Surface-Enhanced Raman Analysis of Underlaying Colorants on Redyed Hair

Forensic examination of hair evidence can help with establishing a connection between a suspect and a crime scene or demonstrate the absence of such connections. Currently, it is primarily done by a subjective microscopic examination which can only elucidate the species of origin and, if human, the part of the body the hair came from. Several years ago, surface-enhanced Raman spectroscopy (SERS) was proposed for advanced forensic analysis of hair (Kurouski, D.; Van Duyne, R. P. In situ detection and identification of hair dyes using surface-enhanced Raman spectroscopy (SERS). Anal. Chem. 2015, 87, 2901−2906. DOI: 10.1021/ac504405u). It was shown that SERS could be used to determine whether hair was dyed or not and even reveal what commercial hair colorant was used. Expanding upon those findings, we show that SERS is capable of probing the original colorant even if hair was redyed afterward. Specifically, we were able to detect and identify the underlaying blue semipermanent colorant on hair redyed by both black semipermanent and black permanent colorants. We also demonstrate that original black permanent colorant could be detected by SERS if the hair was recolored by blue semipermanent dye. However, it could not if the hair was recolored by another (blue or black) permanent dye. We also provide experimental evidence that SERS can be used to detect the dye on hair colored more than two months prior to its spectroscopic examination. These experimental findings substantially expand capabilities of SERS in forensics