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At least 217 records · Page 12

Integrated and dynamic multi-spectroscopic in situ imaging of plant metabolism at the level of subcellular compartments. Final Report

The goals of this project was to develop integrated multi-spectral molecular imaging technologies (Raman, fluorescence, and mass spectrometry), that can assess, and image metabolic processes at the cellular and subcellular levels of plant organs. These imaging technologies were developed in the context of computational capabilities that integrated multi-spectral images with genome scale models of metabolism. The integrated molecular imaging technologies were developed in the biological context of autophagy that remodels membrane lipid topologies, which control spatially defined subcellular regions within plant cells and optimizes plant biomass productivity during environmental stresses that can limit biomass productivity.

09 BIOMASS FUELS↗

Bimolecular Chemistry in the Ultracold Regime

Advances in atomic, molecular, and optical physics techniques allowed the cooling of simple molecules down to the ultracold regime ([Formula: see text]1 mK) and opened opportunities to study chemical reactions with unprecedented levels of control. This review covers recent developments in studying bimolecular chemistry at ultralow temperatures. We begin with a brief overview of methods for producing, manipulating, and detecting ultracold molecules. We then survey experimental works that exploit the controllability of ultracold molecules to probe and modify their long-range interactions. Further combining the use of physical chemistry techniques such as mass spectrometry and ion imaging significantly improved the detection of ultracold reactions and enabled explorations of their dynamics in the short range. We discuss a series of studies on the reaction KRb + KRb → K 2 + Rb 2 initiated below 1 μK, including the direct observation of a long-lived complex, the demonstration of product rotational state control via conserved nuclear spins, and a test of the statistical model using the complete quantum state distribution of the products.

Chemistry↗

Regulation of β-cell death by ADP-ribosylhydrolase ARH3 via lipid signaling in insulitis

Lipids are regulators of insulitis and β-cell death in type 1 diabetes development, but the underlying mechanisms are poorly understood. Here, we investigated how the islet lipid composition and downstream signaling regulate β-cell death. We performed lipidomics using three models of insulitis: human islets and EndoC-βH1 β cells treated with the pro-inflammatory cytokines interlukine-1β and interferon-γ, and islets from pre-diabetic non-obese mice. We also performed mass spectrometry and fluorescence imaging to determine the localization of lipids and enzyme in islets. RNAi, apoptotic assay, and qPCR were performed to determine the role of a specific factor in lipid-mediated cytokine signaling. Across all three models, lipidomic analyses showed a consistent increase of lysophosphatidylcholine species and phosphatidylcholines with polyunsaturated fatty acids and a reduction of triacylglycerol species. Imaging assays showed that phosphatidylcholines with polyunsaturated fatty acids and their hydrolyzing enzyme phospholipase PLA2G6 are enriched in islets. In downstream signaling, omega-3 fatty acids reduce cytokine-induced β-cell death by improving the expression of ADP-ribosylhydrolase ARH3. The mechanism involves omega-3 fatty acid-mediated reduction of the histone methylation polycomb complex PRC2 component Suz12, upregulating the expression of Arh3, which in turn decreases cell apoptosis. Our data provide insights into the change of lipidomics landscape in β cells during insulitis and identify a protective mechanism by omega-3 fatty acids.

59 BASIC BIOLOGICAL SCIENCES↗

Non-Equilibrium Plasma Interactions with Biomaterials, Biological Solutions and Tissues

Cold atmospheric pressure plasma discharges offer an abundant source of reactive oxygen and nitrogen species (RONS) at room temperature enabling unique interactions with biomaterials, biological solutions and tissues. These interactions particularly with living matter are presently an important intellectual frontier in plasma science with promising potential applications ranging from human health care to advanced biomaterial processing. Exciting case studies have been reported that illustrate the huge potential of cold atmospheric plasma technology in wound healing and cancer treatment. The interaction of plasma with conducting and dielectric biomaterials such as tissue strongly influences the plasma properties. In turn this changes the impact of the plasma on the biomaterial. Particularly in the case of living matter, liquid based solutions are ubiquitous which complicates interfacial processes. The lack of insight into the underlying mechanisms of the interaction of plasma with wounds and tumors is currently a bottleneck for the further development of the technology and gives rise to many interesting scientific questions. This project was focused on plasma properties and kinetics during plasma-biomaterial interactions. Both DC pulsed and RF driven atmospheric pressure plasma jets, extensively used by the plasma community were studied. The bio-interfaces included hydrogel as a tissue model, (saline) solutions, bacteria and virus. Plasma diagnostics used include Thomson scattering, Rayleigh scattering, Raman scattering, (two-photon absorption) laser induced fluorescence, optical emission spectroscopy, absorption spectroscopy, molecular beam mass spectrometry and fast imaging allowing to determine electron densities and temperatures, ionic species, reactive species including radicals, gas temperatures, gas composition, electric fields and solution components transferred to the gas phase.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Improved Fundamental Understanding of Aluminum Chemistry and Interactions of Aluminate Anion with Co-Anions: ORNL Project Progress Report

