Actively Controllable Solid-Phase Microextraction in a Hierarchically Organized Block Copolymer-Nanopore Electrode Array Sensor for Charge-Selective Detection of Bacterial Metabolites.
Actively Controllable Solid-Phase Microextraction in a Hierarchically Organized Block Copolymer-Nanopore Electrode Array Sensor for Charge-Selective Detection of Bacterial Metabolites.
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DOI：
10.1021/acs.analchem.1c02998
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发表时间：
2021-11-02
影响因子：
7.4
通讯作者：
Bohn PW
中科院分区：
文献类型：
--
作者：
Jia J;Kwon SR;Baek S;Sundaresan V;Cao T;Cutri AR;Fu K;Roberts B;Shrout JD;Bohn PW
铜绿假单胞菌产生许多吩嗪代谢物，包括绿脓素 (PYO)、吩嗪-1-甲酰胺 (PCN) 和吩嗪-1-羧酸 (PCA)。其中，PYO 作为铜绿假单胞菌感染的生物标志物得到了最广泛的研究。然而，尽管五氯苯甲醚具有广谱抗生素特性，并且在其他二级吩嗪的生物合成途径中作为前体发挥作用，但它引起的关注较少，部分原因是其浓度相对较低，并且受到其他高丰度吩嗪的干扰。本文通过构建分层组织的纳米结构来解决这一挑战，该纳米结构由 pH 响应性嵌段共聚物 (BCP) 膜和填充有金纳米颗粒 (AuNP) 的纳米孔电极阵列 (NEA) 组成，用于分离和检测细菌环境中的 PCA。 BCP@NEA 策略的设计是将细菌培养基的 pH 值调整至 4.5，高于 PCA 的 pKa，但低于 PYO 和 PCN 的 pKa，确保 PCA 带负电荷，并且可以选择性地跨 BCP 膜转运。在 pH 4.5 时，只有 PCA 被转运到充满 AuNPs 的 NEA 中，而 PYO 和 PCN 被阻断。结构表征说明了 NEA 纳米孔体积中 AuNP 的严格空间偏析，允许使用方波伏安法和表面增强拉曼光谱定量测定铜绿假单胞菌分泌的 PCA，作为孵育时间的函数。本研究提出的策略可以通过改变亲水性嵌段的性质来扩展，并随后应用于检测复杂生物样品中低浓度的其他氧化还原活性代谢物，从而帮助了解微生物群落的代谢。电化学 SERS 传感器的横截面 SEM 图像和示意图，其中 BCP 门在 pH 7.0 时关闭（中），BCP 门在 pH 4.5 时打开（右），用于通过方波伏安法和 SERS 选择性渗透传输和检测带负电的分子。
Pseudomonas aeruginosa produces a number of phenazine metabolites, including pyocyanin (PYO), phenazine-1-carboxamide (PCN), and phenazine-1-carboxylic acid (PCA). Among these, PYO has been most widely studied as a biomarker of P. aeruginosa infection. However, despite its broad-spectrum antibiotic properties and its role as a precursor in the biosynthetic route leading to other secondary phenazines, PCA has attracted less attention, partially due to its relatively low concentration and interference from other highly abundant phenazines. This challenge is addressed here by constructing a hierarchically organized nanostructure consisting of a pH-responsive block copolymer (BCP) membrane with nanopore electrode arrays (NEAs) filled with gold nanoparticles (AuNPs) to separate and detect PCA in bacterial environments. The BCP@NEA strategy is designed such that adjusting the pH of the bacterial medium to 4.5, which is above the pKa of PCA but below the pKa of PYO and PCN, ensures that PCA is negatively charged and can be selectively transported across the BCP membrane. At pH 4.5, only PCA is transported into the AuNPs-filled NEAs, while PYO and PCN are blocked. Structural characterization illustrates the rigorous spatial segregation of the AuNPs in the NEA nanopore volume, allowing PCA secreted from P. aeruginosa to be quantitatively determined as a function of incubation time using square-wave voltammetry and surface-enhanced Raman spectroscopy. The strategy proposed in this study can be extended by changing the nature of the hydrophilic block and subsequently applied to detect other redox-active metabolites at low concentration in complex biological samples and, thus, help understand metabolism in microbial communities. Cross-sectional SEM image and schematic illustration of the electrochemical SERS sensor with BCP gate closed at pH 7.0 (middle) and BCP gate open at pH 4.5 (right) for the permselective transport and detection of negatively charged molecules by square wave voltammetry and SERS.
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