Influence of Sample Preparation on SERS Signal Isabela Bianchi-Carvalho, Marcelo José dos Santos Oliveira, Cibely Silva Martin, Santiago Sánchez-Cortés, Carlos José Leopoldo Constantino Chemosensors, 2025 Carbendazim (MBC), a commonly used fungicide from the benzimidazole group, was applied in this study as a probe molecule to understand the influence of sample preparation on the SERS (surface-enhanced Raman scattering) signal. We applied the external standard method (ESM), preparing fresh Ag colloid samples (reduced by hydroxylamine) for each concentration and measuring with and without potassium nitrate (KNO₃) as an aggregation-inducing salt. The impact of sample dilution before or after the addition of the salt to the Ag colloid was also explored. SERS signals were correlated with Ag colloid aggregation observed via transmission electron microscopy (TEM), UV-Vis extinction, dynamic light scattering (DLS), and zeta potential, examining diffusion-limited cluster aggregation (DLCA) and reaction-limited cluster aggregation (RLCA) mechanisms. The optimal results were achieved without KNO₃, with more compact aggregates at lower concentrations and more branched ones at higher concentrations. Dilution of the Ag colloid before salt addition enabled lower detection limits than without any dilution. No SERS signal was observed when the salt was added before dilution. These findings emphasize that a consistent relationship between aggregate morphology and the SERS signal cannot be generalized across analytes. Analyte-specific properties play a crucial role in determining optimal aggregation conditions for SERS analysis.
Challenges in surface-enhanced Raman scattering signal for ethephon detection: Theoretical and experimental approaches Isabela Bianchi‐Carvalho, Cibely S. Martin, Gabriel G. B. Alves, Jaqueline N. Silva, Augusto Batagin‐Neto, et al. Journal of Raman Spectroscopy, 2024 Ethephon, a widely used growth regulator in fruits and vegetables, requires careful monitoring because of its toxicity. However, as far as we know, only two works are found in the literature regarding surface‐enhanced Raman scattering (SERS) ethephon detection. Indeed, obtaining the SERS signal revealed to be challenging. Therefore, we have evaluated the SERS signal of ethephon using theoretical (as density functional theory and charge‐assisted fragment interaction) and experimental approaches, addressing this limited literature knowledge. Theoretical Raman spectra with Ag or Au atoms at reactive sites exhibited enhanced ethephon SERS signal via AgCl bonding, consistent with the experimental data. Multiple experimental procedures were employed to obtain the SERS signal, including pH variations, salt addition, excitation laser lines, time dependency, and different SERS substrates (Ag colloid and Ag island films). Salt addition (NaCl) improved SERS signal, correlating with Ag colloid aggregation. Analysis in Ag colloid showed the pH 7.0 as optimal for ethephon detection, using freshly prepared Ag colloid + ethephon dispersion with ethephon powder being directly dissolved into Ag colloid. Only the AgCl band intensity improved with time. Ag colloid (wet medium — 633 nm laser line) outperformed Ag island films (dry medium — 785 nm laser line).
