Challenges and Strategies of Chemical Analysis of Drugs of Abuse and Explosives by Mass Spectrometry

In analytical science, mass spectrometry (MS) is known as a “gold analytical tool” because of its unique character of providing the direct molecular structural information of the relevant analyte molecules. Therefore, MS technique has widely been used in all branches of chemistry along with in proteomics, metabolomics, genomics, lipidomics, environmental monitoring etc. Mass spectrometry-based methods are very much needed for fast and reliable detection and quantification of drugs of abuse and explosives in order to provide fingerprint information for criminal investigation as well as for public security and safety at public places, respectively. Most of the compounds exist as their neutral form in nature except proteins, peptides, nucleic acids that are in ionic forms intrinsically. In MS, ion source is the heart of the MS that is used for ionizing the electrically neutral molecules. Performance of MS in terms of sensitivity and selectivity depends mainly on the efficiency of the ionization source. Accordingly, much attention has been paid to develop efficient ion sources for a wide range of compounds. Unfortunately, none of the commercial ion sources can be used for ionization of different types of compounds. Moreover, in MS, analyte molecules must be released into the gaseous phase and then ionize by using a suitable ion source for detection/quantification. Under these circumstances, fabrication of new ambient ion source and ultrasonic cutter blade-based non-thermal and thermal desorption methods have been taken into account. In this paper, challenges and strategies of mass spectrometry analysis of the drugs of abuse and explosives through fabrication of ambient ionization sources and new desorption methods for non-volatile compounds have been described. We will focus the literature progress mostly in the last decade and present our views for the future study.

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SIMS (Imaging Secondary Ion Mass Spectrometry) Analysis of a Cross-section Sample From Leonardo Da Vinci’s Adoration of the Magi

10.21203/rs.3.rs-97371/v1 ◽

2020 ◽

Author(s):

Hua Tian ◽

Maurizio Seracini ◽

Katherine Schimmel ◽

Stephen J. Benkovic ◽

Nicholas Winograd

Keyword(s):

Mass Spectrometry ◽

Cross Section ◽

Secondary Ion Mass Spectrometry ◽

Ion Source ◽

Mass Spectrometry Analysis ◽

Sequence Of Events ◽

Wide Range ◽

Ion Mass Spectrometry ◽

Chloride Salts ◽

Secondary Ion

Abstract Paintings often consist of highly complex layered structures that contain a mixture of organic and inorganic materials at each layer depending upon the artist’s technique. A comprehensive analysis of the chemical composition could provide critical information on the sequence of events that led to an artwork’s current state. In this investigation, we have employed a novel imaging technique known as Secondary Ion Mass Spectrometry (SIMS) to chemically map the cross-section of a paint film sampled from Leonardo da Vinci’s Adoration of the Magi at a submicron resolution using a C60+ ion source. A wide range of materials were found to be spatially localized at the different layers such as: protein, carbon, silicates, fatty acids, salts and lead associated compounds. An interaction of chloride salts with the lead white was observed in the priming layer. The chloride salts disrupted most of the priming layer suggesting that a cleaning process took place that removed most of the priming layer before the monochrome brown repaints were added on top at a later time.

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Thermal bursting ionization for ambient mass spectrometry

RSC Advances ◽

10.1039/c5ra22626k ◽

2016 ◽

Vol 6 (3) ◽

pp. 2496-2499 ◽

Cited By ~ 4

Author(s):

Jiying Pei ◽

Kefu Yu ◽

Yinghui Wang

Keyword(s):

Mass Spectrometry ◽

Ambient Ionization ◽

Ambient Mass Spectrometry ◽

Sample Analysis ◽

Liquid Sample ◽

Ionization Source ◽

Complex Liquid

Ambient ionization source, thermal bursting ionization (TBI), was characterized for complex liquid sample analysis with mass spectrometry.

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Prediction of acrylamide formation in biscuits based on fingerprint data generated by ambient ionization mass spectrometry employing direct analysis in real time (DART) ion source

Food Chemistry ◽

10.1016/j.foodchem.2014.09.151 ◽

2015 ◽

Vol 173 ◽

pp. 290-297 ◽

Cited By ~ 24

Author(s):

Lukas Vaclavik ◽

Edoardo Capuano ◽

Vural Gökmen ◽

Jana Hajslova

Keyword(s):

Mass Spectrometry ◽

Real Time ◽

Direct Analysis ◽

Ambient Ionization ◽

Ion Source ◽

Ionization Mass Spectrometry ◽

Ionization Mass ◽

Acrylamide Formation ◽

Ambient Ionization Mass Spectrometry ◽

Fingerprint Data

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Replacement of immunoassay by LC tandem mass spectrometry for the routine measurement of drugs of abuse in oral fluid

Annals of Clinical Biochemistry International Journal of Laboratory Medicine ◽

10.1258/0004563054255632 ◽

2005 ◽

Vol 42 (4) ◽

pp. 277-284 ◽

Cited By ~ 40

Author(s):

KR Allen ◽

R Azad ◽

HP Field ◽

DK Blake

Keyword(s):

