25 results on '"Arian C, van Asten"'
Search Results
2. On-site forensic analysis of colored seized materials: Detection of brown heroin and MDMA-tablets by a portable NIR spectrometer
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Ruben F. Kranenburg, Henk‐Jan Ramaker, and Arian C. van Asten
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Excipients ,Heroin ,Spectroscopy, Near-Infrared ,N-Methyl-3,4-methylenedioxyamphetamine ,Calibration ,Pharmaceutical Science ,Environmental Chemistry ,Powders ,Spectroscopy ,Analytical Chemistry ,Tablets - Abstract
The increasing workload for forensic laboratories and the expanding complexity of the drug market necessitates efficient approaches to detect drugs of abuse. Identification directly at the scene of crime enables investigative forces to make rapid decisions. Additionally, on-site identification of the material also leads to considerable efficiency and cost benefits. As such, paperwork, transportation, and time-consuming analysis in a laboratory may be avoided. Near-infrared (NIR) spectroscopy is an analysis technique suitable for rapid drug testing using portable equipment. A possible limitation of spectroscopic analysis concerns the complexity of seized materials. NIR measurements represent composite spectra for mixtures and diagnostic spectral features can be obscured by excipients such as colorants. Herein, a NIR-based (1300-2600 nm) detection of heroin and MDMA in colored casework (i.e., brown powders and ecstasy tablets) using a portable analyzer is presented. The application includes a multistage data analysis model based on the net analyte signal (NAS) approach. This identification model was specifically designed for mixture analysis and requires a limited set of pure reference spectra only. Consequently, model calibration efforts are reduced to a minimum. A total of 549 forensic samples was tested comprising brown heroine samples and a variety of colored tablets with different active ingredients. This investigation led to a99% true negative and93% true positive rate for heroin and MDMA. These results show that accurate on-site detection in colored casework is possible using NIR spectroscopy combined with an efficient data analysis model. These findings may eventually help in the transition of routine forensic laboratories from laboratory-based techniques to portable equipment operated on scene.
- Published
- 2022
3. Instrument-independent chemometric models for rapid, calibration-free NPS isomer differentiation from mass spectral GC-MS data
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Jennifer L. Bonetti, Ruben F. Kranenburg, Esmee Schoonderwoerd, Saer Samanipour, and Arian C. van Asten
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Law ,Pathology and Forensic Medicine - Published
- 2023
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- View/download PDF
4. Utilizing Surface Acoustic Wave Nebulization (SAWN) for the Rapid and Sensitive Ambient Ionization Mass Spectrometric Analysis of Organic Explosives
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Alina Astefanei, Garry L. Corthals, Lauren Pintabona, Arian C. van Asten, and Supramolecular Separations (HIMS, FNWI)
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Explosive material ,Chemistry ,Ambient ionization mass spectrometry ,Surface acoustic wave ,Analytical chemistry ,Surface acoustic wave nebulization ,Mass spectrometry ,Mass spectrometric ,Spectral line ,Fragmentation (mass spectrometry) ,Structural Biology ,Ionization ,SAWN ,Security ,Explosives ,Forensic science ,Spectroscopy ,Research Article ,Ambient ionization - Abstract
When considering incident investigations and security checks focused on energetic materials, there is an ongoing need for rapid, on-scene chemical identification. Currently applied methods are not capable of meeting all requirements, and hence, portable mass spectrometry is an interesting alternative although many instrumental challenges still exist. To be able to analyze explosives with mass spectrometry outside the traditional laboratory, suitable ambient ionization methods need to be developed. Ideally such methods are also easily implemented in the field requiring limited to no power sources, gas supplies, flow controllers, and heating devices. For this reason, the potential of SAWN (surface acoustic wave nebulization) for the ambient ionization and subsequent mass spectrometric (MS) analysis of organic explosives was investigated in this study. Excellent sensitivity was observed for nitrate-based organic explosives when operating the MS in negative mode. No dominant adduct peaks were observed for the peroxides TATP and HMTD with SAWN-MS in positive mode. The MS spectra indicate extensive fragmentation of the peroxide explosives even under the mild ionization conditions provided by SAWN. The potential of SAWN-MS was demonstrated with the correct identification of nitrate-based organic explosives in pre- and post-explosion case samples in only a fraction of the time and effort required for the regular laboratory analysis. Results show that SAWN-MS can convincingly identify intact organic energetic compounds and mixtures but that sensitivity is not always sufficient to detect traces of explosives in post-explosion residues. Electronic supplementary material The online version of this article (10.1007/s13361-019-02335-y) contains supplementary material, which is available to authorized users.
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- 2019
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5. Spotting isomer mixtures in forensic illicit drug casework with GC-VUV using automated coelution detection and spectral deconvolution
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Arian C. van Asten, Peter J. Schoenmakers, Chris K. Lukken, and Ruben F. Kranenburg
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Chromatography ,Chemistry ,medicine.drug_class ,business.industry ,010401 analytical chemistry ,Clinical Biochemistry ,Pattern recognition ,Cell Biology ,General Medicine ,Spotting ,030226 pharmacology & pharmacy ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Analytical Chemistry ,Peak detection ,Designer drug ,Synthetic drugs ,03 medical and health sciences ,0302 clinical medicine ,medicine ,Illicit drug ,Deconvolution ,Artificial intelligence ,business - Abstract
Analysis of isomeric mixtures is a significant analytical challenge. In the forensic field, for example, over 1000 new psychoactive substances (NPSs), comprising of many closely related and often isomeric varieties, entered the drugs-of-abuse market within the last decade. Unambiguous identification of the isomeric form requires advanced spectroscopic techniques, such as GC-Vacuum Ultraviolet Spectroscopy (GC-VUV). The continuous development of NPSs makes the appearance of a novel compound in case samples a realistic scenario. While several analytical solutions have been presented recently to confidently distinguish NPS isomers, the presence of multiple isomers in a single drug sample is typically not considered. Due to their structural similarities it is possible that a novel NPS coelutes with a known isomer and thus remains undetected. This study investigates the capabilities of VUV spectral deconvolution for peak detection and identification in incompletely resolved drug mixtures. To mimic worst case scenarios, severe coelution was deliberately induced at elevated GC temperatures. The deconvolution software was nevertheless able to correctly detect both substances, even in case of near-identical VUV spectra at almost full coelution. As a next step, spectra were subsequently removed from the reference library to simulate the scenario in which a novel substance was encountered for the first time in forensic case work. However, also in this situation the deconvolution software still detected the coelution. This work shows that a VUV library match score below 0.998 may serve as a warning that a novel substance may be present in a street sample.