The U.S. Department of Energy (DOE)’s Hanford Site in Washington State houses 177 underground storage tanks containing millions of gallons of nuclear and chemical waste with high aluminum content. Aluminum (Al) salt reactions with strong bases produce aluminum hydroxides, like boehmite (γ-AlOOH), which are main components of insoluble nuclear waste sludge. Understanding the morphology, crystallinity, and dissolution behavior of boehmite under waste tank conditions is necessary for improving waste management and mitigation strategies. The ORNL team uses in situ multimodal analysis strategy to study Al chemistry of simulated tank waste using microfluidic reactors and advanced chemical imaging and mass spectrometry (MS) techniques. Because the SALVI device is vacuum compatible and transferrable among different platforms, we can use it in scanning electron microscopy (SEM), vacuum ultraviolet single photon mass spectrometry (VUV SPI-MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to study the chemical speciation and colloid stability in liquids in this project. Additionally, ex situ transmission electron microscopy (TEM) and x-ray diffraction (XRD) spectroscopy can be used to verify particle phase to further the understanding of the Al-bearing phases. This report gives a summary of the technical progress of the ORNL tasks. A plan for year 2 performance is recommended in the summary.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thematic Conference on Remote Sensing for Exploration Geology, 6th, Houston, TX, May 16-19, 1988, Proceedings. Volumes 1 & 2

Papers concerning remote sensing applications for exploration geology are presented, covering topics such as remote sensing technology, data availability, frontier exploration, and exploration in mature basins. Other topics include offshore applications, geobotany, mineral exploration, engineering and environmental applications, image processing, and prospects for future developments in remote sensing for exploration geology. Consideration is given to the use of data from Landsat, MSS, TM, SAR, short wavelength IR, the Geophysical Environmental Research Airborne Scanner, gas chromatography, sonar imaging, the Airborne Visible-IR Imaging Spectrometer, field spectrometry, airborne thermal IR scanners, SPOT, AVHRR, SIR, the Large Format camera, and multitimephase satellite photographs.

Source record↗

Cassini/Huygens Science Instruments, Spacecraft, and Mission

The Cassini spacecraft will take 18 scientific instruments to Saturn. After launch and a seven-year cruise, Cassini will arrive at Saturn and separate into a Saturn orbiter and an atmospheric probe, called Huygens, which will descend to the surface of Titan. The orbiter will orbit the planet for four years, making close flybys of five satellites, including multiple flybys of Titan. Communication with Earth is at X-band; the maximum downlink rate from Saturn is 166 x 10(exp 3) bps. Orbiter instruments are body mounted; the spacecraft must be turned to point some of them toward objects of interest. The orbiter carries 12 instruments. Optical instruments provide imagery and spectrometry. Radar supplies imaging, altimetry, and radiometry. Radio links contribute information about intervening material and gravity fields. Other instruments measure electromagnetic fields and the properties of plasma, energetic particles, and dust particles. The probe is spin stabilized. It returns data via an S-band link to the orbiter. The probe's six instruments include sensors to determine atmospheric physical properties and composition. Radiometric and optical sensors will produce data on thermal balance and obtain images of Titan's atmosphere and surface. Doppler measurements between probe and orbiter will provide wind profiles. Surface sensors will measure impact acceleration, thermal and electrical properties, and, if the surface is liquid, density and refractive index. This design will enable Cassini to determine the composition; the physical, morphological, and geological nature; and the physical and chemical processes of the atmospheres, surfaces, and magnetosphere of the Saturnian system. This paper briefly describes the Cassini mission and spacecraft and, in somewhat more detail, the scientific instruments.

