【作者】 陈宇春；

【导师】 黄承志；

【作者基本信息】 西南师范大学 ， 分析化学， 2003， 硕士

【摘要】 自组装技术是当前超分子化学及材料科学领域中非常活跃的研究领域，环状自组装是一类非常特殊的自组装，对它的研究具有仿生学价值，同时还可能获得具有特殊结构的功能材料。本文详细介绍了自组装环的形成机理：蒸发诱导毛细流机理、二维气泡机理以及干孔机理，概述了毛细流定向组装环在分析科学中的应用进展，如构建芯片阵列和开发利用毛细流动力学因素进行生物物理学研究等。并对自组装环技术在生化和环境分析测定中的应用作了进一步的试验研究。 实验发现，当pH为6.62寸，染料核固红在经过二氯二甲基硅烷处理后的玻璃表面上形成的SOR荧光强度很低，加入一定量蛋白质之后，环的荧光强度有所增强。据此建立了测定微量蛋白质的方法。点样体积为0.2μl时，线性范围为0-100pg，对BSA检测限为2.44pg；对HSA为0.91pg。本方法成功应用于三个血清样品中蛋白质总量的测定，其结果与考马斯亮蓝法（Coomassie Brilliant Blue,CBB G-250）测定结果一致。 在以聚乙烯醇-124为成环辅助剂、使用pH7.31的Tris-HCl缓冲溶液时，槲皮素（QT）可以在适当憎水性的玻璃固载表面上自组装形成—个荧光环。加入Fe³⁺后，在一定浓度范围内，其荧光环的荧光能够被定量猝灭。本文利用这一现象，建立了一种全新的测定痕量Fe³⁺的方法，此法取样量少，灵敏度高（2.52ng／ml），已用于水样和血清中痕量铁Fe³⁺的分析。 在pH4.40条件下，依来铬红B（ERB）自组装环本身的荧光较弱，当有Al³⁺存在时，ERB可以与Al³⁺发生反应，并表现为荧光增强。当点样体积为1.0μl时，自组装环的半径为0.70mm。当ERB的工作浓度为2.0x10^-6M、点样体积为0.1μl时，本方法测定Al³⁺的检测限为1.42fmol。本文成功的将这种方法应用到嘉陵江水样中Al³⁺含量的测定。 在六氢吡啶作为反应介质的条件下，四-（对磺基苯基）卟啉（TPPS₄）所形成的SOR荧光强度分别可以被Cu²⁺和Pb²⁺猝灭。但是由于这两种离子反应最佳时需要的六氢吡啶用量存在较大差异，当在测定Cu²⁺的最佳六氢吡啶浓度时，pb²⁺对TPPS₄的荧光猝灭恰好比较弱；而在测定pb²⁺最佳六氢吡啶浓度时，Cu²⁺的干扰又比较小。因此，我们可以在不同六氢吡啶用量时分别测定Cu²⁺和pb²⁺，不需要消除相互间的干扰。用本方法测定铜的检测限为1.28fmol；测定铅的检测限为6.95fmol。并将合成样品中的铜和铅以不同量进行混合，对测定结果没有影响。 吡罗红Y（PY）是一种吨啫类染料，它在固载表面形成的自组装环的荧光强度很强。 固起表面的毛细流定向组装及其在生物环境化学分析中的应用研究酸性介质中有Cr（VI）存在时，Cr(VIXi］”氧化］’Y ｛ill其分子结构遭到破坏，荧光消失。并且在一定浓度范围内，荧光粹灭程度与 Cr（VI）的浓度成正比。由此建立了测定痕量Cr（VI）的荧光分析法。该方法准确、灵敏、ls作简便，当 PY浓度为 5刀X10”‘M时，检测限为0．50屹／l，与一般荧光分析法相比，检测限提高了约一个数量级。应用于水样中痕量Cr（V）的测定结果令人满意。 在强酸性条件下，钙黄绿素蓝（：’B）工f（IV）f一以】：l＊的比例形成三元络合物，形成的络合物的荧光强度比＊＊毛巾V厂一c络合物荧光强度更大，并且荧光增强的量与厂浓度成了比，在此基础上建立了自组装成环荣光测定附量厂的新方法。当 CB和 Zr(VI浓度均为 1二X10”‘M时，本方法检测限ill．58X10－‘M。用标准加入法测量了三个自来水样品中氟含量，回收率在98．5．105．5％之间，说明本方法具有较好的应用价值。更多还原

