基于蛋白模板金纳米簇及羟基氧化钴纳米片的激活型荧光纳米探针用于免标记和灵敏检测生物硫醇  

Label-free and Sensitive Detection of Biothiols Using a Turn-on Fluorescent Nanoprobe Based on Protein-templated Gold Nanoclusters Coupled with Cobalt Oxyhydroxide Nanoflakes

作　　者：李硕 张桂华 王郁敏 俞英[1] 林碧霞[1] 张立[1] 曹玉娟[1] 郭慢丽[1] LI Shuo;ZHANG Gui-hua;WANG Yu-min;YU Ying;LIN Bi-xia;ZHANG Li;CAO Yu-juan;GUO Man-li(Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine,School of Chemistry,South China Normal University,Guangzhou 510006,China)

机构地区：[1]华南师范大学化学学院广州市生物医药分析化学重点实验室,广东广州510006

出　　处：《分析测试学报》2021年第12期1751-1757,共7页Journal of Instrumental Analysis

基　　金：国家自然科学基金项目(22004039,21575043,21605052,52070080);广东省教育厅青年创新人才项目(2019KQNCX027);广州市生物医药分析化学重点实验室开放基金(2020002);华南师范大学青年教师培育基金(18KJ01)。

摘　　要：该文基于牛血清白蛋白模板金纳米簇(BSA@AuNCs)与羟基氧化钴(CoOOH)纳米片构建了一种激活型荧光纳米探针用于生物硫醇的检测。带负电的BSA@AuNCs能通过静电吸附作用组装到带正电的CoOOH纳米片表面,与此同时,BSA@AuNCs的荧光由于内滤效应(IFE)有效地被CoOOH纳米片猝灭,形成BSA@AuNCs-CoOOH纳米探针。当向纳米探针溶液加入生物硫醇(0.05~150μmol/L)时,生物硫醇与纳米探针中的CoOOH纳米片发生氧化还原反应,CoOOH纳米片被降解生成Co^(2+),同时释放出BSA@AuNCs,BSA@AuNCs荧光信号恢复。结果表明,该纳米探针可以检测低浓度的生物硫醇,对生物硫醇(半胱氨酸、谷胱甘肽和高半胱氨酸)的检出限为30 nmol/L。相对于其他的氨基酸、金属离子及糖类化合物,该纳米探针对生物硫醇具有较高的选择性并成功应用于人血清样品中生物硫醇的检测。Cobalt oxyhydroxide(CoOOH)nanoflakes,an emerging and promising functional twodimensional(2D)nanomaterial with remarkable physical and chemical properties,have received much attention in recent years.Until now,all kinds of fluorescent nanoprobes by integrating CoOOH nanoflakes with fluorescent inorganic nanomaterials have been reported.However,the synthesis procedures for fluorescent inorganic nanomaterials employed in these nanoprobes are generally timeconsuming and complex,and most of them are limited to sensing ascorbic acid.Therefore,investigation on the interaction between CoOOH nanoflakes and biomolecule,and the development of new CoOOHbased fluorescent nanoprobe to broaden biological applications is very interesting and also of great importance.Herein,a turnon fluorescent nanoprobe based on CoOOH nanoflakes and BSAtemplated gold nanoclusters(BSA@AuNCs)was constructed for sensitive and labelfree detection of biothiols.It was found that negative BSA@AuNCs were easily and effectively assemblied on the surface of positive CoOOH nanoflakes to construct a BSA@AuNCs-CoOOH nanoprobe in a short time through the electrostatic interaction between scaffold protein BSA and CoOOH nanoflakes.As a result,the red strong fluorescence emitted by BSA@AuNCs could be efficiently quenched by CoOOH nanoflakes through innerfilter effect(IFE).The CoOOH nanoflakes in the BSA@AuNCs-CoOOH nanoprobe were degraded in the presence of the target biothiol due to the specific redox reaction between biothiols and CoOOH nanoflakes,leading to the release and fluorescence recovery of [e-mail] the basis of the emission increase of BSA@AuNCs,a robust fluorescence sensing strategy for sensitive and selective detection of biothiols was developed,which was demonstrated to be suitable for the quantitative analysis of biothiols(Cys,GSH and Hcy)in the range of 0.05-150μmol/L,with a detection limit as low as 30 nmol/L.Furthermore,this nanoprobe exhibited a high selectivity towards biothiols other than amino acids,metal ions and saccharides.The pract

关 键 词：荧光纳米探针 CoOOH纳米片 蛋白与CoOOH相互作用 蛋白模板金纳米簇 免标记 生物硫醇 

分 类 号：O657.3[理学—分析化学] O629.7[理学—化学]