Fabric analysis by ambient mass spectrometry for explosives and drugs.
ABSTRACT Desorption electrospray ionization (DESI) is applied to the rapid, in-situ, direct qualitative and quantitative analysis of mixtures of explosives and drugs from a variety of fabrics, including cotton, silk, denim, polyester, rayon, spandex, leather and their blends. The compounds analyzed were explosives: trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN) and the drugs of abuse: heroin, cocaine, and methamphetamine. Limits of detection are in the picogram range. DESI analyses were performed without sample preparation and carried out in the presence of common interfering chemical matrices, such as insect repellant, urine, and topical lotions. Spatial and depth profiling was investigated to examine the depth of penetration and lateral resolution. DESI was also used to examine cotton transfer swabs used for travel security sample collection in the screening process. High throughput quantitative analysis of fabric surfaces for targeted analytes is also reported.
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ABSTRACT: FEATURE In spite of, numerous books, which have been devoted to “MALDI mass spectrometry”, it is particularly important to take into account the fact, that the content has involved physical background, instrumentation, and fundamentals of MALDI ionization/desorption process/s. There is a clear trend to present applicability of MALDI method to (bio)macromolecular screening, assay of living systems and imaging of whole organs and bodies, having outstanding contribution to clinical diagnostics and medicine. This book is, thus, first contribution, dedicated to MALDI mass spectrometry for analysis of environmental samples, containing analytes with low molecular weights. PREFACE Nearly thirty years after discovery of matrix–assisted laser desorption/ionization (MALDI) mass spectrometry (MS) (Karas and Hillenkamp, 1984), it can be regarded as robust physical method for analysis of most organic (bio)macromolecular, allowing imaging of living systems, in vitro and in vivo analysis of complex biological human or animal tissues, microorganisms, organs and bodies. The superior instrumental features, including imaging of analytes at attomol concentrational level, cause for an irreplaceability, achieving reliable analytical information about molecules, having weights 10–100 kDa. It stands to reason, that MALDI–MS has place for many interdisciplinary scientific fields such as biochemistry, medicinal chemistry, pharmacology or clinical diagnostics for proteomics, metalloproteomics, lipidomics and/or metallic genomics. Many instrumental elaborations and exponential grown practical implementations have resulted in reviewing of the physical background, instrumentation, and applications to (bio)macromolecules in numerous books, textbooks, monographs and review articles. We have to challenge in this book, therefore, to highlight the outstanding contributions and prospectives of MALDI–MS as a method for analysis of analytes, having low molecular weights. Our book has been devoted to environmental analysis, involving organic and metal–organic pollutants and metallomics of inorganic hazardous air, surface and groundwater, wastewater, soils, sediments and manure pollutants, taking into account that soil proteomics has general connotation in (bio)macromolecular analysis. The content has extended to application to food, criminal and nuclear forensic analysis, thus aiming to inspirit large interdisciplinary interest. Therefore, it was written to serve as a practical guide with high–quality applied research character, to number of MSc educational programmes such as 'Analytical Chemistry', 'Ecological chemistry', 'Geochemistry', 'Environmental Chemistry'; PhD educational programmes in chemistry, ecology, toxicology, agricultural, food sciences and/or earth sciences; MSc programmes in "Physical methods in the forensic chemical analysis", programmes in "Forensic research" and/or "Nuclear Forensics". TABLE OF CONTENT Preface 1 About the contributors Acknowledgement Chapter 1 Critical overview of hybrid mass spectrometric methods for environmental analysis 11 1.1. Soft–ionization mass spectrometric methods in environmental analysis 16 1.2. Hard–ionization mass spectrometric methods in environmental analysis 29 References 32 Chapter 2 Background of the maldi–ms methods 41 2.1. Essence of the ionization/desorption mechanism – ir– and uv–maldi methods 44 2.2. Mass spectrometric maldi–tof method 59 2.3. Mass spectrometric maldi–Orbitrap method 63 References 70 Chapter 3 Sample preparation techniques for maldi mass spectrometry 77 3.1. Solid–state maldi–ms matrixes 79 3.1.1. Physical and chemical properties 79 126.96.36.199. Cationization of the matrix components 80 188.8.131.52. Sublimation 80 184.108.40.206. Protonation/deprotonation and coordination ability with the alkali metal ions 82 220.127.116.11. Absorption and photoexcitation properties of matrix molecules 83 3.1.2. Chemical composition of maldi–ms matrixes 87 18.104.22.168. Organic