School of Chemistry and Molecular Engineering, East China Normal University, Dongchuan Road 500, Shanghai, 200241, China.
School of Chemistry and Molecular Engineering, East China Normal University, Dongchuan Road 500, Shanghai, 200241, China.
Talanta. 2024 Feb 1;268(Pt 1):125304. doi: 10.1016/j.talanta.2023.125304. Epub 2023 Oct 13.
Acquirement of chemical expression in practical brain system is vital to understand the molecular mechanism involved in physiological and pathological processes in brain. Though nanochannels have been demonstrated to be promising platform for electrochemical sensor, it is a great challenge for nanochannels to be employed in practical brain biofluid. In this work, we rationally designed and created the biomimetic asymmetric nanochannels for sensing of K through integrating in situ modification of a two-component mesoporous carbon-silica (MCS) thin film with a pore size of ∼3.6 nm at anodic alumina nanochannel array (AAO) with the ∼40 nm pores (denoted as MCS/AAO). Apparent rectification phenomenon in such functionalized nanochannel array was achieved based on diode-like ion transport. Then, 4'-aminobenzeno-18-crown-6 (SP) was selected to be chemically decorated at MCS/AAO as the specific recognition for K (SP/MCS/AAO). The developed SP/MCS/AAO exhibited good selectivity towards K detection against the coexisting interferences in brain, and possessed a good linear response to K concentration in the range of 0.5-10 mM with a detection limit of 0.1 mM. Combined with microdialysis technique, the variation of K was successfully determined in rat brain microdialysates and serums. Compared with normal rats, the concentration of K was found to be greatly decreased in the cerebral microdialysates and serum of rats with hypertensive model (SHR). This work unveiled a powerful platform for K, and promised to be extended to design new strategy for detecting other chemical species, in particular non-electroactive species in biofluid related to physiological and pathological events.
在实际的大脑系统中获得化学表达对于理解大脑中生理和病理过程涉及的分子机制至关重要。尽管纳米通道已被证明是电化学传感器的有前途的平台，但将纳米通道应用于实际的脑生物流体仍然是一个巨大的挑战。在这项工作中，我们通过整合原位修饰具有约 3.6nm 孔径的两组件介孔碳 - 硅（MCS）薄膜与具有约 40nm 孔径的阳极氧化铝纳米通道阵列（AAO），合理设计并创建了用于感测 K 的仿生不对称纳米通道（表示为 MCS/AAO）。基于类似二极管的离子传输，在这种功能化的纳米通道阵列中实现了明显的整流现象。然后，选择 4'-氨基苯并-18-冠-6（SP）作为化学修饰物在 MCS/AAO 上进行化学修饰，作为对 K 的特异性识别（SP/MCS/AAO）。所开发的 SP/MCS/AAO 对脑内共存干扰物质的 K 检测表现出良好的选择性，并且在 0.5-10mM 的范围内对 K 浓度具有良好的线性响应，检测限为 0.1mM。结合微透析技术，成功地在大鼠脑微透析液和血清中测定了 K 的变化。与正常大鼠相比，在高血压模型（SHR）大鼠的脑微透析液和血清中发现 K 的浓度大大降低。这项工作揭示了一个强大的 K 检测平台，并有望扩展到设计用于检测与生理和病理事件相关的生物流体中其他化学物质，特别是非电活性物质的新策略。
