苄胺衍生物制备纳米复合体及其与蛋白的作用
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摘要
碳纳米管是一种重要的载体材料,在生物医学领域具有独特的应用价值,但是由于其在任何溶剂中都不溶也不能稳定分散的特性,使得它在这个领域的应用出现了障碍。在众多的改性碳纳米管的方法中,本文采用了用两性小分子的表面活性剂来非共价修饰碳纳米管,提高它在水中的分散性,从而可以为下一步的应用打下基础。
本论文对两性小分子表面活性剂在有机相中的制备条件等进行了一定的探索,并成功制得了可以分散碳纳米管的两性小分子。利用市售的葡萄糖酸内酯和常见的化学试剂(纯度>99%)——过量的苄胺液体(分析纯),在无水甲醇中进行反应。
本文中所用的碳纳米管为CVD法生成的多壁碳纳米管。实验室采用一定浓度的硝酸溶液进行氧化纯化多壁碳纳米管,将碳纳米管表面的这些多余的杂质氧化去除,剩余纯化的碳纳米管。
本论文采用甲醇、乙醇、异丙醇等不同浓度的水溶液以及纯水作为表面活性剂分散碳纳米管的初始处理溶剂,并对处理后的碳纳米管分散水溶液进行紫外-可见光谱全波长扫描,最终确定了异丙醇水溶液为碳纳米管的最佳处理溶剂以及最佳浓度30%,甲醇、乙醇水溶液的最佳浓度分别为15%,15%,这就奠定了下一步的研究基础。
用经过各个最佳浓度的溶剂处理之后的碳纳米管,对实验中的牛血清蛋白分子进行有效的吸附,并通过紫外-可见分光光度计全波长扫描,以及在三种不同的温度(25℃、45℃、65℃)下通过圆二色光谱仪考察牛血清蛋白被分散性的碳纳米管吸附之后二级结构的变化情况,并利用一定的软件对蛋白二级结构中的主要成分进行计算,定量的分析碳纳米管吸附蛋白的性能以及其对蛋白二级结构的影响。
Carbon nanotube is an important material as carrier which has particular applied value in the field of Biological and medical science.while, their characteristic nature of insoluble in any solvent, largely limits their application.Among so many modified methods of carbon nanotubes, we choose small amphiprotic molecule to modify carbon nanotubes by non covalent bond, so the disperstiveness of the modified carbon nanotubes in water will be increased.
In this paper, we have quested the Preparation Conditions of the small amphiprotic molecule which can be a well surface active agent to carbon nanotubes. The glucolactone we used in the laboratory was available in the market, and its purity quotient is>99%,and another reactant is superfluous benzylamine (analytically pure). The reaction happened in absolute methanol under determinate condition.
The carbon nanotubes we used in this paper is prepared by the method of CVD. It was purified by the aqueous solution of nitric acid which is a certain consistency. In this process, the excrescent impurityies at surface of carbon nanotubes were removed by the way of oxygenize, and the pure carbon nanotubes were received.
In this paper, we used different consistency of methanol, ethanol, and isopropanol aqueous solution as the initial processed solvents of carbon nanotubes. And the processed carbon nanotubes dispersed again in the water to obtain a well dispersion, which were detectd by the ultraviolet spectrograph. So we can choose out the best initial processed solvents of carbon nanotubes. They are 15% methano,15% ethanol,30% isopropanol, in which the 30%isopropanol is the best one.
The carbon nanotubes processed by the best initial processed solvents can adsorb BSA(Bovine Serum Albumin) in water. And the solutions were detected by ultraviolet spectrograph and the Circular Dichroism Spectrometer at three different temperatures(25℃、45℃、65℃). In addition to this, the changes of secondary structure in BSA (Bovine Serum Albumin) can be calculated by a soft named CDpro. So we can analyze the structure of BSA in ration.