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- 2021
6. Characterization and comparison of smokeless powders by on-line two-dimensional liquid chromatography
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Rick S. van den Hurk, Noor Abdulhussain, Anouk S.A. van Beurden, Mabel E. Dekker, Annemieke Hulsbergen, Ron A.H. Peters, Bob W.J. Pirok, Arian C. van Asten, Analytical Chemistry and Forensic Science (HIMS, FNWI), HIMS Other Research (FNWI), and Supramolecular Separations (HIMS, FNWI)
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Chromatography, Reverse-Phase ,Organic Chemistry ,Chromatography, Gel ,Lobeline ,General Medicine ,Powders ,Biochemistry ,Analytical Chemistry - Abstract
Smokeless powders (SPs) are one of the most commonly used propellants for ammunition but can also be abused as energetic material in improvised explosive devices (IEDs) such as pipe bombs. After a shooting or explosion, unburnt or partially burnt particulates may be observed which can be used for forensic investigation. SPs comprise mainly nitrocellulose (NC) and additives. Therefore, the characterization of both NC and the additives is of significant forensic importance. Typically, the identification, classification, and chemical profiling of smokeless powders are based exclusively on the analysis of the additives. In this study, information regarding the NC base component was combined with the chemical analysis of the additives using two-dimensional liquid chromatography (2D-LC). The system combines size-exclusion chromatography (SEC) and reversed-phase liquid chromatography (RPLC) in an on-line heart-cut 2D-LC configuration. In the first dimension, the NC is characterized by its molecular-weight distribution (MWD) while being separated from the additives. The additives are then transferred to the second-dimension separation using a novel analyte-transfer system. In the second dimension, the additives are separated to obtain a detailed profile of the low-molecular-mass compounds in the SP. With this approach, the MWD of the NC and the composition of the additives in SP have been obtained within an hour. A discrimination power of 90.53% was obtained when studying exclusively the NC MWD, and 99.47% for the additive profile. This novel combination enables detailed forensic comparison of intact SPs. Additionally, no extensive sample preparation is required, making the developed method less labor intensive.
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- 2022
- Full Text
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7. Isomer-Specific Two-Color Double-Resonance IR
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Fred A M G, van Geenen, Ruben F, Kranenburg, Arian C, van Asten, Jonathan, Martens, Jos, Oomens, and Giel, Berden
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Psychotropic Drugs ,Molecular Structure ,Infrared Rays ,Lasers ,Spectrum Analysis ,Forensic Sciences ,Article ,Methamphetamine - Abstract
The capability of an ion trap mass spectrometer to store ions for an arbitrary amount of time allows the use of a single infrared (IR) laser to perform two-color double resonance IR–IR spectroscopic experiments on mass-to-charge (m/z) selected ions. In this single-laser IR2MS3 scheme, one IR laser frequency is used to remove a selected set of isomers from the total trapped ion population and the second IR laser frequency, from the same laser, is used to record the IR spectrum of the remaining precursor ions. This yields isomer-specific vibrational spectra of the m/z-selected ions, which can reveal the structure and identity of the initially co-isolated isomeric species. The use of a single laser greatly reduces the experimental complexity of two-color IR2MS3 and enhances its application in fields employing analytical MS. In this work, we demonstrate the methodology by acquiring single-laser IR2MS3 spectra in a forensic context, identifying two previously unidentified isomeric novel psychoactive substances (NPS) from a sample that was confiscated by the Amsterdam Police.
