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At least 577 records · Page 32

High-Resolution Tandem Mass Spectrometry-Based Analysis of Model Lignin–Iron Complexes: Novel Pipeline and Complex Structures

Understanding the chemical nature of soil organic carbon (SOC) with great potential to bind iron (Fe) minerals is critical for predicting the stability of SOC. Organic ligands of Fe are among the top candidates for SOCs able to strongly sorb on Fe minerals, but most of them are still molecularly uncharacterized. To shed insights into the chemical nature of organic ligands in soil and their fate, this study developed a protocol for identifying organic ligands using ultrahigh-performance liquid chromatography-high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) and metabolomic tools. The protocol was used for investigating the Fe complexes formed by model compounds of lignin-derived organic ligands, namely, caffeic acid (CA), p-coumaric acid (CMA), vanillin (VNL), and cinnamic acid (CNA). Isotopologue analysis of 54/56 Fe was used to screen out the potential UHPLC-HRMS (m/z) features for complexes formed between organic ligands and Fe, with multiple features captured for CA, CMA, VNL, and CNA when 35/37 Cl isotopologue analysis was used as supplementary evidence for the complexes with Cl. MS/MS spectra, fragment analysis, and structure prediction with SIRIUS were used to annotate the structures of mono/bidentate mono/biligand complexes. The analysis determined the structures of monodentate and bidentate complexes of FeL x Cl y (L: organic ligand, x = 1–4, y = 0–3) formed by model compounds. The protocol developed in this study can be used to identify unknown organic ligands occurring in complex environmental samples and shed light on the molecular-level processes governing the stability of the SOC.

54 ENVIRONMENTAL SCIENCES↗

Electronic and optical properties of Zn-doped β-Ga 2 O 3 Czochralski single crystals

β-Ga 2 O 3 has several soluble deep acceptors that impart insulating behavior. In this study, we investigate Zn doping (0.25at.%) in bulk Czochralski and vertical gradient freeze β-Ga 2 O 3 . Representative crystals were assessed for orientation (electron backscatter diffraction and Raman spectroscopy), purity (glow discharge mass spectrometry and secondary ion mass spectrometry), optical properties (ultraviolet to near infrared absorption), and electrical properties (resistivity and current–voltage). Purity measurements indicate that Zn evaporation is insufficient to inhibit doping of Zn into β-Ga 2 O 3 . Hybrid functional calculations show Zn substitutes nearly equally on tetrahedral and octahedral sites, with less than ~0.1eV preference for the octahedral (Ga II ) site. Furthermore, calculations show that Zn Ga acts as a deep acceptor with trapping levels ~1.3 and ~0.9eV above the valence band for one and two holes, respectively. The solubility and electronic behavior of Zn dopants are consistent with measured concentrations >1×10 18 atoms/cm 3 and electrical measurements that show resistivity 10 11 –10 13 Ωcm, with no p-type conduction.

36 MATERIALS SCIENCE↗

Mass Spectrometry-Based High-Throughput Quantification of Bioproducts in Liquid Culture

To meet the ever-increasing need for high-throughput screening in metabolic engineering, information-rich, fast screening methods are needed. Mass spectrometry (MS) provides an efficient and general approach for metabolite screening and offers the capability of characterizing a broad range of analytes in a label-free manner, but often requires a range of sample clean-up and extraction steps. Liquid extraction surface analysis (LESA) coupled MS is an image-guided MS surface analysis approach that directly samples and introduces metabolites from a surface to MS. Here, we combined the advantages of LESA–MS and an acoustic liquid handler with stable isotope-labeled internal standards. This approach provides absolute quantitation of target chemicals from liquid culture-dried droplets and enables high-throughput quantitative screening for microbial metabolites. In this paper, LESA–MS was successfully applied to quantify several different metabolites (itaconic acid, triacetic acid lactone, and palmitic acid) from different yeast strains in different mediums, demonstrating its versatility, accuracy, and efficiency across a range of microbial engineering applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-Depth Mass Spectrometry-Based Single-Cell and Nanoscale Proteomics

Leukemic stem cells are highly dynamic and heterogeneous. Analysis of leukemic stem cells at the single cell level should provide a wealth of insights that would not be possible using bulk measurements. Mass spectrometry (MS)-based proteomic workflows can quantify hundreds or thousands of proteins from a biological sample and has proven invaluable for biomedical research, but samples comprising large numbers of cells are typically required due to limited sensitivity. Recent developments in sample processing, chromatographic separations and MS instrumentation are now extending in-depth proteome profiling to single mammalian cells. We describe specific techniques that increase the sensitivity of single-cell proteomics by orders of magnitude, enabling the promise of single cell proteomics to become a reality. We anticipate such techniques could significantly advance our understanding of leukemic stem cells.

