Using surface-enhanced Raman scattering for simultaneous multiplex detection and quantification of thiols associated to axillary malodour

Abstract

Axillary malodour is caused by the microbial conversion of human-derived precursors to volatile organic compounds. Thiols strongly contribute to this odour but are hard to detect due to being present in low quantities. Additionally, thiols are highly volatile and small making sampling and analysis difficult including by gas chromatography-mass spectrometry. This makes their detection and quantification extremely difficult. In this study, surface-enhanced Raman scattering (SERS) combined with chemometrics was utilised to simultaneously quantify four malodourous thiols associated with axillary odour both in individual and multiplex solutions. Univariate and multivariate methods of partial least squares regression (PLS-R) were used to calculate the limit of detection (LoD) and results compared. Both methods yielded comparable LoD values, with LoDs using PLS-R ranging from 0.0227 ppm to 0.0153 ppm for the thiols studied. These thiols were then examined and quantified simultaneously in 120 mixtures using PLS-R. The resultant models showed high linearity (Q2 values between 0.9712 and 0.9827 for both PLS-1 and PLS-2) and low values of root mean squared error of predictions (0.0359 ppm and 0.0459 ppm for PLS-1 and PLS-2, respectively). To test this approach further, these models were challenged with 15 new blind test samples collected independently from the initial samples. This test demonstrated that SERS combined with PLS-R could be used to predict the unknown concentrations of these thiols in a mixture. These results display the ability of SERS for the simultaneous multiplex detection and its potential for future development for detecting gaseous thiols produced from skin or body sites.