Binding and Orientation of Carbamate Pesticides on Silica Surfaces
Binding and Orientation of Carbamate Pesticides on Silica Surfaces
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DOI：
10.1021/acs.jpcc.3c02312
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发表时间：
2023-04
期刊：
影响因子：
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通讯作者：
L. Bromley;Pablo E. Videla;Jerry L. Cartagena-Brigantty;Victor S. Batista;L. Velarde
中科院分区：
文献类型：
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作者：
L. Bromley;Pablo E. Videla;Jerry L. Cartagena-Brigantty;Victor S. Batista;L. Velarde
甲萘威（1-萘基- N -氨基甲酸甲酯）是最广泛使用的氨基甲酸酯类农药之一，也是常见的地面和地表水污染物。尽管如此，对这种农药和矿物颗粒之间的具体相互作用与环境影响，包括土壤和粉尘气溶胶界面缺乏了解。在这里，我们通过应用振动和频率产生（vSFG）光谱和原子模拟的组合来研究西维因在亲水二氧化硅表面的吸附。我们发现，通过氨基甲酸酯基团（主要是- NH端，其次是- C - O酯部分）和表面硅烷醇和硅烯酸酯之间的氢键相互作用，羰基分子很容易吸附到二氧化硅/空气界面上。平均而言，这导致萘芳环的取向大致平行于表面。我们对氨基甲酸酯类农药在二氧化硅表面相互作用的表征，对于理解氨基甲酸酯类农药在与环境相关的下游过程中通过界面的运输、稳定和潜在降解机制特别有价值。
: Carbaryl (1-naphthyl- N -methyl carbamate) is one of the most abundantly used carbamate pesticides and a common ground and surface water contaminant. Despite this, there is a lack of understanding regarding the specific interactions between this pesticide and mineral particles with environmental impact, including soil and dust aerosol interfaces. Here, we examine the adsorption of carbaryl to hydrophilic silica surfaces by applying a combination of vibrational Sum Frequency Generation (vSFG) spectroscopy and atomistic simulations. We find that carbaryl molecules readily adsorb to silica/air interfaces by hydrogen-bonding interactions between the carbamate group (primarily the − NH terminus, secondarily the ester − C � O ester moiety) and the surface silanols and silenolates. On average, this results in the naphthyl aromatic ring being oriented roughly parallel to the surface. Our characterization of interactions of carbamate pesticides at silica surfaces is particularly valuable for understanding the transport, stabilization, and potential degradation mechanisms of carbamate pesticides by interfaces during downstream processes of environmental relevance.