Jaffe, Leonard D.↗

In Situ Geochronology on the Mars 2020 Rover with KArLE (Potassium-Argon Laser Experiment)

If extinct and/or extant life is discovered on Mars, knowledge of the chronology of the biosphere will be of paramount importance. KArLE will provide absolute ages of Mars 2020 rocks, which will allow us to understand them in the context of Mars' geologic history, connect them to other landing sites, and compare Martian epochs of habitability with the Earth's history and evolution of life. KArLE significantly enhances the ability of Mars 2020 to meet its science objectives by performing in situ age dating on key lithologies, enabling targeted searches for ancient biosignatures and increasing the chances of identifying evidence for Martian microbial life. The KArLE investigation makes its measurements on a core sample obtained with the rover drill, inserted into a small, mechanically simple chamber, followed by interrogation by laser-induced breakdown spectroscopy (LIBS), mass spectrometry, and optical imaging. The KArLE experiment is flexible enough to accommodate any partner providing these instrument components, a creative approach that extends the ability of the Mars 2020 payload to accomplish an additional highly-desirable science measurement for low cost and risk and minimal extra hardware.

Cohen, B. A.↗

The Potassium-Argon Laser Experiment (KarLE): In Situ Geochronology for Mars and Beyond

The search for life in the solar system depends upon discovering the right moments in planetary evolution: when habitable environments existed, when they declined, and when geologic processes operated to preserve traces of life after death. However, an incomplete knowledge of absolute Martian geochronology limits our ability to understand the timing of Martian evolutionary milestones, major climate changes, and stratigraphic epochs [1, 2]. Absolute dating relates these habitability markers to planetarywide geologic, atmospheric, and climate history places, and ties their occurrence to the history of the solar system, especially the Earth-Moon system and the timescale of evolution of life on Earth. KArLE is being developed to anchor the relative timeline of geological events to an absolute chronology that puts Mars into a wider solar system context. KArLE makes its measurements on rock samples that can be obtained by landers or rovers and inserted into a small, mechanically simple chamber. KArLE interrogates the samples using laser-induced breakdown spectrocopy (LIBS), mass spectrometry, and optical imaging. The KArLE experiment is flexible enough to accommodate any partner providing these instrument components, a creative approach that extends the ability of mission payloads to accomplish an additional highly-desirable science measurement for low cost and risk and minimal extra hardware.

Cohen, Barbara A.↗

An approach for broad molecular imaging of the root-soil interface via indirect matrix-assisted laser desorption/ionization mass spectrometry

Understanding of rhizospheric processes is limited by the need for imaging complex molecular transformations at relevant spatial scales within the root soil continuum. In this work, we demonstrate a method to enable this analysis by first extracting organic compounds from the rhizosphere onto a PVDF membrane while maintaining their 2D distribution. We then image the distribution of chemical compounds using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). This approach permitted us to visualize and identify compounds on the root surface and presumed root exudates in the rhizosphere. Within a 1.8 cm x 0.6 cm sampling area of a switchgrass rhizosphere, we could observe at least four chemically distinct zones. Using high performance Fourier transform ion cyclotron MS, we were able to accurately annotate numerous molecules co-localized to each of these zones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Secondary Ion Mass Spectral Imaging of Metals and Alloys

Secondary Ion Mass Spectrometry (SIMS) is an outstanding technique for Mass Spectral Imaging (MSI) due to its notable advantages, including high sensitivity, selectivity, and high dynamic range. As a result, SIMS has been employed across many domains of science. In this review, we provide an in-depth overview of the fundamental principles underlying SIMS, followed by an account of the recent development of SIMS instruments. The review encompasses various applications of specific SIMS instruments, notably static SIMS with time-of-flight SIMS (ToF-SIMS) as a widely used platform and dynamic SIMS with Nano SIMS and large geometry SIMS as successful instruments. We particularly focus on SIMS utility in microanalysis and imaging of metals and alloys as materials of interest. Additionally, we discuss the challenges in big SIMS data analysis and give examples of machine leaning (ML) and Artificial Intelligence (AI) for effective MSI data analysis. Finally, we recommend the outlook of SIMS development. It is anticipated that in situ and operando SIMS has the potential to significantly enhance the investigation of metals and alloys by enabling real-time examinations of material surfaces and interfaces during dynamic transformations.