Liang, Yiran↗

ORNL Report of Analysis for the Verification of NRMP CRM U030A

In support of the Certified Reference Material (CRM) program managed by the Nuclear Reference Material Program (NRMP), the Material Signatures and Isotopic Standards (MSIS) group of Oak Ridge National Laboratory (ORNL) was asked to prepare a set of CRM U030A units for use as standards for isotopic analysis using multicollector thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICP-MS) instruments. This report documents the results of the verification measurements performed on three randomly selected units by the MSIS group’s ISO/IEC 17025:2017 accredited operating procedure CSD-AM-CIMS-IN20, Determination of Uranium and Plutonium Isotopic Composition using Thermal Ionization Mass Spectrometry [1], and in accordance with the quality assurance plan as described in QAP-X-96-CSD/RML-001, Nuclear Analytical Chemistry Laboratory Section Quality Assurance Plan [2].

Mathew, Kattathu [Oak Ridge National Laboratory (O↗

Natural Abundance Isotope Ratio Measurements of Organic Molecules Using 21 T FTICR MS

Subtle variations in stable isotope ratios at natural abundance are challenging to measure but can yield critical insights into biological, physical, and geochemical processes. Well established methods, particularly multi-collector, gas-source or plasma isotope ratio mass spectrometry (IRMS) are the gold standard for stable isotope measurement but inherent limitations in these approaches make them ill-suited to determining site-specific and multiply substituted isotopic abundances of all but a few compounds, or to characterizing mixtures or larger intact molecules. Additionally, Fourier transform mass spectrometry (FTMS), namely Orbitrap mass spectrometry, has recently demonstrated the ability to measure natural abundance isotope ratios with chemically informative accuracy and precision. Here, we report the first use of Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the accurate (<1‰) and precise (<1‰ standard error) simultaneous determination of $δ$ 13 C and $δ$ 15 N in caffeine isotopologues and provide a discussion of the critical instrumental parameters necessary to make such measurements. Finally, we report the ability to make these measurements with online liquid chromatography, expanding the ability of this technique to explore mixtures in the future.

07 ISOTOPE AND RADIATION SOURCES↗

Assessment of the Biological Impact of Engineered Nanomaterials Using Mass Spectrometry-based MultiOmics Approaches

The widespread use of engineered nanomaterials (ENMs) has expanded further than our understanding of their toxicity, prompting research into the biological responses against exposure to such materials. Genomics and transcriptomics have been extensively used to evaluate the biological effects of exposure to various ENMs. By determining gene activities, these studies provided valuable information to infer how cells respond to the toxicological effects of many ENMs. The application of mass spectrometry (MS)-based omics tools, such as proteomics, lipidomics, and metabolomics, offer post-genomic perspectives of what cellular processes are altered. Individually, these technologies have revealed the proteome, lipidome, and metabolome landscape upon exposure to ENMs. Together, these approaches demonstrate the ENM-induced adaptation in a broad range of cellular processes at multiple levels and the complexity of ENM-cell interactions. As a result, integrating multiple layers of MS-based omics data is trending to complement genomics data. In this review chapter, we discuss the applications of these tools for a comprehensive systems-level characterization of the biological responses induced by engineered nanomaterials.

Engineered nanomaterials, Proteomics, Metabolomics↗

Data from A Mass Spectrometry-Based High-Throughput Screening Method for Engineering Fatty Acid Synthases with Improved Production of Medium Chain Fatty Acids

Microbial cell factories have been extensively engineered to produce free fatty acids (FFAs) as key components of crucial nutrients, soaps, industrial chemicals, and fuels. However, our ability to control the composition of microbially synthesized FFAs is still limited, particularly, for producing medium‐chain fatty acids (MCFAs). This is mainly due to the lack of high‐throughput approaches for FFA analysis to engineer enzymes with desirable product specificity. Here we report a mass spectrometry (MS)‐based method for rapid profiling of MCFAs in Saccharomyces cerevisiae by using membrane lipids as a proxy. In particular, matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐ToF) MS was used to detect shorter acyl chain phosphatidylcholines from membrane lipids and a higher m/z peak ratio at 730 and 758 was used as an indication for improved MCFA production. This colony‐based method can be performed at a rate of ~2 s per sample, representing a substantial improvement over gas chromatography‐MS (typically >30 min per sample) as the gold standard method for FFA detection. To demonstrate the power of this method, we performed site‐saturation mutagenesis of the yeast fatty acid synthase and identified nine missense mutations that resulted in improved MCFA production relative to the wild‐type strain. Colony‐based MALDI‐ToF MS screening provides an effective approach for engineering microbial fatty acid compositions in a high‐throughput manner.