本论文对两性小分子表面活性剂在有机相中的制备条件等进行了一定的探索,并成功制得了可以分散碳纳米管的两性小分子。利用市售的葡萄糖酸内酯和常见的化学试剂(纯度>99%)——过量的苄胺液体(分析纯),在无水甲醇中进行反应。
本文中所用的碳纳米管为CVD法生成的多壁碳纳米管。实验室采用一定浓度的硝酸溶液进行氧化纯化多壁碳纳米管,将碳纳米管表面的这些多余的杂质氧化去除,剩余纯化的碳纳米管。
本论文采用甲醇、乙醇、异丙醇等不同浓度的水溶液以及纯水作为表面活性剂分散碳纳米管的初始处理溶剂,并对处理后的碳纳米管分散水溶液进行紫外-可见光谱全波长扫描,最终确定了异丙醇水溶液为碳纳米管的最佳处理溶剂以及最佳浓度30%,甲醇、乙醇水溶液的最佳浓度分别为15%,15%,这就奠定了下一步的研究基础。
用经过各个最佳浓度的溶剂处理之后的碳纳米管,对实验中的牛血清蛋白分子进行有效的吸附,并通过紫外-可见分光光度计全波长扫描,以及在三种不同的温度(25℃、45℃、65℃)下通过圆二色光谱仪考察牛血清蛋白被分散性的碳纳米管吸附之后二级结构的变化情况,并利用一定的软件对蛋白二级结构中的主要成分进行计算,定量的分析碳纳米管吸附蛋白的性能以及其对蛋白二级结构的影响。
Carbon nanotube is an important material as carrier which has particular applied value in the field of Biological and medical science.while, their characteristic nature of insoluble in any solvent, largely limits their application.Among so many modified methods of carbon nanotubes, we choose small amphiprotic molecule to modify carbon nanotubes by non covalent bond, so the disperstiveness of the modified carbon nanotubes in water will be increased.
In this paper, we have quested the Preparation Conditions of the small amphiprotic molecule which can be a well surface active agent to carbon nanotubes. The glucolactone we used in the laboratory was available in the market, and its purity quotient is>99%,and another reactant is superfluous benzylamine (analytically pure). The reaction happened in absolute methanol under determinate condition.
The carbon nanotubes we used in this paper is prepared by the method of CVD. It was purified by the aqueous solution of nitric acid which is a certain consistency. In this process, the excrescent impurityies at surface of carbon nanotubes were removed by the way of oxygenize, and the pure carbon nanotubes were received.
In this paper, we used different consistency of methanol, ethanol, and isopropanol aqueous solution as the initial processed solvents of carbon nanotubes. And the processed carbon nanotubes dispersed again in the water to obtain a well dispersion, which were detectd by the ultraviolet spectrograph. So we can choose out the best initial processed solvents of carbon nanotubes. They are 15% methano,15% ethanol,30% isopropanol, in which the 30%isopropanol is the best one.
The carbon nanotubes processed by the best initial processed solvents can adsorb BSA(Bovine Serum Albumin) in water. And the solutions were detected by ultraviolet spectrograph and the Circular Dichroism Spectrometer at three different temperatures(25℃、45℃、65℃). In addition to this, the changes of secondary structure in BSA (Bovine Serum Albumin) can be calculated by a soft named CDpro. So we can analyze the structure of BSA in ration.
引文
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[30]VanderWal R. L., Ticich T. M., Curtis V. E. Diffusion flame synthesis of single walled carbon nanotubes[J]. Chem. Phys. Lett.,2000,323:217-223.
[31]Alvarez L., Guillard T., Olalde G., et al. Large scale solar production of fullerenes and carbon nanotubes[J]. Synth. Met.,1999,103: 2476-2477.
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[37]郑伟玲.碳纳米管的功能化及其在复合材料中的应用[D].汕头大学,2009.
[38]Zhu J, Kim J D, Peng H Q, Margrave J L, Khabashesku V N, Barrera E V. Improving the dispersion and integration of single-walled carbon nanotubes in epoxy composites through functionalization[J]. Nano Lett.,2003,3:1107.
[39]Jin L, Bower B, Zhou O. Alignment of carbon nanotubes in a polymer matrix by mechanical stretching. Appl[J]. Phys. Lett.,1998,73:1197.
[40]Tasis, D., Tagmatarchis,N., Bianco,A., Prato; M. Chemistry of carbon nanotubes[J]. Chem. Rev 2006,106:1105-1136.
[41]王雪.功能化纳米管及超支化聚合物的制备和在医药上的应用[D].上海交通大学,2009.
