Comparison and classification of methamphetamine seized in Japan and Thailand using gas chromatography with liquid-liquid extraction and solid-phase microextraction Kenji Kuwayama et al.

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3 INTRODUCT ION

4 Methamphetami ne Caffeine Amphetamine

5 Methamphetami ne Amphetamine

6  eat  inject  smoke  inhale

7 Methamph etamine 1-phenyl-2- propanone (P2P) Ephedrine compound

8  Presumptive Test  Thin Layer Chromatography (TLC)  Gas Chromatography Flame Ionization Detector (GC-FID)  Gas Chromatography Mass Spectrometry (GC-MS)  High Performance Liquid Chromatography (HPLC)  Fourier Transform Infrared (FTIR) Spectroscopy ที่มา : United Nations Office on Drugs and Crime

9 Two GC method for MA impurity profiling NRIPS ONCB The national Research Intitute of Police Science The Office of the Narcotics Control Board JAPAN THAILAND

10 LLE JAPAN THAI

11 Chromatograms obtained using the ONCB method tablet crystal THAI

12 Chromatograms obtained from an MA crystal ONCB NRIPS

13 The aim of this study Improve the analytical method for profiling MA impurity Compare and classification MA crystals seized in different countries Information in criminal investigation ; traffic routes, the source of supply and relationships between seizures

14 Method Liquid-Liquid Extraction ( LLE ) Solid-Phase Microextraction (SPME ) GC-FID & GC- MS

15 Technique LLE sample centri fuge Shak ing solut ion Organic layer GC

16 Technique SPME SPME fiber GC Head space

17 FI D Technique GC-FID

18 Technique GC-MS

19 MATERIALS AND METHODS MATERIALS AND METHODS

20 Reagents and chemical 1. MA.HCl crystals seized in Japan (69) and Thailand (42) 2. Std. d-MA.HCl 3. l-ephedrine.HCl 4. dl-Dimethylamphetamine.HCl 5. cis-1,2-dimethyl-3-phenylaziridine 6. n-Alkanes : Internal Standard 7. Solvents 8. SPME holder and fiber coated with DVB/CAR/PDMS 9. Inlet liner for SPME

21 1.GC-FID Agilent – 6890 Auto inject : 7683 Gas chromatographic analysis

22 2.GC-MS Agilent – 6890 Agilent 5973N MSD

23 COLUMN GC-FID & GC- MS DB-5 capillary column ( 30 m. x 0.32 mm. x film thickness 1.0 µm. )

24 LLE procedure ( NRIPS ) MA.HCl 50 mg buffer solution1 mL 0.5 mL Ethyl acetate + Istd. GCGC Shak ing Centrifuge 3000 rpm 5 min Istd. n-decane (C 10,IS1) n-pentadecane (C 15,IS2) n-eicosane (C 20,IS3) n-octacosane (C 28,IS4) 0.02 mg/ml

25 SPME procedure SPME fiber GC MA.HCl 10 mg Headspace at 85 O C 35 min

26 Condition: GC-FID & GC- MS Initial temperature : 50 0 C held 1 min. increase of 10 0 C/min. to C held 10 min. Inject temperature : C Detector temperature : C Carrier gas : He (g) flow rate 2 mL / min. Injection : 1 µL splitless mode Condition for SPME were the same as those for LLE

27 RESULTS

28 Data processing for LLE & SPME Peak data integrated by Chemstation software Processed using the Drug Micro-Component Analysis & Comparison System (DMCPS) Calculation of Euclidean distances Cluster analysis by Ward method

29 Data processing for LLE Istd.

30 Typical chromatograms obtained from MA crystal using NRIPS Ephedrine (pseudoephedrine) Istd.

31 Data processing for SPME

32 Typical chromatograms obtained samples by SPME Empty vial without MA

33 Typical chromatograms obtained samples by SPME

34 1.Optimization of analytical procedure ONCB optimized for the analyzed of MA tablet NRIPS optimized for the analyzed of MA crystal considered more efficient than the ONCB LLE

35 2.Cluster analysis of sample seized in Japan and Thailand MA crystals seized Japan = 69 sample Thai = 42 sample NRIPS method Fourteen characteristic impurity peak Cluster analysis

36 2.Cluster analysis of sample seized in Japan and Thailand No.sam. (J/T) 15/19 25/017/1512/8 NRIPS method

37 Typical chromatograms of MA samples in each group using the NRIPS Group A Group B High purity 1,3-dimethyl-2-phenyl naphthalene 1-benzyl-3-methylnaphthalene

38 Typical chromatograms of MA samples in each group using the NRIPS Group C Group D cis-1,2-dimethyl-3-phenylaziridine Ephedrine (pseudoephedrine)

39 3.Comparison and classification of sample in the high purity group by SPME When MA crystals were extracted with SPME and analyzed by GC (SPME ), the chromatograms had many impurities while the chromatograms in case of LLE had few impurities Characteristic peaks for data processing seven peaks Many impurity MA

40 3.Comparison and classification of sample in the high purity group by SPME 15/19 NRIPS SPME

41 Chromatograms were distinguished clearly from SPME method, whereas in the case of LLE it was difficult to compare and classify samples in the high-purity group because there were so few impurities. The SPME method enables us to compare and classify high-purity MA 3.Comparison and classification of sample in the high purity group by SPME

42 CONCLUSIO N

43 Compared LLE ONCB NRIPS Superior for detecting and separating MA impurities Classified into four groups 14 peaks characteristic

44 LLE SP M E Effective for comparing high-purity MA because it detected many characteristic peaks

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46 QUESTION