Identification of Oxidation Products of Squalene in Solution and in Latent Fingerprints by ESI-MS and LC/APCI-MS

Abstract

An investigation was carried out to identify oxidation products of squalene (SQ) in latent fingerprints. Oxidation products of SQ incubated in solution with Rose Bengal as a photooxidizer were isolated by semipreparative HPLC-UV and identified by direct infusion ESI-MS and flow injection APCI-MS. Squalene hydroperoxides ranging from squalene monohydroperoxide (SQ-[OOH]) to SQ-[OOH]5 were identified together with SQ epoxide. SQ-[OOH] was the main oxidation product. An LC/APCI-MS method was developed and used to monitor the fate of SQ in solution and in latent fingerprints and the formation of SQ-[OOH] and SQ epoxide. SQ-[OOH] and SQ epoxide were detected in freshly deposited prints but increased markedly after 1 day and continued to increase up to 5 days after print deposition. By day 7, these substances could no longer be detected in prints. SQ was rapidly depleted from prints such that by day 7 it was no longer detected. A similar pattern was seen for SQ stored in the light in dichloromethane but with a slower formation of SQ-[OOH] and SQ epoxide. The oxidation of SQ in solution in the presence and absence of photooxidizer was shown by TLC to proceed as follows: SQ-->SQ-[OOH]+SQ epoxide. SQ-[OOH]-->SQ-[OOH]2-->SQ-[OOH]3-->SQ-[OOH]4+SQ-[OOH]5, with oxidation being more rapid in the presence of photooxidizer. SQ-[OOH]4 and SQ-[OOH]5 could still be detected at 20 days in a solution of SQ aged in solution in the absence of photooxidizer. The oxidation products of SQ should make suitable targets for development of new reagents for visualizing latent fingerprints in forensic science.