Quantitative SERS Detection of Dopamine in Cerebrospinal Fluid by Dual-Recognition-Induced Hot Spot Generation
Quantitative SERS Detection of Dopamine in Cerebrospinal Fluid by Dual-Recognition-Induced Hot Spot Generation
复制标题
双识别诱导热点生成定量 SERS 检测脑脊液中的多巴胺
DOI：
10.1021/acsami.8b01063
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发表时间：
2018-05-09
影响因子：
9.5
通讯作者：
Liu, Baohong
中科院分区：
文献类型：
--
作者：
Zhang, Kun;Liu, Yu;Liu, Baohong
中枢神经系统细胞外多巴胺（DA）浓度的可靠分析对于深入了解其生物学和病理学功能至关重要。然而，这种神经递质的定量测定仍然是一个挑战，因为患者的脑脊液（CSF）中DA的浓度极低。基于硼酸酯对二醇和N-羟基琥珀酰亚胺酯对胺基的特异性识别，提出了一种简单、高灵敏度的DA表面增强拉曼散射（Sers）检测方法。这是通过首先将3，3 '-二硫代二丙酸二（N-羟基琥珀酰亚胺酯）固定在金薄膜表面上以捕获DA，然后引入3-巯基苯基硼酸（3-MPBA）官能化的银纳米颗粒以产生具有纳米颗粒在镜上几何形状的许多等离子体“热点”来实现的。这种双重识别机制不仅避免了复杂的基于生物元素的操作，而且有效地降低了背景信号。直接使用识别探针3-MPBA作为拉曼报告分子，“信号”Sers方法被用来定量DA的浓度从1 pM到1 μ M，检测限为0.3 pM。此外，我们的双识别定向Sers检测表现出高抗脑干扰，并成功地应用于监测患者的CSF样品中的DA。
Reliable profiling of the extracellular dopamine (DA) concentration in the central nervous system is essential for a deep understanding of its biological and pathological functions. However, quantitative determination of this neurotransmitter remains a challenge because of the extremely low concentration of DA in the cerebrospinal fluid (CSF) of patients. Herein, on the basis of the specific recognition of boronate toward diol and N-hydroxysuccinimide ester toward the amine group, a simple and highly sensitive strategy was presented for DA detection by using surface-enhanced Raman scattering (SERS) spectroscopy as a signal readout. This was realized by first immobilizing 3,3'-dithiodipropionic acid di(N-hydroxysuccinimide ester) on gold thin film surfaces to capture DA, followed by introducing 3-mercaptophenylboronic acid (3-MPBA)-functionalized silver nanoparticles to generate numerous plasmonic "hot spots" with the nanoparticle-on-mirror geometry. Such a dual-recognition mechanism not only avoids complicated bioelement-based manipulations but also efficiently decreases the background signal. With the direct use of the recognition probe 3-MPBA as a Raman reporter, the "signal-on" SERS method was employed to quantify the concentration of DA from 1 pM to 1 mu M with a detection limit of 0.3 pM. Moreover, our dual-recognition-directed SERS assay exhibited a high resistance to cerebral interference and was successfully applied to monitoring of DA in CSF samples of patients.