Mass Spectrometry ◽

Tandem Mass Spectrometry ◽

Oral Fluid ◽

Drugs Of Abuse ◽

Multiple Reaction Monitoring ◽

Gradient Elution ◽

Tandem Mass ◽

Drug Concentrations ◽

Wide Range ◽

The Matrix

Background: There is increasing interest in the use of oral fluid as the matrix for the detection of drugs of abuse which requires the use of sensitive immunoassays to achieve the low detection limits required. The use of liquid chromatography linked to tandem mass spectrometry (LC/MS/MS) is explored as a possible replacement for immunoassay in screening for drugs of abuse in oral fluid samples. Methods: Oral fluid samples collected from 72 subjects attending an addiction clinic were screened for opiates, cocaine, methadone and benzodiazepines using both enzyme-linked immunosorbent assays (ELISA) and LC/MS/MS. The latter analysis used a short gradient elution with individual drugs detected by multiple reaction monitoring using tandem mass spectrometry. Results between the two methods were compared qualitatively using the cut-off concentrations defined by the ELISA assays. Results: With regard to the ELISA assays which show group specificity, LC/MS/ MS detected the presence of 6-monoacetylmorphine, morphine or dihydrocodeine in all but two of 49 samples positive for opiates. Of 55 samples positive for benzodiazepines by ELISA, all but two were confirmed by LC/MS/MS. Overall, LC/MS/MS compared favourably with ELISA for detection of specific drugs or their metabolites in the case of morphine, methadone and the cocaine metabolite benzoylecgonine. Many of the discrepant results between the two assays were a result of samples with drug concentrations near to the cut-off concentrations and the imprecision of these assays at very low concentrations. Conclusion: LC/MS/MS offers a more flexible, specific and sensitive alternative to the screening of oral fluid samples for drugs of abuse than ELISA. A wide range of drugs and metabolites can be detected from a single sample injection.

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A Collison nebulizer as an ion source for mass spectrometry analysis

Technical Physics Letters ◽

10.1134/s1063785014120116 ◽

2014 ◽

Vol 40 (12) ◽

pp. 1078-1081 ◽

Cited By ~ 4

Author(s):

V. V. Pervukhin ◽

D. G. Sheven’ ◽

Yu. N. Kolomiets

Keyword(s):

Mass Spectrometry ◽

Ion Source ◽

Mass Spectrometry Analysis ◽

Spectrometry Analysis

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Novel exosome biomarker candidates for Alzheimer´s disease unraveled through Mass Spectrometry analysis

10.21203/rs.3.rs-787466/v2 ◽

2021 ◽

Author(s):

Tânia Soares Martins ◽

Rui Marçalo ◽

Cristóvão B. da Cruz e Silva ◽

Dário Trindade ◽

José Catita ◽

...

Keyword(s):

Mass Spectrometry ◽

Multivariate Analyses ◽

Cost Effective ◽

Accurate Diagnosis ◽

Functional Enrichment ◽

Mass Spectrometry Analysis ◽

Spectrometry Analysis ◽

Wide Range ◽

Go Terms ◽

Peripheral Biomarker

Abstract Exosomes are small extracellular vesicles (EVs) present in human biofluids that can transport specific disease-associated molecules. Consequently blood-derived exosomes have emerged as important peripheral biomarker sources for a wide range of diseases, among them Alzheimer’s disease (AD). Although there is no effective cure for AD, an accurate diagnosis, relying on easily accessible peripheral biofluids, is still necessary to discriminate this disease from other dementias, test potential therapies and even monitor rate of disease progression. The ultimate goal is to produce a cost-effective and widely available alternative, which can also be employed as a first clinical screen. In this study, EVs with exosome-like characteristics were isolated from serum of Controls and AD cases through precipitation- and column-based methods, followed by mass spectrometry analysis. The resulting proteomes were characterized by Gene Ontology (GO) functional enrichment and multivariate analyses. Although GO terms were similar for exosomes proteomes of Controls and ADs, using both methodologies, a clear segregation of disease cases was obtained when using the precipitation-based method. Nine significantly different abundant proteins were identified between Controls and AD cases, representing putative biomarker candidate targets. Among them AACT and C4BPα, two Aβ-binding proteins, whose exosome levels were further validated in individuals from independent cohorts using antibody-based approaches. The findings discussed represent an important contribution to the identification of novel exosomal biomarker candidates useful as potential blood-based tools for AD diagnosis.

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Simultaneous determination of perfluoroalkyl substances and bile acids in human serum using ultra-high-performance liquid chromatography–tandem mass spectrometry

Analytical and Bioanalytical Chemistry ◽

10.1007/s00216-019-02263-6 ◽

2019 ◽

Vol 412 (10) ◽

pp. 2251-2259 ◽

Cited By ~ 10

Author(s):

Samira Salihović ◽

Alex M. Dickens ◽

Ida Schoultz ◽

Frida Fart ◽

Lisanna Sinisalu ◽

...

