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Kaseman, Derrick C.

Publications and source records attributed to Kaseman, Derrick C..

10 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Determination of Synthetic Opioids Belonging to the Fentanyl Class in Silt Using Electron Ionization Gas Chromatography-Mass Spectrometry (GC-MS).

An extraction protocol from silt sediment of fentanyl and three analogs: acetylfentanyl, thiofentanyl and acetylthiofentanyl, spiked at two concentrations each and separately (at ~1 and ~10 µg/g), is described. In addition, the identity of the fentanyls preliminarily identified by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) analysis, can be corroborated by reacting each opioid in the silt’s extract with 2,2,2-trichloroethoxycarbonyl chloride (Troc-Cl). Further, reaction between Troc-Cl and each opioid generates two unique products that can be used to retrospectively identify the original opioid therefore serving as a corroborating tool for known opioids as well as new, unknown fentanyl analogs.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Evaluation of Subetadex-α-methyl, a Polyanionic Cyclodextrin Scaffold, as a Medical Countermeasure against Fentanyl and Related Opioids

Subetadex-α-methyl (SBX-Me), a modified, polyanionic cyclodextrin scaffold, has been evaluated for its utilization as a medical countermeasure (MCM) to neutralize the effects of fentanyl and related opioids. Initial in vitro toxicity assays demonstrate that SBX-Me has a nontoxic profile, comparable to the FDA-approved cyclodextrin-based drug Sugammadex. Pharmacokinetic analysis showed rapid clearance of SBX-Me with an elimination half-life of ~7.4 h and little accumulation in major organs. SBX-Me was also evaluated for its ability to counteract the effects of fentanyl, carfentanil, and remifentanil in rats. Recovery times in rats exposed to sublethal fentanyl doses were found to be shorter when treated with SBX-Me after opioid exposure. The recovery times were reduced from ~35 to ~17 min for fentanyl, ~172 to ~59 min for carfentanil, and ~18 to ~12 min for remifentanil. SBX-Me increased the elimination half-life for fentanyl and remifentanil from 5.37 to 6.42 h and 8.24 to 9.74 h, respectively. These data support SBX-Me as a solid platform from which further research can be launched for the development of a MCM against the effects of fentanyl and its analogs. Furthermore, the data suggests that SBX-Me and other analogs are attractive candidates as broad spectrum opioids targeting MCMs.

Chemistry↗
DOE OSTI2024

Use of carbonyldiimidazole as a derivatization agent for the detection of pinacolyl alcohol, a forensic marker for Soman, by EI-GC–MS and LC-HRMS in official OPCW proficiency test matrices

Pinacolyl alcohol (PA), a key forensic marker for the nerve agent Soman (GD), is a particularly difficult analyte to detect by various analytical methods. In this work, we have explored the reaction between PA and 1,1'-carbonyldiimidazole (CDI) to yield pinacolyl 1H-imidazole-1-carboxylate (PIC), a product that can be conveniently detected by gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Regarding its GC–MS profile, this new carbamate derivative of PA possesses favorable chromatographic features such as a sharp peak and a longer retention time (RT = 16.62 min) relative to PA (broad peak and short retention time, RT = 4.1 min). Additionally, the derivative can also be detected by LC-HRMS, providing an avenue for the analysis of this chemical using this technique where PA is virtually undetectable unless present in large concentrations. From a forensic science standpoint, detection of this low molecular weight alcohol signals the past or latent presence of the nerve agent Soman (GD) in a given matrix (i.e., environmental or biological). The efficiency of the protocol was tested separately in the analysis and detection of PA by EI-GC–MS and LC-HRMS when present at a 10 μg/mL in a soil matrix featured in the 44th PT and in a glycerol-rich liquid matrix featured in the 48th Official Organization for the Prohibition of Chemical Weapons (OPCW) Proficiency Test when present at a 5 μg/mL concentration. In both scenarios, PA was successfully transformed into PIC, establishing the protocol as an additional tool for the analysis of this unnatural and unique nerve agent marker by GC–MS and LC-HRMS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

On the effects of quadrupolar relaxation in Earth’s field NMR spectra

There is growing interest in using low-field magnetic resonance experiments for routine chemical characterization. Earth’s field NMR is one such technique that can garner structural information and enable sample differentiation with low cost and highly portable designs. The resulting NMR spectra are primarily influenced by $J$-couplings, resulting in so-called $J$-coupled spectra (JCS). Many small molecules include atoms with NMR-active nuclei that are quadrupolar either at natural abundance or are often isotopically enriched (e.g., 2 H, 6 Li, 11 B, 14 N, 17 O, etc.) where the effects of quadrupolar J-couplings and relaxation on JCS of strongly- and weakly-coupled spin systems have not been explored to date. Herein, using a set of seven fluoropyridine samples with unique substitution and $J$-couplings, we demonstrate that the 14 N relaxation rates can induce drastic line-broadening in the JCS. This includes a previously unexplored unique line broadening mechanism enabled by strongly coupled spins at low-field. In conclusion, numerical simulations are used to model and refine the magnitudes and signs of $J$-couplings, as well as indirectly determine the 14 N relaxation rates in a single 1D experiment that has a higher fidelity than observed in high-field NMR experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Methods and systems for J-coupled nuclear magnetic resonance

A nuclear magnetic resonance (NMR) system is configured to detect combinatorial signatures stemming from homonuclear and heteronuclear J-couplings. The system comprises a pre-polarization system, a detector, and NMR electronics, wherein the detector includes an NMR magnet with a magnetic field of strength between 300 mT and 10 μT.

