Paper spray ionization mass spectrometry applied to forensic chemistry – drugs of abuse, inks and questioned documents

Domingos, Eloilson; Carvalho, Thays Colletes de; Vaz, Boniek Gontijo; Vasconcelos, Géssica A.; Thompson, Christopher J.; Augusti, Rodinei; Rodrigues, Rayza R.T.; Tose, Lílian V.; Santos, Heloá; Araújo, Joyce R.; Romão, Wanderson

doi:10.1039/c7ay01091e

Cited by 49 publications

(44 citation statements)

References 49 publications

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“…7 The most abundant cannabinoids present in the Cannabis plant are: 9,10 (i) cannabidiol (CBD), an anticonvulsant drug tested in treatments of epileptic patients, 11 in addition to being anxiolytic, anti-inflammatory, antipsychotic, antispasmodic and analgesic; 12 (ii) cannabigerol (CBG), which has antiproliferative and antiglaucoma activities 13 as well as antibiotic, anti-inflammatory, antifungal and analgesic activities; 12 (iii) cannabinol (CBN), 1 a sedative and anticonvulsant that is anti-inflammatory; 12 (iv) cannabichromene (CBC), which is anti-inflammatory, antifungal and analgesic; 12 and (v) Δ 9 -tetrahydrocannabinol (Δ 9 -THC), the main psychoactive compound of the Cannabis plant. 1,[14][15][16][17][18] Most cannabinoids have a 21 carbon atom structural feature, with possible variations in the length of their side chains (C1-C5) attached to the aromatic ring. In the most common homologs, the n-pentyl side chain is replaced by n-propyl, and these analogues are named using the suffix "varin", for example, Δ 9 -tetrahydrocannabivarin (Δ 9 -THCV), cannabidivarin (CBDV) and cannabinovarin (CBNV).…”

Section: Introductionmentioning

confidence: 99%

Analysis of Isomeric Cannabinoid Standards and Cannabis Products by UPLC‑ESI‑TWIM-MS: a Comparison with GC‑MS and GC × GC-QMS

Santos¹,

Tose²,

Silva³

et al. 2018

J. Braz. Chem. Soc.

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The Cannabis sativa L. plant has a complex chemical composition, containing various chemical compounds such as terpenes, sugars, hydrocarbons, steroids, flavonoids, and amino acids. Few works have attempted to identify the constitutional isomers of cannabinoids that are found in the plant. The present study reported the analysis of seven cannabinoid standards: five neutral and two acidic, as well as Cannabis products (hashish and marijuana) and parts of the Cannabis plant (flower and leaf) using mono-dimensional gas chromatography coupled with mass spectrometry (GC-MS) and two-dimensional gas chromatography coupled with quadrupole MS (GC × GC-QMS), ultra performance liquid chromatography coupled with electrospray ionization-quadrupole-time of flight (UPLC-ESI-QTOF)-MS and UPLC-ESI-travelling wave ion mobility (TWIM)-MS. The results of GC-MS demonstrated close retention times (∆t R = 1.303 min) in separation of the five cannabinoid standards, whereas GC × GC-QMS provided a substantially better identification and distinction of constitutional isomers of cannabinoids, where a total of 11 cannabinoids were identified in the hashish sample. UPLC-QTOF-MS and UPLC-TWIM-MS data obtained complete chemical information, in which ESI(+) revealed the presence of seven constitutional isomers of Δ 9-tetrahydrocannabinol (∆ 9-THC), whereas ESI(-) proved the presence of four isomers of Δ 9-tetrahydrocannabinolic acid A (Δ 9-THCA A).

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Section: Introductionmentioning

confidence: 99%

Analysis of Isomeric Cannabinoid Standards and Cannabis Products by UPLC‑ESI‑TWIM-MS: a Comparison with GC‑MS and GC × GC-QMS

Santos¹,

Tose²,

Silva³

et al. 2018

J. Braz. Chem. Soc.

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“…methanol (CH 3 OH) or acetonitrile (ACN), fiber tip shape, and distance of fiber tip to mass spectrometer inlet ( Figure 1B). The standard conditions were evaluated by fixing the volume of sample and spray solvent as 10 and 20 μL, respectively, which are often used in PSI-MS. 8,15 The experiments showed the increase of total ion current (TIC) values producing greater stability of analyte signal and better ionization efficiency while reducing the effect of the background. Spray voltage lower than 2.5 kV produced an unstable ionization process during the analysis, while voltages higher than 4.0 kV showed higher background noise.…”

Section: Optimization Of Fsi-ms Conditionsmentioning

confidence: 99%

“…Spray voltage lower than 2.5 kV produced an unstable ionization process during the analysis, while voltages higher than 4.0 kV showed higher background noise. Thus, a spray voltage of 3.5 kV was chosen for both positive and negative ion modes of ionization, which represents a voltage commonly applied in PSI-MS. 8,22 The blank PP fiber was then analyzed by FSI(+) to determine the optimal spray solvent (methanol or acetonitrile).…”