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- 2021
8. Performance evaluation of handheld Raman spectroscopy for cocaine detection in forensic case samples
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Renee de Ridder, Joshka Verduin, Marcel Heerschop, Peter H. J. Keizers, Yannick Weesepoel, Annette van Esch, Arian C. van Asten, Ruben F. Kranenburg, Martin Alewijn, and Supramolecular Separations (HIMS, FNWI)
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Drugs of abuse ,Materials science ,on-scene detection ,Pharmaceutical Science ,Special Issue ‐ Research Articles ,TruNarc ,Spectrum Analysis, Raman ,portable device ,01 natural sciences ,Gas Chromatography-Mass Spectrometry ,Analytical Chemistry ,03 medical and health sciences ,symbols.namesake ,0302 clinical medicine ,Law Enforcement ,Cocaine ,Limit of Detection ,Partial least squares regression ,False positive paradox ,Environmental Chemistry ,Humans ,030216 legal & forensic medicine ,Cocaine base ,Spectral data ,Spectroscopy ,VLAG ,Retrospective Studies ,Detection limit ,Team Authenticity & Nutrients ,Chromatography ,Raman spectrometer ,illicit drug analysis ,010401 analytical chemistry ,Reproducibility of Results ,Special Issue ‐ Research Article ,0104 chemical sciences ,illicit-drug analysis ,on‐scene detection ,symbols ,Feasibility Studies ,Central Nervous System Stimulants ,Raman spectroscopy ,Identification criteria - Abstract
Handheld Raman spectroscopy is an emerging technique for rapid on‐site detection of drugs of abuse. Most devices are developed for on‐scene operation with a user interface that only shows whether cocaine has been detected. Extensive validation studies are unavailable, and so are typically the insight in raw spectral data and the identification criteria. This work evaluates the performance of a commercial handheld Raman spectrometer for cocaine detection based on (i) its performance on 0–100 wt% binary cocaine mixtures, (ii) retrospective comparison of 3,168 case samples from 2015 to 2020 analyzed by both gas chromatography–mass spectrometry (GC–MS) and Raman, (iii) assessment of spectral selectivity, and (iv) comparison of the instrument's on‐screen results with combined partial least square regression (PLS‐R) and discriminant analysis (PLS‐DA) models. The limit of detection was dependent on sample composition and varied between 10 wt% and 40 wt% cocaine. Because the average cocaine content in street samples is well above this limit, a 97.5% true positive rate was observed in case samples. No cocaine false positives were reported, although 12.5% of the negative samples were initially reported as inconclusive by the built‐in software. The spectral assessment showed high selectivity for Raman peaks at 1,712 (cocaine base) and 1,716 cm−1 (cocaine HCl). Combined PLS‐R and PLS‐DA models using these features confirmed and further improved instrument performance. This study scientifically assessed the performance of a commercial Raman spectrometer, providing useful insight on its applicability for both presumptive detection and legally valid evidence of cocaine presence for law enforcement., The performance of a handled Raman spectrometer for cocaine detection is evaluated by validation samples, spectral assessment, and retrospective comparison. Raman and GC–MS results of 3,168 cases samples from 2015 to 2020 were compared. Limits of detection were dependent of sample composition and varied between 10 and 40 wt% cocaine. A 97.5% true positive rate was observed in case samples. Instrument performance was assessed and further improved by a combined partial least square regression (PLS‐R) and discriminant analysis (PLS‐DA) model.
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- 2020
9. Deliberate evasion of narcotic legislation: Trends visualized in commercial mixtures of new psychoactive substances analyzed by GC-solid deposition-FTIR
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Laura I. Stuyver, Annique van Beek, Renee de Ridder, Erik Colmsee, Ruben F. Kranenburg, Arian C. van Asten, HIMS Other Research (FNWI), and Supramolecular Separations (HIMS, FNWI)
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Chromatography ,Brand names ,Infrared spectroscopy ,Pentedrone ,Mass spectrometry ,Pathology and Forensic Medicine ,Analytical Chemistry ,Ethylone ,chemistry.chemical_compound ,chemistry ,Materials Chemistry ,Deposition (phase transition) ,Physical and Theoretical Chemistry ,Drug analysis ,Fourier transform infrared spectroscopy ,Law ,Spectroscopy - Abstract
List-based approaches for judicial control of synthetic drugs inevitably introduce a group of legal highs that do not fall under the scope of legislation but may exhibit similar effects and associated health risks as illicit substances. Differences between controlled and uncontrolled components may be as minor as a single molecular group rearrangement. This phenomenon complicated forensic drug analysis in recent years due to both the rise of new psychoactive substances (NPS), and selectivity limitations of the workhorse gas chromatography-mass spectrometry (GC−MS) technique, especially with respect to ring-isomers. Our study demonstrates the value of GC-solid deposition-Fourier-transform infrared spectroscopy (FTIR) as a complementary technique for NPS identification in multi-drug mixtures. The instrument design using direct deposition of the GC effluent on a cryogenically cooled ZnSe-disk allows for signal enhancement of minor constituents by collecting eluting peaks of multiple GC injections. Highly diagnostic spectra were obtained for all ortho, meta and para-isomers of fluoroamphetamine (FA), fluoromethamphetamine (FMA), methylmethcathinone (MMC) and methylethcathinone (MEC). Combined results of GC−MS and GC-solid deposition-FTIR revealed the presence of up to 11 individual NPS mixed together in liquid samples sold as research chemicals or room odorizer in The Netherlands. Sample compositions rapidly evolved over time with recently controlled substances such as 4-fluoroamphetamine (4-FA), pentedrone, ethylone and 4-methylethcathinone (4-MEC) being replaced by uncontrolled isomers or analogues as 2-fluoroamphetamine (2-FA), 2- or 4-fluoromethamphetamine (2-FMA, 4-FMA) and dimethylone. In 12 different samples all marketed under two brand names, a total of 9 different compositions were identified in samples from 2018 and 2019.
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- 2021
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10. Probabilistic peak detection in CE-LIF for STR DNA typing
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Arian C. van Asten, Ate D. Kloosterman, Gabriel Vivó-Truyols, and Michael Woldegebriel
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Genetics ,Propagation of uncertainty ,business.industry ,Computer science ,Gaussian ,010401 analytical chemistry ,Clinical Biochemistry ,Posterior probability ,Probabilistic logic ,Pattern recognition ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Analytical Chemistry ,Set (abstract data type) ,Electropherogram ,03 medical and health sciences ,symbols.namesake ,0302 clinical medicine ,STR analysis ,symbols ,030216 legal & forensic medicine ,Artificial intelligence ,Raw data ,business - Abstract
In this work, we present a novel probabilistic peak detection algorithm based on a Bayesian framework for forensic DNA analysis. The proposed method aims at an exhaustive use of raw electropherogram data from a laser-induced fluorescence multi-CE system. As the raw data are informative up to a single data point, the conventional threshold-based approaches discard relevant forensic information early in the data analysis pipeline. Our proposed method assigns a posterior probability reflecting the data point's relevance with respect to peak detection criteria. Peaks of low intensity generated from a truly existing allele can thus constitute evidential value instead of fully discarding them and contemplating a potential allele drop-out. This way of working utilizes the information available within each individual data point and thus avoids making early (binary) decisions on the data analysis that can lead to error propagation. The proposed method was tested and compared to the application of a set threshold as is current practice in forensic STR DNA profiling. The new method was found to yield a significant improvement in the number of alleles identified, regardless of the peak heights and deviation from Gaussian shape.