Williams, Robert F.↗
DOE OSTI2022

Methods and systems for low to ultra-low magnetic field nuclear magnetic resonance for detecting chemical nerve agents

A nuclear magnetic resonance (NMR) system is configured to detect chemical threat material. The system comprises a magnet configured to generate a magnetic field of about 300 millitesla or less; and a probe configured to detect nuclear relaxation of at least two nuclei selected from the group consisting of 1H, 19F, 31P and 14N, and detect the spin density of nuclei selected from the group consisting of 1H, 19F, 31P and 14N, following excitation.

Williams, Robert F.↗
DOE OSTI2020

A review of the application of 2D isotropic-anisotropic correlation NMR spectroscopy in structural studies of chalcogenide glasses

The application of solid-state high-resolution NMR spectroscopy in the structural investigation of chalcogenide glasses in Ge/As/P/Si-X (X = S, Se,Te) systems has remained challenging even for the spin-1/2 nuclides ( 29 Si, 31 P, 77 Se, 125 Te), owing to their low natural abundance (except for 31 P), slow spin-lattice relaxation rate and large CSA and chemical shift distribution induced line broadening effects. However, most of these deleterious effects can be successfully overcome in two-dimensional (2D) isotropic-anisotropic correlation NMR experiments, especially when performed at high magnetic field and in conjunction with the Car-Purcell-Meiboom-Gill (CPMG) echo train acquisition. Here, we present a short introduction to the basic principles of such experiments and review their applications over the last decade in deciphering various short- and intermediate- range structural characteristics of chalcogenide glasses in S-Se, Se-Te, Ge-Se, As-Se and Si-Se systems as well as in investigating the molecular dynamics in a P-Se supercooled liquid. We anticipate possible future applications of these 2D isotropic-anisotropic correlation NMR experiments, particularly in conjunction with density functional theory-based calculations of NMR chemical shift tensor parameters and additional signal enhancement schemes, in addressing complex structural correlations and distributions in chalcogenide glasses.

2D NMR↗
DOE OSTI2020

Correction of Q Factor Effects for Simultaneous Collection of Elemental Analysis and Relaxation Times by Nuclear Magnetic Resonance

A new method for measurement of elemental analysis by nuclear magnetic resonance (NMR) of unknown samples is discussed in this report as a quick and robust means to measure elemental ratios without the use of internal or external calibration standards. The determination of elemental ratios was done by normalizing the signal intensities by the frequency dependent quality factor (Q) and the gyromagnetic ratios (γ) for each measured nucleus. The correction for the frequency dependence was found by characterizing the output signal of the probe as a function of the quality factor (Q) and the frequency, and the correction for γ was discussed in a previous study. A Carr–Purcell–Meiboom–Gill (CPMG) pulse sequence was used for evaluation of the relative signal intensities, which allows for derivation of elemental ratios, and was correspondingly used to simultaneously measure the T 2 * of samples for an added parameter for more accurate identification of unknown samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Efficient Control of Atom Arrangement in Ternary Metal Chalcogenide Nanoparticles Using Precursor Oxidation State

Controlling both the concentration and the distribution of elements in a given material is often crucial to extracting and optimizing synergistic properties of the various constituents. An interesting class of such multielement materials is metal chalcogenide nanoparticles, which exhibit a wide range of composition-dependent optoelectronic properties including both bandgap-mediated processes and localized surface plasmon resonance properties, each of which is useful in applications ranging from energy conversion to sensing. Because metal chalcogenide nanoparticles can support several different metal elements in a variety of chalcogen lattices, this material class has particularly benefited from the ability to control both atom concentration and atom arrangement to tailor final particle properties. The primary method to access complex, multimetallic chalcogenide particles is via a postsynthetic cation exchange strategy. One-pot syntheses have been less explored to access these complex particles, although this route is desirable for economy and scalability. In this work, we compare the composition and morphology outcomes from cation exchange and one-pot preparation approaches using a Cu/Ag/Se system, which is already known to exhibit both binary and ternary metal chalcogenide phases. We show that at similar concentrations of the two metal cations, initial reaction conditions for the one-pot method yield multicomponent nanoparticles, whereas cation exchange yields homogeneous ternary metal chalcogenide structures. We then show that by tuning the precursor oxidation state for the one-pot method, this approach can be used to access homogeneous ternary metal chalcogenide particles that are similar in atom arrangement to the particles obtained using cation exchange. Taken together, our results demonstrate reliable synthetic methods that yield a variety of controlled compositions and composition morphologies in the Cu/Ag/Se system. Importantly, we demonstrate that this entire collection of architectures can all be accessed via a one-pot method simply by modifying metal precursor chemistry. The mechanistic insights gained and the resulting streamlined syntheses outlined indicate pathways to easily scaled, highly tailorable syntheses for rapid translation into downstream technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