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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Recognition and characterization of hierarchical interstellar structure. I - Correlation function

The problem of the quantitative description of multiscale structure in interstellar cloud complexes and gravitational collapse calculations is considered, emphasizing the recognition and characterization of hierarchical fragmentation structure. The response of the two-point correlation function to a variety of analytical models for density structure is discussed for simple clustering of pointlike clouds to more complex models involving clouds with a distribution of sizes and densities and hierarchical substructure. By expressing the density distribution as the superposition of individual clouds, it is shown that the correlation function generates two types of terms: those involving each cloud's density convolved with itself and those involving pairs of different clouds. Major distortion of the correlation function are introduced by the presence of any image features with size scales a significant fraction of the image size.

Houlahan, Padraig↗
DOE OSTI2024

Experimental and Computational Evaluation of Lipidomic In-Source Fragmentation as a Result of Postionization with Matrix-Assisted Laser Desorption/Ionization

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) can provide spatially resolved molecular information about a sample. Recently, a postionization approach (MALDI-2) has been commercially integrated with MALDI-MSI, allowing for bettered sensitivity and consequent improved spatial resolution. While advantages of MALDI-2 have previously been established, we demonstrate here statistically increased in-source fragmentation (ISF) results from postionization with a commercial instrument. Via lipid standard analyses, known MALDI ISF pathways (e.g., loss of trimethylamine) were statistically increased in MALDI-2 compared to MALDI-1 (65–172% increase in fragmentation). Gas phase molecular modeling with density functional theory estimated that the most-weighted virtual orbitals to excite within lipids involve ester and phosphate bonds. Protonated lipid excitation energies are furthermore red-shifted compared to those of other adduct types [e.g., 254 nm for protonated PC(16:0/18:1)] and approach the MALDI-2 laser energy (266 nm). Analysis of rat brain homogenate detected statistically more positive-ion mode peaks with MALDI-2 (1090) than that with MALDI-1 (719), where Kernel density estimations showed that the majority of this enhancement occurs with low m/z ions (i.e., m/z 75–500). Taken together with the lipid standard data, these observations may indicate ISF due to postionization. Finally, while artifact contributions from matrix blanks were also noted, both experimental and computational data sets suggest that the overall extent of ISF is statistically increased in MALDI-2 compared to MALDI-1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Proteins with Novel Structure, Function and Dynamics

Recently, a small enzyme that ligates two RNA fragments with the rate of 10(exp 6) above background was evolved in vitro (Seelig and Szostak, Nature 448:828‐831, 2007). This enzyme does not resemble any contemporary protein (Chao et al., Nature Chem. Biol. 9:81‐83, 2013). It consists of a dynamic, catalytic loop, a small, rigid core containing two zinc ions coordinated by neighboring amino acids, and two highly flexible tails that might be unimportant for protein function. In contrast to other proteins, this enzyme does not contain ordered secondary structure elements, such as alpha‐helix or beta‐sheet. The loop is kept together by just two interactions of a charged residue and a histidine with a zinc ion, which they coordinate on the opposite side of the loop. Such structure appears to be very fragile. Surprisingly, computer simulations indicate otherwise. As the coordinating, charged residue is mutated to alanine, another, nearby charged residue takes its place, thus keeping the structure nearly intact. If this residue is also substituted by alanine a salt bridge involving two other, charged residues on the opposite sides of the loop keeps the loop in place. These adjustments are facilitated by high flexibility of the protein. Computational predictions have been confirmed experimentally, as both mutants retain full activity and overall structure. These results challenge our notions about what is required for protein activity and about the relationship between protein dynamics, stability and robustness. We hypothesize that small, highly dynamic proteins could be both active and fault tolerant in ways that many other proteins are not, i.e. they can adjust to retain their structure and activity even if subjected to mutations in structurally critical regions. This opens the doors for designing proteins with novel functions, structures and dynamics that have not been yet considered.

