Detection of Persistent Organic Pollutants by Using SERS Sensors Based on Organically Functionalized Ag Nanoparticles

In this work, we have developed a simple method to carry out the quantitative analysis of deethylhydroxyatrazine (DEHA), the most abundant metabolite of atrazine herbicide (ATZ), based on the surface-enhanced Raman scattering technique. Since this ATZ product can undergo pH-dependent tautomerization, a previous characterization of the DEHA vibrational spectrum was accomplished. This study consisted of the Raman scattering study, both experimental and theoretical, of the enolic and ketonic tautomers of this molecule. SERS spectra were recorded at different pH in order to assess the effect of the metal surface in nanoparticles along with the pH on the structure of DEHA and to find the optimal experimental conditions of the quantitative detection of DEHA. Additionally, the interaction of DEHA with two types of humic acid reference standards, the Elliot humic and leonardite humic ones, was also performed by SERS. This interaction was conducted with two different objectives: to evaluate the interaction mechanism of the ATZ degradation product with humic substances and to check if this interaction can modify the sensitivity of the SERS detection of DEHA. The results presented in this study have clearly demonstrated that SERS spectroscopy is a very powerful technique for characterizing DEHA and other triazine sub-products at a very low concentration in water and also for analyzing the interaction of these important pollutants with humic substances.

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“…The electric field enhancement is associated with localized surface plasmon resonance (LSPR) induced on the metal surface [28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

“…the Raman intensity is based on the adsorption of the analyzed molecules on nanostructured noble metal surfaces. The electric field enhancement is associated with localized surface plasmon resonance (LSPR) induced on the metal surface [28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Sensing Atrazine Herbicide Degradation Products through Their Interactions with Humic Substances by Surface-Enhanced Raman Scattering

et al. 2021

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“…Such great enhancement is, under certain conditions, sufficient for a single or few molecule detection, making SERS an extremely useful technique for a very sensitive chemical and biomolecular detection . The enhancement of the Raman intensity requires localization of the analyzed molecules near or at nanostructured noble metal surfaces and is associated to localized surface plasmon resonance (LSPR) induced on the metal surface . Currently, the most employed SERS substrates are metal nanoparticles (NPs) in suspension, that is, colloids …”

Section: Introductionmentioning

confidence: 99%

Abiotic degradation of s‐triazine pesticides analyzed by surface‐enhanced Raman scattering

Rubira

Constantino

Otero

et al. 2019

J Raman Spectroscopy

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In this work, we explore the use of surface‐enhanced Raman scattering (SERS) on silver (Ag) nanoparticles for the detection of triazine pesticide atrazine and prometryn as well as their degradation products. This tecnique was used to monitor the pesticide degradation both in the commercial samples as well as by the effects of heat and humidity. We have studied the adsorption affinity of these pesticides as well as their degradation products on the employed SERS substrates in order to check the optimal conditions in the detection of both the original pesticide and their degradation products. The presence of these products in triazine pesticides with high solubility in water is of great interest for the human health, but what's even more important is the fact that the pesticide degradation can be favored by very mild conditions of humidity, temperature, and pH, thus leading to high levels of structural modifications, which produce other final compounds with an even higher impact on both human health and environment.

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“…3−5 The sensitivity and uniformity of the SERS response strongly depends on the morphology of the metal plasmonic surface, as well as on its surface chemistry, which can be modulated to enhance the applicability of these systems. 6,7 The enhancement can be controlled by nanofabrication of the surface structure in terms of size, shape, and spacing of features of the surface to which the SERS analyte molecules bind.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Surface enhanced Raman spectroscopy (SERS) has seen constant growth since its discovery over 30 years ago. One of the most active areas of SERS is the development of effective substrates upon which sample molecules can be adsorbed giving rise to strong enhancement efficiencies and reproducibility. , Its potential as an analytical technique has been widely studied, and SERS sensors have been developed for pollutants, insecticides, or drugs. − The sensitivity and uniformity of the SERS response strongly depends on the morphology of the metal plasmonic surface, as well as on its surface chemistry, which can be modulated to enhance the applicability of these systems. , The enhancement can be controlled by nanofabrication of the surface structure in terms of size, shape, and spacing of features of the surface to which the SERS analyte molecules bind.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and Detection of Sport Doping Drugs on Metallic Plasmonic Nanoparticles of Different Morphology

et al. 2012

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A comparative study of different plasmonic nanoparticles with different morphologies (nanospheres and triangular nanoprisms) and metals (Ag and Au) was done in this work and applied to the ultrasensitive detection of aminoglutethimide (AGI) drug by surface enhanced Raman spectroscopy (SERS) and plasmon resonance. AGI is an aromatase inhibitor used as an antitumoral drug with remarkable pharmacological interest and also in illegal sport doping. The application of very sensitive spectroscopic techniques based on the localization of an electromagnetic field on plasmonic nanoparticles confirms the previous study of the adsorption of drugs onto a metal surface due to the near field character of these techniques. The adsorption of AGI on the above substrates was investigated at different pH values and surface coverages, and the results were analyzed on the basis of AGI/metal affinity, considering the interaction mechanism, the existence of two binding sites in AGI, and the influence of the interface on the adsorption in terms of surface charge due to the presence of other ions linked to the surface. Finally, a comparative quantitative detection of AGI was performed on both spherical and triangular nanoprism nanoparticles, and a limit of detection lower than those reported so far was deduced on the latter nanoparticles.

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Detection of Persistent Organic Pollutants by Using SERS Sensors Based on Organically Functionalized Ag Nanoparticles

Cited by 4 publications

References 67 publications

Sensing Atrazine Herbicide Degradation Products through Their Interactions with Humic Substances by Surface-Enhanced Raman Scattering

Sensing Atrazine Herbicide Degradation Products through Their Interactions with Humic Substances by Surface-Enhanced Raman Scattering

Abiotic degradation of s‐triazine pesticides analyzed by surface‐enhanced Raman scattering

Adsorption and Detection of Sport Doping Drugs on Metallic Plasmonic Nanoparticles of Different Morphology

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