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. 2023 Jun 13;8(25):22887-22898.
doi: 10.1021/acsomega.3c01878. eCollection 2023 Jun 27.

Plasmon Chemistry on Ag Nanostars: Experimental and Theoretical Raman/SERS Study of the Pesticide Thiacloprid Bond Cleavage by the Plasmon Deactivation Effect

Freddy Celis  1 , Andrés Aracena  2 , Macarena García  1 , Rodrigo Segura Del Río  3 , Santiago Sanchez-Cortes  4 , Patricio Leyton  5
Affiliations

Plasmon Chemistry on Ag Nanostars: Experimental and Theoretical Raman/SERS Study of the Pesticide Thiacloprid Bond Cleavage by the Plasmon Deactivation Effect

Freddy Celis et al. ACS Omega. .

Abstract

Silver nanoparticles (AgNPs) were synthetized and employed in surface-enhanced Raman scattering measurements to study the chemical behavior when thiacloprid (Thia) interacts with the surface of Ag nanospheres (AgNSp) and Ag nanostars (AgNSt) upon excitation of the system with a 785 nm laser. Experimental results show that the deactivation of the localized surface plasmon resonance induces structural changes in Thia. When AgNSp are used, it is possible to observe a mesomeric effect in the cyanamide moiety. On the other hand, when AgNSt are employed, it promotes the cleavage of the methylene (-CH2-) bridge in Thia to produce two molecular fragments. To support these results, theoretical calculations based on topological parameters described by the atoms in molecules theory, Laplacian of the electron density at the bond critical point (∇2ρ BCP), Laplacian bond order, and bond dissociation energies were made, confirming that the bond cleavage is centered at the -CH2- bridge in Thia.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) Experimental [red(—)], theoretical scaled [blue(—)], and theoretical unscaled (—) Raman spectra of Thia. (b) Simulated structure of Thia from the CIF file by using DFT theoretical calculation with the corresponding acronym for each molecular group.
Figure 2
Figure 2
High-resolution SEM images of (a) AgNSt and (b) AgNSp.
Figure 3
Figure 3
UV–visible spectra of (a) Ag NPs, (b) Thia, and (c) AgNPs + Thia (10–5 M) compared with Thia. (d) UV–visible maxima absorption band of Thia, AgNSp, AgNSt, and AgNPs-Thia.
Figure 4
Figure 4
(a) Comparison of the Raman (—) spectrum of Thia with the SERS spectra onto the AgNSp [red(—)] and AgNSt [blue(—)]. Comparison of Raman/SERS spectra in the selected region: (b) 100–400, (c) 2000–2400, and (d) 2800–3200 cm–1.
Figure 5
Figure 5
(a) Resonance hybrid for the TZDr-CIm fragment and (b) optimized structure of Thia onto the silver surface.
Figure 6
Figure 6
(a) Spectral reproducibility of Thia onto AgNSt. (b) Proposed mechanism to produce two fragments from the Thia structure. (c,d) Orientation of two theoretical simulations. (e) Formation of the TNI to cleavage a bond. (f) Energy representation of the Ag surface/Thia system.
Figure 7
Figure 7
(a) Frontiers molecular orbitals of neutral Thia (i), anionic Thia (ii), and the optimized structure of Thia without extra electrons (iii). (b) Frontiers molecular orbitals of Thia onto the Ag surface. In the red oval is presented the electronic population of the amplified CIm group.
See this image and copyright information in PMC

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