Proteins↗
DOE OSTI2026

High Semi-Volatile Organic Aerosol Contributions Associated with Ammonium Nitrate in the Coastal Urban Environment

Organic components often contribute 50% or more of the submicron aerosol mass in coastal urban environments, but their partitioning between the gas and particle phases is controlled by a complex mixture of unidentified organic compounds that are poorly constrained by observations. This study compares daily filter organic functional groups (OFG) with online organic mass fragments from La Jolla, California, as part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), quantifying the contributions of four types of non-volatile (NV) organic emission sources to the submicron composition. Daily filters retained only 0.79–0.98 µg/m3 NV submicron organic mass concentration, even though 1.8–1.9 µg/m3 non-refractory (NR) submicron organic mass concentration was measured online. The 62–64% of measured NR submicron organic mass concentration that exceeded what remained on the filters after 23-hr sampling is interpreted as semi-volatile, consistent with the moderate correlation of the NR NV difference to NR ammonium, NR nitrate, and biomass burning-related NV and NR organic factors. The association between semi-volatile organic components and ammonium nitrate likely results from both co-emission and co-evaporation. Size-resolved filter analysis showed that NV organic mass concentration accounts for 68% of NR organic mass concentration for 0.5–1 µm dry diameter but account for 9.0% for 0.18–0.5 µm dry diameter showing the differences in volatility between particle modes. Importantly, volatility of organic components was size-dependent Information Classification: General and associated with ammonium nitrate and biomass burning, providing guidance for constraining atmospheric aerosol properties in global models.

Pelayo, Christian↗
DOE OSTI2025

Tidal–hydrological dynamics of water temperature across freshwater forested wetlands on the northeastern Pacific coast

Abstract Tidal freshwater forests were once extensive across temperate coastlines, but loss and fragmentation have made estimation of their ecosystem functions challenging. We measured water temperature for 2 years in three Sitka spruce tidal forests, a restoration site, and an adjacent emergent marsh on the Columbia River, Washington, United States. We assessed spatial variability of water temperature within sites including the effects of hydrology, differences among bay and tributary tidal forests, and differences between the tidal forests and the mainstem Columbia, the restoration site, and the emergent marsh. The tidal forests nearest to the bay had lower interior water temperatures than their channel confluences by up to 2.5°C (weekly median temperature) and 2.0°C (weekly maximum temperature), with most cooling occurring during the low‐flow months of July–September. Tributary sites had maximum temperatures up to 1.9°C cooler than bay sites and 4.2°C cooler than the mainstem. Temperatures in the two bay sites decreased by −0.16°C/100 m and −0.07°C/100 m, on average. The restoration site had the smallest within‐site temperature gradient. Differences in maximum temperatures were greatest when tidal range was low, while higher tidal ranges were associated with warmer and more variable site interiors relative to their confluences. These results suggest that water temperatures in these tidal forests can provide temperature refugia for cold water biota including salmon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Use of Split‐Intein Proteins to Design a Small Molecule Biosensor in Plants

Understanding how plants perceive their environment is fundamental to advancing agricultural productivity and sustainability. Many biological small molecules, including those involved in microbial recognition, act rapidly at the plant cell surface, but the absence of tools to visualise these dynamics has limited our ability to dissect plant–microbe communication. To address this gap, we sought to create a genetically encoded biosensor that couples ligand-induced protein dimerization with the production of a fluorescent reporter. Inteins are peptide regions that excise themselves from precursor proteins and ligate the flanking chains (exteins). When each half of a split intein is fused to one of two dimerizing proteins, ligand binding brings them into proximity, inducing intein splicing and ligation of flanking extein sequences (Kang et al. 2022). Similar to previous studies, we split the yeast vacuolar ATPase subunit 1 (VMA1) intein, creating a protein biosensor that produces eGFP upon protein dimerization after ligand binding (Figure 1A) (Mootz et al. 2003). Specifically, eGFP halves (i.e., non-functional N- and C-terminal GFP fragments) were fused to the intein halves, resulting in two fusion proteins: N-terminal GFP::N-terminal intein and C-terminal intein::C-terminal GFP (Figure 1A).

Boone, Brandon A. [Oak Ridge National Laboratory (↗
NASA NTRS1987

Star formation in molecular clouds - Observation and theory

Star-formation (SF) processes occurring on the scale of giant molecular clouds (10 to the 6th solar masses and 10 to the 20th cm) or smaller are discussed, reviewing the results of recent theoretical and observational investigations. Topics examined include the origin of stellar masses; bimodal SF; initial mass functions; binary stars, bound clusters, and hierarchical fragmentation; and the efficiency of SF. The properties of molecular clouds and the origin of substructures in molecular clumps are explored in detail, and consideration is given to gravitational collapse and protostars, bipolar outflows from young stellar objects, visible young stellar objects, and the implications for binary-star and planetary-system formation.