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- 2017
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11. Mass-Spectrometry-Based Identification of Synthetic Drug Isomers Using Infrared Ion Spectroscopy
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Arian C. van Asten, Fred A. M. G. van Geenen, Jonathan Martens, Giel Berden, Jos Oomens, Ruben F. Kranenburg, HIMS Other Research (FNWI), Molecular Spectroscopy (HIMS, FNWI), and Supramolecular Separations (HIMS, FNWI)
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FELIX Molecular Structure and Dynamics ,Psychotropic Drugs ,Molecular Structure ,Spectrophotometry, Infrared ,Synthetic Drugs ,Infrared ,Chemistry ,010401 analytical chemistry ,Infrared spectroscopy ,Stereoisomerism ,010402 general chemistry ,Mass spectrometry ,01 natural sciences ,Mass Spectrometry ,Article ,Dissociation (chemistry) ,Spectral line ,0104 chemical sciences ,Analytical Chemistry ,Ion ,Computational chemistry ,Infrared multiphoton dissociation ,FELIX ,Spectroscopy ,Density Functional Theory - Abstract
Infrared ion spectroscopy (IRIS), a mass-spectrometry-based technique exploiting resonant infrared multiple photon dissociation (IRMPD), has been applied for the identification of novel psychoactive substances (NPS). Identification of the precise isomeric forms of NPS is of significant forensic relevance since legal controls are dependent on even minor molecular differences such as a single ring-substituent position. Using three isomers of fluoroamphetamine and two ring-isomers of both MDA and MDMA, we demonstrate the ability of IRIS to distinguish closely related NPS. Computationally predicted infrared (IR) spectra are shown to correspond with experimental spectra and could explain the molecular origins of their distinctive IR absorption bands. IRIS was then used to investigate a confiscated street sample containing two unknown substances. One substance could easily be identified by comparison to the IR spectra of reference standards. For the other substance, however, this approach proved inconclusive due to incomplete mass spectral databases as well as a lack of available reference compounds, two common analytical limitations resulting from the rapid development of NPS. Most excitingly, the second unknown substance could nevertheless be identified by using computationally predicted IR spectra of several potential candidate structures instead of their experimental reference spectra.
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- 2020
12. Emerging techniques for the detection of pyrotechnic residues from seized postal packages containing fireworks
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Karlijn D.B. Bezemer, Peter J. Schoenmakers, Jennifer R. Verkouteren, Arian C. van Asten, Mattijs Koeberg, Greg Gillen, Thomas P. Forbes, Shannon T. Krauss, Annemieke Hulsbergen, and Supramolecular Separations (HIMS, FNWI)
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Screening techniques ,Solid particle ,business.industry ,010401 analytical chemistry ,Pyrotechnics ,Fireworks ,01 natural sciences ,DART ion source ,Article ,0104 chemical sciences ,Pathology and Forensic Medicine ,03 medical and health sciences ,0302 clinical medicine ,Environmental science ,Screening tool ,030216 legal & forensic medicine ,Process engineering ,business ,Law - Abstract
High volume screening of parcels with the aim to trace the illegal distribution and selling of fireworks using postal services is challenging. Inspection services have limited manpower and means to perform extensive visual inspection. In this study, the presence of solid pyrotechnic residues collected from cardboard shipping parcels containing fireworks was investigated for direct in-field chemical detection. Two emerging trace detection techniques, i.e., capillary electrophoresis (CE)-based inorganic oxidizer detector and infrared thermal desorption (IRTD) coupled with direct analysis in real time mass spectrometry (DART-MS) were investigated for their potential as screening tools. Detection of non-visible pyrotechnic trace residues from real-case seized parcels was demonstrated using both screening techniques. However, the high nitrate background in the commercial CE system complicated its screening for black powder traces. In addition to rapid screening, IRTD-DART-MS allowed differentiation between flash and black powder by identification of the molecular inorganic ions. Compared to the portable CE instrument, rapid screening using IRTD-DART-MS is currently limited to laboratory settings. The capabilities of these emerging techniques established solid particle and trace residue chemical detection as interesting options for parcel screening in a logistic setting.
- Published
- 2019
13. Towards chemical profiling of ignitable liquids with comprehensive two-dimensional gas chromatography: Exploring forensic application to neat white spirits
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Gabriel Vivó-Truyols, Peter J. Schoenmakers, Andjoe A.S. Sampat, Arian C. van Asten, and Martin Lopatka
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Chromatography ,Chemistry ,010401 analytical chemistry ,Poison control ,01 natural sciences ,0104 chemical sciences ,Pathology and Forensic Medicine ,Forensic science ,03 medical and health sciences ,Bottling line ,0302 clinical medicine ,Principal component analysis ,Solid Phase Micro Extraction ,Profiling (information science) ,030216 legal & forensic medicine ,Compositional variation ,Law ,Temporal discrimination - Abstract
The application of GC×GC-FID and GC×GC-MS for the chemical analysis and profiling of neat white spirit is explored and the benefit of the enhanced peak capacity offered by comprehensive two-dimensional gas chromatography is demonstrated. An extensive sampling exercise was conducted throughout The Netherlands and the production and logistics in terms of bottling and distribution of white spirits were studied. An exploratory approach based on target-peak tables and principal component analysis was employed to study the brand-to-brand differences and production variations over time. Despite the complex chemical composition of white spirit samples this study shows that chemical variation during productions is actually quite limited. Hence care has to be taken with the chemical comparison for forensic purposes. Although some clustering was noticed on brand level, the large scale production process leads to a very consistent composition across stores and brands. However, because of the broad specifications of this commodity product, substantial chemical variation was found over time. This temporal discrimination could be of forensic value when considering white spirits supplies in individual households.
