Mass spectrometric characterization of cannabinoids in raw Cannabis sativa L. samples (original) (raw)
Related papers
Rapid Communications in Mass Spectrometry, 2012
RATIONALE: Dozens of synthetic cannabinoid analogs purposefully meant to circumvent legal restrictions associated with controlled substances continue to be manufactured and promoted as producing 'legal highs'. These designer drugs are difficult to identify in conventional drug screens not only because routine protocols have not been developed for their detection, but also because their association with complex plant matrices during manufacture generally requires laborintensive extraction and sample preparation for analysis. To address this new and important challenge in forensic chemistry, Direct Analysis in Real Time Mass Spectrometry (DART-MS) is applied to the analysis of these designer drugs. METHODS: DART-MS was employed to sample synthetic cannabinoids directly on botanical matrices. The ambient ionization method associated with DART-MS permitted the analysis of solid herbal samples directly, without the need for extraction or sample preparation. The high mass resolution time-of-flight analyzer allowed identification of these substances despite their presence within a complex matrix and enabled differentiation of closely related analogs. RESULTS: DART-MS was performed to rapidly identify the synthetic cannabinoids AM-251 and JWH-015. For each cannabinoid, three hundred micrograms (300 mg) of material was easily detected within an excess of background matrix by mass. CONCLUSIONS: New variations of herbal blends containing a wide range of base components and laced with synthetic cannabinoids are being produced, making their presence difficult to track by conventional methods. DART-MS permits rapid identification of trace synthetic cannabinoids within complex biological matrices, with excellent sensitivity and specificity compared with standard methods.
Journal of Chromatography A, 2004
A method was developed and validated for the simultaneous determination of five cannabinoids, viz. cannabidiol (CBD), cannabidiol acid (CBD-COOH), cannabinol (CBN), 9-tetrahydrocannabinol (THC), and 3-carboxy-9-all-trans-tetrahydrocannabinol (THC-COOH) in cannabis products. The cannabinoids were extracted from the grinded cannabis samples with a mixture of methanol-chloroform and analysed using liquid chromatography with ion-trap-mass-spectrometry (LC-IT-MS n). For quantification the two most abundant diagnostic MS-MS ions of the analyte in the sample and external standard were monitored. For confirmation purposes the EU criteria as described in Commission Decision 2002/657/EC were followed. Fully satisfactory results were obtained, that is, unequivocal confirmation according to the most stringent EU criteria was possible. The limits of quantification were 0.1 g/kg for CBD, 0.04 g/kg for CBD-COOH, 0.03 g/kg for CBN, 0.28 g/kg for THC and 9.9 g/kg for THC-COOH. The repeatabilities, defined by R.S.D., were 2% for CBN, THC and THC-COOH at the concentration levels of respectively 0.023, 3.3 and 113 g/kg and 5% for CBD-COOH at the level of 0.34 g/kg (n = 6).
Molecules
Gas chromatography (GC) techniques for analyzing and determining the cannabinoid profile in cannabis (Cannabis sativa L.) are widely used in standard laboratories; however, these methods may mislabel the profile when used under rapid conditions. Our study aimed to highlight this problem and optimize GC column conditions and mass spectrometry (MS) parameters to accurately identify cannabinoids in both standards and forensic samples. The method was validated for linearity, selectivity, and precision. It was observed that when tetrahydrocannabinol (Δ9-THC) and cannabidiolic acid (CBD-A) were examined using rapid GC conditions, the resulting derivatives generated identical retention times. Wider chromatographic conditions were applied. The linear range for each compound ranged from 0.02 μg/mL to 37.50 μg/mL. The R2 values ranged from 0.996 to 0.999. The LOQ values ranged from 0.33 μg/mL to 5.83 μg/mL, and the LOD values ranged from 0.11 μg/mL to 1.92 μg/mL. The precision values ranged f...
High performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) has been successfully applied to cannabis plant extracts in order to identify cannabinoid compounds after their quantitative isolation by means of supercritical fluid extraction (SFE). MS conditions were optimized by means of a central composite design (CCD) approach, and the analysis method was fully validated. Six major cannabinoids [tetrahydrocannabinolic acid (THCA), tetrahydrocannabinol (THC), cannabidiol (CBD), tetrahydrocannabivarin (THCV), cannabigerol (CBG), and cannabinol (CBN)] were quantified (RSD < 10%), and seven more cannabinoids were identified and verified by means of a liquid chromatograph coupled to a quadrupole-time-of-flight (Q-ToF) detector. Finally, based on the distribution of the analyzed cannabinoids in 30 Cannabis sativa L. plant varieties and the principal component analysis (PCA) of the resulting data, a clear difference was observed between outdoor and indoor grown plants, which was attributed to a higher concentration of THC, CBN, and CBD in outdoor grown plants.