Shu, Frank H.↗
NASA NTRS2011

Risk Management of Jettisoned Objects in LEO

The construction and maintenance of the International Space Station (ISS) has led to the release of many objects into its orbital plane, usually during the course of an extra-vehicular activity (EVA). Such releases are often unintentional, but in a growing number of cases, the jettison has been intentional, conducted after a careful assessment of the net risk to the partnership and to other objects in space. Since its launch in 1998 the ISS has contributed on average at least one additional debris object that is simultaneously in orbit with the station, although the number varies widely from zero to eight at any one moment. All of these objects present potential risks to other objects in orbit. Whether it comes from known and tracked orbiting objects or from unknown or untrackable objects, collision with orbital debris can have disastrous consequences. Objects greater than 10cm are generally well documented and tracked, allowing orbiting spacecraft or satellites opportunities to perform evasive maneuvers (commonly known as Debris Avoidance Maneuvers, or DAMs) in the event that imminent collision is predicted. The issue with smaller debris; however, is that it is too numerous to be tracked effectively and yet still poses disastrous consequences if it intercepts a larger object. Due to the immense kinetic energy of any item in orbit, collision with debris as small as 1cm can have catastrophic consequences for many orbiting satellites or spacecraft. Faced with the growing orbital debris threat and the potentially catastrophic consequences of a collision-generated debris shower originating in an orbit crossing the ISS altitude band, in 2007 the ISS program manger asked program specialists to coordinate a multilateral jettison policy amongst the ISS partners. This policy would define the acceptable risk trade rationale for intentional release of a debris object, and other mandatory constraints on such jettisons to minimize the residual risks whenever a jettison was accepted. Although ISS-related debris often presents untenable risks to the EVA crew, IVA crew, or to a departing cargo vehicle for a controlled disposal, such released objects also present a ballistic nuisance to the visiting vehicle traffic, and a potential fragmentation threat to the hundreds of other functional and debris objects whose perigees lie below the ISS orbital altitude. Thus, every such jettison decision is a conscious risk trade.

Bacon, John B.↗
NASA NTRS1996

Orbital debris removal using ground-based lasers

Orbiting the Earth are spent rocket stages, non-functioning satellites, hardware from satellite deployment and staging, fragments of exploded spacecraft, and other relics of decades of space exploration: orbital debris. The United States Space Command tracks and maintains a catalog of the largest objects. The catalog contains over 7000 objects. Recent studies have assessed the debris environment in an effort to estimate the number of smaller particles and the probability of a collision causing catastrophic damage to a functioning spacecraft. The results of the studies can be used to show, for example, that the likelihood of a collision of a particle larger than about one centimeter in diameter with the International Space Station during a 10-year period is a few percent, roughly in agreement with earlier estimates for Space Station Freedom. Particles greater than about one centimeter in diameter pose the greatest risk to shielded spacecraft. There are on the order of 105 such particles in low Earth orbit. The United States National Space Policy, begun in 1988, is to minimize debris consistent with mission requirements. Measures such as venting unused fuel to prevent explosions, retaining staging and deployment hardware, and shielding against smaller debris have been taken by the U.S. and other space faring nations. There is at present no program to remove debris from orbit. The natural tendency for upper atmospheric drag to remove objects from low Earth orbit is more than balanced by the increase in the number of debris objects from new launches and fragmentation of existing objects. In this paper I describe a concept under study by the Program Development Laboratory of Marshall Space Flight Center and others to remove debris with a ground-based laser. A longer version of this report, including figures, is available from the author.

Taylor, Charles R.↗
DOE OSTI2024

Leading order track functions in a hot and dense QGP

We study the modifications to the fragmentation pattern of partons into charged particles in the presence of a hot and dense quark gluon plasma. To this end, we analyze the perturbative renormalization group equations of the track functions, which describe the energy fraction carried by charged hadrons. Focusing on pure Yang-Mills theory, we compute the lowest-order moments of the medium-modified track functions, which are found to be sensitive to the reduced phase space for emissions in the medium and to energy loss. We use the extracted moments to calculate the energy energy correlator (EEC) on tracks in the collinear limit. The EEC on medium-evolved tracks does not differ qualitatively from the EEC on vacuum tracks despite being sensitive to the color decoherence transition and suppressing the distribution due to quenching, as seen in other jet observables. Published by the American Physical Society 2024

