DART MSI of drugs of abuse in hair

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1 DART MSI of drugs of abuse in hair Wilco Duvivier, Teris van Beek, Michel Nielen October 5, 2017

2 Forensic hair evidence Forensically interesting: Many compounds accumulate in hair Prolonged detectability versus body fluids Non-invasive sampling, easy storage Conventional hair analysis: + Sensitive LC- or GC-MS(/MS) analysis + Segmentation to estimate time of drug intake - Destructive and inefficient sample preparation Digestion and analysis - Only rough estimated time of drug intake (>1 month intervals) Moosmann et al., TIAFT2013 2

3 Hair scan concepts: hair scan What if we....could target intact locks of hair..would not need MALDI matrix or other sample preparation..could make hair analysis fast and easy to perform Ambient ionization mass spectrometry 3

4 DART ionization DART: Direct Analysis in Real Time Metastable species He(2 3 S) ºC Analyte Charged analyte ions He DART glow discharge Mass spectrometer sample Radostina Manova 4

5 DART hair scan method Intact lock of hair attached to stainless steel mesh Scanned at 0.2 mm/s, DART source at 250 C Orbitrap MS: ~ 1 scan per second with high mass resolution Ideal DART temperature setting for THC on hair 8x10 5 T actual = 135 C Average intensity THC signal 7x10 5 6x10 5 5x10 5 4x10 5 3x10 5 2x10 5 1x DART gas beam temperature setting ( C) Duvivier et al., Rapid Commun. Mass Spectrom. 2014, 28,

6 DART-MS scan accuracy Hair spiked with cannabis extract and quinine using TLC-sprayer through 2 mm slit (x-scan at 0.2 mm/s) Spatial resolution: ~ 2.5 mm (~ 1 week history) Improvement over conventional hair analysis 6

7 Drug user hair samples Chronogram of chronic cannabis user hair sample (high THC content: ~5 ng/mg) Duvivier et al., Rapid Commun. Mass Spectrom. 2014, 28,

8 Expansion of method: cocaine Cocaine: different concentrations spiked on blank hair EIC: Blank 0.00 EIC: ng/mg 5.09E2 EIC: ng/mg = SoHT cut-off Cocaine analysis using DART hair scan suitable for forensic applications! 1.95E3 Duvivier et al., Analytical Chemistry 2016, 88,

9 Expansion of method: cocaine Cocaine user hair sample (> 50 ng/mg) Reported use: 2.5 gram daily (!) TIC 7.83E6 Cocaine m/z E6 9

10 Expansion of method: cocaine Cocaine user hair sample (0.5 ng/mg = SoHT cut-off) Reported use: twice a month gram TIC 6.69E6 Cocaine m/z E3 10

11 Confirmation by MS/MS Q-orbitrap instrument (Thermo Q-Exactive) Data dependent MS/MS: m/z of known compounds in inclusion list, when detected: selected for fragmentation in HCD cell Full scan and MS/MS data also retrospective! 11

12 TIC (full scan) Cocaine Cocaine user hair sample Confirmation by MS/MS Continuous cocaine use Amphetamine THC MDMA Recent amphetamine use? _10ppmMix_DART_pos250-DD6 #20 RT: 0.18 AV: 1 NL: 1.05E6 F: FTMS + p NSI d Full ms @hcd35.00 [ ] C 10 H 16 O 2 N = ppm No evidence of cannabis use MDMA use: continuous; recently increased? C 8 H 15 = ppm C 17 H 22 O 4 N = C 5 H 9 = ppm ppm C 9 H 12 O N = ppm 0 Duvivier et al. Analytical Chemistry 2016, 88, m/z Relative Abundance 12

13 Retrospective data analysis Multiple drugs detected with different trends Duvivier et al., Analytical Chemistry 2016, 88,

14 External contamination or incorporated THC? External contamination is a major issue in forensic hair analysis What is measured using the DART-MS hair scan? Incorporated compounds, or External contamination < < 14

15 Metabolite detection Cocaine user hair sample Cocaine m/z m/z E7 Benzoyl- m/z ecgonine 7.38E6 main metabolite BZE at 20% of cocaine intensity shows that detected cocaine is incorporated, not from external contamination

16 Conclusions Direct analysis of intact locks of hair, with sufficient sensitivity and better time resolution Analysis time in the order of minutes Targeted analysis with confirmation by exact mass and data dependent product ion scans Multiple additional hits found using retrospective data analysis Metabolite detection proves measurement of incorporated compounds

17 Acknowledgments Wilco Duvivier Michel Nielen Thijs Meijer Saskia Sterk Ed Pennings