Conversion↗

Soil metabolome response to whole-ecosystem warming at the Spruce and Peatland Responses under Changing Environments experiment

In this study, a suite of complementary environmental geochemical analyses, including NMR and gas chromatography-mass spectrometry (GC-MS) analyses of central metabolites, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) of secondary metabolites, and lipidomics, was used to investigate the influence of organic matter (OM) quality on the heterotrophic microbial mechanisms controlling peatland CO2, CH4, and CO2:CH4 porewater production ratios in response to climate warming. Our investigations leverage the Spruce and Peatland Responses under Changing Environments (SPRUCE) experiment, where air and peat warming were combined in a whole-ecosystem warming treatment. We hypothesized that warming would enhance the production of plant-derived metabolites, resulting in increased labile OM inputs to the surface peat, thereby enhancing microbial activity and greenhouse gas production. Because shallow peat is most susceptible to enhanced warming, increases in labile OM inputs to the surface, in particular, are likely to result in significant changes to CO2 and CH4 dynamics and methanogenic pathways. In support of this hypothesis, significant correlations were observed between metabolites and temperature consistent with increased availability of labile substrates, which may stimulate more rapid turnover of microbial proteins. An increase in the abundance of methanogenic genes in response to the increase in the abundance of labile substrates was accompanied by a shift toward acetoclastic and methylotrophic methanogenesis. Our results suggest that as peatland vegetation trends toward increasing vascular plant cover with warming, we can expect a concomitant shift toward increasingly methanogenic conditions and amplified climate–peatland feedbacks.

Wilson, Rachel M.↗

Mixed Element Microparticle Characterization by Electron Probe Microanalysis

Abstract Microparticle compositional characterization for nuclear forensics has traditionally been achieved by “gold-standard” destructive analytical techniques such as large geometry-secondary ion mass spectrometry and fission track-thermal ionization mass spectrometry, but long processing times and total sample consumption eliminate the option of subsequent analysis by other methods. Electron probe microanalysis has long been widely employed for rapid, nondestructive, micrometer-scale compositional measurements and imaging in fields such as material science and geology and may therefore need to be reevaluated as an alternative tool for microparticle analysis for the nuclear forensics community. This study presents the use of electron probe microanalysis for imaging and quantitative characterization of homogeneous microparticles utilizing a calibration curve based on high-precision quadrupole-inductively coupled plasma-mass spectrometry analyses. Samples of opportunity synthesized at Savannah River National Laboratory, nickel-doped cerium oxide microparticles, were selected as analogs for plutonium-doped uranium oxide microparticles. Positive detection and accurate quantification of variable amounts of nickel dopant down to trace levels (10s of parts per million) suggest applicability of this technique to other mixed element systems (e.g., actinides). Quantitative single-particle characterization via electron probe microanalyzer may thus provide a high fidelity, nondestructive complement to techniques currently in use.

Riche, Alexis T. (ORCID:0009000121978126)↗

Anion Reactivity in Cation‐Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution

Abstract The demand for high energy‐density, mass‐producible cathode materials has spurred the exploration of new material structures and compositions. Lithium‐excess, cation‐disordered rocksalt (DRX) materials are a new class of transition metal oxides that display high capacity and environmental friendly composition. These materials achieve their high capacities partially through oxygen redox, which leads to oxygen loss and detrimental reactivity with the electrolyte. It has previously been shown that oxygen loss can be suppressed by partial substitution of the lattice oxygen for fluorine, but the explicit mechanism behind this effect remains unknown. In this work, differential electrochemical mass spectrometry (DEMS) and titration mass spectrometry are used to quantify the primary electrochemical reactions occurring during the first cycle in DRX materials. Comparing a DRX oxide and a DRX oxyfluoride, it is shown that fluorination limits oxygen redox and suppresses oxygen loss. Additionally, DEMS is coupled with fluoride‐scavenging to demonstrate that small amounts of fluorine dissolve from DRX oxyfluorides during the first cycle. Finally, these techniques are extended over the first several cycles, demonstrating that CO 2 evolution persists and fluoride dissolution continues to a diminishing extent during the first few cycles. These findings motivate surface modifications to control interfacial reactivity and improve long‐term cycling.