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- 2016
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14. Revealing hidden information in GC–MS spectra from isomeric drugs: Chemometrics based identification from 15 eV and 70 eV EI mass spectra
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Sander Affourtit, Ruben F. Kranenburg, Johan A. Westerhuis, Daniela Peroni, Arian C. van Asten, Age K. Smilde, Supramolecular Separations (HIMS, FNWI), and Biosystems Data Analysis (SILS, FNWI)
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Multivariate statistics ,Chemistry ,010401 analytical chemistry ,Feature selection ,Linear discriminant analysis ,01 natural sciences ,0104 chemical sciences ,Pathology and Forensic Medicine ,Analytical Chemistry ,Chemometrics ,03 medical and health sciences ,0302 clinical medicine ,Principal component analysis ,Materials Chemistry ,Mass spectrum ,030216 legal & forensic medicine ,Physical and Theoretical Chemistry ,Gas chromatography–mass spectrometry ,Biological system ,Law ,Spectroscopy ,Electron ionization - Abstract
Drug isomer differentiation has become a relevant problem in forensic drug testing laboratories as new psychoactive substances include many closely related and isomeric forms. Both legislative and public safety requirements demand unambiguous identification of the isomers. A novel approach for ring-isomeric differentiation using GC–MS by means of low energy Electron Ionization (EI) in combination with chemometric data analysis was developed. An ionization energy of 15 eV combined with a high efficiency EI source yields more information rich and thus discriminating mass spectra for ring-isomeric, cathinone-type drugs. Through multivariate statistics using Principal Component Analysis (PCA) followed by Linear Discriminant Analysis (LDA) mass spectral data can be exploited to confidently distinguish isomeric classes. Including feature selection of the mass spectra further enhanced the discriminative power of these models. In this way, all examined classes of cathinone and fluoroamphetamine isomers could be robustly identified, even through their conventional 70 eV mass spectrum from a quadrupole-MS instrument. A characteristic Likelihood Ratio (LR) based indicator was developed to quantify the selectivity of the models which proved to be useful for comparison, optimization and identification purposes. The potential of the method was demonstrated with six forensic case samples, providing 100% correct isomer identification. In general, this new approach enables robust classification of drug isomers that is currently not possible with conventional GC–MS methods without the use of additional spectroscopic analyses.
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- 2020
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15. Paper Spray and Extraction Spray Mass Spectrometry for the Direct and Simultaneous Quantification of Eight Drugs of Abuse in Whole Blood
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Yue Ren, Nicholas E. Manicke, Ryan D. Espy, Arian C. van Asten, Zheng Ouyang, S.F. Teunissen, R. Graham Cooks, and Analytical Chemistry and Forensic Science (HIMS, FNWI)
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Paper ,Detection limit ,Drugs of abuse ,Chromatography ,Illicit Drugs ,010405 organic chemistry ,Chemistry ,010401 analytical chemistry ,Extraction (chemistry) ,MDMA ,Tandem mass spectrometry ,Mass spectrometry ,01 natural sciences ,Mass Spectrometry ,0104 chemical sciences ,Analytical Chemistry ,Limit of Detection ,medicine ,Humans ,Sample preparation ,Whole blood ,medicine.drug - Abstract
Determination of eight drugs of abuse in blood has been performed using paper spray or extraction spray mass spectrometry in under 2 min with minimal sample preparation. A method has been optimized for quantification of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA), 3,4-methylenedioxy-N-ethylamphetamine (MDEA), morphine, cocaine, and Delta 9-tetrahydrocannabinol (THC) from a single blood spot. Sample to sample variations of 1-5% relative standard deviation were achieved using stable isotope-labeled internal standards and tandem mass spectrometry. Limits of detection for all drugs were below typical physiological and toxicological levels. Paper spray and extraction spray each used less than 10 mu L of whole blood. These methods exhibit the potential for performing rapid and high-throughput assays for selective on-site multicompound quantitative screening of illicit drugs.
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- 2014
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16. The interface between forensic science and technology: how technology could cause a paradigm shift in the role of forensic institutes in the criminal justice system
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Jorrit van den Berg, Saskia Verheij, Carola Koper, Erwin van Eijk, Ate D. Kloosterman, Anna Mapes, Zeno Geradts, Arian C. van Asten, Marcel van der Steen, Lectoraat Forensisch Onderzoek, and Analytical Chemistry and Forensic Science (HIMS, FNWI)
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Engineering ,Jurisprudence ,Technology ,Technological revolution ,business.industry ,media_common.quotation_subject ,Forensic Sciences ,ComputingMilieux_LEGALASPECTSOFCOMPUTING ,Articles ,Data science ,General Biochemistry, Genetics and Molecular Biology ,Forensic science ,Identification (information) ,Digital evidence ,Paradigm shift ,Forensic profiling ,ComputingMilieux_COMPUTERSANDSOCIETY ,Quality (business) ,General Agricultural and Biological Sciences ,business ,media_common ,Criminal justice - Abstract
In this paper, the importance of modern technology in forensic investigations is discussed. Recent technological developments are creating new possibilities to perform robust scientific measurements and studies outside the controlled laboratory environment. The benefits of real-time, on-site forensic investigations are manifold and such technology has the potential to strongly increase the speed and efficacy of the criminal justice system. However, such benefits are only realized when quality can be guaranteed at all times and findings can be used as forensic evidence in court. At the Netherlands Forensic Institute, innovation efforts are currently undertaken to develop integrated forensic platform solutions that allow for the forensic investigation of human biological traces, the chemical identification of illicit drugs and the study of large amounts of digital evidence. These platforms enable field investigations, yield robust and validated evidence and allow for forensic intelligence and targeted use of expert capacity at the forensic institutes. This technological revolution in forensic science could ultimately lead to a paradigm shift in which a new role of the forensic expert emerges as developer and custodian of integrated forensic platforms.
