NMR evidence for hydrogen bonding stabilized anti conformation of 1-methoxy-1-methyl-3-phenylurea and the concentration detection by SERS

•NMR was employed to study the conformational aspects of MMPU.•DFT calculations were conducted to predict the electronic and structural properties.•Anti-MMPU is stabilized by intramolecular H-bonding.•Ag@SiO2 nanocomposite was synthesized and characterized.•SERS-based trace detection protocol for MMPU was developed. Phenylurea-based herbicides have been widely used to control the plant growth. Due to their toxicity, strict regulations to limit their usage have been applied. Developing trace detection protocols of substituted phenylureas has attracted more attention, especially with the availability of a wide range of spectroscopic and analytical techniques. In this study, the conformational and structural properties of 1-methoxy-1-methyl-3-phenylurea (MMPU) which belongs to the family of phenylurea-based herbicides have been characterized. The anti-configuration, facilitated by the intramolecular hydrogen bonding between the oxygen atom of the methoxy moiety and the acidic amide proton, was observed using the nuclear magnetic resonance (NMR) spectroscopy through the Selective Nuclear Overhauser Effect (SelNOE) approach. The density functional theory (DFT) calculations suggested that the anti form is at least 9 kcal/mol more stable than the corresponding syn structure. Possible degradation pathways of such a class of herbicides can be explored when a firm understanding of their electronic and conformational behaviors is established. The detection of trace MMPU has been successfully developed using the surface-enhanced Raman scattering (SERS) spectroscopic tool. The most enhanced peak associated with the carbonyl group stretching vibration which appears nearly at 1600 cm−1 has presented a Raman enhancement factor of 3.24 × 105 and a micrommolar limit of detection.