传感器类型
量子点生物传感器
检测对象
靶标DNA/寡核苷酸(target DNA/oligonucleotide,TGT-1/TGT-2);样品基质为Tris-borate缓冲液(TB)中的核酸溶液,文中关联脊髓性肌萎缩症相关SNP诊断序列。
检测原理
固定化CdSe/ZnS量子点(QD)作为FRET供体,寡核苷酸探针通过生物素-亲和素或双硫醇自组装固定在QD表面。靶标DNA与探针杂交后,标记Cy3或A647的靶标/报告寡核苷酸靠近QD,供体激发态能量通过FRET转移至受体,产生受体敏化发射。分析信号采用受体发射与供体发射的FRET比值,随靶标浓度增加而升高。减小有效传感面积可降低供体背景,多受体标记可提高FRET效率;无蛋白双硫醇界面减少非特异吸附并支持尿素再生。
检测灵敏度
LOD: ≤2 nM (2 pmol);定量测试范围: 2–80 nM (2–80 pmol);先前光纤体系 LOD: 1 nM (1.3 pmol);微分析外推 LOD: ca. 0.3 fmol (300 fM in 1.25 mL)
效应效果
体系选择性良好:直接法中100 nM TGT-1与NC(A647)对比度优于7:1;加入25%甲酰胺后对NC和1BPM-1对比度达8:1,2 nM靶标信号比100 nM单碱基错配高40%。夹心法中报告液加0.1 mg/mL BSA后TGT-1(NL)与NC(NL)对比度接近6:1。无蛋白界面经7 M尿素再生后,NC背景无显著变化,TGT信号可恢复至接近背景,第3、5、7周期FRET比值统计相似。相比NA界面DSG交联再生效率91%(未交联53%),无蛋白界面更稳定。杂交时间约60 min,短于先前光纤4 h,支持可重复、多路复用核酸传感。
传感器的构成
- 基底/换能器:熔融石英光纤(fused silica optical fiber)或硼硅酸盐玻璃珠(borosilicate glass bead),承载界面并用于荧光/总内反射读出。
- 表面偶联层:3-氨基丙基三乙氧基硅烷(APTES)硅烷化玻璃珠,提供氨基用于连接双齿配体。
- 量子点固定配体:N-5-羧基戊基-6,8-硫辛酰胺(TA-ACA)双齿配体,经TCEP还原为二硫醇盐,与CdSe/ZnS量子点壳层配位固定。
- 量子点供体:CdSe/ZnS量子点(gQD/rQD),表面MPA(3-巯基丙酸)配体,作为FRET供体。
- 识别元件:寡核苷酸探针(Probe-1/Probe-2/Probe-3),生物素化探针经NeutrAvidin(NA)固定或双硫醇探针直接自组装到QD。
- 蛋白界面层:NeutrAvidin(NA)与BSA封闭,提高选择性但再生时不稳定。
- 信号标记物:Cy3或Alexa Fluor 647(A647)标记靶标/报告寡核苷酸(TGT/REP),作为FRET受体。
- 封闭/添加剂:BSA加入报告液以降低非特异吸附;甲酰胺/尿素用于杂交选择性与再生。
中文摘要
本文报道了利用固定化量子点(QD)作为供体的固相荧光共振能量转移(FRET)核酸杂交检测体系,并围绕界面化学优化其灵敏度、检出限与再生复用性能。在该体系中,与杂交事件相关的受体染料在固定化QD供体附近产生FRET敏化发射,作为分析信号。通过减小有效传感面积,可降低QD供体光致发光背景,使更微量的受体发射可被分辨,从而降低检出限;在每个杂交事件上结合多个受体染料可提高FRET效率,增强信号。以往常用界面蛋白层提高选择性,但再生条件下蛋白层瞬时失稳会阻碍高效再生。作者提出无蛋白界面化学,利用双齿配体与双硫醇末端探针构建稳定界面,实现了对低至2 pmol靶标核酸的特异性检测,并显著改善了传感器再生与重复使用能力。
英文摘要
The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling the regeneration and reuse of solid-phase QD-FRET hybridization assays. FRET-sensitized emission from acceptor dyes associated with hybridization events at immobilized QD donors provides the analytical signal in these assays. The minimization of active sensing area reduces background from QD donor PL and allows the resolution of smaller amounts of acceptor emission, thus lowering the LOD. The association of multiple acceptor dyes with each hybridization event can enhance FRET efficiency, thereby improving sensitivity. Many previous studies have used interfacial protein layers to generate selectivity; however, transient destabilization of these layers is shown to prevent efficient regeneration. To this end, we report a protein-free interfacial chemistry and demonstrate the specific detection of as little as 2 pmol of target, as well as an improved capacity for regeneration.