- Published
- 2015
17. The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography-IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations
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Arian C. van Asten, Cornelia I. Blaga, Mattijs Koeberg, Chris A. van Driel, Antoine E. D. M. van der Heijden, Jildert Bruinsma, and Karlijn D.B. Bezemer
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Chromatography ,Hydrogen ,010401 analytical chemistry ,Analytical chemistry ,chemistry.chemical_element ,Poison control ,Fractionation ,01 natural sciences ,0104 chemical sciences ,Pathology and Forensic Medicine ,03 medical and health sciences ,chemistry.chemical_compound ,0302 clinical medicine ,chemistry ,Genetics ,Acetone ,030216 legal & forensic medicine ,Gas chromatography ,Isotope-ratio mass spectrometry ,Hydrogen peroxide ,Carbon - Abstract
Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone–TATP combinations. The extent of negative (d13C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (d2H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (d18O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations. © 2016 American Academy of Forensic Sciences
- Published
- 2015
18. Test Sample for the Spatially Resolved Quantification of Illicit Drugs on Fingerprints Using Imaging Mass Spectrometry
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Shin Muramoto, Thomas P. Forbes, Greg Gillen, Arian C. van Asten, and Analytical Chemistry and Forensic Science (HIMS, FNWI)
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Paper ,Silicon ,Chromatography ,Chemistry ,Calibration curve ,Illicit Drugs ,Surface Properties ,Spatially resolved ,Fingerprint (computing) ,Desorption electrospray ionization mass spectrometry ,Analytical chemistry ,Mass spectrometry imaging ,Mass Spectrometry ,Analytical Chemistry ,Molecular Imaging ,Secondary ion mass spectrometry ,Sebum ,Biomimetic Materials ,Calibration ,Dermatoglyphics ,Test sample - Abstract
A novel test sample for the spatially resolved quantification of illicit drugs on the surface of a fingerprint using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and desorption electrospray ionization mass spectrometry (DESI-MS) was demonstrated. Calibration curves relating the signal intensity to the amount of drug deposited on the surface were generated from inkjet-printed arrays of cocaine, methamphetamine, and heroin with a deposited-mass ranging nominally from 10 pg to 50 ng per spot. These curves were used to construct concentration maps that visualized the spatial distribution of the drugs on top of a fingerprint, as well as being able to quantify the amount of drugs in a given area within the map. For the drugs on the fingerprint on silicon, ToF-SIMS showed great success, as it was able to generate concentration maps of all three drugs. On the fingerprint on paper, only the concentration map of cocaine could be constructed using ToF-SIMS and DESI-MS, as the signals of methamphetamine and heroin were completely suppressed by matrix and substrate effects. Spatially resolved quantification of illicit drugs using imaging mass spectrometry is possible, but the choice of substrates could significantly affect the results.
- Published
- 2015
19. Quantitative analysis of target components by comprehensive two-dimensional gas chromatography
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Peter J. Schoenmakers, Arian C. van Asten, Albert C. Tas, Age K. Smilde, Valentijn G. van Mispelaar, Analytical Chemistry and Forensic Science (HIMS, FNWI), HIMS (FNWI), and Epidemiology and Data Science
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Fragrance analysis ,Accuracy and precision ,Chromatography, Gas ,Gas chromatography, comprehensive two-dimensional ,data analysis ,Integration ,parallel design ,Sensitivity and Specificity ,Biochemistry ,Analytical Chemistry ,Software ,Chromatograms ,Computer software ,intermethod comparison ,Analytical research ,conference paper ,autoanalysis ,Gas chromatography ,Chromatography ,Data reduction ,Targets ,accuracy ,quantitative analysis ,Chemistry ,business.industry ,Organic Chemistry ,Reproducibility of Results ,General Medicine ,Multiway data ,Automation ,Data set ,priority journal ,Two-dimensional chromatography ,Quantitative analysis (finance) ,Packaging ,business - Abstract
Quantitative analysis using comprehensive two-dimensional (2D) gas chromatography (GC) is still rarely reported. This is largely due to a lack of suitable software. The objective of the present study is to generate quantitative results from a large GC x GC data set, consisting of 32 chromatograms. In this data set, six target components need to be quantified. We compare the results of conventional integration with those obtained using so-called "multiway analysis methods". With regard to accuracy and precision, integration performs slightly better than Parallel Factor (PARAFAC) analysis. In terms of speed and possibilities for automation, multiway methods in general are far superior to traditional integration. © 2003 Elsevier B.V. All rights reserved.
