Browsing by Author "Dhummakupt, Elizabeth S."

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    Detection of chemical warfare agent simulants and hydrolysis products in biological samples by paper spray mass spectrometry
    (RSC, 2017-05) McKenna, Josiah; Dhummakupt, Elizabeth S.; Connell, Theresa; Demond, Paul S.; Miller, Dennis B.; Nilles, J. Michael; Manicke, Nicholas E.; Glaros, Trevor; Chemistry and Chemical Biology, School of Science
    Paper spray ionization coupled to a high resolution tandem mass spectrometer (a quadrupole orbitrap) was used to identify and quantitate chemical warfare agent (CWA) simulants and their hydrolysis products in blood and urine. Three CWA simulants, dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), and diisopropyl methylphosphonate (DIMP), and their isotopically labeled standards were analyzed in human whole blood and urine. Calibration curves were generated and tested with continuing calibration verification standards. Limits of detection for these three compounds were in the low ng mL−1 range for the direct analysis of both blood and urine samples. Five CWA hydrolysis products, ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), isobutyl methylphosphonic acid (iBuMPA), cyclohexyl methylphosphonic acid (CHMPA), and pinacolyl methylphosphonic acid (PinMPA), were also analyzed. Calibration curves were generated in both positive and negative ion modes. Limits of detection in the negative ion mode ranged from 0.36 ng mL−1 to 1.25 ng mL−1 in both blood and urine for the hydrolysis products. These levels were well below those found in victims of the Tokyo subway attack of 2 to 135 ng mL−1. Improved stability and robustness of the paper spray technique in the negative ion mode was achieved by the addition of chlorinated solvents. These applications demonstrate that paper spray mass spectrometry (PS-MS) can be used for rapid, sample preparation-free detection of chemical warfare agents and their hydrolysis products at physiologically relevant concentrations in biological samples.
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    Direct Analysis of Aerosolized Chemical Warfare Simulants Captured on a Modified Glass-Based Substrate by “Paper-Spray” Ionization
    (ACS, 2017-09) Dhummakupt, Elizabeth S.; Mach, Phillip M.; Carmany, Daniel; Demond, Paul S.; Moran, Theodore S.; Connell, Theresa; Wylie, Harold S.; Manicke, Nicholas E.; Nilles, J. Michael; Glaros, Trevor; Chemistry and Chemical Biology, School of Science
    Paper spray ionization mass spectrometry offers a rapid alternative platform requiring no sample preparation. Aerosolized chemical warfare agent (CWA) simulants trimethyl phosphate, dimethyl methylphosphonate, and diisopropyl methylphosphonate were captured by passing air through a glass fiber filter disk within a disposable paper spray cartridge. CWA simulants were aerosolized at varying concentrations using an in-house built aerosol chamber. A custom 3D-printed holder was designed and built to facilitate the aerosol capture onto the paper spray cartridges. The air flow through each of the collection devices was maintained equally to ensure the same volume of air sampled across methods. Each approach yielded linear calibration curves with R2 values between 0.98–0.99 for each compound and similar limits of detection in terms of disbursed aerosol concentration. While the glass fiber filter disk has a higher capture efficiency (≈40%), the paper spray method produces analogous results even with a lower capture efficiency (≈1%). Improvements were made to include glass fiber filters as the substrate within the paper spray cartridge consumable. Glass fiber filters were then treated with ammonium sulfate to decrease chemical interaction with the simulants. This allowed for improved direct aerosol capture efficiency (>40%). Ultimately, the limits of detection were reduced to levels comparable to current worker population limits of 1 × 10–6 mg/m3.
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    Paper Spray Ionization: Applications and Perspectives
    (Elsevier, 2019) McBride, Ethan M.; Mach, Phillip M.; Dhummakupt, Elizabeth S.; Dowling, Sarah; Carmany, Daniel O.; Demond, Paul S.; Rizzo, Gabrielle; Manicke, Nicholas E.; Glaros, Trevor; Chemistry and Chemical Biology, School of Science
    Paper spray ionization has grown to become one of the most successful ambient ionization methods within the past decade. Requiring little to no sample preparation and being remarkably simple to construct, this technique has seen application in a wide number of fields. This review approaches the mechanism of how paper spray works, and seeks to better classify what it is and is not in a rapidly expanding field of ambient techniques. Additionally, many applications of the technique in clinical, forensic, environmental, and reaction monitoring regimes are explored. Finally, perspectives towards the future of how paper spray could be utilized will be expanded upon, including unexplored substrates and possibilities for the 'omics space.
