Integrating SERS and PSI-MS with Dual Purpose Plasmonic Paper Substrates for On-Site Illicit Drug Confirmation.

Forensic laboratory backlogs are replete with suspected drug samples. Shifting analysis toward the point of seizure would save significant time and public funds. Moreover, a two-tiered identification strategy for controlled substance testing that relies on two independent, discerning methods could entirely circumvent the need for forensic laboratory testing. To this end, we coupled Raman spectroscopy and paper spray ionization mass spectrometry (PSI-MS) on a single instrumental platform. Both methods are capable of ambient analysis with fieldable instruments, yet Raman is often limited to bulk analysis. Critical to this work is the development of a gold nanoparticle (AuNP)-embedded paper swab to extend the capability of Raman spectroscopy to trace evidence via surface-enhanced Raman scattering (SERS). Plasmonic papers are characterized with respect to SERS signals and compatibility with PSI-MS analysis. Proof-of-principle is established with the identification of five representative drugs, and detection limits on the scale of 1-100 ng are achieved for both PSI-MS and SERS. The integrated SERS-PSI-MS system achieved 99.8% accurate chemical identification in a blind study consisting of 500 samples. Additionally, we demonstrate facile discrimination of several JWH-018 isomers via SERS even when MS and MS2 spectra are indistinguishable. Successful coupling of SERS and PSI-MS to enable on-site chemical analysis by two independent methods can potentially lead to a desirable paradigm shift in the handling of drug evidence.

Filter Cone Spray Ionization Coupled to a Portable MS System: Application to On-Site Forensic Evidence and Environmental Sample Analysis.

The complexity of field-borne sample matrices and the instrumental constraints of portable mass spectrometers (MS) often necessitate that preparative steps are added prior to ambient MS methods when operated on-site, but the corresponding decrease in throughput and experimental simplicity can make field operation impractical. To this end, we report a modified ambient MS method, filter cone spray ionization (FCSI), specifically designed for simple, yet robust, processing of bulk forensic evidence and environmental samples using a fieldable MS system. This paper-crafted source utilizes low-cost laboratory consumables to produce a conical structure that serves as a disposable, spray-based ionization source. Integrated extraction and filtration capabilities mitigate sample heterogeneity and carryover concerns and expedite sample processing, as characterized through the analysis of a variety of authentic forensic evidence types (e.g., abused pharma tablets, counterfeit/adulterated tablets, crystal-based drugs, synthetic marijuana, toxicological specimens) and contaminated soil samples. The data presented herein suggests that the FCSI-MS design could prove robust to the rigors of field-borne, bulk sample screening, overcoming the inefficiencies of other ambient MS methods for these sample classes. Novel applications of FCSI-MS are also examined, such as the coupling to trace evidence vacuum filtration media.

Analytical Validation of a Portable Mass Spectrometer Featuring Interchangeable, Ambient Ionization Sources for High Throughput Forensic Evidence Screening.

Forensic evidentiary backlogs are indicative of the growing need for cost-effective, high-throughput instrumental methods. One such emerging technology that shows high promise in meeting this demand while also allowing on-site forensic investigation is portable mass spectrometric (MS) instrumentation, particularly that which enables the coupling to ambient ionization techniques. While the benefits of rapid, on-site screening of contraband can be anticipated, the inherent legal implications of field-collected data necessitates that the analytical performance of technology employed be commensurate with accepted techniques. To this end, comprehensive analytical validation studies are required before broad incorporation by forensic practitioners can be considered, and are the focus of this work. Pertinent performance characteristics such as throughput, selectivity, accuracy/precision, method robustness, and ruggedness have been investigated. Reliability in the form of false positive/negative response rates is also assessed, examining the effect of variables such as user training and experience level. To provide flexibility toward broad chemical evidence analysis, a suite of rapidly-interchangeable ion sources has been developed and characterized through the analysis of common illicit chemicals and emerging threats like substituted phenethylamines. Graphical Abstract ᅟ.