【作者】 曹旭妮；

【导师】 金利通；

【作者基本信息】 华东师范大学 ， 分析化学， 2004， 博士

【摘要】 在世纪之交的时刻，各国政府和科学界对纳米科学技术予以极大的关注，很多国家从战略的高度部署纳米科技的研究。纳米科技的陡然升温不仅仅是尺度的缩小问题，实质是由于纳米科技在推动人类社会产生巨大变革方面所具有的重要意义所决定的。原因在于：(1)纳米科技将促使人类认知的革命。纳米科技领域是知识创新和技术创新的源泉，新的规律、新的原理和新的理论的建立给基础科学研究提供了极好的机遇。(2)纳米科技将引发一场新的工业革命。当物质的结构单元小到纳米量级时，会产生特异的表面效应、体积效应和量子效应，其电学、磁学、光学和化学性质也相应地发生显著的变化，呈现出常规材料不具备的优越性能。因此纳米微粒在催化、电子材料、微器件、增强材料及传感器材料等方面有着广阔的应用前景。鉴于此，纳米科技对未来工业的革命性影响和对传统产业技术改造的广泛性具有深远的意义。正因为如此，各国正加强纳米技术相关领域的研究，努力占领战略制高点。 分析科学在各研究领域中起着“眼睛”的作用。在生命科学相关领域的研究中，随着它们的迅速的发展，人们对生命现象的观察和研究的不断的深入，许多传统的、常规的生物分析化学方法与手段已不能满足生命科学研究的需要。人们正迫切需要新的分析方法来实时、活体获得更多的生物化学的信息。纳米技术的发展将史无前例地把分析工作者更加深入地融合到生命科学领域。毫无疑问，在纳米尺度上的生物分析化学必将成为传统分析化学学科向前发展的新的生长点。同时，电分析化学是分析化学中重要的一个研究领域之一，将它与纳米技术有机的结合，是一个崭新的领域，将有利于原创性地建立一些电分析化学的新理论、新技术和新方法，对电分析本身的发展具有推动作用。 本论文的工作主要集中在纳米技术与电分析化学相结合最活跃的研究领域之一——新型纳米材料修饰电极(电化学传感器)的研制。论文重点研究了纳米材料修饰电极与传统常规材料修饰电极相比呈现出的更优越的性能。此外，论文的另一个工作重点在于将研制的新型纳米材料修饰电极应用于色谱电化学中，并实现生物活性分子、药物的分析测定，这为生命科学及其相关领域的研究提供许多重要的分析方法。论文工作努力实现将纳米技术、生命科学和电分析化学三者的结合。具体内容如下：纳米材料修饰电极及其在电分析化学中的应用研究中文摘要第一部分:功能化碳纳米管修饰电极的研制与应用(一)按基化碳纳米管修饰电极色谱电化学分析检测生物活性分子和药物 碳纳米管因为其独特的电学、物理、化学性质而引起人们的普遍关注。但因为其不溶于普通的溶剂而限制了它的操作和应用。将碳纳米管氧化竣基化后可以明显改善这一状况。本文将价格较为低廉的多壁碳纳米管进行梭基化改性，并制备了新型的纳米修饰电极(MWNT-C00H CME)。 一、该修饰电极显示了对疏基化合物良好的催化活性。将该修饰电极用于安培检测半 肤氨酸(L一eys)和谷肤甘肤(osH)两种琉基化合物。在3 .oxlo一7一1.0火10一3 mo比 浓度范围内，L一Cys和GsH的浓度分别与氧化峰的峰电流呈良好的线性关系，检 出限分别为1.2x10一7 mo比和2.2、1了m。比。与微渗析采样技术结合，将该修饰电极用于色谱电化学测定了大鼠脑内和人全血中L一半肤胺酸和谷肤甘肤的含量，为疏基化合物的生理学研究提供了新的手段。二、该修饰电极能有效降低嗓吟化合物氧化的过电位并提高电流响应。将该修饰电极 与HPLC和微渗析采样技术联用测定了大鼠脑内次黄嗦吟(HX)和黄嘿吟(X) 的含量。该方法简单、稳定性高。结果表明，在一定浓度范围内，HX和X的浓 度分别与氧化峰的峰电流呈良好的线性关系，检出限分别为2.0劝。一7 mol几和 1 .6x10一“m。比。为纳米材料在生命科学中的应用提供一种新型的电化学传感器。三、首次将该修饰电极用于色谱电化学检测6一疏基嚓吟，其检测限(2.0xl0’7mol/L) 较玻碳电极和其他修饰电极相比大幅度的降低。由于微渗析技术对于药物动力学 等方面的研究具有独特的优势。将该方法与微渗析取样技术相结合，实现了6一琉 基嗓吟在家兔体内的药物代谢动力学的研究，其血药浓度随时间的变化过程符合 一室开放模型。同时，还详细研究了6.MP与牛血清白蛋白(BSA)相互作用， 测得6一Mp与BsA的结合常数和结合位点数分别为3.97xl护(mol/L)一’和 1 .51。这为6一疏基嗓吟进一步的药理研究提供了重要依据。(二)狡基化多壁碳纳米管屎3一甲基唾吩修饰电极用于色谱电化学同时分离检测环境水样中的芳香胺 聚3一甲基唾吩是一种很好的导电聚合物膜，该聚合膜具有抗污染能力强、稳定性好、导电性好的特点。本文将梭基化多壁碳纳米管与聚3一甲基嚷吩膜复合，制备新型的纳米复 2纳米材料修饰电极及其在电分析化学中的应用研究中文摘要合膜修饰电极。结果表明该修饰电极可明显催化芳香胺化合物的氧化反应，与梭基化多壁碳纳米管修饰电极相比具有更好的催化作用。将该纳米修饰?更多还原