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    Pressure sensitive adhesives and paper spray-mass spectrometry for the collection and analysis of fentanyl-related compounds from shipping materials
    (Wiley, 2023-09) Prunty, Sarah; Carmany, Daniel; Dhummakupt, Elizabeth S.; Manicke, Nicholas E.; Chemistry and Chemical Biology, School of Science
    The rise of fentanyl and fentanyl analogs in the drug supply pose serious threats to public health. Much of these compounds enter the United States through shipping routes. Here we provide a method for fentanyl screening and analysis that utilizes pressure-sensitive adhesive (PSA) lined paper to recover drug residues from parcel-related surfaces. The paper used is commercially available repositionable notes (also called post-it or sticky notes). From this paper, mass spectra were obtained by paper spray-mass spectrometry (PS-MS), where PSA paper served as both a sampling and analysis substrate. Seven fentanyl-related compounds were analyzed: fentanyl, 4-anilino-N-phenethylpiperidine (4-ANPP), N,1-diphenethyl-N-phenylpiperidin-4-amine (phenethyl-4-ANPP), valerylfentanyl, 4-fluoroisobutyrylfentanyl (4-FIBF), carfentanil, and p-fluorofentanyl. These compounds were recovered by PSA paper and identified by PS-MS from packaging tape and plastic at 50 ng and from cardboard and shipping labels at 100 ng. The impact of cutting agents on PS-MS analysis of fentanyl analogs was explored. No trends of analyte suppression were found at high concentrations of the cutting agents caffeine, diphenhydramine, and lidocaine when recovered from surfaces. A cartridge that required no precise cutting of PSA paper prior to sampling or analysis was evaluated for use in PS-MS for fentanyl screening. Recovery and detection of fentanyl from plastic sheeting was demonstrated with this cut-free cartridge. The cut-free cartridge showed somewhat less consistency and lower analyte signal than the standard cartridge, but performance was suitable for potential screening applications. In combining PSA surface sampling with PS-MS for drug screening, both sampling and detection of fentanyl-related compounds is simple, rapid, and low-cost.
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    Pressure-Sensitive Adhesive Combined with Paper Spray Mass Spectrometry for Low-Cost Collection and Analysis of Drug Residues
    (American Chemical Society (ACS), 2021-09-28) Nguyen, Chau Bao; Wichert, William R. A.; Carmany, Daniel O.; McBride, Ethan M.; Mach, Phillip M.; Dhummakupt, Elizabeth S.; Glaros, Trevor; Manicke, Nicholas E.; Chemistry and Chemical Biology, School of Science
    Illicit drug use causes over half a million deaths worldwide every year. Drugs of abuse are commonly smuggled through customs and border checkpoints and, increasingly, through parcel delivery services. Improved methods for detection of trace drug residues from surfaces are needed. Such methods should be robust, fieldable, sensitive, and capable of detecting a wide range of drugs. In this work, commercially produced paper with a pressure-sensitive adhesive coating was utilized for the collection and analysis of trace drug residues by paper spray mass spectrometry (MS). This modified substrate was used to combine sample collection of drug residues from surfaces with rapid detection using a single paper spray ticket. The all-in-one ticket was used to probe different surfaces commonly encountered in forensic work including clothing, cardboard, glass, concrete, asphalt, and aluminum. A total of 10 drugs (acetyl fentanyl, fentanyl, clonazolam, cocaine, heroin, ketamine, methamphetamine, methylone, U-47700, and XLR-11) were evaluated and found to be detectable in the picogram range using a benchtop mass spectrometer and in the low nanogram range using a portable ion trap MS. The novel approach demonstrates a simple yet effective sampling strategy, allowing for rapid identification from difficult surfaces via paper spray mass spectrometry.