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利用多尺度纳米材料通过三明治纳米结构制备的高灵敏度超薄表面增强拉曼散射(SERS)基底用于水果曲面上农药的检测

Highly sensitive thin SERS substrate by sandwich nanoarchitecture using multiscale nanomaterials for pesticide detection on curved surface of fruit.

作者信息

Park Jisoo, Kim Jihoon, Kim Jinbo, Kim Kahyun, Kim Jiwon, You Jungmok, Kim Dae Woo, Kim Jeonghun

机构信息

Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 03722, South Korea.

Department of Plant & Environmental New Resources and Graduate School of Biotechnology, College of Life Sciences, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 446-701, South Korea.

出版信息

J Hazard Mater. 2025 Aug 15;494:138450. doi: 10.1016/j.jhazmat.2025.138450. Epub 2025 Apr 30.

Abstract

Various flexible surface-enhanced Raman scattering (SERS) substrates have been developed for the Raman detection of environmental pollutants due to their high sensitivity, low cost, and rapid sampling capabilities. However, achieving high reproducibility, reliability, and sensitivity in large areas remains challenging. In this study, we present a simple fabrication method for a layered, sandwich-nanoarchitectured SERS substrate consisting of multiscale nanomaterials of (1) 0D, Au nanoparticles (AuNPs), (2) 1D, TEMPO-oxidized nanocellulose fibers (TC), and (3) 2D, MXene (TiCT). The resulting MXene@AuNP@MXene@TC (MX@Au@MX@TC) film demonstrated enhanced SERS performance based on the synergistic effect of efficient charge transfer (CT) and the presence of numerous nanogaps. Vertical plasmonic coupling in the MX@Au@MX@TC film, combined with the uniform adsorption of the target molecules, led to an ultra-low limit of detection of 10 M and an enhancement factor of 9.9 × 10 for rhodamine 6 G (R6G). In addition, the substrate exhibited excellent reliability, providing uniform and stable signals across various spatial scales with a relative standard deviation of 2.29 %. Furthermore, the SERS substrate detected thiram (0.02 μg/cm²) via direct in-situ sampling on curved fruit surfaces, offering insights into the scalable, cost-effective production of flexible SERS substrates for practical use.

摘要

由于具有高灵敏度、低成本和快速采样能力,各种柔性表面增强拉曼散射(SERS)基底已被开发用于环境污染物的拉曼检测。然而,在大面积上实现高重现性、可靠性和灵敏度仍然具有挑战性。在本研究中,我们提出了一种简单的制备方法,用于制备一种分层的、三明治纳米结构的SERS基底,该基底由以下多尺度纳米材料组成:(1)零维的金纳米颗粒(AuNP),(2)一维的2,2,6,6-四甲基哌啶-1-氧基(TEMPO)氧化纳米纤维素纤维(TC),以及(3)二维的MXene(TiCT)。所得的MXene@AuNP@MXene@TC(MX@Au@MX@TC)薄膜基于高效电荷转移(CT)的协同效应和大量纳米间隙的存在,表现出增强的SERS性能。MX@Au@MX@TC薄膜中的垂直等离子体耦合,结合目标分子的均匀吸附,导致罗丹明6G(R6G)的超低检测限为10⁻¹¹ M,增强因子为9.9×10⁵。此外,该基底表现出优异的可靠性,在各种空间尺度上提供均匀且稳定的信号,相对标准偏差为2.29%。此外,该SERS基底通过在弯曲的水果表面直接原位采样检测到了福美双(0.02μg/cm²),为实际应用中可扩展、经济高效地生产柔性SERS基底提供了思路。

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