Keyword(s):

Mass Spectrometry ◽

Liquid Chromatography ◽

Tandem Mass Spectrometry ◽

Bile Acids ◽

Ion Source ◽

Mass Spectrometry Analysis ◽

Tandem Mass ◽

Chromatography Tandem Mass Spectrometry ◽

Liquid Chromatography Tandem Mass

AbstractThere is evidence of a positive association between per- and polyfluoroalkyl substances (PFASs) and cholesterol levels in human plasma, which may be due to common reabsorption of PFASs and bile acids (BAs) in the gut. Here we report development and validation of a method that allows simultaneous, quantitative determination of PFASs and BAs in plasma, using 150 μL or 20 μL of sample. The method involves protein precipitation using 96-well plates. The instrumental analysis was performed with ultra-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS), using reverse-phase chromatography, with the ion source operated in negative electrospray mode. The mass spectrometry analysis was carried out using multiple reaction monitoring mode. The method proved to be sensitive, robust, and with sufficient linear range to allow reliable determination of both PFASs and BAs. The method detection limits were between 0.01 and 0.06 ng mL−1 for PFASs and between 0.002 and 0.152 ng mL−1 for BAs, with the exception of glycochenodeoxycholic acid (0.56 ng mL−1). The PFAS measured showed excellent agreement with certified plasma PFAS concentrations in NIST SRM 1957 reference serum. The method was tested on serum samples from 20 healthy individuals. In this proof-of-concept study, we identified significant associations between plasma PFAS and BA levels, which suggests that PFAS may alter the synthesis and/or uptake of BAs.

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Amorphous Ge-Bi-Se Thin Films: A Mass Spectrometric Study

Scientific Reports ◽

10.1038/s41598-019-55773-9 ◽

2019 ◽

Vol 9 (1) ◽

Cited By ~ 1

Author(s):

Ravi Mawale ◽

Govinda Mandal ◽

Marek Bouška ◽

Jan Gutwirth ◽

Pankaj Lochan Bora ◽

...

Keyword(s):

Mass Spectrometry ◽

Thin Films ◽

Laser Ablation ◽

Density Functional ◽

Structural Information ◽

Time Of Flight ◽

Mass Spectrometry Analysis ◽

Individual Species ◽

Ablation Time ◽

Flight Mass Spectrometry

AbstractThe Ge-Bi-Se thin films of varied compositions (Ge content 0–32.1 at. %, Bi content 0–45.7 at. %, Se content 54.3–67.9 at. %) have been prepared by rf magnetron (co)-sputtering technique. The present study was undertaken in order to investigate the clusters generated during the interaction of laser pulses with Ge-Bi-Se thin films using laser ablation time-of-flight mass spectrometry. The stoichiometry of the clusters was determined in order to understand the individual species present in the plasma plume. Laser ablation of Ge-Bi-Se thin films accompanied by ionization produces about 20 positively and/or negatively charged unary, binary and ternary (Gex+, Biy+, Sez+/−, GexSez+/−, BiySez+/− and GexBiySez−) clusters. Furthermore, we performed the laser ablation experiments of Ge:Bi:Se elemental mixtures and the results were compared with laser ablation time-of-flight mass spectrometry analysis of thin films. Moreover, to understand the geometry of the generated clusters, we calculated structures of some selected binary and ternary clusters using density functional theory. The generated clusters and their calculated possible geometries can give important structural information, as well as help to understand the processes present in the plasma processes exploited for thin films deposition.

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Screening of Phosphodiesterase-5 Inhibitors and Their Analogs in Dietary Supplements by Liquid Chromatography–Hybrid Ion Trap–Time of Flight Mass Spectrometry

Molecules ◽

10.3390/molecules25122734 ◽

2020 ◽

Vol 25 (12) ◽

pp. 2734

Author(s):

Unyong Kim ◽

Hyun-Deok Cho ◽

Myung Hee Kang ◽

Joon Hyuk Suh ◽

Han Young Eom ◽

...

Keyword(s):

Mass Spectrometry ◽

Dietary Supplements ◽

Ion Trap ◽

Structural Information ◽

Screening Method ◽

Time Of Flight ◽

Ion Source ◽

Phosphodiesterase 5 Inhibitors ◽

Flight Mass Spectrometry ◽

Phosphodiesterase 5

An accurate and reliable method based on ion trap–time of flight mass spectrometry (IT–TOF MS) was developed for screening phosphodiesterase-5 inhibitors, including sildenafil, vardenafil, and tadalafil, and their analogs in dietary supplements. Various parameters affecting liquid chromatographic separation and IT–TOF detection were investigated, and the optimal conditions were determined. The separation was achieved on a reversed-phase column under gradient elution using acetonitrile and water containing 0.2% acetic acid at a flow rate of 0.2 mL/min. The chromatographic eluents were directly ionized in the IT–TOF system equipped with an electrospray ion source operating in the positive ion mode. The proposed screening method was validated by assessing its linearity, precision, and accuracy. Sequential tandem MS was conducted to obtain structural information of the references, and the fragmentation mechanism of each reference was proposed for providing spectral insight for newly synthesized analogs. Structural information, including accurate masses of both parent and fragment ions, was incorporated into the MSn spectral library. The developed method was successfully applied for screening adulterated dietary supplement samples.

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