Screening in Hair for Drugs (On Shimadzu Model)

Authors: Serge Auger, Jean Lacoursière, and Pierre Picard
Themes: High-Throughput, hair, Luxon-MS/MS
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Introduction

Since the hair root is vascularized during its growth, illicit drugs present in the blood stream may enter the hair shaft via the root where they will be sequestered. Therefore, the use of illicit drugs can be revealed by analyzing a small hair sample. To increase the analysis throughput of hair samples, the Luxon Ion Source® coupled to tandem mass spectrometry (MS/MS) was used for the identification and quantification of drugs of abuse.

Our goal for this application note is to use an automated sample preparation method for the screen of drugs in hair sample using a single operation in LUXON-MS/MS.

LUXON-MS/MS offers specificity combined with an ultra-fast analysis for an unrivaled screening method. To develop this application, we focused on performing a quick and simple sample preparation. Drugs are analyzed simultaneously with quantitative screening results obtained in less than 9 seconds per sample.

Luxon Ionization Source

The Luxon Ion Source® (Figure 1) is the second-generation sample introduction and ionization source based on the LDTD® technology for mass spectrometry. Luxon Ion Source® uses Fiber-Coupled Laser Diode (Figure 2) to obtain unmatchable thermal uniformity providing more precision, accuracy and speed. The process begins with dry samples which are rapidly evaporated using indirect heat. The thermally desorbed neutral molecules are carried into a corona discharge region. High efficiency protonation and strong resistance to ionic suppression characterize this type of ionization and is the result of the absence of solvent and mobile phase. This thermal desorption process yields high-intensity molecular ion signal in less than 1 second sample-to-sample and allows working with very small volumes.

Figure 1 - Luxon Ion Source®

Figure 1 – Luxon Ion Source®

Figure 2 - Schematic of the Luxon Ionization Source Shimadzu

Figure 2 – Schematic of the Luxon Ionization Source

Sample Preparation Method

Automated Sample Extraction

Figure 3 - Automated extraction system

Figure 3 – Automated extraction system

LDTD®-MS/MS Parameters

LDTD

Model: Luxon SH-960, Phytronix

Carrier gas: 6 L/min (air with 20 µL/min water)

Laser pattern:

MS/MS

MS model: LC-8060, Shimadzu

Ionization: APCI

Table 1 – Mass spectrometer transitions (Positive)
Drugs Transition CE
Amphetamine (AMP) 136 → 119 15
Amphetamine-D 5 141 → 96 15
Methamphetamine (MET) 150 → 119 15
Methamphetamine-D 9 159 → 125 15
MDA 180 → 133 20
MDA-D 5 185 → 138 20
MDMA 194 → 163 10
MDMA-D 5 199 → 165 10
MDEA 208 → 163 12
Diethylpropion (DEP) 206 → 100 25
Diethylpropion-D 10 216 → 110 25
PCP 244 → 159 15
PCP-D 5 249 → 164 15
Mazindol (MAZ) 285 → 242 20
Mazindol-D 4 289 → 242 20
Morphine (MOR) 286 → 152 50
Morphine-D 6 292 → 152 50
Codeine (COD) 300 → 152 50
Codeine-D 6 306 → 152 50
Cocaine (COC) 304 → 182 20
Cocaine-D 3 307 → 185 20
6-Monoacetylmorphine (6-MAM) 328 → 165 35
6-Monoacetylmorphine-D 6 334 → 165 35
Table 2 – Mass spectrometer transitions (Negative)
Drugs Transition CE
THC 313 → 245 -30
THC-D 3 316 → 248 -30

Results and Discussion

Initial Cut-off Test

Table 3 shows the suggested screening cut-offs currently used in the industry.

Table 3 – Analytes and Cut-offs
Analyte Cut-off
Amphetamine 200 pg/mg Hair
Methamphetamine 200 pg/mg Hair
MDA 200 pg/mg Hair
MDMA 200 pg/mg Hair
MDEA 200 pg/mg Hair
Morphine 200 pg/mg Hair
PCP 200 pg/mg Hair
Cocaine 250 pg/mg Hair
Codeine 200 pg/mg Hair
6-MAM 200 pg/mg Hair
Diethylpropion 200 pg/mg Hair
Mazindol 200 pg/mg Hair
THC 50 pg/mg Hair

Desorption peak

Figure 4 shows a typical desorption peak for a blank sample for Cocaine and Figure 5 shows a typical desorption peak for a cut-off sample for Cocaine. Similar results were obtained for the other drugs.

Figure 4 – Desorption peak of blank sample for Cocaine

Figure 4 – Desorption peak of blank sample for Cocaine

 

Figure 5 - Desorption peak of cut-off sample for Cocaine

Figure 5 – Desorption peak of cut-off sample for Cocaine

Precision

Spiked samples around the decision point and blank solutions are used to validate the precision of the method. The peak area against the internal standard (IS) ratio was used to normalize the signal. Replicate extractions are deposited on a LazWell™ plate and dried before analysis.

The following acceptance criteria were used:

Table 4 shows the precision results at the cut-off level.

Table 4 – Inter-run precision
Amphetamine Methamphetamine
Conc (pg/mg) 200 Conc (pg/mg) 200
N 6 N 6
Mean 186.7 Mean 223.7
%CV 18.4 %CV 17.7
MDA MDMA
Conc (pg/mg) 200 Conc (pg/mg) 200
N 6 N 6
Mean 194.5 Mean 222.9
%CV 19.4 %CV 16.9
Diethylpropion MDEA
Conc (pg/mg) 200 Conc (pg/mg) 200
N 6 N 6
Mean 181.1 Mean 215.1
%CV 17.8 %CV 14.4
PCP Mazindol
Conc (pg/mg) 200 Conc (pg/mg) 200
N 6 N 6
Mean 217.2 Mean 228.8
%CV 14.7 %CV 14.9
Morphine Codeine
Conc (pg/mg) 200 Conc (pg/mg) 200
N 6 N 6
Mean 204.5 Mean 216.0
%CV 15.8 %CV 7.9
Cocaine 6-Monoacetylmorphine
Conc (pg/mg) 250 Conc (pg/mg) 200
N 6 N 6
Mean 263.8 Mean 218.2
%CV 4.8 %CV 16.4
THC
Conc (pg/mg) 50
N 6
Mean 57.0
%CV 7.2

Conclusion

Luxon Ion Source® combined to a Shimadzu LC-8060 mass spectrometer system allows ultra-fast (9 seconds per sample) screening of drugs in hair using a simple and automated sample preparation method.