Barata, João (ORCID:0000000342864555)↗
DOE OSTI2025

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport↗
NASA NTRS2007

Interpretation of TEPC Measurements in Space Flights for Radiation Monitoring

For the proper interpretation of radiation data measured in space, the results of integrated radiation transport models were compared with the tissue equivalent proportional counter (TEPC) measurements. TEPC is a simple, time-dependent approach to radiation monitoring for astronauts on board the International Space Station. Another and a newer approach to microdosimetry is the use of silicon-on-insulator (SOI) technology launched on the MidSTAR-1 mission in low Earth orbit (LEO). In the radiation protection practice, the average quality factor of a radiation field is defined as a function of linear energy transfer (LET), Qave(LET). However, TEPC measures the average quality factor as a function of the lineal energy y, Qave(y), defined as the average energy deposition in a volume divided by the average chord length of the volume. The deviation of y from LET is caused by energy straggling, delta-ray escape or entry, and nuclear fragments produced in the detector volume. The response distribution functions of the wall-less and walled TEPCs were calculated from Monte-Carlo track simulations. Using an integrated space radiation model (which includes the transport codes HZETRN and BRYNTRN, and the quantum nuclear interaction model QMSFRG) and the resultant response distribution functions from Monte-Carlo track simulations, we compared model calculations with the walled-TEPC measurements from NASA missions in LEO and made predictions for the lunar and the Mars missions. Good agreement was found for Qave(y) between the model and measured spectra from past NASA missions. The Qave(y) values for the trapped or the solar protons ranged from 1.9-2.5. This over-estimates the Qave(LET) values which ranged from 1.4-1.6. Both quantities increase with shield thickness due to nuclear fragmentation. The Qave(LET) for the complete GCR spectra was found to be 3.5-4.5, while flight TEPCs measured 2.9-3.4 for Qave(y). The GCR values are decreasing with the shield thickness. Our analysis of the measurements of TEPCs can be used for a proper interpretation of observed data of monitoring the space radiation environment.

Kim, Myung-Hee Y.↗
NASA NTRS1996

Fibronectin regulates calvarial osteoblast differentiation

The secretion of fibronectin by differentiating osteoblasts and its accumulation at sites of osteogenesis suggest that fibronectin participates in bone formation. To test this directly, we determined whether fibronectin-cell interactions regulate progressive differentiation of cultured fetal rat calvarial osteoblasts. Spatial distributions of alpha 5 integrin subunit, fibronectin, osteopontin (bone sialoprotein I) and osteocalcin (bone Gla-protein) were similar in fetal rat calvaria and mineralized, bone-like nodules formed by cultured osteoblasts. Addition of anti-fibronectin antibodies to cultures at confluence reduced subsequent formation of nodules to less than 10% of control values, showing that fibronectin is required for normal nodule morphogenesis. Anti-fibronectin antibodies selectively inhibited steady-state expression of mRNA for genes associated with osteoblast differentiation; mRNA levels for alkaline phosphatase and osteocalcin were suppressed, whereas fibronectin, type I collagen and osteopontin were unaffected. To identify functionally relevant domains of fibronectin, we treated cells with soluble fibronectin fragments and peptides. Cell-binding fibronectin fragments (type III repeats 6-10) containing the Arg-Gly-Asp (RGD) sequence blocked both nodule initiation and maturation, whether or not they contained a functional synergy site. In contrast, addition of the RGD-containing peptide GRGDSPK alone did not inhibit nodule initiation, although it did block nodule maturation. Thus, in addition to the RGD sequence, other features of the large cell-binding fragments contribute to the full osteogenic effects of fibronectin. Nodule formation and osteoblast differentiation resumed after anti-fibronectin antibodies or GRGDSPK peptides were omitted from the media, showing that the inhibition was reversible and the treatments were not cytotoxic. Outside the central cell-binding domain, peptides from the IIICS region and antibodies to the N terminus did not inhibit nodule formation. We conclude that osteoblasts interact with the central cell-binding domain of endogenously produced fibronectin during early stages of differentiation, and that these interactions regulate both normal morphogenesis and gene expression.