Crafton, Matthew J.↗

Standardized multi-omics of Earth’s microbiomes reveals microbial and metabolite diversity

Despite advances in sequencing, lack of standardization makes comparisons across studies challenging and hampers insights into the structure and function of microbial communities across multiple habitats on a planetary scale. Here we present a multi-omics analysis of a diverse set of 880 microbial community samples collected for the Earth Microbiome Project. We include amplicon (16S, 18S, ITS) and shotgun metagenomic sequence data, and untargeted metabolomics data (liquid chromatography-tandem mass spectrometry and gas chromatography mass spectrometry). We used standardized protocols and analytical methods to characterize microbial communities, focusing on relationships and co-occurrences of microbially related metabolites and microbial taxa across environments, thus allowing us to explore diversity at extraordinary scale. In addition to a reference database for metagenomic and metabolomic data, we provide a framework for incorporating additional studies, enabling the expansion of existing knowledge in the form of an evolving community resource. We demonstrate the utility of this database by testing the hypothesis that every microbe and metabolite is everywhere but the environment selects. Our results show that metabolite diversity exhibits turnover and nestedness related to both microbial communities and the environment, whereas the relative abundances of microbially related metabolites vary and co-occur with specific microbial consortia in a habitat-specific manner. We additionally show the power of certain chemistry, in particular terpenoids, in distinguishing Earth’s environments (for example, terrestrial plant surfaces and soils, freshwater and marine animal stool), as well as that of certain microbes including Conexibacter woesei (terrestrial soils), Haloquadratum walsbyi (marine deposits) and Pantoea dispersa (terrestrial plant detritus). This Resource provides insight into the taxa and metabolites within microbial communities from diverse habitats across Earth, informing both microbial and chemical ecology, and provides a foundation and methods for multi-omics microbiome studies of hosts and the environment.

59 BASIC BIOLOGICAL SCIENCES↗

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl,sec-butyl, iso-butyl, andtert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. The mass spectra confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a minor channel (<7.7%) through HNO loss and formation of an aldehyde. These high pressure experiments were also used to determine the disproportionation/recombination ratio for iso-butyl radicals as 0.3. Reanalysis of the lower-temperature literature and the present data yielded rate constants for the disproportionation reaction, iso-butyl + iso-butyl = iso-butene + iso-butane. A chemical kinetics model was developed for the reactions of the butyl isomers that included new paths for highly energized adducts. These adducts are formed by the addition of H, CH 3 or C 2 H 5 to the butyl radicals. Accompanying theoretical investigations show that chemically activated pathways are competitive with stabilization of the adduct by collision under the conditions of the laser schlieren experiments. These calculations also show that at 10 bar and T< 1000 K stabilization is the only important reaction, but at higher temperatures, even at 10 bar, chemically activated product channels should also be considered. Branching fractions and rate coefficients are presented for these reactions. Furthermore, this study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. Overall, the results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Vision - Multimodal, multitask retrieval of molecular structure from measured signatures for reference-free compound identification

We are currently at risk of generating false conclusions based on limited methods to identify small molecules in biological systems and in chemical forensics. By definition, the chemical structures of novel small molecules have not been determined, let alone measured or synthesized. Currently, unambiguous structure determination of small molecules is constrained by the time and effort needed to isolate compounds and perform de novo structure elucidation using laboratory-based methods, significantly extending the time to inform mitigation strategies. To address this gap, we have developed a deep learning approach to directly map molecular structure to experimental signatures. We aim to unify measurement technologies employed in untargeted small molecule identification studies—such as infrared (IR) spectrometry, tandem mass spectrometry (MS/MS), ion mobility spectrometry-derived collision cross section (CCS)—through use of a multimodal, multitask deep learning architecture. Where existing methods require direct generation of information-rich spectra and/or properties, an inherently difficult task, we will simplify molecular signature-based identification by posing the problem as a recognition or retrieval task. The model is thus presented with relevant endpoints – structure and one or more molecular signatures – and need only determine whether they are semantically related. Thus, our approach offers the following advantages over existing techniques: (i) circumvents difficulties associated with direct generation of molecular signatures from structure and structure from signatures; (ii) incorporates multiple molecular signatures simultaneously, as available, to support identification; and (iii) enables rapid computation of structural embeddings toward broad coverage of known chemical space. Taken together, the approach removes the need to explicitly obtain or compute reference spectra, representing a powerful method for compound identification that requires only experimentally observed signatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Gradient Magnetic Simulation Final Report 2025