【Abstract】 Nowadays, nano science and technology has attracted much attention for two reasons. First, it offers the opportunity to understand the world at a deeper level. Researches in nano science and technology need new knowledge, and therefore it is time to set up new methods, new principles and even new theories. At this point, we can say that nano science and technology gives fundamental researches a wonderful perspective. Second, nano science and technology can make a great impact on our economy and society. In recent work, it has been discovered that the tiny objects (0.1~100 nm) can have electrical, magnetic, optical, chemical properties completely different from those of the same materials in bulk form. These discoveries will lead to powerful devices with new capabilities and also new materials that will impact all sectors of technology. Nano science and technology are now changing our lives. As a result, governments in most countries response to the scientific and societal challenges posed by nano science and technology, and implement many effective plans to galvanize its development.On the other hand, analytical chemistry has great importance in many research fields. As we know, with the fast development in life science, traditional analytical methods cannot meet the needs to in situ and in vivo acquire the information any more. It requires more and more new methods to understand life processes. Combined with nanotechnology, analytical chemistry can provide many new methods for the researches in life science. In other words, bioanalytical chemistry based on nanotechnology will create a new world for traditional analytical chemistry. Electroanalytical chemistry is one of the most important fields in analytical chemistry. Today, many wonderful nanomaterials have been applied in electroanalytcial chemistry and some important progresses along these lines have recently achieved. Of course, this is a new area worthy of attention and it also helps to set up new methods, new techniques and new theories.My dissertation research focuses on developing modified electrodes based on nanomaterials,which is one of most active areas in electroanalytical chemistry. All of modified electrodes we developed exhibit wonderful properties different from those based on the same materials in bulk form. In addition, this dissertation research also tries to apply these novel modified electrodes towards chromatography coupled with electrochemical detection for biological and pharmaceutical molecules, which are promising for the researches in life science. During the three years, we are adhering to an organic combination of electroanalytical chemisty, nanotechnology and life science. The details are given as follows:Part I: Study and Application of Functionalized Carbon Nanotubes Modified Electrodes(i) In Vivo Monitoring of Biological and Pharmaceutical Molecules by Liquid Chromatography Coupled with a Modified electrode based on Multi-Wall Carbon Nanotubes Functionalized with Carboxylic Acid GroupsSince the discovery of carbon nanotubes in 1991, they have attracted much attention because of remarkable nanostructures combining high surface area, high electrical conductivity, good chemical stability and significant mechanical strength. Depending on their atomic structure, the subtle electronic properties suggest that carbon nanotubes have the ability to promote electron-transfer reactions when used as an electrode in chemical reactions. However, the purified carbon nanotubes flocculate rapidly in aqueous or common organic solution, hindering their further manipulation and application. Important progress along these lines was recently achieved. In this previous work, a stable colloidal suspension in water could be made for the single-wall carbon nanotubes fuctionalized with carboxylic acid group with the assistance of anionic surfactant. In this part, much cheaper multi-wall carbon nanotubes were functionalized with carboxylic acid group (MWNT-COOH). It was found that MWNT-COOHs in common solvents did not flocculate so rapidly as MW更多还原