36 MATERIALS SCIENCE↗

Development of microchannel plates in advanced wind-tunnel instrumentation

Microchannel plate (MCP) electron multiplier dynamic range has been increased 3 to 4 orders of magnitude at ambient temperatures, through enhanced input count rate capability and reduced background or 'dark' noise. The previous upper limit of roughly 10(exp 7) - 10(exp 8) cm(exp -2)s(exp -1) at ambient has been extended to levels approach 10(exp 10) cm(exp -2)s(exp -1) under continuous dc operation. The lower limit, previously set by an irreducible background component (approximately 0.6 cm(exp -2)s(exp -1)), has been lowered to the cosmic ray limit of .01 cm(exp -2)s(exp -1). The high end improvement was achieved by conductively cooling a very low resistance MCP by bonding it to a heat sink, while maintaining pulse-counting operation with multianode readouts. The low-end improvement was achieved by removing all radioisotopes from the MCP matrix glass. The detectors will benefit optical and mass spectrometry, flow visualization, plasma diagnostics, magnetometry, and other high signal flux applications. Very low MCP background noise will benefit X-ray and UV astronomy, medical imaging, trace isotope mass spectrometry, and other applications where the signal flux is often extremely low.

Feller, W. Bruce↗

In Situ Chemical Monitoring and Imaging of Contents within Microfluidic Devices Having a Porous Membrane Wall Using Liquid Microjunction Surface Sampling Probe Mass Spectrometry

The ability to observe dynamic chemical processes (e.g., signaling, transport, etc.) in vivo or in situ using nondestructive chemical imaging opens a new door to understanding the complex dynamics of developing biological systems. With the advent of “biology-on-a-chip” devices has come the ability to monitor dynamic chemical processes in a controlled environment, using these engineered habitats to capture key features of natural systems while allowing visual observation of system development. Having the capability to spatially and temporally map the chemical signals within these devices may yield new insights into the forces that drive biosystem development. Here, a porous membrane sealed microfluidic device was designed to allow normal microfluidic operation while enabling continuous, location specific sampling and chemical characterization by liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS). LMJ-SSP was used to extract fluids with nL-to-μL/min flow rates directly from selected areas of the microfluidic device without negatively impacting the device function. These extracts were subsequently characterized using MS. This technique was used to acquire MS images of the entirety of several multi-input microfluidic devices having different degrees of fluid mixing. LMJ-SSP MS imaging visualized the spatial distribution of chemical components within the microfluidic channels and could visualize chemical reactions occurring in the device. These microfluidic devices with a porous membrane wall are wholly compatible with the construction of biology-on-a-chip devices. This ultimately would enable correlation of biosystem physical structure with an evolving chemical environment

47 OTHER INSTRUMENTATION↗

The Spatial Distribution of Soluble Organic Matter and Their Relationship to Minerals in the Asteroid (162173) Ryugu

We performed in-situ analysis on a ~1 mm-sized grain A0080 returned by the Hayabusa2 spacecraft from near-Earth asteroid (162173) Ryugu to investigate the relationship of soluble organic matter (SOM) to minerals. Desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) imaging mapped more than 200 CHN, CHO, CHO–Na (sodium adducted), and CHNO soluble organic compounds. A heterogeneous spatial distribution was observed for different compound classes of SOM as well as among alkylated homologues on the sample surface. The A0080 sample showed mineralogy more like an Ivuna-type (CI) carbonaceous chondrite than other meteorites. It contained two different lithologies, which are either rich (lithology 1) or poor (lithology 2) in magnetite, pyrrhotite, and dolomite. CHN compounds were more concentrated in lithology 1 than in lithology 2; on the other hand, CHO, CHO–Na, and CHNO compounds were distributed in both lithologies. Such different spatial distribution of SOM is likely the result of interaction of the SOM with minerals, during precipitation of the SOM via fluid activity, or could be due to difference in transportation efficiencies of SOMs in aqueous fluid. Organic-related ions measured by time-of-flight secondary ion mass spectrometry (ToF–SIMS) did not coincide with the spatial distribution revealed by DESI-HRMS imaging. This result may be because the different ionization mechanism between DESI and SIMS, or indicate that the ToF–SIMS data would be mainly derived from methanol-insoluble organic matter in A0080. In the Orgueil meteorite, such relationship between altered minerals and SOM distributions was not observed by DESI-HRMS analysis and field-emission scanning electron microscopy, which would result from differences of SOM formation processes and sequent alteration process on the parent bodies or even on the Earth. Alkylated homologues of CHN compounds were identified in A0080 by DESI-HRMS imaging as observed in the Murchison meteorite, but not from the Orgueil meteorite. These compounds with a large C number were enriched in Murchison fragments with abundant carbonate grains. In contrast, such relationship was not observed in A0080, implying different formation or growth mechanisms for the alkylated CHN compounds by interaction with fluid and minerals on the Murchison parent body and asteroid Ryugu.