NASA Program Space Physiology and Countermeasures↗
DOE OSTI2025

The impact of kidney function on Alzheimer’s disease blood biomarkers: implications for predicting amyloid-β positivity

Impaired kidney function has a potential confounding effect on blood biomarker levels, including biomarkers for Alzheimer’s disease (AD). Given the imminent use of certain blood biomarkers in the routine diagnostic work-up of patients with suspected AD, knowledge on the potential impact of comorbidities on the utility of blood biomarkers is important. We aimed to evaluate the association between kidney function, assessed through estimated glomerular filtration rate (eGFR) calculated from plasma creatinine and AD blood biomarkers, as well as their influence over predicting Aβ-positivity. We included 242 participants from the Translational Biomarkers in Aging and Dementia (TRIAD) cohort, comprising cognitively unimpaired individuals (CU; n = 124), mild cognitive impairment (MCI; n = 58), AD dementia (n = 34), and non-AD dementia (n = 26) patients all characterized by [ 18 F] AZD-4694. Plasma samples were analyzed for Aβ42, Aβ40, glial fibrillary acidic protein (GFAP), neurofilament light chain (NfL), tau phosphorylated at threonine 181 (p-tau181), 217 (p-tau217), 231 (p-tau231) and N-terminal containing tau fragments (NTA-tau) using Simoa technology. Kidney function was assessed by eGFR in mL/min/1.73 m 2 , based on plasma creatinine levels, age, and sex. Participants were also stratified according to their eGFR-indexed stages of chronic kidney disease (CKD). We evaluated the association between eGFR and blood biomarker levels with linear models and assessed whether eGFR provided added predictive value to determine Aβ-positivity with logistic regression models. Biomarker concentrations were highest in individuals with CKD stage 3, followed by stages 2 and 1, but differences were only significant for NfL, Aβ42, and Aβ40 (not Aβ42/Aβ40). All investigated biomarkers showed significant associations with eGFR except plasma NTA-tau, with stronger relationships observed for Aβ40 and NfL. However, after adjusting for either age, sex or Aβ-PET SUVr, the association with eGFR was no longer significant for all biomarkers except Aβ40, Aβ42, NfL, and GFAP. When evaluating whether accounting for kidney function could lead to improved prediction of Aβ-positivity, we observed no improvements in model fit (Akaike Information Criterion, AIC) or in discriminative performance (AUC) by adding eGFR to a base model including each plasma biomarker, age, and sex. While covariates like age and sex improved model fit, eGFR contributed minimally, and there were no significant differences in clinical discrimination based on AUC values. We found that kidney function seems to be associated with AD blood biomarker concentrations. However, these associations did not remain significant after adjusting for age and sex, except for Aβ40, Aβ42, NfL, and GFAP. While covariates such as age and sex improved prediction of Aβ-positivity, including eGFR in the models did not lead to improved prediction for any biomarker. Our findings indicate that renal function, within the normal to mild impairment range, does not seem to have a clinically relevant impact when using highly accurate blood biomarkers, such as p-tau217, in a biomarker-supported diagnosis.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2004

Anthropogenic Land-use Change and the Dynamics of Amazon Forest Biomass

This project was focused on assessing the effects of prevailing land uses, such as habitat fragmentation, selective logging, and fire, on biomass and carbon storage in Amazonian forests, and on the dynamics of carbon sequestration in regenerating forests. Ancillary goals included developing GIs models to help predict the future condition of Amazonian forests, and assessing the effects of anthropogenic climate change and ENS0 droughts on intact and fragmented forests. Ground-based studies using networks of permanent plots were linked with remote-sensing data (including Landsat TM and AVHRR) at regional scales, and higher-resolution techniques (IKONOS imagery, videography, LIDAR, aerial photographs) at landscape and local scales. The project s specific goals were quite eclectic and included: Determining the effects of habitat fragmentation on forest dynamics, floristic composition, and the various components of above- and below-ground biomass. Assessing historical and physical factors that affect trajectories of forest regeneration and carbon sequestration on abandoned lands. Extrapolating results from local studies of biomass dynamics in fragmented and regenerating forests to landscape and regional scales in Amazonia, using remote sensing and GIS. Testing the hypothesis that intact Amazonian forests are functioning as a significant carbon sink. Examining destructive synergisms between forest fragmentation and fire. Assessing the short-term impacts of selective logging on aboveground biomass. Developing GIS models that integrate current spatial data on forest cover, deforestation, logging, mining, highway and roads, navigable rivers, vulnerability to wild fires, protected areas, and existing and planned infrastructure projects, in an effort to predict the future condition of Brazilian Amazonian forests over the next 20-25 years. Devising predictive spatial models to assess the influence of varied biophysical and anthropogenic predictors on Amazonian deforestation.

