Unveiling the Neglected Role of Silver Ions’ Leaching for Recovered Functionality of Carboxylate SAMs on Ag

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry Pub Date : 2025-09-23 DOI:10.1021/acs.analchem.5c03988

Bohan Shan, Yunhan Hu, Tongzhou Xu, Zhengyuan Zhao, Haodong Zhong, Yunhan Ling, Weipeng Wang, Zhengjun Zhang

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Abstract

The full release of surface-enhanced Raman spectroscopy (SERS) potential relies on modification of the substrate surface. However, chemical functionalization on silver substrates has, in some cases, resulted in anomalous behaviors that are difficult to explain. In this study, we investigate the role of Ag⁺ leaching from a silver surface in disrupting the performance of carboxyl-terminated self-assembled monolayers (SAMs). Using 4-mercaptobenzoic acid (4-MBA) as a model, we demonstrate that Ag⁺ released during SAM formation coordinates with carboxylate groups, inducing both aberrant SERS responses and multilayer adsorption that cannot be removed by conventional rinsing. To address this issue, we introduce a deoxygenation treatment─immersing freshly deposited AgNRs in KBH₄ solution under inert atmosphere─to remove surface oxides and suppress Ag⁺ release. Treated Ag-4-MBA nanosensors exhibit restored, stable, and accurate pH responsiveness and reliably detect 30 ppm gaseous acetic acid. Our findings elucidate Ag⁺ interference on carboxyl and develop a robust strategy to enhance the reliability of silver-based SERS sensors, paving the way for their broader applications in molecular sensing.

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揭示银离子浸出对银上羧酸SAMs功能恢复的忽视作用

表面增强拉曼光谱（SERS）电位的充分释放依赖于衬底表面的修饰。然而，在某些情况下，银底物上的化学功能化导致了难以解释的异常行为。在这项研究中，我们研究了银表面Ag+浸出在破坏端羧基自组装单层膜（SAMs）性能中的作用。以4-巯基苯甲酸（4-MBA）为模型，我们证明了在SAM形成过程中释放的Ag+与羧酸基配合，诱导了异常的SERS响应和常规冲洗无法去除的多层吸附。为了解决这个问题，我们引入了一种脱氧处理方法──将新沉积的agnr浸入惰性气氛下的KBH4溶液中──以去除表面氧化物并抑制Ag+的释放。经过处理的Ag-4-MBA纳米传感器表现出恢复、稳定和准确的pH响应性，并可靠地检测30 ppm的气态乙酸。我们的研究结果阐明了Ag+对羧基的干扰，并开发了一种强大的策略来提高银基SERS传感器的可靠性，为其在分子传感中的更广泛应用铺平了道路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Analytical Chemistry 化学-分析化学

CiteScore

12.10

自引率

12.20%

发文量

1949

审稿时长

1.4 months

期刊介绍： Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.