Transcript 51312326

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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INTRODUCTI
ON
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Methamphetamin
e
Caffeine
Amphetamine
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Methamphetamin
e
Amphetamine
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



eat
inject
smoke
inhale
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H
N
Methamph
etamine
O
1-phenyl-2-
OH
H
N
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)
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Spectroscopy
Two GC method for MA
impurity profiling
NRIPS
ONCB
national Research Intitute
The Office of the Narcoti
of Police Science
Control Board
JAPAN
THAILAND
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JAPAN
THAI
LLE
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using the ONCB method
tablet
THAI
crystal
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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
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Method
Liquid-Liquid
Extraction
( LLE )
Solid-Phase
Microextraction
(SPME )
GC-FID & GC-MS
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Technique
LLE
sample
GC
centrif
uge
Organic
layer
solut
ion
Shaki
ng
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Technique
SPME
SPME fiber
Head space
SPME fiber
GC
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Technique GCFID
FI
D
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Technique
GC-MS
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MATERIALS
AND
METHODS
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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
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chromatographic
analysis
1.GC-FID
Agilent – 6890
Auto inject : 7683
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2.GC-MS
Agilent – 6890
Agilent 5973N MSD
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COLUMN
GC-FID & GCMS
DB-5 capillary
column
( 30 m. x 0.32
mm. x film
thickness 1.0
µm. )
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LLE procedure (
buffer
NRIPS
)
solution1
mL
0.5 mL Ethyl
acetate + Istd.
Shak
MA.HCl
ing
50 mg
Centrifuge 3000 rpm
5
min
G
C
Istd.
n-decane (C10,IS1) n-pentadecane (C1
n-octacosane (C28,IS4)
0.022424 mg
SPME procedure
Headspace
at 85OC
35 min
SPME fiber
MA.HCl 10 mg
SPME fiber
GC
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Condition: GC-FID & GCMS
Initial temperature : 50 0C held
1 min. increase of
10 0C/min. to 300 0C held 10 min.
Inject temperature : 240 0C
Detector temperature : 300 0C
Carrier
gas
:
He
(g)
flow
dition for SPME were the same as those for
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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 &
Calculation of Euclidean distances
Comparison System (DMCPS)
Cluster analysis by Ward method
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Data processing for LLE
Istd.
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Typical chromatograms obtained from
MA crystal using NRIPS
Istd.
Ephedrine (pseudoephedrine)
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for SPME
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Typical chromatograms
obtained samples by SPME
Empty vial without M
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obtained samples by SPME
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1.Optimization of analytical
procedure
LLE
ONCB
optimized for the
analyzed of MA tablet
NRIPS
optimized for the
analyzed of MA crystal
considered more
efficient than the ONCB
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2.Cluster analysis of sample seized
in Japan and Thailand
Japan = 69 sample
MA crystals seized
Thai = 42 sample
NRIPS method
Cluster analysis
Fourteen characteristic impurity p
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2.Cluster analysis of sample seized
in Japan and Thailand
15/19
o.sam. (J/T)
NRIPS metho
25/0
17/15
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12/8
Typical chromatograms of MA samples in
each group using the NRIPS
High purity
Group A
Group B
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
cis-1,2-dimethyl-3-phenylaziridine
Group C
Ephedrine (pseudoephedrine)
Group D
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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
MA
had few impurities
Many impurity
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3.Comparison and classification of sample in
the high purity group by SPME
15/19
SPME
NRIPS
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3.Comparison and classification of sample in
the high purity group by SPME
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.
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CONCLUSION
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Compared
LLE
ONCB
Superior for detecting a
NRIPS
separating MA impuriti
14 peaksClassified int
characteristic
four groups
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LLE
Effective for comparing high-purity
SP because it detected many characteristi
M
E
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QUESTION
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