MONITORING CLANDESTINE ACTIVITIES BY THE MINI 12

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1 MONITORING CLANDESTINE ACTIVITIES BY THE MINI 12 Patrick W. Fedick, Christopher J. Pulliam, Dalton T. Snyder, Ryan M. Bain, and R. Graham Cooks Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States Center for Analytical Instrumentation Development, West Lafayette, Indiana 47907, United States

2 WHY IS PORTABLE INSTRUMENTATION IMPORTANT IN FORENSICS? Immediate results Expedited criminal investigations Providing timely information to law enforcement and forensic practitioners Results obtained directly at a crime scene Decrease chain-of-custody problems Reduce sample degradation issues Alleviate the need for evidence transport to off-site laboratories

3 AMBIENT IONIZATION DEVELOPMENTS Desorption ElectroSpray Ionization (DESI) R. G. Cooks, Science, 2004 Low Temperature Plasma (LTP) R. G. Cooks, Analytical Chemistry, 2008 Paper Spray Ionization (PS) R. G. Cooks, Analytical Chemistry, 2010 Swab Touch Spray (TS) R. G. Cooks, Analyst, 2014

4 MINI 12 Anal. Chem., (2014) 86, DOI: /ac403766c

5 THREE VIGNETTES Mini 12 Mass Spectrometer Multigenerational CID Organic Gunshot Residue Analysis Paper SERS Raman Spectroscopy followed by MS

6 MULTIGENERATIONAL COLLISION-INDUCED DISSOCIATION FOR CHARACTERIZATION OF ORGANIC COMPOUNDS Anal. Chem., (2016) 88, DOI: /acs.analchem.6b02209

7 SOFTWARE - FULL CONTROL

8 MULTIGENERATIONAL CID

9 COMPOUNDS THAT LOSE H 2 O IN MS 2 Conventional CID on the LTQ Multigenerational CID on the Mini

10 ISOMERIC CATHINONES Conventional CID on the LTQ Multigenerational CID on the Mini 12

11 SWAB TOUCH SPRAY MASS SPECTROMETRY FOR RAPID ANALYSIS OF ORGANIC GUNSHOT RESIDUE FROM HUMAN HAND AND VARIOUS SURFACES USING COMMERCIAL AND FIELDABLE MASS SPECTROMETRY SYSTEMS. Forensic Chemistry, (2017) 5, DOI: /j.forc

12 GUNSHOT RESIDUE (ELEMENTAL) Colorimetric Tests Atomic Absorption Tests SEM Tests

13 ORGANIC GUNSHOT RESIDUE (MOLECULAR) >136 COMPOUNDS Science & Justice (2016), DOI: /j.scijus

14 EXPERIMENTAL SETUP

15 CLOSE UP OF SWABS SETUP Anal. Chim. Acta. (2015) 861, DOI: /j.aca

16 LTQ SPECTRA Methyl Centralite Ethyl Centralite A m/z 241 B m/z 269 Relative Abundance m/z Relative Abundance m/z

17 4 DIFFERENT 9MM HANDGUNS Ammunition Federal Ammunition 9mm Luger 115 Grain Full Metal Jacket Independence 9mm Luger 124 Grain Full Metal Jacket Winchester 9mm Luger 147 Grain Full Metal Jacket Federal Ammunition American Eagle 147 Grain Full Metal Jacket Flat Point Compound Methyl Centralite Ethyl Centralite Methyl Centralite Ethyl Centralite Methyl Centralite Ethyl Centralite Methyl Centralite Ethyl Centralite Exposed Hand Vinyl Glove Nitrile Glove Latex Glove Not Detected Not Detected Not Detected Not Detected Not Detected Not Detected Not Detected Not Detected THE LOWER LIMIT OF DETECTION FOR BOTH MC AND EC WERE LOWER THAN 50ng ON THE LTQ XL.

18 MINI 12 SPECTRA A m/z 241 B m/z 269 Relative Abundance Relative Abundance m/z m/z DETECTED AFTER 1 ROUND WAS DISCHARGED

19 FORENSIC SAMPLING AND ANALYSIS FROM A SINGLE SUBSTRATE FOR SURFACE-ENHANCED RAMAN SPECTROSCOPY FOLLOWED BY PAPER SPRAY MASS SPECTROMETRY Under Review

20 SWGDRUG SCIENTIFIC WORKING GROUP FOR THE ANALYSIS OF SEIZED DRUGS (SWGDRUG) RECOMMENDATIONS Techniques for the analysis of drug samples are classified into three categories (see Table 1) based on their maximum potential discriminating power. IIIB.3.1 When a validated Category A technique is incorporated into an analytical scheme, at least one other technique (from either Category A, B or C) shall be used.

21 EXPERIMENTAL SETUP Drugs Explosives Chemical Warfare Agent Simulants

22 DRUG MIXTURE HEROIN AND FENTANYL a) Intensity Intensity Raman Shift (cm -1 ) Fentanyl Raman Shift (cm -1 ) b) Relative Intensity Relative Intensity Heroin Intensity m/z Raman Shift (cm -1 ) 370 m/z 370 Heroin m/z Fentanyl m/z Street Heroin Cut with Fentanyl

23 EXPLOSIVES - TRINITROTOLUENE e) Intensity f) Relative Abundance m/z Raman Shift (cm -1 ) m/z

24 CWAS DIISOPROPYL METHYLPHOSPHONATE a) Intensity b) Relative Intensity m/z Raman Shift (cm -1 ) m/z

25 CONCLUSION The full control of the Mini 12 allows for new ways of scanning ions, which provides additional information. Portable mass spectrometers allow in-situ, rapid analysis of forensically relevant compounds. New sampling techniques coupled with the Mini 12 could help cut down on backlogged samples.

26 THANK YOU!

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