RESUMO
In this work, we propose a matrix-free approach for the analysis of fingermarks (FMs) contaminated with five cosmetic products containing different active pharmaceutical ingredients (APIs) using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). For this purpose, a magnetic SALDI substrate based on Fe3O4-CeO2 magnetic nanoparticles was prepared, characterized, and optimized for the analysis of contaminated FMs without sample pretreatment. Initially, groomed FM and cosmetic products were separately analyzed, and their major components were successfully detected. Subsequently, FMs contaminated with Ordinary serum and Skinoren, Dermovate, Bepanthen, and Eucerin creams were analyzed, and components of FM and cosmetics were detected. The stability of the cosmetics in FMs was studied over an interval of 28 days, and all components showed good stability in FM for 4 weeks. Recovery of contaminated FMs from different surfaces utilizing a few microliters of the magnetic substrate was carried out using a simple external magnetic field from ceramic, plastic, metal, and glass. Successful retrieval of the API and FM components was achieved with magnetic recovery, and glass exhibited the best recovery, whereas ceramic tile demonstrated the lowest recovery. This was supported by atomic force microscopy study, which revealed that the ceramic surface had higher roughness than the other surfaces employed in this study, which adversely affected the magnetic maneuvering. This proof-of-concept investigation extends the application of SALDI-MS in forensic analysis of contaminated FMs by exploring cosmetics as exogenous materials and their stability and recovery from different surfaces.
RESUMO
In this study, FeNi magnetic alloy nanoparticles (MANPs) were employed for the forensic analysis of four poisons-dimethametryn, napropamide, thiodicarb, and strychnine-using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). FeNi MANPs were prepared via coprecipitation using two reducing agents, sodium borohydride (NaBH4) and hydrazine monohydrate (N2H4·H2O), to optimize the prepared MANPs and investigate their effect on the performance of SALDI-MS analysis. Thereafter, SALDI-MS analysis was carried out for the detection of three pesticides and a rodenticide. The prepared substrate offered sensitive detection of the targeted analytes with LOD values of 1 ng/mL, 100 pg/mL, 10 ng/mL, and 200 ng/mL for dimethametryn, napropamide, thiodicarb, and strychnine, respectively. The relative standard deviation (%RSD) values were in the range of 2.30-13.97% for the pesticides and 15-23.81% for strychnine, demonstrating the good spot-to-spot reproducibility of the FeNi substrate. Finally, the MANPs were successfully employed in the analysis of poison-spiked blood serum using a minute quantity of the sample with an LOD of 700 ng/mL dimethametryn and napropamide, 800 ng/mL thiodicarb, and 500 ng/mL strychnine. This study has great potential regarding the analysis of several poisons that may be found in human serum, which is significant in cases of self-harm.
