流动注射胶束化学发光法测定西咪替丁的研究

在碱性条件下K3Fe(CN)6可直接氧化西咪替丁产生化学发光信号,吐温-80的存在可大大增强此反应的化学发光强度。基于此,建立了胶束流动注射化学发光法测定西咪替丁的新方法。在优化的实验条件下,该法的线性范围为1.0×10-7~5.0×10-4g/mL,检出限为2×10-8g/mL,相对标准偏差为1.6%(n=11,ρ=5.0×10-7g/mL)。该法已用于西咪替丁制剂中西咪替丁的测定。     

流动注射电化学发光测定利福平的研究

发现利福平对电生BrO-氧化Luminol的强化学发光有很强的抑制作用。将在线恒电流电解产生BrO-与流动注射技术结合,建立了流动注射电化学发光测定利福平的新方法。该方法线性范围为1×10-8～1×10-6g/mL,检出限为3×10-9g/mL,相对标准偏差为1.7%(n=11,c=2.0×10-7g/mL)。     

流动注射化学发光分析法测定三类磺胺类药物

研究发现可溶性锰(Ⅳ)氧化磺胺类药物(磺胺甲基异口恶唑、磺胺嘧啶和磺胺脒)可以产生弱的化学发光,甲醛对这一化学发光反应有较强的增敏作用,据此建立了一种测定磺胺类药物的流动注射化学发光分析法。该方法对3种磺胺类药物磺胺甲基异口恶唑、磺胺嘧啶、磺胺脒的检出限分别为2×10-8、3×10-8、2×10-8g/mL;线性范围分别为6.0×10-8~1.0×10-5、1.0×10-7~8.0×10-6、4.0×10-8~8.0×10-6g/mL。对6.0×10-6g/mL磺胺甲基异口恶唑、4.0×10-6g/mL磺胺嘧啶和4.0×10-6g/mL磺胺脒的相对标准偏差分别为1.1%、1.2%和2.2%(n=11)。此法已用于复方新诺明片剂中磺胺甲基异口恶唑的测定,结果与药典方法测定值一致。并对化学发光反应的机理进行了探讨。     

流动注射后化学发光法测定异烟肼

本文发现了异烟肼在铁氰化钾-钙黄绿素化学发光反应体系中的后化学发光反应。优化了反应条件,建立了一种利用后化学发光反应测定异烟肼的流动注射化学发光分析法。方法的检出限为6×10-8g/mL, 相对标准偏差为1.8% (2.0×10-6 g/mL 异烟肼,n=11）,线性范围为2.0×10-7~1.0×10-5 g/mL。此法已用于异烟肼片剂中异烟肼含量的测定,结果与药典方法测定值一致。     

流动注射化学发光法测定DL-酪氨酸

在甲醛存在下 ,高锰酸钾与DL 酪氨酸能够发生化学发光反应 ,产生很强的化学发光。据此采用流动注射技术 ,建立了一种测定DL 酪氨酸的化学发光分析法。方法的检出限为 2 .9× 1 0 - 8g/mL ,相对标准偏差为 1 .5 % ( 1 .0× 1 0 - 6g/mLDL 酪氨酸 ,n =1 1 ) ,线性范围为 1 .0× 1 0 - 7g/mL～ 5 .0× 1 0 - 6g/mL。     

流动注射化学发光法测定安痛定注射液中的氨基比林

在甲醛存在下 ,高锰酸钾与氨基比林能够发生化学发光反应 ,产生很强的化学发光 ,据此采用流动注射技术建立了一种测定氨基比林的化学发光分析法。方法的检出限为 3 .0× 10 -8g/mL ,相对标准偏差为 1.3 % (4 .0× 10 -6g/mL氨基比林 ,n =11) ,线性范围为 1.0× 10 -7～ 8.0× 10 -5g/mL氨基比林。该法已用于安痛定注射液中氨基比林含量的测定。     

流动注射电化学发光法测定头孢氨苄

根据在强酸性介质中初生态Mn(Ⅲ)直接氧化头孢氨苄产生强化学发光,将在线恒电流电解产生Mn(Ⅲ)与流动注射技术结合,建立了流动注射电化学发光测定头孢氨苄的新方法。在优化的实验条件下,测定头孢氨苄的线性范围为1.0×10-7~6.0×10-5g/mL,检出限为5×10-8g/mL,相对标准偏差为1.8%(c=5.0×10-6g/mL,n=11)。方法简便快速,用于头孢氨苄胶囊中头孢氨苄含量的测定,结果满意。     

流动注射结合化学发光法测定没食子酸

基于没食子酸与铬 (Ⅵ )的氧化还原反应 ,产生的铬 (Ⅲ )催化鲁米诺 H2 O2 化学发光体系的研究 ,结合流动注射技术 ,优化反应条件 ,建立了一种高灵敏度的快速测定没食子酸的新方法。方法的线性范围为 2 .0× 1 0 - 9～ 5 .0× 1 0 - 6g/mL ,检出限为 1 .2× 1 0 - 9g/mL ,对 1 .0× 1 0 - 7g/mL的没食子酸进行了 1 1次平行测定 ,相对标准偏差为 2 .1 %。方法成功地用于健民咽喉片中没食子酸的测定。     

铁氰化钾-鲁米诺体系后化学发光反应及其分析应用研究 ————-分子印迹-后化学发光法测定双嘧达莫

研究了双嘧达莫在铁氰化钾-鲁米诺化学发光反应体系中的后化学发光反应, 并在研究其反应的动力学性质、化学发光光谱、荧光光谱以及一些相关问题的基础上, 探讨了反应机理; 合成了双嘧达莫的分子印迹聚合物, 以此聚合物为分子识别物质, 利用铁氰化钾-鲁米诺-双嘧达莫后化学发光体系, 建立了测定双嘧达莫的高选择性分子印迹-后化学发光分析方法. 所建方法的线性范围为1.0×10-8-1.0×10-6 g/mL(r=0.999 2), 检出限为3×10-9 g/mL, 相对标准偏差为2.7%(1.0×10-7 g/mL双嘧达莫, n=11).     

流动注射化学发光抑制法测定吡罗昔康

基于吖啶橙在氢氧化钠介质中能被高锰酸钾氧化产生较强的化学发光,吡罗昔康能强烈抑制其化学发光,建立了高锰酸钾-吖啶橙-吡罗昔康化学发光抑制测定吡罗昔康的新方法。吡罗昔康在1.0×10-5~7.0×10-4g/mL范围内与化学发光强度呈良好线性关系,方法的检出限为4.5×10-6g/mL,对1.0×10-5g/mL吡罗昔康连续进行6次测定的相对标准偏差为3.6%。     

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.