催化K2S2O8氧化靛红固体基质室温磷光法测定痕量Se(V)

基于痕量Se4+催化K₂S₂O₈氧化靛红（Isa）的灵敏反应而导致体系的磷光剧烈猝灭的学术思想,建立了一种高灵敏（检出限（LD）为0.015 pg/mL）催化固体基质室温磷光法(SS RTP)测定痕量Se（IV)的新方法。方法的线性范围为4.00×10–8~4.00×10–6 μg/mL。工作曲线的回归方程为△I_P=2.948+63.24C_Se(IV)(pg/mL),n = 7。相关系数( r )为 0.9997。方法已成功用于水样中痕量Se（IV）的测定,结果与紫外分光光度法相吻合,并探讨了测定痕量Se（IV）的反应机理。     

固体基质室温燐光猝灭法测定人发和水中痕量汞

基于水杨基荧光酮羧甲基纤维素铅发光分子微球(Pb(CMC)2-THBF)在滤纸基质上可发射强而稳定的室温燐光,由此建立了Pb(CMC)2-THBF固体基质室温燐猝灭测定痕量汞的新方法.Hg2 的含量在2.5~100.0(pg/mL)内与ΔIp值成线性关系,其线性回归方程为ΔIp=12.73 0.4699CHg2 (pg/mL),r=0.9991,检出限为3.2×10-13g/mL.该方法用于人发和水样中痕量汞的测定,结果满意.同时探讨了固体基质室温燐光猝灭测定痕量汞的机理.     

4.0代树枝状分子-卟啉标记伴刀豆凝集素亲和吸附固体基质室温磷光法测定人血清中甲胎蛋白异质体

提出一种4．0代树枝状分子（4.0G-D）-卟啉（P）双发光分子新的磷光标记试剂（4．0G-D-P）．基于4．0G-D-P标记伴刀豆凝集素（ConA）的产物（4.0G-D-P-Con A）能在聚酰胺素膜（PAM）上发射强而稳定的室温磷光（RTP）,而且该标记产物能与甲胎蛋白异质体（AFP-V）发生特异性的亲和吸附（AA）反应,其反应产物保持了4．0G-D-P双发光分子RTP的优良特性,且△Ip值与AFP-V的含量呈线性关系,加入Tween-80可以提高△Ip值,据此建立了Tween-80—4．0G-D-P双发光分子标记Con A亲和吸附固体基质室温磷光法（AA-SS-RTP）测定人血清中AFIP-V的新方法．直接法的检出限为0．31pg／mL（4．0G-D）和0．43pg／mL（P）,灵敏度较高．无论用4．0G-D或P的激发／发射波长测定人血清中AFP-V的含量,结果与酶联免疫法（ELISA）相吻合．     

以滤纸为基质室温磷光法测定痕量多环芳烃的研究

1 前言 固体基质室温磷光法(SS-RTP)是一种发展很快的微量技术与痕量分析相结合的新技术.SS -RTP法以其简便、快速、灵敏的特点在环境污染物及药物分析方面得到了广泛的应用 [1],尤其对于痕量多环芳烃的分析十分有效.文献报道过应用环糊精诱导室温磷光法 [2]和胶束增稳室温磷光法[3]测定的方法.本文用国产快速定量滤纸作固体基质,探讨了测定萘、苊和屈磷光发光的条件,建立了以滤纸为基质的测定痕量萘、苊和屈的SS-RTP法.     

催化K2S2O8氧化亚甲基蓝固体基质室温磷光法测定痕量Bi(Ⅲ)

基于Bi(Ⅲ)能催化K₂S₂O₈氧化亚甲基蓝(MB)的反应,使MB的室温磷光（RTP）强度剧烈猝灭,且Bi(Ⅲ)的含量与体系的?IP成线性关系,据此可建立Bi(Ⅲ)催化K₂S₂O₈氧化R固体基质室温磷光法(SS RTP)测定痕量Bi(Ⅲ)的新方法。方法的线性范围为0.040~1.0 ×10-15 g/mL,工作曲线的回归方程?I_P=2.336+27.26×10–15C_Bi3+(g/mL),n=6,相关系数r=0.9980,检出限（LD）为1.9 ×10–15 g/mL,RSD为2.1%。方法灵敏、简便、快速、选择性与重现性好,用于水样品中痕量Bi(Ⅲ)的测定,结果满意。同时,讨论了催化K₂S₂O₈氧化MB SSRTP测定痕量Bi(Ⅲ)的反应机理。     