[42]刘演新.多壁碳纳米管的表面接枝改性及其衍生物[D].北京化工大学,2008.
[43]吴敏,张征林,丁绍松.碳纳米管的研究及应用[J].化工时刊,2001,12：1-4.
[44]郭贵全.聚合物改性碳纳米管及其在催化-生物学领域的应用[D].2007.
[45]蔡方凯.分散定向碳纳米管阵列的制备及场发射性能[J].电子元件与材料,2009,8(28)：8-10.
[46]研究快报.石墨烯和碳纳米管混合材料.中国光学期刊网[J].
[47]余颖,曾艳,杜飞鹏,陈正华.塑料表面碳纳米管抗静电覆膜的研究[J].华中师范人学学报(自然科学版),2004,38(1)：78-80.
[48]李宏伟,高绪珊,童俨.含碳纳米管的新型抗静电纤维的制备和性能.第六届功能性纺织品及纳米技术研讨会论文集[J].2006-5：114-117.
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[50]蒋永剑,虞先浚,张延岭.碳纳米管作为载体在生物医学中的应用[J].中国现代普通外科进展,2008.12,11(6)：520-523.
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[2]Ming Z, He D, Zhang X Y, et al.Thermal stability of carbon nanotubes under S.5 GPa [J]. Carbon,1997,35(10):1671-1673.
[3]Vix-Guterl C, Dentzer J, Ehrburger P, et al[J]. Surface properties and microtexture of catalytic multi-walled carbon nanotubes. Carbon,2001,39(2):318-320.
[4]Tasisi,D.,Tagmatarchis,N.,Bianco,A.,Prato,M.Chem.Rev.2006,106:1106-1125.
[5]Dyke,C.A.,Tour,[J]. M.Chem. Eur.J.2004,10,812-817.
[6]Chen J., Hamon, M.A., Chen Y., Rao,A.M., Eklund, P.C., Haddon,R.C.Solution properties of single-walled carbon nanotubes [J]. Since 1998,282:95-98.
[7]Jin,Z.,Sun,X.,,Xu,G.,S.H.,Ji,W.Nonliner optical properties of some polymer/multi-walled carbon nanotubes composites[J]. Chem.Phys.Lett.2000,318:505-510.
[8]Sun, Y.;Wilson,S.R.;Schuster,D.I.High dissolution and strong light emission of carbon nanotubes in aromatic amine solvents[J]. J.Am.Chem.soc.2001,123:5348-5349.
[9]Ebbesen T. W. Carbon nanotubes[J]. Physics Today, New York,1996,49:26.
[10]Iijima S. Helical microtubes of graphite carbon [J].Nature,1991,354:56-58.
[11]赵娜.碳纳米管对水中PPCPs吸附研究[D].北京化工大学,2009.
[12]徐鑫.碳纳米管固定脂肪酶用于1-苯基乙醇的拆分[D].北京化工大学,2009.
[13]Qin L.-C., Zhao X., Hirahara K., et al. The smallest carbon nanotube[J]. Nature,2000, 408:50.
[14]Hertel T., Walkup. R. E., Avouris P. Deformation of carbon nanotubes by surface van der Waals forces. Phys. Rev. B,1998,58:13870-13873.
[15]吕计男.纳米管力学行为的数值模拟[D].中国科技人学,2008.
[16]姚小虎,韩强,辛浩.单壁碳纳米管非线性力学行为的数值模拟[J].物理学报,2008.1,57(1)：329-337.
[17]Yakobson B. I., Smally R. E. Fullerene nanotubes:beyond author[J]. Am. Sci.,1997,85: 324-337.
[18]Dresselhaus M. S., Dresselhaus G., Eklund P. Carbon nanotubes:many researches have predicted remarkable and unique properties for carbon nanotubes[J]. Phys. World, 1998,11:33-38.
[19]Ajayan P M. Nanotubes from carbon [J]. Chem Rev,1999,99(7):1787-1799
[20]Baughman R. H., Zakhidov A. A., de Heer W. A. Carbon nanotubes-the route toward applications[J]. Science,2002,297:787-792.
[21]Pederson M R, Broughton J Q. Nano capillarity in fullerene tubules [J]. Phys Rev Lett, 1992,69(18):2689-2692.
