Department of Biophysics, Faculty of Sciences, University of P. J. Šafárik, Jesenná 5, 040 01 Košice, Slovakia.
Department of Biology and Physiology, University of Veterinary Medicine and Pharmacy, Komenského 73, 041 81 Košice, Slovakia.
Spectrochim Acta A Mol Biomol Spectrosc. 2022 Mar 5;268:120629. doi: 10.1016/j.saa.2021.120629. Epub 2021 Nov 15.
Pesticide use worldwide exhibits a positive effect on agricultural production while it may negatively affect organisms living in soil, water or the air. Importantly, numerous negative health effects also occur in humans exposed to (accumulated) pesticides or their metabolites over a long period of time. To prevent both environmental catastrophes and adverse human health impacts, initial studies of the selected pesticides need to be performed together with the constant post-approval control; risk assessment analysis and on site monitoring have to be continuously carried out. Given this, Raman spectroscopy, especially surface-enhanced Raman spectroscopy (SERS), during the last decade has become a powerful analytical technique since it can offer quick, selective, and in situ detection of selected pollutants found in analyzed samples at very low concentrations. Moreover, the structural changes caused by the pollutant-biomacromolecule interaction can also be recognized in the molecule-specific Raman spectral signatures of biomolecules. In this study, we report a vibrational characterization of the fungicide molecule Tebuconazole (TB) which is listed to be a possible carcinogen. Even though its international and common use there is no evidence about the use of Raman/SERS spectroscopy to detect it sensitively and selectively as well as to analyse its impacts on biological systems. Therefore, we have recorded and calculated Raman and infrared spectra of TB. Furthermore, SERS spectra of TB were also registered and comprehensively analysed in view of the employed SERS substrates, dependence on the excitation wavelengths and pH of the analysed molecular systems. The molecule of TB interacts preferentially through the triazole moiety with the colloidal metal nanoparticles (NPs) whereas the silver NPs prepared by reduction of silver nitrate with hydroxylamine hydrochloride resulted to be the most effective ones. Consequently, the limit of detection was determined to be 1.4 μM≈430 ppb. The present paper thus could serve significantly for further investigations focused on both conducting vibrational analyses of structurally related molecules as well as providing a more precise explanation of the mechanism of action of TB and its influence on biological macromolecules.
全世界范围内使用农药对农业生产具有积极影响，但也可能对土壤、水或空气中的生物产生负面影响。重要的是，人类长期暴露于（积累）农药或其代谢物中，也会产生许多负面的健康影响。为了防止环境灾难和对人类健康的不利影响，需要对选定的农药进行初步研究，并结合持续的批准后控制；必须不断进行风险评估分析和现场监测。有鉴于此，拉曼光谱，特别是表面增强拉曼光谱（SERS），在过去十年中已成为一种强大的分析技术，因为它可以提供快速、选择性和原位检测分析样品中非常低浓度的选定污染物。此外，还可以在生物分子的分子特异性拉曼光谱特征中识别出污染物-生物大分子相互作用引起的结构变化。在本研究中，我们报告了杀菌剂 TB 的振动特性，TB 被列为可能的致癌物质。尽管它在国际上和普遍使用，但没有证据表明使用拉曼/ SERS 光谱来灵敏和选择性地检测它，以及分析它对生物系统的影响。因此，我们记录并计算了 TB 的拉曼和红外光谱。此外，还记录并综合分析了 TB 的 SERS 光谱，以研究所采用的 SERS 基底、激发波长和分析分子体系的 pH 值的依赖性。TB 分子优先通过三唑部分与胶体金属纳米粒子（NPs）相互作用，而通过还原硝酸银与盐酸羟胺制备的银 NPs 被证明是最有效的 NPs。因此，检测限确定为 1.4 μM≈430 ppb。因此，本文可以为进一步的研究提供重要依据，这些研究不仅关注对结构相关分子进行振动分析，还为 TB 的作用机制及其对生物大分子的影响提供更精确的解释。
