【作者】 吴宗方；

【导师】 刘昌华；

【作者基本信息】 西南大学 ， 无机化学， 2011， 硕士

【摘要】 仿生材料是基于自然界中生物的特点或特性制备的具有特殊形貌或功能的材料。在很多方面都有着重要的应用。因其具备良好的生物相容性,能使固定的生物活性分子保持良好的活性,在生物化学方面也有着重要的应用。基于直接电子传递的第三代电化学生物传感器是一种先进检验技术,它有很多的优点,如体积小、灵敏度高、响应速度快、不需要对样品进行预处理、成本低廉等。因此,在医学、军事、环境监测及食品安全等方面都有着重要的应用。而生物传感器制备的关键就是电极表面生物活性分子活性的保持,因此,本文中利用了新制备的仿生材料优异的生物相容性制备了一系列的性能优良的生物传感器,本文所做的具体工作如下：1.手性膦酸锆/血红蛋白/金电极的安培型过氧化氢传感器的研究共电沉积手性膦酸锆Zr(PO4)(H2PO4)0.50·(HO3PCH2NCH2SC2H3COOH)0.5091.6J2O (ZrPMT)、血红蛋白(Hb)于金电极表面,制备了安培型过氧化氢生物传感器。制备的生物传感器对于过氧化氢(H2O2)有着良好的响应,检出限为1.6×10-7mol L-1,线性范围为5×10-7 molL-1～1.2×10-4 mol L-1,相关系数0.99(S/N=3),且该传感器有良好的稳定性和较强的抗干扰能力。2.基于肠状二氧化锡纳米簇固载血红蛋白的酶型生物传感器成功制备了一种全新形貌的二氧化锡-肠状二氧化锡纳米簇并将其应用于过氧化氢生物传感器的制备。制备的二氧化锡展现出优异的生物相容性和对血红蛋白的吸附性能。以共电沉积法,将二氧化锡和血红蛋白沉积到金电极上制成了性能优良的过氧化氢生物传感器。该传感器对过氧化氢的还原有着灵敏的响应,响应线性范围为1×10-5 mol L-1到1.6×10-2 molL-1,最低检出限为3.5×10-6mol L-1 (S/N=3),相关系数为0.99(n=23)。传感器的选择性和重现性同样令人满意。3.基于石墨烯/壳聚糖复合膜的新型电流型甲胎蛋白免疫传感器制备了一种新型的无标记型免疫传感器来检测甲胎蛋白。制备过程是首先将壳聚糖/石墨烯复合膜滴涂于玻碳电极表面,接着吸附纳米金,最后吸附甲胎蛋白抗体。这种方法简单快捷,制备的传感器有很好的响应、选择性及重现性,检测范围为0.01到20ng mL-1,最低检测出限为3 pg mL-1(3σ).线性回归方程为△I(μA)=0.569+0.984 CAFP(ng mL-1),相关系数为0.998,有一定的实际应用价值。更多还原

【Abstract】 Bionic materials are a kind of materials based on the imitation of characteristics of natural creatures, which possess special morphologies or properties and many applications. Bionic materials can keep the bioactivity of biological molecules due to the good compatibility, and consequently be widely used in biochemistry.The third generation biosensor based on direct electron transfer is an advanced technology, it possesses many advantages, such as small size, high sensitivity, short response time, no need for pretreatment of samples, and low cost. Therefore, biosensor has wide application in many fields, such as medical science, military, environmental monitoring and food security. The key to the construction of biosensor is the preservation of the bioactivity of the biological molecules. Therefore, several kinds of biosensors were fabricated using novel bionic materials. Details are summarized as follows:Part 1 Amperometric hydrogen peroxide biosensor based on electro-codeposition of chiral zirconium phosphonate/Hemoglobin on gold electrodeA new kind of material-chiral zirconium phosphonate (Zr(P04)(H2PO4)0.50·(H03PCH2NCH2SC2H3COOH)o.5o-1.6H20) (abbreviated as ZrPMT), was employed for the construction of hydrogen peroxide biosensor. UV-Vis absorption spectra displayed that hemoglobin (Hb) retained its native structure after interaction with ZrPMT, showing that ZrPMT provided good compatibility. Cyclic voltammetry experiment showed that ZrPMT could greatly improve the electron transformation between the modified electrode and electrolyte. The biosensor was prepared by electro-codepositing of ZrPMT and Hb onto gold electrode (Au), this method was simple and easy, and the biosensor exhibited good response to the reduction of hydrogen peroxide with linear range from 5×10-7 mol L-1 to 1.2×10-4 mol L-1, and detection limit of 1.6×10-7 mol L-1, coefficient constant of 0.99 (S/N=3), the stability and selectivity were also good.Part 2 Enzyme biosensor based on Hemoglobin entrapped in intestine-like SnO2 nano-cluster A new morphology of SnO2, intestine-like nano-cluster was employed for the fabrication of hydrogen peroxide biosensor. The prepared SnO2 exhibited excellent biocompatibility and adsorption of hemoglobin, and the biosensor constructed by electro-codepositing of SnO2 and hemoglobin on gold electrode exhibited sensitive response to the reduction of hydrogen peroxide, and the linear range was from 1×10-5 mol L-1 to 1.6×10-2 mol L-1 with coefficient constant of 0.99 (n=23), and the detect limit was estimated to be 3.5×10-6 mol L-1 (S/N=3). The selectivity, reproducibility and stability were also good.Part 3 A novel label-free electrochemical immunosensor for the detection of a-fetoprotein based on graphene/chitosan compositeA novel label-free immunosensor was fabricated for the detection of a-fetoprotein. The construction process of the immunosensor was firstly cast chitosan/graphene composite on the electrode, and then adsorbed nanogold particles on the composite, and finally adsorbed a-fetoprotein antibody. This method is very simple and the proposed immunosensor possessed high sensitivity, good selectivity and reproducibility, the detect range was from 0.01 to 20 ng mL-1 with a detect limit of 3 pg mL-1 (3σ), and the regrssion equation was△I (μA)=0.569+0.984 CAFP (ng mL-1) with a coefficient of 0.998, showing potential application in clinical diagnosis.更多还原