA)和人血清白蛋白(HSA)的线性范围分别为0.001～10μg.mL-1和0.001～1μg.mL-1,检出限分别为0.23 ng.mL-1和0.89 ng.mL-1。方法已用于实际样品的测定,其结果令人满意。     

矿石中微量铍的测定——铬天青S-聚乙二醇辛基苯基醚分光光度法

近年来应用表面活性剂,提高铬天青S(CAS)光度法测定铍的灵敏度的报道日益增多,但多数是应用阳离子表面活性剂作增感剂。本文应用非离子表面活性剂-聚乙二醇辛基苯基醚(乳化剂OP),在溶液pH4.0～6.0的条件下,铍与CAS及OP生成三元络合物,最大吸收峰在620毫微米处,摩尔吸收系数ε=8.75×10~4。采用EDTA作掩蔽剂消除干扰离子的影响。本法可不经分离直接用于矿石中微量铍的测定,结果良好。     

乳化剂OP存在下蛋白质与虎红的超分子显色反应研究及分析应用

在pH 2.36～3.29 的Britton-Robinson缓冲介质中,在乳化剂OP存在条件下,虎红与蛋白质发生超分子显色反应形成红色的超分子复合物,该超分子复合物的最大吸收波长为565 nm,而试剂的最大吸收波长为568 nm,紫移了3 nm.在565 nm处考察了多种蛋白质的响应情况,结果表明测定牛血清白蛋白(BSA)、人血清白蛋白(HSA)及γ-球蛋白(IgG)时具有高灵敏度,它们的表观摩尔吸光系数ε565和桑德尔灵敏度s分别为1.836×106、 2.213×106、 2.932×106 L·mol-1·cm-1,和0.036、 0.031、 0.061 μg/cm,其线性范围分别为2～36、 2～36 和2～40 mg/L.除阴、阳离子表面活性剂外,其余大部分物质不干扰蛋白质的测定.所拟方法应用于新鲜人尿液和人血清中总蛋白的测定,结果与考马斯亮蓝G-250法基本一致.     

OP存在下苯基萤光酮光度法测定多金属矿物中微量锗

在阳离子表面活性剂存在下,应用苯基萤光酮光度测定锗的方法已日益增多,而非离子表面活性剂OP在测定矿石中锗方面的应用尚未见报导。本实验结果表明,OP同样能显著提高苯基萤光酮(PF)-锗的显色反应的灵敏度。在25毫升显色液中维持酸度为0.08—2.5NHCl,1—4毫升10%OP和0.5—6毫升0.06%PF时,络合物吸光度最大且恒定,在505nm处有最大吸收,在0—10微克锗/25毫升范围内遵守比尔定律,络合物的摩尔吸光系数ε_(505)=1.3×10~5,组成比为Ge:PF=1:2。显色后5分钟即达完全并可     

在β-环糊精和阳离子表面活性剂作用下5-Br-TADEB 分光光度法测定微量铑

研究了在 β-环糊精 ( β- CD)和各种不同类型表面活性剂存在下 5-溴 - ( 2 -噻唑偶氮 ) - 5-二乙氨基苯甲酸 ( 5- Br- TADEB)与铑的显色反应。在 p H 4.0～5.7的 HAc- Na Ac介质中 ,Rh3 +与 5- Br- TADEB形成稳定的 1∶ 2蓝色络合物 ,最大吸收波长位于 687nm处。阴离子和非离子表面活性剂对体系无明显作用 ,β- CD和阳离子表面活性剂分别加入使体系灵敏度提高 2 0 % ,而当 β- CD与阳离子表面活性剂同时加入则可使体系灵敏度提高 50 % ,其表观摩尔吸光系数ε=1 .1 4× 1 0 5L·mol-1·cm-1。该方法已用于含铑催化剂中微量铑的测定     

5-Br-PADAP分光光度法测定微量锇(ⅤⅢ)

2-(5-溴-2-吡啶偶氮)-5-二乙氨基苯酚(简称5-Br-PADAP)是很灵敏的显色剂,它已用于光度法测定铜、锰、铀、铑等多种离子,都获得了满意的结果。本文系统地研究了Os(Ⅷ)-5-Br-PADAP-OP(OP的全名为聚乙二醇辛基苯基醚)体系的显色反应条件及用于光度法测定锇(Ⅷ)的可能性。实验证明,在非离子表面活性剂OP的存在下,锇(Ⅷ)与5-Br-PADAP形成可溶于水的紫红色络合物,最大吸收波长在580nm,反应适宜     

刚果红-OP-蛋白质体系共振光散射特性的研究及牛尿中白蛋白的测定

蛋白质的测定对于生命科学的研究、临床诊断和疾病的治疗均有十分重要的意义~([1]).本文研究了刚果红(Congo Red,CR)与牛血清白蛋白的相互作用.实验表明:在非离子表面活性剂聚乙二醇辛基苯基醚(乳化剂OP)的存在下及pH=4.35的B-R缓冲介质中,蛋白质与刚果红形成复合物,使573 nm处的共振散射光谱得到加强,并且增强的共振光散射信号与蛋白质的浓度成正比.据此,建立了共振光散射技术测定微量蛋白质的新方法.     

铬天青S-Cu(Ⅱ)配合物探针吸光光度法测定蛋白质的研究

在pH 5.0 B-R缓冲介质中,蛋白质与铬天青S-Cu（Ⅱ）配合物发生结合反应形成超分子复合物,使体系的最大吸收波长红移了30 nm,由此提出了普通光度法测定蛋白质（BSA）的新方法。最佳条件下,该复合物的最大吸收波长位于620 nm处,表观摩尔吸光系数ε=6.13×105L.mol-1.cm-1,蛋白质（BSA）量在10-60μg/mL范围内遵循比耳定律。方法可直接用于蛋清中蛋白质的测定,回收率为100%-105%。     

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.