A unique bridging facets assembly of gold nanorods

gold nanorodsThe paper “A unique bridging facets assembly of gold nanorods for the detection of thiram through SERS” has been published by Prof Ranjit Thapa, Professor of Physics and his PhD student, Ms Anjana Tripathi, in ACS Sustainable Chemistry & Engineering having an Impact Factor of 8.198.


The addition of Au NRs (Gold Nanorods) to TRM (Thiram) of higher and lower concentrations, yields side-by-side assembly (SSA) and bridging facets assembly (BFA), respectively, and exhibited excellent hotspots for the ultra-low detection of TRM. Bridging facets of Au NRs, such as (5 12 0) and (5 0 12) planes are mainly responsible for the BFA. This kind of interaction is observed for the first time and not reported elsewhere. The detailed facets of Au NRs, namely side facets, bridging facets, and pyramid facets, were discussed with the 3D model of Au NRs. The computational studies confirm the SSA and BFA for Au NRs with varying concentrations of TRM are well in agreement with the experimental results.

Research in brief

Au NRs were synthesized successfully using the seed-mediated method and characterized by UV-Vis analysis, SEM, TEM, FT-IR, Raman, and XPS analysis. Synthesized Au NRs were employed for the detection of TRM. Upon adding Au NRs to TRM of higher and lower concentrations yields side by side (SSA) and bridging facet assembly (BFA), validated by TEM analysis. This unique BFA was observed for the first time and not reported before to the best of our knowledge. Elemental mapping confirms the good adsorption of TRM over Au NRs, and FT-IR, Raman, SERS, and XPS analysis confirm the adsorption of TRM on Au NRs through Au-S bond. A uniformity study was performed for the TRM-Au NRs sample using 25 random places and obtained an RSD of ≤ 10% for each peak in SERS. This shows TRM is uniformly adsorbed on Au NRs. LOD and EF were achieved at 10 pM and 2.8 ×106, respectively. Hence, Au NRs are considered an excellent substrate for the detection of TRM. The unique assembly of BFA may play a significant role in the research community to further study the facet-dependent interactions of nanostructures. The computational study was performed to know the reason behind SSA and BFA. The density functional theory (DFT) was carried out using the Vienna Ab-initio Simulation Package (VASP). The Perdew-Burke-Ernzerhof (PBE) functional within Generalized Gradient Approximation (GGA) is adopted to treat the exchange-correlation interactions. These studies confirm the formation of a strong bond between Au and S, as well as the SSA and BFA for higher and lower TRM concentrations with Au NRs. The binding energy of TRM in SSA and BFA is -3.81 eV and 3.19 eV respectively. From the theory, it shows that TRM of lower concentration form BFA and higher concentration of TRM, due to high barrier energy for TRM diffusion, Au NRs form SSA. In this respect, we calculated the activation barrier for thiram migration from edge site (BFA) to in between site (SSA). Results indicate that TRM needs 2.40 eV energy to migrate from the edge site to in between site to form side-by-side assembly. Therefore, for diffusion from edge to in between (SSA) site high-energy barrier is required i.e. higher concentration is required for such configuration. Hence, at low concentration, TRM will form bridge facet assembly and due to high barrier energy for TRM diffusion, the side-by-side assembly is possible only at high concentration.

Practical implementation/social implications

Concerns have grown in recent years about the widespread use of the pesticide thiram (TRM), which has been linked to negative effects on local ecosystems. This highlights the critical need for quick and accurate point-of-need pesticide analysis tools for real-time applications. The detection of TRM using gold nanorods (Au NRs) with a limit of detection (LOD) of 10-11 M (10 pM) and an enhancement factor (EF) of 2.8 × 106 along with 6.2% of signal homogeneity (with respect to peak at 1378 cm-1) achieved through surface-enhanced Raman scattering (SERS). The interaction of Au NRs with TRM is sensitive, and ultra-low detection of hazardous TRM through SERS makes an ideal technique for environmental protection, real-time applications, and analysis of one-of-a-kind materials.


Bhavya M. B, Akshaya K. Samal
Institute: Centre for Nano and Material Sciences, Jain University, Jain Global Campus
Ramanagara, Bangalore 562112, India

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