Over the course of nearly 2 years, the goal of this project has been to identify methods for the separation of uranium oxide particles from other geologic materials. The primary motivation is to assess methods for enhancing the extraction and throughput of actinide particles from environmental samples, enabling the evaluation of these trace actinides through more traditional methods such as thermal ionization mass spectrometry or secondary ion mass spectrometry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Single-Particle Isotopic Analysis Using the Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Coupled to an Orbitrap Mass Spectrometer

Isotope ratio (IR) determinations on individual particles can provide valuable information relative to the sample, including processing and dating, which could be valuable to geological and nuclear material analysis communities. In comparison to “bulk” measurements, in which all particle information is lost and homogenized within a sample, “particle” measurements allow for fingerprinting and can provide unique insights related to the sample’s nano- and micro- compositions. Furthermore, the complex nature of particles, with potential isobaric interferences from either the matrix or other elements within the same particle, poses a significant analytical challenge for conventional mass spectrometry platforms employed for elemental analysis due to their limited mass resolution. Presented here is the first demonstration of an ultrahigh resolution method for single particle (SP) isotopic analysis using the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma ionization source coupled to an Orbitrap mass spectrometer and FTMS Booster X2T acquisition/processing system. For proof of concept, well-characterized CeO 2 microparticles with a nominal diameter of 1.0 μm were analyzed at a mass resolution of ∼330,000. Important instrumental parameters were optimized to enable the detection of single particles. The 142 Ce/ 140 Ce ratio of individual particles and the population average were determined and compared to an SP inductively coupled plasma time-of-flight mass spectrometry (ICP-TOF-MS) analysis. The isotopic accuracy and precision were determined by two methods and found to be in good agreement with the SP-ICP-TOF-MS method, with the linear regression slope method providing a more accurate ratio, showing a ∼1.4% relative difference from the ratio determined from a particle digest. The encouraging performance of the method was further supported by a determined detection limit of 2.9 fg ( 142 Ce). The developed method is anticipated to overcome many of the challenges posed by isobaric interferences encountered in conventional mass spectrometry techniques when analyzing real-world samples for particle isotopic composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Femtosecond Laser Desorption Postionization MS vs ToF-SIMS Imaging for Uncovering Biomarkers Buried in Geological Samples

The study of lipid molecular fossils by traditional biomarker analysis requires bulk sample crushing, followed by solvent extraction, and then the analysis of the extract by gas chromatography-mass spectrometry (GC–MS). This traditional analysis mixes all organic compounds in the sample regardless of their origins, with a loss of information on the spatial distribution of organic molecules within the sample. These shortcomings can be overcome using the chemical mapping of intact samples. Spectroscopic techniques such as UV fluorescence or Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are among those elemental and molecular mapping techniques. This study employed femtosecond (fs) laser ablation combined with single-photon ionization, a method called fs-laser desorption postionization mass spectrometry (fs-LDPI-MS). In this work, a pulsed ~75 fs, 800 nm laser was used to ablate the geological sample, which was then photoionized after a few microseconds by a pulsed 7.9 eV vacuum ultraviolet laser. An organic carbon-rich geological sample was used for this study to map hydrocarbon biomarkers in sediments that were previously studied by GC–MS. The petrography of this sample was examined by optical and fluorescence microscopy. It is demonstrated here that fs-LDPI-MS combined with petrography for multimodal imaging can expose buried compounds within the sample via in situ layer removal. When used in conjunction with traditional organic geochemical analysis, this method has the potential to determine the spatial distribution of organic biomarkers in geological material. Finally, fs-LDPI-MS imaging data are compared with ToF-SIMS imaging that is commonly used for such studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of Mass-Independent Perturbations of Cadmium in Nuclear Debris Samples

The isotopic composition of cadmium in nuclear debris was measured by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). Mass-independent perturbations due to fission product decay on the isotopes of Cd were observed. Relative fission yields for masses 111, 112, 114 and 116 were determined in each sample of nuclear debris and compared with reported values found in irradiated plutonium and uranium fuels. Mass spectrometry measurements of the valley fission product endpoints are extremely challenging due to the low cumulative fission yields and small amounts of each isotope that are produced. To overcome these challenges, a new purification method for Cd was developed and validated by examination of a number of geological reference materials.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