基于可控相转变温度热敏高分子的人IgG酶联荧光免疫分析

以温度敏感高分子聚N－异丙基丙烯酰胺－丙烯酰胺[P(NIP-AA)]作为载体,建立了酶联荧光免疫分析人IgG的新方法。AA摩尔含量为8％的高分子P(NIP-AA)其临界溶解温度为37 °C。竞争型免疫测定中,被固定的IgG和标准溶液（或样品）在33 °C均相条件下竞争性地与辣根过氧化物酶标记抗体反应,升高温度分离出高分子免疫复合物,沉淀重新溶解后通过偶联过氧化氢与对羟基苯乙酸的荧光反应进行定量,线性范围为100-1000 ng/mL,检测限为2.0 ng/mL。方法灵敏、快速操作简便,且提高了免疫反应效率。此外,灵敏度与用传统微孔板做载体相似,但测定时间更快（从100-120分钟减少到30分钟）。该法用于测定人血清中IgG的含量,结果满意。     

室温磷光分析法的进展与应用

本文对近5年来国内外室温磷光法的研究进展进行了综述,包括固体基质室温磷光、表面活性剂有序介质增稳室温磷光、环糊精诱导室温磷光、敏化和猝灭室温磷光、无保护流体室温磷光、室温磷光化学传感器、生物大分子的室温磷光研究与应用,引用文献158篇.     

固体基质室温燐光分析法测定痕量银

基于AgCl·PVA·Ag+ 吸附FIn- 所形成的离子缔合物AgCl·PVA·Ag+ ·FIn- 能在滤纸基质上发射强而稳定的室温光信号的特性 ,建立了以滤纸为基质的固体基质室温光测定痕量银的新方法。该离子缔合物对应于聚乙烯醇 (PVA)存在下Fajans(法扬斯 )法的终点。在一定条件下 ,离子缔合物的光强度与吸附层的Ag+ 含量成正比 ,线性范围为 1.72～ 8.6× 10 - 1 2 g 斑 ,(0 .4 μL 斑 ) ,工作曲线对应的回归方程ΔIp =2 80 .81+35 4 5mAg+ (10 - 1 2 g 斑 ) ,n =6 ,相关系数r =0 .9995。该方法快速、灵敏、准确。用于人发、茶叶中银的测定 ,与AAS法基本相符。     

一种催化固体基质室温磷光法测定奋乃静

建立了罗丹明6G(Rhodamene.6G,Rhod 6G+)电子效应催化固体基质室温磷光法(SS-RTP)测定痕量奋乃静(Perphenazine,PPH)的新方法.方法的线性范围为0.080~28×10-9g/L,线性相关系数为0.999 l,相对标准偏差为1.5%~3.1%,检出限为4.8×10-14g/L.方法应用于血样、脉样中残留奋乃静含量的测定,结果令人满意.     

同步-导数固体基质室温磷光光谱法快速同时分析a-萘乙酸和6-苄氨基嘌呤

研究了植物激素α-萘乙酸和6-苄氨基嘌呤混合物体系的同步-导数固体基质室温磷光光谱. 在pH 9.5的条件下, 以1.5 mol/L的KI-CH3COOLi为重原子微扰剂, 选择Δλ=180 nm, 在240～340 nm的波长范围内对两者的混合物进行了同步磷光光谱扫描, 并做一阶导数处理. 结果表明, 二者的同步磷光光谱得到了较好的分离, 同步导数磷光峰分别位于257 nm和305 nm, 可同时分别对其进行定量分析. α-萘乙酸和6-苄氨基嘌呤的检出限分别为14.88 ng和6.75 ng. 方法可用于蔬菜中α-萘乙酸和6-苄氨基嘌呤的测定.     

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.