Ryugu↗

Toward Revealing Microcystin Distribution in Mouse Liver Tissue Using MALDI-MS Imaging

Cyanotoxins can be found in water and air during cyanobacterial harmful algal blooms (cHABs) in lakes and rivers. Therefore, it is very important to monitor their potential uptake by animals and humans as well as their health effects and distribution in affected organs. Herein, the distribution of hepatotoxic peptide microcystin-LR (MC-LR) is investigated in liver tissues of mice gavaged with this most common MC congener. Preliminary matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) imaging experiments performed using a non-automated MALDI matrix deposition device and a MALDI-time-of-flight (TOF) mass spectrometer yielded ambiguous results in terms of MC-LR distribution in liver samples obtained from MC-LR-gavaged mice. The tissue preparation for MALDI-MS imaging was improved by using an automated sprayer for matrix deposition, and liver sections were imaged using an Nd:YAG MALDI laser coupled to a 15 Tesla Fourier-transform ion cyclotron resonance (FT-ICR)-mass spectrometer. MALDI-FT-ICR-MS imaging provided unambiguous detection of protonated MC-LR (calculated m/z 995.5560, z = +1) and the sodium adduct of MC-LR (m/z 1017.5380, z = +1) in liver sections from gavaged mice with great mass accuracy and ultra-high mass resolution. Since both covalently bound and free MC-LR can be found in liver of mice exposed to this toxin, the present results indicate that the distribution of free microcystins in tissue sections from affected organs, such as liver, can be monitored with high-resolution MALDI-MS imaging.

59 BASIC BIOLOGICAL SCIENCES↗

Spatially resolved absolute quantitation in thin tissue by mass spectrometry

Mass spectrometry (MS) has become the de facto tool for routine quantitative analysis of biomolecules. MS is increasingly being used to reveal the spatial distribution of proteins, metabolites, and pharmaceuticals in tissue and interest in this area has led to a number of novel spatially resolved MS technologies. Most spatially resolved MS measurements are qualitative in nature due to a myriad of potential biases, such as sample heterogeneity, sampling artifacts, and ionization effects. As applications of spatially resolved MS in the pharmacological and clinical fields increase, demand has become high for quantitative MS imaging and profiling data. As a result, several varied technologies now exist that provide differing levels of spatial and quantitative information. Furthermore, this review provides an overview of MS profiling and imaging technologies that have demonstrated quantitative analysis from tissue. Focus is given on the fundamental processes affecting quantitative analysis in an array of MS imaging and profiling technologies and methods to address these biases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Resolution UV Spectroscopy for Solar System Exploration

A new generation of high resolution UV imaging spacecraft (Polar, Galileo, HST) are studying the airglow and aurora of the Earth and the jovian planets. To keep pace with these technological improvements we have developed a laboratory program to provide electron collision cross sections of the major molecular planetary gasses. Molecular spectra under optically thin conditions have been measured with a high resolution UV spectrometer in tandem with an electron impact collision chamber. The results of various studies are reported in this paper.

spectrometry UV imaging electron cross sections mo↗

Advances in mass spectrometry-enabled multiomics at single-cell resolution

We report biological organisms are multifaceted, intricate systems where slight perturbations can result in extensive changes in gene expression, protein abundance and/or activity, and metabolic flux. These changes occur at different timescales, spatially across cells of heterogeneous origins, and within single-cells. Hence, multimodal measurements at the smallest biological scales are necessary to capture dynamic changes in heterogeneous biological systems. Of the analytical techniques used to measure biomolecules, mass spectrometry (MS) has proven to be a powerful option due to its sensitivity, robustness, and flexibility with regard to the breadth of biomolecules that can be analyzed. Recently, many studies have coupled MS to other analytical techniques with the goal of measuring multiple modalities from the same single-cell. It is with these concepts in mind that we focus this review on MS-enabled multiomic measurements at single-cell or near-single- cell resolution.

47 OTHER INSTRUMENTATION↗