金-银双金属纳米簇@多壁碳纳米管-二氧化钛纳米材料为新型氧化还原探针构建电化学免疫传感器  

Electrochemical Immunosensor Based on Au-Ag Bimetallic Nanoclusters@CNTs-TiO_(2) Nanomaterials as Novel Redox Probes

作　　者：黄小梅[1,2,3] 邓祥 邓子禾[4] HUANG Xiao-mei;DENG Xiang;DENG Zi-he(Department of Chemistry and Chemical Engineering,Sichuan University of Arts and Science,Dazhou 635000,China;Key Laboratory of Exploitation and Study of Distinctive Plants in Education Department of Sichuan Province,Dazhou 635000,China;Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education,Zigong 643000,China;College of Chemistry and Chemical Engineering,Shihezi University,Shihezi 832000,China)

机构地区：[1]四川文理学院化学化工学院,四川达州635000 [2]四川省教育厅特色植物开发利用研究重点实验室,四川达州635000 [3]四川省高等学校绿色化学重点实验室,四川自贡643000 [4]石河子大学化学化工学院,新疆石河子832000

出　　处：《分析测试学报》2022年第5期675-681,共7页Journal of Instrumental Analysis

基　　金：四川省科技厅应用基础研究项目(2019YJ0307);特色植物开发研究四川省高校重点实验室项目(TSZW2005,TSZW2004);绿色催化四川省高校重点实验室开放基金(LYJ1802);达州市科技局应用基础研究项目(18YYJC0002)。

摘　　要：该研究合成了具有独特“珍珠项链”结构的金-银双金属纳米簇@多壁碳纳米管-二氧化钛纳米复合材料(Au-Ag NCs@CNTs-TiO_(2)NPs)作为信号标签、载体和信号放大器,构建了一种高灵敏“三明治”式电化学免疫传感器用于糖类抗原19-9(CA19-9)的检测。首先将具有过氧化物模拟酶特性的磁性Au-Fe_(3)O_(4)NPs用于修饰电极,然后通过化学键合作用将anti-CA19-9抗体和BSA固载于电极表面,再通过特异性反应结合不同浓度的抗原和具有氧化还原活性和放大作用的Au-Ag NCs@CNTs-TiO_(2)NPs/Ab_(2)/BSA生物耦合物形成夹心免疫结构进行检测。结果表明,通过双重过氧化物模拟酶催化底液中的H_(2)O_(2),有效地放大了响应信号,在最优条件下,CA19-9在0.01~200 U/mL浓度范围内线性关系良好,最低检出限为0.003 U/mL。采用标准加入法测得免疫传感器的回收率为94.6%~105%,相对标准偏差(RSD)为4.3%~6.5%,表明该免疫传感器有望用于临床血清样品中CA19-9的检测。A highly sensitive"sandwich"electrochemical immunosensor was constructed for the de⁃tection of carbohydrate antigen 19-9(CA19-9),by synthesizing a unique"pearl necklace"struc⁃ture of gold-silver bimetallic nanoclusters multi-walled carbon nanotubes-titanium dioxide nanocom⁃posites(Au-Ag NCs@CNTs-TiO_(2)NPs)used as a signal label,carrier and signal amplifier.First⁃ly,the magnetic Au-Fe_(3)O_(4)NPs with peroxidase mimetic properties were used to modify the elec⁃trode,then the anti-CA19-9 antibody and BSA were immobilized on the electrode surface through chemical bonding,and subsequently,the antibody was bound by specific reaction.Finally,Au-Ag NCs@CNTs-TiO_(2)NPs/Ab_(2)/BSA biological coupling with redox activity and amplification was combined to form a sandwich immune structure.The experimental results showed that the response signal was effectively amplified by using double peroxide analog enzyme to catalyze H_(2)O_(2)in the sub⁃strate.Under the optimal experimental conditions,CA19-9 showed a good linearity in the concen⁃tration range of 0.01-200 U/mL,with a detection limit of 0.003 U/mL.The recoveries of the im⁃munosensor ranged from 94.6%to 105%,with relative standard deviations(RSD)of 4.3%-6.5%,indicating that the immunosensor could be used for the detection of CA19-9 in clinical serum sam⁃ples.

关 键 词：双金属纳米簇 协同作用 Au-Ag NCs@CNTs-TiO_(2)纳米复合材料 糖类抗原19-9 

分 类 号：O657.1[理学—分析化学] Q939.91[理学—化学]