纳米材料的合成、表征及其在生物传感器中的应用
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摘要
纳米材料的出现为生物传感器的发展提供了很好的平台。利用纳米材料独特的物理和化学性质,基于纳米材料的生物传感器的性能目前已被提高到一个新的水平,如具有灵敏度高、响应速度快、检测范围宽、选择性好和稳定性高等优点。本论文通过调控纳米材料的组成、结构、尺寸和形状,制备出新颖的纳米生物传感器,使用TEM、SEM、XRD、EDS、FTIR、UV-vis、EIS、CV等表征手段对纳米材料及其生物传感器的组成、结构、尺寸、形貌、晶体结构和性能等进行了表征。本论文获得的主要成果如下:
1.用水热法制备了形状新颖的钛酸铋纳米片亚微球(NBTSMs)。借助氢键和静电相互作用,NBTSMs和蛋白质可以有序地组装在玻碳电极上,从而制备出高性能的生物传感器。研究发现,NBTSMs材料对酶有很好的生物相容性;能够实现酶与电极间的直接电子转移;对H_2O_2有较好的电催化性能,如宽的检测范围(2-430μM)、低的检测限(0.46μM)、小的米氏常数(204μM)、高的稳定性和好的可重复性。
2.通过二次生长的方法合成了以ZnO纳米棒为主轴,SnO_2纳米棒为枝丫的ZnO/SnO_2复合纳米材料。将ZnO/SnO_2复合纳米材料与血红蛋白(Hb)、壳聚糖(Chi)一起构筑了新颖的纳米生物传感器。研究发现,ZnO/SnO_2复合纳米材料具有很好的生物相容性;能够实现酶与电极间的直接电子转移;对H2O_2有较好的电催化性能,如宽的检测范围(2-370μM)、低的检测限(0.57μM)、高的稳定性和好的可重复性。
3.将立方形的AucoreCo_3O_(4shell)纳米材料与聚丙烯酸(PAA)、辣根过氧化物酶(HRP)一起构筑了新的纳米生物传感器。通过紫外可见谱、电化学阻抗和循环伏安测量发现,AucoreCo_3O_(4shell)-PAA-HRP复合膜具有很好的生物相容性和电化学性质。复合膜中的HRP在磷酸缓冲溶液(PBS)中有一对可逆的氧化还原峰;对H_2O_2有较好的电催化性能,如宽的检测范围(2-370μM)、高的动力学常数(7.4 s~(-1))和比较小的米氏常数(0.91 mM)。
Nanomaterials have offered a good platform for the development of electrochemical biosensors. Now, the performance of biosensors has greatly improved through using nanomaterials because nanomaterials possess unique physical and chemical properties. for example, these biosensors based on nanomaterials have high sensitivity, fast response, wide linear range, well selectivity and high stability. The major results of the thesis are as follows:
1. Nanoplated bismuth titanate sub-microspheres (NBTSMs) were for the first time synthesized by a facile hydrothermal synthesis strategy. The NBTSMs were employed as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins through a combined hydrogen bond and electrostatic assembly process. The NBTSMs-based composite film has good biocompabiliity, direct electron transfer capacity, and good electrocatalytic properties such as wide linear range (2-430μM), low detection limit (0.46μM), low Michaelis-Menten constant (204μM), and good stability and reproducibility.
2. ZnO/SnO_2 Composite nanomaterials were prepared with SnO_2 nanorods as the template via a secondary growth methode. A completely new biosensor composed of ZnO/SnO_2 composite nanomaterials, chitosan, and hemoglobin was fabricated. The ZnO/SnO_2-based composite film has good biocompabiliity, direct electron transfer capacity, and good electrocatalytic properties such as wide linear range (2-370μM), low detection limit (0.57μM), and good stability and reproducibility.
3. A new biosensor composed of cube-shaped AucoreCo_3O_(4shell) nanoparticles, polyacrylic acid (PAA), and horseradish peroxidase (HRP) was fabricated. The biocompatibility and electrochemical properties of the resulting AucoreCo_3O_(4shell)-PAA-HRP composite film were studied by UV-visible spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The immobilized HRP shows a pair of quasi-reversible redox peaks at -0.31 V in 20 mM PBS (pH 7.0), and the biosensor shows a fast amperometric response to hydrogen peroxide with a linear range of 2-370μM. The kinetic parameters such as ks (electron transfer rate constant) and KM (Michaelis–Menten constant) are evaluated to be about 7.4 s~(-1) and 0.91 mM, respectively.
