Kenji Kuwayama et al.
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Transcript of Kenji Kuwayama et al.
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
INTRODUCTION
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Methamphetamine
Caffeine Amphetamine
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Methamphetamine
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
ที่��มา : 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
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
Shaking
Centrifuge 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 : 500 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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RESULTSRESULTS
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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 naphthalene
1-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
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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
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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QUESTIONQUESTION