【Abstract】 Self-assembly technique is one of the most interesting research fields in supermolecular chemistry and material sciences. Ring-like self-organization is attracting for its potential application in material sciences and bionic value. Mechanisms including evaporation induced capillary flow, 2-D bubbles and dried-hole hypotheses are discussed, and further experiments were tested concerning the analytical applications of SOR in biochemical and environmental analysis.At pH 6.62 and with the aid of poly (vinyl alcohol)-124 (PVA-124), a droplet of nuclear fast red (NFR) solution can form a fluorescent SOR on hydrophobic glass slide, and the presence of protein can enhance its fluorescence intensity. When the volume of the droplet is 0.2ul, linear response is observed in the range 0-100pg, and the limit of determination is 2.44pg for BSA and 0.9Ipg for HSA. The results of determination for three serum samples were identical with those obtained according to the Bradford method using Coomassie Brilliant Blue (CBB G-250).When the pH is 7.33, quercetin can form an SOR on a dimethyl dichlorosilane (DMCS) modified glass slides with the aid of poly (vinyl alcohol)-!24. Its maximum fluorescence intensity can be quantitatively quenched by iron (III) over the range 7.56-132.64ng/ml and the limit of determination is 2.52ng/ml. Four water samples and two human serum samples were determined satisfactorily.When a 1.0ul droplet of the fluorescent complex of aluminum (III)-eriochrome red B (ERB) was spotted to the surface of DMCS pretreated glass slide, an SOR with the outer radius of 0.70mm can be obtained. Linear response was observed between maximum fluorescence intensity of the SOR with the content of aluminum the range of 0.02-0.20pmol, and the limit of determination is 1.42fmol with three folds of signal to noise. This method was applied successfully to the determination of trace amount of aluminum (III) in a series of river samples and the results were identical with those obtained according to the standard method using Eriochrome cyanine R (ECR).An SOR method was established for the simultaneous determination of trace amounts of copper and lead. Under alkalescent conditions controlled by hexahydro -pyridine, the SOR of a,p,y,6-Tetrakis (4-sulfonylphenyl) Porphine (TPPS4) which is formed on the glass slide modified by dimethyl dichlorosilane has very strong fluorescence, but its fluorescence intensity can be quenched quantitatively by copper and lead. When the volume of the droplet is 1.0ul and content of TPPS4 is 1.08xl0-12mol/ring, linear response is observed in the range 0-l.25x10-12mol and the limit of determination is l.72fmol for copper; linear response is observed in the range 0-3.80x10-12mol and the limit of determination is 6.63 fmol for lead. Trace amounts of copper and lead in synthetic samples have been determined simultaneously and satisfactorily.Owing to the oxidation of chromium (VI). the fluorescence of an SOR of Pyronine Y (PY) is quenched by chromium (VI). This reaction can be applied to determine trace amount chromium (VI) in water samples. When the volume of the droplet is 1 .0ul and content of PY is 5.0x10-6M, linear response is observed in the range 0-30ug/l and the limit of determination is 0.50ug/l.Under low pH conditions, the addition of fluoride to the zirconium-calcein blue (CB) complex increases the fluorescence intensity that based on the formation of a strongly fluorescent 1:1:1 ternary complex. Using SOR method, fluorine can be determined down to 1.58x 10-8M and the linear range is 0-1 .0x 10-6M.更多还原