Journal of AOAC INTERNATIONAL
Background Cannabis legalization is expanding rapidly throughout the United States, but there is no reliable means of establishing recent use. Objective To develop and validate a bioanalytical method for determination of Δ9-tetrahydrocannabinol (Δ9-THC), cannabinol, 11-hydroxy-Δ9-THC, 11-nor-9-carboxy-Δ9-THC, and 8β,11-dihydroxy-Δ9-THC in whole blood microsamples by liquid chromatography high-resolution mass spectrometry (LC-HRMS). Methods Cannabinoid extraction from whole blood was performed using a mixture of n-hexane/ethyl acetate (90:10, v/v). Chromatographic separation was performed with a C18 column using a binary mobile phase gradient of water and acetonitrile, each with 0.1% formic acid. Detection was performed by positive ion mode heated electrospray ionization with full scan MS on an Orbitrap mass spectrometer. A clinical study was performed in 30 subjects to identify recent cannabis use based on analysis of cannabinoids in blood samples up to 200 min post-smoking. Results...
Chromatographic and Spectroscopic Data of Cannabinoids from Cannabis sativa L
Journal of Liquid Chromatography & Related Technologies, 2005
Chromatographic and spectroscopic data was determined for 16 different major cannabinoids from Cannabis sativa plant material as well as 2 human metabolites of D 9 -tetrahydrocannabinol. Spectroscopic analysis included UV absorbance, infrared-spectral analysis, (GC-) mass spectrometry, and spectrophotometric analysis. Also, the fluorescent properties of the cannabinoids are presented. Most of this data is available from literature but scattered over a large amount of scientific papers. In this case, analyses were carried out under standardised conditions for each tested cannabinoid so spectroscopic data can be directly compared. Different methods for the analysis of cannabis preparations were used and are discussed for their usefulness in the identification and determination of separate cannabinoids. Data on the retention of the cannabinoids in HPLC, GC, and TLC are presented.
Journal of Food and Drug Analysis
A routine method for determining cannabinoids in Cannabis sativa L. inflorescence, based on Fast gas chromatography coupled to mass spectrometry (Fast GC/MS), was developed and validated. To avoid the decarboxylation of carboxyl group of cannabinoids, different derivatization approaches, i.e. silylation and esterification (diazomethane-mediated), reagents and solvents (pyridine or ethyl acetate), were tested. The methylation significantly increased the signal-to-noise ratio of all carboxylic cannabinoids, except for cannabigerolic acid (CBGA). Since diazomethane is not commercially available, is considered a hazardous reactive and requires 1-day synthesis by specialized chemical staff, silylation was used along the whole validation of a routine method. The method gave a fast (total analysis time < 7.0 min) and satisfactory resolution (R > 1.1), with a good repeatability (intraday < 8.38%; interday < 11.10%) and sensitivity (LOD < 11.20 ng/mL). The Fast GC/MS method suitability for detection of cannabinoids in hemp inflorescences, was tested; a good repeatability (intraday < 9.80%; interday < 8.63%), sensitivity (LOD < 58.89 ng/mg) and robustness (<9.52%) was also obtained. In the analyzed samples, the main cannabinoid was cannabidiolic acid (CBDA, 5.19 ± 0.58 g/ 100 g), followed by cannabidiol (CBD, 1.56 ± 0.03 g/100 g) and CBGA (0.83 g/100 g). D9tetrahydrocannabivarine (THCV) was present at trace level. Therefore, the developed routine Fast GC/MS method could be a valid alternative for a fast, robust and high sensitive determination of main cannabinoids present in hemp inflorescences.
Molecules
Cannabis is gaining increasing attention due to the high pharmacological potential and updated legislation authorizing multiple uses. The development of time- and cost-efficient analytical methods is of crucial importance for phytocannabinoid profiling. This review aims to capture the versatility of analytical methods for phytocannabinoid profiling of cannabis and cannabis-based products in the past four decades (1980–2021). The thorough overview of more than 220 scientific papers reporting different analytical techniques for phytocannabinoid profiling points out their respective advantages and drawbacks in terms of their complexity, duration, selectivity, sensitivity and robustness for their specific application, along with the most widely used sample preparation strategies. In particular, chromatographic and spectroscopic methods, are presented and discussed. Acquired knowledge of phytocannabinoid profile became extremely relevant and further enhanced chemotaxonomic classification...