1.用水热法制备了形状新颖的钛酸铋纳米片亚微球(NBTSMs)。借助氢键和静电相互作用,NBTSMs和蛋白质可以有序地组装在玻碳电极上,从而制备出高性能的生物传感器。研究发现,NBTSMs材料对酶有很好的生物相容性;能够实现酶与电极间的直接电子转移;对H_2O_2有较好的电催化性能,如宽的检测范围(2-430μM)、低的检测限(0.46μM)、小的米氏常数(204μM)、高的稳定性和好的可重复性。
2.通过二次生长的方法合成了以ZnO纳米棒为主轴,SnO_2纳米棒为枝丫的ZnO/SnO_2复合纳米材料。将ZnO/SnO_2复合纳米材料与血红蛋白(Hb)、壳聚糖(Chi)一起构筑了新颖的纳米生物传感器。研究发现,ZnO/SnO_2复合纳米材料具有很好的生物相容性;能够实现酶与电极间的直接电子转移;对H2O_2有较好的电催化性能,如宽的检测范围(2-370μM)、低的检测限(0.57μM)、高的稳定性和好的可重复性。
3.将立方形的AucoreCo_3O_(4shell)纳米材料与聚丙烯酸(PAA)、辣根过氧化物酶(HRP)一起构筑了新的纳米生物传感器。通过紫外可见谱、电化学阻抗和循环伏安测量发现,AucoreCo_3O_(4shell)-PAA-HRP复合膜具有很好的生物相容性和电化学性质。复合膜中的HRP在磷酸缓冲溶液(PBS)中有一对可逆的氧化还原峰;对H_2O_2有较好的电催化性能,如宽的检测范围(2-370μM)、高的动力学常数(7.4 s~(-1))和比较小的米氏常数(0.91 mM)。
Nanomaterials have offered a good platform for the development of electrochemical biosensors. Now, the performance of biosensors has greatly improved through using nanomaterials because nanomaterials possess unique physical and chemical properties. for example, these biosensors based on nanomaterials have high sensitivity, fast response, wide linear range, well selectivity and high stability. The major results of the thesis are as follows:
1. Nanoplated bismuth titanate sub-microspheres (NBTSMs) were for the first time synthesized by a facile hydrothermal synthesis strategy. The NBTSMs were employed as a supporting matrix to explore a novel immobilization and biosensing platform of redox proteins through a combined hydrogen bond and electrostatic assembly process. The NBTSMs-based composite film has good biocompabiliity, direct electron transfer capacity, and good electrocatalytic properties such as wide linear range (2-430μM), low detection limit (0.46μM), low Michaelis-Menten constant (204μM), and good stability and reproducibility.
2. ZnO/SnO_2 Composite nanomaterials were prepared with SnO_2 nanorods as the template via a secondary growth methode. A completely new biosensor composed of ZnO/SnO_2 composite nanomaterials, chitosan, and hemoglobin was fabricated. The ZnO/SnO_2-based composite film has good biocompabiliity, direct electron transfer capacity, and good electrocatalytic properties such as wide linear range (2-370μM), low detection limit (0.57μM), and good stability and reproducibility.
3. A new biosensor composed of cube-shaped AucoreCo_3O_(4shell) nanoparticles, polyacrylic acid (PAA), and horseradish peroxidase (HRP) was fabricated. The biocompatibility and electrochemical properties of the resulting AucoreCo_3O_(4shell)-PAA-HRP composite film were studied by UV-visible spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The immobilized HRP shows a pair of quasi-reversible redox peaks at -0.31 V in 20 mM PBS (pH 7.0), and the biosensor shows a fast amperometric response to hydrogen peroxide with a linear range of 2-370μM. The kinetic parameters such as ks (electron transfer rate constant) and KM (Michaelis–Menten constant) are evaluated to be about 7.4 s~(-1) and 0.91 mM, respectively.
引文
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