- Published
- 2003
- Full Text
- View/download PDF
20. Surface characterization of industrial fibers with inverse gas chromatography
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Sander Koster, Arian C. van Asten, and Nico van Veenendaal
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Chromatography, Gas ,Chromatography ,Surface Properties ,Chemistry ,Textiles ,Organic Chemistry ,Analytical chemistry ,General Medicine ,Interaction energy ,Biochemistry ,Surface energy ,Analytical Chemistry ,Gibbs free energy ,Surface tension ,symbols.namesake ,Synthetic fiber ,Adsorption ,Inverse gas chromatography ,symbols ,Thermodynamics ,Fiber - Abstract
Inverse gas chromatography (IGC) was applied for the determination of the surface characteristics of Tenax carbon fibers and Akzo Nobel Twaron fibers. Furthermore, IGC procedures for the determination of dispersive and acid-base interactions were validated. The data show that too high values for the dispersive component of the surface energy are obtained when the adsorption area occupied by a single adsorbed n-alkane molecule is estimated from parameters of the corresponding liquid. Comparable values are obtained when the Doris-Gray methodology (area per methylene unit) or measured probe areas are employed. For the fibers studied in this work meaningful Gibbs energy values of the acid-base interaction were only obtained with the polarizability approach. When the dispersive interaction of the polar probes with the fiber surface was scaled to the n-alkane interaction via surface tension, the boiling point, or the vapor pressure of the probes often negative acid-base interaction energies were found. From the temperature dependence of the Gibbs energy, the enthalpy of the acid-base interactions of various probes with the carbon and Twaron aramid fibers was determined. However, from these enthalpy values no meaningful acid-base surface parameters could be obtained. Generally, the limited accuracy with which these parameters can be obtained make the usefulness of this procedure questionable. Also the Gibbs energy data of acid-base interaction can provide a qualitative basis to classify the acidity-basicity of the fiber surface. This latter approach requires only a limited data set and is sufficiently rapid to enable the use of IGC as a screening tool for fibers at a production site. For several polar probes significant concentration effects on carbon fibers were observed. At very low probe loadings the interaction with the fiber surface suddenly increases. This effect is caused by the heterogeneity of the interaction energy of the active sites at the surface. A simple procedure to measure the adsorption isotherm at infinite dilution was developed. The determination of the concentration dependence of the interaction of an n-alkane, an acidic and a basic probe was incorporated in the IGC screening procedure of carbon fibers to monitor this heterogeneity.
- Published
- 2000
- Full Text
- View/download PDF
21. Accurate quantitation of pentaerythritol tetranitrate and its degradation products using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry
- Author
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Peter J. Schoenmakers, Hanneke Brust, Arian C. van Asten, Antoine E. D. M. van der Heijden, Jan Dalmolen, Mattijs Koeberg, and Analytical Chemistry and Forensic Science (HIMS, FNWI)
- Subjects
Ionization ,Standards ,Explosive material ,Crime-scene presence ,Liquid chromatography ,Explosions ,Poison control ,High Tech Systems & Materials ,Pentaerythritol tetranitrate ,Atmospheric-pressure chemical ionization ,Mass spectrometry ,Biochemistry ,Mass Spectrometry ,Analytical Chemistry ,Accurate quantitation ,Degradation ,chemistry.chemical_compound ,Liquid chromatography–mass spectrometry ,Atmospheric ionization ,Pentaerythritol Tetranitrate ,Chromatography, High Pressure Liquid ,TS - Technical Sciences ,Industrial Innovation ,Chromatography ,Atmospheric pressure ,Fluid Mechanics Chemistry & Energetics ,Organic Chemistry ,General Medicine ,LC-MS ,Atmospheric Pressure ,chemistry ,Calibration ,EM - Energetic Materials ,Explosives ,Degradation (geology) ,Forensic science ,Crime - Abstract
After an explosion of pentaerythritol tetranitrate (PETN), its degradation products pentaerythritol trinitrate (PETriN), dinitrate (PEDiN) and mononitrate (PEMN) were detected using liquid chromatography-atmospheric-pressure chemical-ionization-mass spectrometry (LC-APCI-MS). Discrimination between post-explosion and naturally degraded PETN could be achieved based on the relative amounts of the degradation products. This information can be used as evidence when investigating a possible relationship between a suspect and a post-explosion crime scene. The present work focuses on accurate quantitation of PETN and its degradation products, using PETriN, PEDiN and PEMN standards specifically synthesized for this purpose. With the use of these standards, the ionization behavior of these compounds was studied, and a quantitative method was developed. Quantitation of PETN and trace levels of its degradation products was shown to be possible with accuracy between 85.7% and 103.7% and a precision ranging from 1.3% to 11.5%. The custom-made standards resulted in a more robust and reliable method to discriminate between post-explosion and naturally-degraded PETN. © 2014 Elsevier B.V.
- Published
- 2013
22. On the added value of forensic science and grand innovation challenges for the forensic community
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Arian C. van Asten and Analytical Chemistry and Forensic Science (HIMS, FNWI)
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Quality Control ,Engineering ,Information value ,business.industry ,Digital forensics ,Forensic Sciences ,ComputingMilieux_LEGALASPECTSOFCOMPUTING ,Data science ,Quality Improvement ,Organizational Innovation ,Pathology and Forensic Medicine ,Forensic science ,Professional Competence ,Age estimation ,Added value ,Forensic engineering ,Costs and Cost Analysis ,Profiling (information science) ,Humans ,business ,Criminal justice ,Grand Challenges - Abstract
In this paper the insights and results are presented of a long term and ongoing improvement effort within the Netherlands Forensic Institute (NFI) to establish a valuable innovation programme. From the overall perspective of the role and use of forensic science in the criminal justice system, the concepts of Forensic Information Value Added (FIVA) and Forensic Information Value Efficiency (FIVE) are introduced. From these concepts the key factors determining the added value of forensic investigations are discussed; Evidential Value, Relevance, Quality, Speed and Cost. By unravelling the added value of forensic science and combining this with the future needs and scientific and technological developments, six forensic grand challenges are introduced: i) Molecular Photo-fitting; ii) chemical imaging, profiling and age estimation of finger marks; iii) Advancing Forensic Medicine; iv) Objective Forensic Evaluation; v) the Digital Forensic Service Centre and vi) Real time In-Situ Chemical Identification. Finally, models for forensic innovation are presented that could lead to major international breakthroughs on all these six themes within a five year time span. This could cause a step change in the added value of forensic science and would make forensic investigative methods even more valuable than they already are today.