crystals of neutral molecules and molecular co–crystals 87 22.214.171.124. Crystal of organic salts 89 3.2. Liquid matrixes 93 3.3. Sample preparation techniques for solid–state analysis 93 3.3.1. Dried droplet technique 93 3.3.2. Crushed crystal approach 103 3.3.3. Fast evaporation 103 3.3.4. Overlayer and sandwich method 103 3.3.5. Spin–coating approach 103 3.3.6. Electrospray approach 104 3.3.7. Special sample preparation techniques 105 References 105 Chapter 4 Quantitative solid-state maldi mass spectrometric data processing 115 4.1. Mass spectral data processing 116 4.2. Solid–state maldi–quantitation 124 4.3. Method performance parameters 130 4.4. Factors effecting the intensity of the analyte ms signals 132 4.4.1. Concentration of the matrix component 132 4.4.2. Matrix crystal growth 133 4.4.3. Detector saturation 133 4.4.4. Laser beam direction 133 4.4.5. Behavior of ion plumes 133 4.4.6. Solvent effect on the ionization efficiency 133 References 134 Chapter 5 Application of maldi–ms for environmental analysis of organic pollutants 139 5.1. Analysis of pollutants in air 141 5.2. Analysis of surface and groundwater as well as wastewater 143 5.3. Soil analysis 154 References 174 Chapter 6 Application of maldi–ms for environmental analysis of metal–organic pollutants 181 6.1. Analysis of surface and groundwater 183 6.2. Soil analysis 193 References 203 Chapter 7 Application of maldi–ms for environmental analysis of inorganic pollutants 207 References 227 Chapter 8 Application of maldi–ms for analysis in foodstuffs matrices 231 8.1. Lipidomics, employing maldi mass spectrometry 233 8.2. Analysis of milk 238 8.3. Analysis of flesh 239 8.4. Analysis of wine 240 8.5 Analysis of beer 241 8.6. Analysis of honey 246 8.7. Analysis of tea and fruit juices 246 8.8. Determination of bacteria and microbial communities in foodstuffs matrixes 250 8.9. Analysis of other foodstuff matrixes and ingredients 251 References 257 Chapter 9 Special application of maldi–ms method – criminal forensic analysis 265 9.1 Latent fingermarks analysis 275 9.2 Analysis of paper and inkjet printed documents 277 9.3 Analysis of drugs of abuse and doping 278 9.4 Plant imaging 279 References 283 Chapter 10 Special application of maldi–ms method – nuclear forensic analysis 295 References 310 Appendix 313 Index 3331st, pp. 1-358 03/2015; Lambert Academic Publishing, Saarbrücken., ISBN: 978-3-659-33320-0
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ABSTRACT: The impregnation of items of clothing with drugs of abuse that are then smuggled through airports and ports of entry is a growing problem for law enforcement. This work describes the application of portable Raman spectroscopic techniques for the analysis of a range of natural and artificial fibre items of clothing impregnated with drugs of abuse. Textile pieces were soaked with the solutions of the drugs then left overnight to dry prior to spectroscopic examination. The feasibility of detection of the characteristic Raman spectral bands in the presence of background matrix signals is demonstrated, even for dyed clothing. Definitive evidence for contamination of the items of clothing concerned can be acquired within 20–25 s, without any form of sample pre-treatment or extraction being necessary. The feasibility of automatic spectral recognition of such illicit materials by Raman spectroscopy has been investigated by searching a database stored on the spectrometer computer and the use of principal component analysis. Copyright © 2014 John Wiley & Sons, Ltd.Journal of Raman Spectroscopy 03/2014; 45(3). DOI:10.1002/jrs.4444 · 2.52 Impact Factor
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ABSTRACT: Desorption electrospray ionization mass spectrometry (DESI-MS) is an emerging analytical technique that permits the rapid and direct analysis of biological or environmental samples under ambient conditions. Highlighting the versatility of this technique, DESI-MS has been used for the rapid detection of illicit drugs, chemical warfare agents, agricultural chemicals, and pharmaceuticals from a variety of sample matrices. In diagnostic veterinary toxicology, analyzing samples using traditional analytical instrumentation typically includes extensive sample extraction procedures, which can be time consuming and labor intensive. Therefore, efforts to expedite sample analyses are a constant goal for diagnostic toxicology laboratories. In the current report, DESI-MS was used to directly analyze stomach contents from a dog exposed to the organophosphate insecticide terbufos. The total DESI-MS analysis time required to confirm the presence of terbufos and diagnose organophosphate poisoning in this case was approximately 5 min. This highlights the potential of this analytical technique in the field of veterinary toxicology for the rapid diagnosis and detection of toxicants in biological samples.Journal of veterinary diagnostic investigation: official publication of the American Association of Veterinary Laboratory Diagnosticians, Inc 03/2014; 26(3). DOI:10.1177/1040638714528176 · 1.23 Impact Factor