[22]Ajayan P. M., Schadler L. S., Braun P. V. Nanocomposite Science and Technology, Wiley-VCH Verlag GmbH & Co[J]. KGaA, Weinheim, Germany,2003.
[23]Nalwa H. S. Handbook of Nanostructured Materials and Nano technology[J]. Vol.5, Academic Press, New York, USA,2000.
[24]Carrol D L, Redlich P, BlaseX, et al. Effects of nanodomain formation on theelectronic structure of doped carbon nanotubes [J]. Phys Rev Lett,1998,81(11):2332-2335.
[25]Frank S, Poncharal P, Wang Z L, et al. Carbon nanotube quantum resistors [J]. Science, 1998,280(5370):1744-1746.
[26]Ajayan P. M., Schadler L. S., Braun P. V. Nanocomposite Science and Technology, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany,2003.
[27]Chengyu Wei, Srivastava D, Kyeongjae Cho. Molecular dynamics study of temperature dependent plastic collapse of carbon nanotubes under axial compression [J]. Computer Modeling in Engineering & Sciences,2002,3(2):255-26.
[28]Ruoff R S, Lorents D C. Mechanical and thermal properties of carbon nanotubes [J]. Carbon,1995,33(7):925-930
[29]杨东.水溶性碳纳米管的制各及其初步应用[D].复旦大学,2008.
[30]VanderWal R. L., Ticich T. M., Curtis V. E. Diffusion flame synthesis of single walled carbon nanotubes[J]. Chem. Phys. Lett.,2000,323:217-223.
[31]Alvarez L., Guillard T., Olalde G., et al. Large scale solar production of fullerenes and carbon nanotubes[J]. Synth. Met.,1999,103: 2476-2477.
[32]Huang J. Y., Yasuda H., Mori H. Highly curved carball-milling[J]. Chem. Phys. Lett., 1999,303:130-134.
[33]罗勇,应鹏展,苏慧仙,贾良菊.碳纳米管的制备方法概况[J].煤矿机械,2004,(6)：1-2.
[34]Bahr J. L., Tour J. M., Chemistry of Materials,2001,13:3823.
[35]杨英惠.纳米管的合成方法[J].现在材料动态,2003,(2)：1.
[36]陈辉强,颖怀.纳米材料的激光发放制备[J].纳米加工艺,2005.6,2(3)：2-3.
[37]郑伟玲.碳纳米管的功能化及其在复合材料中的应用[D].汕头大学,2009.
[38]Zhu J, Kim J D, Peng H Q, Margrave J L, Khabashesku V N, Barrera E V. Improving the dispersion and integration of single-walled carbon nanotubes in epoxy composites through functionalization[J]. Nano Lett.,2003,3:1107.
[39]Jin L, Bower B, Zhou O. Alignment of carbon nanotubes in a polymer matrix by mechanical stretching. Appl[J]. Phys. Lett.,1998,73:1197.
[40]Tasis, D., Tagmatarchis,N., Bianco,A., Prato; M. Chemistry of carbon nanotubes[J]. Chem. Rev 2006,106:1105-1136.
[41]王雪.功能化纳米管及超支化聚合物的制备和在医药上的应用[D].上海交通大学,2009.
[42]刘演新.多壁碳纳米管的表面接枝改性及其衍生物[D].北京化工大学,2008.
[43]吴敏,张征林,丁绍松.碳纳米管的研究及应用[J].化工时刊,2001,12：1-4.
[44]郭贵全.聚合物改性碳纳米管及其在催化-生物学领域的应用[D].2007.
[45]蔡方凯.分散定向碳纳米管阵列的制备及场发射性能[J].电子元件与材料,2009,8(28)：8-10.
[46]研究快报.石墨烯和碳纳米管混合材料.中国光学期刊网[J].
[47]余颖,曾艳,杜飞鹏,陈正华.塑料表面碳纳米管抗静电覆膜的研究[J].华中师范人学学报(自然科学版),2004,38(1)：78-80.
[48]李宏伟,高绪珊,童俨.含碳纳米管的新型抗静电纤维的制备和性能.第六届功能性纺织品及纳米技术研讨会论文集[J].2006-5：114-117.
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