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- 2013
23. Fragrance allergy: assessing the safety of washed fabrics
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Jean-Paul Marty, Christophe J. Le Coz, Dominique Tennstedt, Gérard Lainé, Françoise Giordano-Labadie, Annick Pons-Guiraud, Sylvie Siest, M C Jacobs, Arian C. van Asten, David A. Basketter, Catherine Laverdet, Daniel Berthod, M. Vigan, Marie-Anne Germaux, O. Bayrou, Ludovic Martin, and Marie Baeck
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Adult ,Male ,Detergents ,Dermatology ,Clothing ,chemistry.chemical_compound ,Young Adult ,Cyclohexenes ,Eugenol ,Immunology and Allergy ,Humans ,Hypersensitivity, Delayed ,Food science ,Aged ,Aldehydes ,Skin exposure ,Patch test ,Middle Aged ,Perfume ,Isoeugenol ,Skin reaction ,chemistry ,Fragrance allergy ,Contact allergy ,Dermatitis, Allergic Contact ,Female - Abstract
Background: Previously, a quantitative risk assessment suggested there was no risk of induction of fragrance allergy from minor residues of fragrance chemicals on washed fabrics. Objective: To investigate whether there was any risk of the elicitation of contact allergy from fragrance chemical residues on fabric in individuals who were already sensitized. Methods: Thirty-six subjects with a positive patch test to isoeugenol (n = 19) or hydroxyisohexyl 3-cyclohexene carboxaldehyde (n = 17) were recruited. Dose-response and fabric patch tests were performed, respectively, with filter paper and a cotton sample loaded with fragrance in ethanol-diethylphthalate (DEP) and applied in a Finn Chamber (R) or a Hill Top Chamber (R). Results: Only two subjects reacted to an isoeugenol patch test concentration of 0.01% (>20x the estimated likely skin exposure level), none reacted to lower concentrations. Of 36 subjects, 18 reacted to the fabric patch treated with ethanol-DEP vehicle alone and 20 to the fragrance-chemical-treated fabric patch. These were only minor non-specific skin reactions. They were also quite evenly distributed between the two fragrance chemical allergic groups. Conclusions: On the basis of the examples studied, fragrance chemical residues present on fabric do not appear to present a risk of the elicitation of immediate or delayed allergic skin reactions on individuals already sensitized.
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- 2010
24. Theoretical and experimental aspects of indirect detection in capillary electrophoresis
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Hans Poppe, X. Xu, Gerard Bruin, and Arian C. van Asten
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Chromatography ,Chemistry ,Capillary action ,Organic Chemistry ,Analytical chemistry ,General Medicine ,Biochemistry ,Analytical Chemistry ,Ion ,Electropherogram ,Capillary electrophoresis ,Experimental system ,Sensitivity (control systems) ,Uv detection - Abstract
Theoretical and experimental aspects of indirect UV detection are considered. Based on a mathematical treatment of the transport of ions through the capillary, resulting in an eigenvector-eigenvalue problem, some guidelines are formulated about how to increase efficiency and sensitivity in an indirect (UV) detection system. Also, the existence of system peaks can be explained properly. An experimental system consisting of seven amino acids as sample ions and salicylate at pH 11.0 as the UV-absorbing ion was chosen in order to compare theoretical and experimental results. Constructed electropherograms, produced with a computer program based on the above-mentioned mathematical treatment, are also presented and compared with experimental electropherograms.
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- 1992
- Full Text
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25. Fragrance allergy: assessing the risk from washed fabrics
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Annick Pons-Guiraud, Namali V. Corea, Catherine Laverdet, Arian C. van Asten, David A. Basketter, Catherine Clapp, and Jean-Paul Marty
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medicine.medical_specialty ,Allergy ,Dose-Response Relationship, Immunologic ,Dermatology ,medicine.disease_cause ,Dermatitis, Contact ,Risk Assessment ,Mice ,Allergen ,Immunology and Allergy ,Medicine ,Animals ,Humans ,Allergic contact dermatitis ,Mathematical Computing ,Sensitization ,Laundering ,business.industry ,Textiles ,Skin exposure ,Allergens ,Patch Tests ,medicine.disease ,Surgery ,Perfume ,medicine.anatomical_structure ,Fragrance allergy ,Contact allergy ,Consumer Product Safety ,Models, Animal ,business ,Risk assessment - Abstract
The prevalence of contact allergy to fragrance ingredients increased during the last part of the 20th century with the consequence that a substantial number of individuals are at risk of experiencing allergic contact dermatitis (ACD) if they have a sufficient degree of skin exposure to the chemical to which they have become sensitized. Such exposure does not necessarily have to arise from the type of source that originally induced the sensitization. A number of sources of exposure are clearly associated with risk of elicitation of ACD, but the role of fragrance deposited on fabrics, for example as a result of laundry processes, also can be questioned. In this article, firstly, the risk of the induction of fragrance-related ACD from exposure to fragrance via fabric is considered. Using a quantitative risk-assessment approach, the risk appears to be extremely low. The possibility that fragrance residues on laundered fabrics might elicit reactions in those already sensitized by a different route is also discussed. Clinically, clothing pattern dermatitis associated with fragrance allergy is almost never observed, although this could be investigated clinically by exposing sensitized individuals to the relevant fragrance allergen.
- Published
- 2006
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