Publications by authors named "Ruben F Kranenburg"

6 Publications

  • Page 1 of 1

Spotting isomer mixtures in forensic illicit drug casework with GC-VUV using automated coelution detection and spectral deconvolution.

J Chromatogr B Analyt Technol Biomed Life Sci 2021 Mar 29;1173:122675. Epub 2021 Mar 29.

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, Amsterdam 1090 GD, the Netherlands; Co van Ledden Hulsebosch Center (CLHC), Amsterdam Center for Forensic Science and Medicine, PO Box 94157, Amsterdam 1090 GD, the Netherlands.

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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http://dx.doi.org/10.1016/j.jchromb.2021.122675DOI Listing
March 2021

Isomer-Specific Two-Color Double-Resonance IRMS Ion Spectroscopy Using a Single Laser: Application in the Identification of Novel Psychoactive Substances.

Anal Chem 2021 02 20;93(4):2687-2693. Epub 2021 Jan 20.

FELIX Laboratory, Institute for Molecules and Materials, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.

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 (/) selected ions. In this single-laser IRMS 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 /-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 IRMS and enhances its application in fields employing analytical MS. In this work, we demonstrate the methodology by acquiring single-laser IRMS 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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http://dx.doi.org/10.1021/acs.analchem.0c05042DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7859929PMC
February 2021

Performance evaluation of handheld Raman spectroscopy for cocaine detection in forensic case samples.

Drug Test Anal 2021 May 7;13(5):1054-1067. Epub 2021 Jan 7.

Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, The Netherlands.

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 (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.
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http://dx.doi.org/10.1002/dta.2993DOI Listing
May 2021

Rapid and robust on-scene detection of cocaine in street samples using a handheld near-infrared spectrometer and machine learning algorithms.

Drug Test Anal 2020 Oct 27;12(10):1404-1418. Epub 2020 Jul 27.

Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, the Netherlands.

On-scene drug detection is an increasingly significant challenge due to the fast-changing drug market as well as the risk of exposure to potent drug substances. Conventional colorimetric cocaine tests involve handling of the unknown material and are prone to false-positive reactions on common pharmaceuticals used as cutting agents. This study demonstrates the novel application of 740-1070 nm small-wavelength-range near-infrared (NIR) spectroscopy to confidently detect cocaine in case samples. Multistage machine learning algorithms are used to exploit the limited spectral features and predict not only the presence of cocaine but also the concentration and sample composition. A model based on more than 10,000 spectra from case samples yielded 97% true-positive and 98% true-negative results. The practical applicability is shown in more than 100 case samples not included in the model design. One of the most exciting aspects of this on-scene approach is that the model can almost instantly adapt to changes in the illicit-drug market by updating metadata with results from subsequent confirmatory laboratory analyses. These results demonstrate that advanced machine learning strategies applied on limited-range NIR spectra from economic handheld sensors can be a valuable procedure for rapid on-site detection of illicit substances by investigating officers. In addition to forensics, this interesting approach could be beneficial for screening and classification applications in the pharmaceutical, food-safety, and environmental domains.
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http://dx.doi.org/10.1002/dta.2895DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7590077PMC
October 2020

Mass-Spectrometry-Based Identification of Synthetic Drug Isomers Using Infrared Ion Spectroscopy.

Anal Chem 2020 05 29;92(10):7282-7288. Epub 2020 Apr 29.

Van't Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, Amsterdam 1090 GD, The Netherlands.

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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http://dx.doi.org/10.1021/acs.analchem.0c00915DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7240807PMC
May 2020

Distinguishing drug isomers in the forensic laboratory: GC-VUV in addition to GC-MS for orthogonal selectivity and the use of library match scores as a new source of information.

Forensic Sci Int 2019 Sep 26;302:109900. Epub 2019 Jul 26.

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Postbus 94157, Amsterdam 1090 GD, Netherlands; Co van Ledden Hulsebosch Center (CLHC), Amsterdam Center for Forensic Science and Medicine, Postbus 94157, Amsterdam 1090 GD, Netherlands.

Currently, forensic drug experts are facing chemical identification challenges with the increasing number of new isomeric forms of psychoactive substances occurring in case samples. Very similar mass spectra for these substances could easily result in misidentification using the regular GC-MS screening methods in combination with colorimetric testing in forensic laboratories. Building on recent work from other groups, this study demonstrates that GC-VUV is a powerful technique for drug isomer differentiation, showing reproducible and discriminating spectra for aromatic ring-isomers. MS and VUV show complementary selectivity as VUV spectra are ring-position specific whereas MS spectra are characteristic for the amine moieties of the molecule. VUV spectra are very reproducible showing less than 0.1‰ deviation in library match scores and therefore small spectral differences suffice to confidently distinguish isomers. In comparison, MS match scores gave over 10‰ deviation and showed significant overlap in match score ranges for several isomers. This poses a risk for false positive identifications when assigning compounds based on retention time and GC-MS mass spectrum. A strategy was developed, based on Kernel Density Estimations of match scores, to construct Receiver Operating Characteristic (ROC) curves and estimate likelihood ratios (LR values) with respect to the chemical differentiation of drug related isomers. This approach, and the added value of GC-VUV is demonstrated with the chemical analysis of several samples from drug case work from the Amsterdam area involving both compounds listed in Dutch drug legislation (3,4-MDMA; 3,4-MDA; 4-MMC; 4-MEC and 4-FA) as well as their unlisted and thus uncontrolled isomers (2,3-MDMA; 2,3-MDA; 2- and 3-MMC; 2- and 3-MEC and 2- and 3-FA).
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http://dx.doi.org/10.1016/j.forsciint.2019.109900DOI Listing
September 2019