Section: Optimization Of Fsi-ms Conditionsmentioning

confidence: 99%

“…2 Since the development of desorption electrospray ionization and direct analysis in real time techniques by Cooks and coworkers 3 and Cody and co-workers, 4 respectively, the field of AMS has expanded bringing up a variety of new ionization methods such as paper spray ionization (PSI), 5 among other methodologies. 1,6,7 PSI-MS is very popular in forensic chemistry due to its practicality, speed, low cost, use of less sample, and reproducibility, as reported in studies on document analysis, 8 explosives, 9 food safety, 10 beverage adulteration, 11 and drugs of abuse. [12][13][14] Also, the application of PSI-MS allows the evaluation of evidence without any pretreatment or modification while preserving the chemical features of the sample that is crucial to finding clues in complex samples such as blood, [15][16][17][18] plasma, 19 urine, 18,20 and saliva, 18 which are biological matrices often studied in forensic toxicology.…”

Section: Introductionmentioning

confidence: 99%

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Fiber spray ionization mass spectrometry in forensic chemistry: A screening of drugs of abuse and direct determination of cocaine in urine

Filho

Santos

Borges

et al. 2020

Rapid Comm Mass Spectrometry

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Rationale Ambient mass spectrometry techniques are much required in forensic chemistry to evaluate evidence with low analytical interference, high confidence, and accuracy. However, traditional methodologies, such as paper spray ionization, have been shown to present low sensitivity in the analysis of illicit drugs from biological matrices. Methods Fiber spray ionization mass spectrometry (FSI‐MS) was developed using a capillary polypropylene (PP) hollow fiber. Seized samples of drugs, i.e. a tablet, blotter paper, hashish, and cocaine powder, were analyzed. Cocaine was quantified from whole urine by dipping the fiber directly into solution. FSI‐MS was tested for the analysis of a sample of urine obtained from a drug abuse suspect. Results The FSI(+) analysis showed the detection of different types of synthetic drugs in tablet and blotter paper samples, e.g. amphetamine, cathinones, phenethylamines, and opioids, while pure cocaine and different types of coca alkaloids were identified from cocaine powder with good sensitivity and high mass accuracy. The hashish analysis by FSI(−) revealed signals of cannabinoids, cannabinoid acids, and cannabinoid derivatives, detected mainly as [M − H]− ions or chlorine adducts [M + Cl]−. The quantification of cocaine in whole urine showed good sensitivity and precision with limits of detection and quantification of 5.16 and 17.21 ng/mL, respectively, linearity above 0.999, and relative standard deviation below 2.71%. The evaluation of seized sample of urine showed the detection of cocaine with relative ion intensity greater than 36%, as well as the metabolites benzoylecgonine and cocaethylene with a relative intensity of 1.4% and 6%, respectively. Conclusions The developed FSI‐MS method has the potential to be applied to forensic sample evaluation as well as to determine illicit drugs from biological matrices in toxicological analysis. The use of a capillary PP fiber has advantages as an extractor agent and ionizing substrate, and also the feature of it being dipped directly into the sample, thus preserving the integrity of the sample, which makes this a very promising ambient mass spectrometry method and relevant to forensic chemistry.

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“…For this reason, the authors recommend to be careful with the low sensitivity of this technique that was observed to possibly occur due to an ionic suppression process, caused by the matrix effect (extracted impurities from the surface of the blotter paper). The results provided a limit of detection of around 0.17 ppb [ 47 ].…”

Section: Current Analytical Approaches To Target Analysesmentioning

confidence: 99%

New Advances in Toxicological Forensic Analysis Using Mass Spectrometry Techniques

Mogollón

Quiroz-Moreno

Prata

et al. 2018

Journal of Analytical Methods in Chemistry

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Paper spray ionization mass spectrometry applied to forensic chemistry – drugs of abuse, inks and questioned documents

Abstract: Paper spray ionization mass spectrometry (PS-MS) technique is a versatile and powerful tool to solve numerous problems in forensic chemistry.

Cited by 49 publications

References 49 publications

Analysis of Isomeric Cannabinoid Standards and Cannabis Products by UPLC‑ESI‑TWIM-MS: a Comparison with GC‑MS and GC × GC-QMS

Analysis of Isomeric Cannabinoid Standards and Cannabis Products by UPLC‑ESI‑TWIM-MS: a Comparison with GC‑MS and GC × GC-QMS

Fiber spray ionization mass spectrometry in forensic chemistry: A screening of drugs of abuse and direct determination of cocaine in urine

New Advances in Toxicological Forensic Analysis Using Mass Spectrometry Techniques

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