Laurance, William F.↗
NASA NTRS1993

The identification of a naturally occurring cell surface growth inhibitor related to a previously described bovine sialoglycopeptide

A 66-kDa sialoglycoprotein has been identified as the parental membrane molecule of an earlier described sialoglycopeptide (SGP), an 18-kDa molecule released by protease treatment of intact bovine cerebral cortex cells that was shown to be a potent inhibitor of cellular proliferation. The 66-kDa parental sialoglycoprotein (p-SGP) was purified approximately 2,400-fold, to apparent homogeneity, from bovine cerebral cortex cell membranes by its release during incubation with 3 M NaCl, preparative isoelectric focusing and lectin affinity chromatography. Although a membrane-associated molecule, the p-SGP appeared to be tightly bound to the cell membrane, since it was not released during incubations in the absence of 3 M NaCl. Incubation of the membrane preparations with 3 M urea proved to be too harsh, and the antigenicity required to follow the purification of the p-SGP was abolished. Analyses by SDS-PAGE, under reducing and nonreducing conditions, suggested that the p-SGP membrane component was a single polypeptide without subunit structure. The p-SGP was shown to be structurally related to the SGP fragment by immunoblots with IgG raised to the SGP inhibitor, and functionally related to the SGP by its ability to inhibit Swiss 3T3 proliferation at concentrations strikingly similar to that previous measured with the SGP fragment.

Non-NASA Center↗
NASA NTRS2017

Mass Spectra Deconvolution of Gaseous Mixtures Containing Volatile Organic Compounds

The Spacecraft Atmosphere Monitor (S.A.M.) analyzes all gaseous pollutants in the 1-150Th mass-to-charge range based on their positive-ion mass spectra. Of particular interest is the Trace Gas Analysis (TGA) mode of operation in which S.A.M detects minute amounts of volatile organic compounds (VOC). Pollutant component of the ambient air is sampled on demand in twenty full mass spectra per second. All spectra is accumulated in two-second intervals by an on-board Field Programmable Gate Arrays (FPGA) unit. Mass spectra represents the number of detected fragment ions in a given mass-to-charge ratio channel. Electron impact ionization of neutral molecules results in creation of numerous fragment ions and most of organic compounds will contribute several identical fragments. Despite the presence of these molecular isobars, we developed the deconvolution algorithm capable of identifying target species based on their characteristic fragmentation patterns. We investigate the efficiency of deconvolution algorithm as a function of mass resolution with which mass spectrum is acquired. Higher the mass resolution, better the chances are to distinguish between stereoisomers using their fragmentation propensities, but also results in higher data volumes to be processed by a set of small footprint software stacks hosted by an on-board computer. Finding the balance between deconvolution accuracy and generated data volume under time constrains and limited computing resources is the main topic of this study.

Darrach, M.↗
DOE OSTI2024

Delocalization error poisons the density-functional many-body expansion

The many-body expansion is a fragment-based approach to large-scale quantum chemistry that partitions a single monolithic calculation into manageable subsystems. This technique is increasingly being used as a basis for fitting classical force fields to electronic structure data, especially for water and aqueous ions, and for machine learning. Here, we show that the many-body expansion based on semilocal density functional theory affords wild oscillations and runaway error accumulation for ion–water interactions, typified by F − (H 2 O) N with N ≳ 15. We attribute these oscillations to self-interaction error in the density-functional approximation. The effect is minor or negligible in small water clusters, explaining why it has not been noticed previously, but grows to catastrophic proportion in clusters that are only moderately larger. This behavior can be counteracted with hybrid functionals but only if the fraction of exact exchange is ≳50%, whereas modern meta-generalized gradient approximations including ωB97X-V, SCAN, and SCAN0 are insufficient to eliminate divergent behavior. Other mitigation strategies including counterpoise correction, density correction (i.e., exchange–correlation functionals evaluated atop Hartree–Fock densities), and dielectric continuum boundary conditions do little to curtail the problematic oscillations. In contrast, energy-based screening to cull unimportant subsystems can successfully forestall divergent behavior. These results suggest that extreme caution is warranted when the many-body expansion is combined with density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