Comparison and Comparison and classification of classification of

methamphetamine seized methamphetamine seized in Japan and Thailand in Japan and Thailand

using using gas chromatography with gas chromatography with liquid-liquid extraction liquid-liquid extraction

and solid-phase and solid-phase microextractionmicroextraction

Kenji Kuwayama Kenji Kuwayama et al.et al.

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INTRODUCTION

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Methampheta

mine

Caffeine Amphetamine

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Methampheta

mine

Amphetamine

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eat inject smoke inhale

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HN

OH

O

HN

Methamphetamine

1-phenyl-2-propanone (P2P)

Ephedrine compound

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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

ท่ีมา : United Nations Office on Drugs and Crime

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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

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LLE

JAPAN THAI

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Chromatograms obtained using the ONCB method

tablet

crystal

THAI

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Chromatograms obtained from an MA crystal

ONCB

NRIPS

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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

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MethodMethod

Liquid-Liquid Extraction( LLE )

Solid-Phase Microextraction

(SPME )

GC-FID & GC-MS

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Technique LLE

sample

centrifuge

Shaking

solution

Organic layer

GC

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Technique SPME

SPME fiber

SPME fiber

GC

Head space

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FID

Technique GC-FID

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Technique GC-MS

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MATERIALS AND

METHODS

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Reagents and chemical1. MA.HCl crystals seized in Japan

(69) and Thailand (42)2. Std. d-MA.HCl3. l-ephedrine.HCl4. dl-Dimethylamphetamine.HCl5. cis-1,2-dimethyl-3-phenylaziridine6. n-Alkanes : Internal Standard7. Solvents 8. SPME holder and fiber coated with

DVB/CAR/PDMS9. Inlet liner for SPME

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1.GC-FIDAgilent – 6890

Auto inject : 7683

Gas chromatographic analysis

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2.GC-MSAgilent – 6890

Agilent 5973N MSD

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COLUMN GC-FID & GC-

MS DB-5 capillary

column 30( m. x 0.32

mm. x film thickness 10.

µm. )

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LLE procedure ( NRIPS )

MA.HCl 50 mg

buffer solution1 mL0.5 mL Ethyl acetate + Istd.

GC

ShakingCentrifuge 3000 rpm

5 min

Istd. n-decane (C10,IS1) n-pentadecane (C15,IS2) n-eicosane (C20,IS3) n-octacosane (C28,IS4) 0.02 mg/ml

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SPME procedure

SPME fiber

SPME fiber

GC

MA.HCl 10 mg

Headspace at 85OC 35 min

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Condition: GC-FID & GC-MS Initial temperature : 50 0 C held

1 min. increase of 10 0C/min. to 300 0 C held 10 min.

Inject temperature : 2 4 0 0 C Detector temperature : 300

0 C Carrier gas : He (g) flow rate 2mL / min.

Injection : 1 µL splitless mode Condition for SPME were the same as those for LLE

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RESULTS

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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

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Data processing for Data processing for LLELLE

Istd.

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Typical chromatograms obtained from MA crystal using

NRIPS

Ephedrine (pseudoephedrine)

Istd.

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Data Data processing processing for SPMEfor SPME

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Typical chromatograms obtained samples by

SPME

Empty vial without MA

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Typical chromatograms obtained samples by SPME

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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

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2.Cluster analysis of sample seized in Japan and Thailand MA crystals seized

Japan = 69 sample

Thai = 42 sample

NRIPS method

Fourteen characteristic impurity peakCluster analysis

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2.Cluster analysis of sample seized in Japan and Thailand

No.sam. (J/T)15/19 25/0 17/15 12/8

NRIPS method

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Typical chromatograms of MA samples in each group using the

NRIPS

Group A

Group B

High purity

1,3-dimethyl-2-phenyl naphthalene1-benzyl-3-methylnaphthalene

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Typical chromatograms of MA samples in each group using the

NRIPS

Group C

Group D

cis-1,2-dimethyl-3-phenylaziridine

Ephedrine (pseudoephedrine)

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3.Comparison and classification of sample in the high purity group by

SPMEWhen 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

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3.Comparison and classification of sample in the high purity group by

SPME

15/19

NRIPS

SPME

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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

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CONCLUSION

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ComparedLLE

ONCB

NRIPSSuperior for detecting and separating MA impurities

Classified into four groups

14 peakscharacteristic

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LLE

SPMEEffective for comparing high-purity MA because it detected many characteristic peaks

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QUESTION