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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Synthesis of Carbohydrates from Methanol Using Electrochemical Partial Oxidation over Palladium with the Integrated Formose Reaction

Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. Furthermore, while a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm -2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21-28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Size-related decline in dryland shrubs is related to reductions in hydraulic efficiency and carbon assimilation and not nonstructural carbohydrate depletion

Plant growth and survival are fundamentally constrained by water transport from roots to leaves, impacting carbon assimilation and associated labile carbon pools. However, physiological constraints on growth and survival vary with plant age, due to changes in metabolic sinks, and increases in hydraulic path length from rhizosphere to canopy. We investigated crown dieback, growth, hydraulics, carbon assimilation and carbohydrate storage in relation to increasing basal diameter of two dominant shrub species (Caragana korshinskii and Artemisia ordosica) at the southeastern edge of the Tengger Desert, China. The aim was to identify mechanisms of decreased performance with plant size in dryland shrubs. Clear contrasts in stomatal regulation of leaf water potentials were detected between species. Despite these contrasts, radial growth, hydraulic transport efficiency (Ks), and photosynthetic efficiency similarly declined in both species with increasing plant size, while non-structural carbohydrate (NSC) reserves remained unchanged. Xylem embolism (PLC) increased with plant size, resulting in significant reductions in carbon assimilation in both species. Results indicate that hydraulic, and potentially carbon assimilation constraints, rather than reductions in carbohydrate storage, govern growth-related dryland shrub decline. These findings improve our understanding of how population demography impacts dryland forest response to climate change.

Zhang, Hongxia↗
DOE OSTI2026

Capacity of Arctic fjord sediments to degrade carbohydrates from permafrost active layer

The degradation of organic matter (OM) by microorganisms in thawing permafrost produces greenhouse gases. Terrestrial OM is transported into fjords through hydrological runoff, but it is unclear whether the microbial mechanisms of OM degradation on land persist after soils enter marine environments, which differ greatly in conditions and microbial communities. This question is particularly relevant for low-OM soils, which dominate Arctic landscapes and are more exposed to oxidants. Here, we compared OM-degrading capacity in permafrost-affected active layer soils and adjacent fjord sediments from Kongsfjorden, Svalbard, focusing on carbohydrate-active enzymes (CAZymes), which target some of the most abundant types of organic matter in soils. Using multi-omics approaches—metagenomics, metagenome-assembled genomes (MAGs), metabolomics, metatranscriptomics, and metaproteomics—we examined CAZyme presence, distribution, and activity. Despite environmental differences, both soils and sediments harbored diverse glycoside hydrolases and polysaccharide lyases, most of which showed evidence of activity. Verrucomicrobia expressed the highest number of CAZyme transcripts, indicating that they dominated active carbohydrate degradation in fjord sediments, while Acidobacteria and Actinobacteria were more active in soils. Notably, CAZymes in fjord sediments targeted primarily soil-derived OM, and the proportions of enzymes degrading terrestrial OM, marine OM, and microbial necromass—remnants of dead microbial cells were similar across both environments. These results suggest that microbial communities in both soils and fjord sediments are equipped to degrade carbohydrates, and that burial of terrestrial-derived OM in fjord sediments may not protect it from microbial breakdown under Arctic warming.

Chukwufumnanya, Abuah [University of Tennessee, Kn↗
DOE OSTI2021

Synergistic Improvement of Carbohydrate and Lignin Processability by Biomimicking Biomass Processing

The sustainability and economic feasibility of modern biorefinery depend on the efficient processing of both carbohydrate and lignin fractions for value-added products. By mimicking the biomass degradation process in white-rote fungi, a tailored two-step fractionation process was developed to maximize the sugar release from switchgrass biomass and to optimize the lignin processability for bioconversion. Biomimicking biomass processing using Formic Acid: Fenton: Organosolv (F 2 O) and achieved high processability for both carbohydrate and lignin. Specifically, switchgrass pretreated by the F 2 O process had 99.6% of the theoretical yield for glucose release. The fractionated lignin was also readily processable by fermentation via Rhodococcus opacus PD630 with a lipid yield of 1.16 g/L. Scanning electron microscope analysis confirmed the fragmentation of switchgrass fiber and the cell wall deconstruction by the F 2 O process. 2D-HSQC NMR further revealed the cleavage of aryl ether linkages (β-O-4) in lignin components. These results revealed the mechanisms for efficient sugar release and lignin bioconversion. The F 2 O process demonstrated effective mimicking of natural biomass utilization system and paved a new path for improving the lignin and carbohydrate processability in next generation lignocellulosic biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2020

Process to produce 5-hydroxymethylfurfural (HMF) from carbohydrates using a solvent system containing water and a polar aprotic solvent

A method to produce 5-hydroxymethylfurfural (HMF) from C6 carbohydrates. The method includes the steps of reacting a reactant comprising at least one C6 carbohydrate, in a reaction mixture comprising at least about 5% (v/v) water, a polar, aprotic solvent, and an acid, for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the C6 carbohydrate present in the reactant is converted to 5-hydroxymethyl furfural (“HMF”).

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

Current limitations of solid-state NMR in carbohydrate and cell wall research

High-resolution investigation of cell wall materials has emerged as an important application of biomolecular solid-state NMR (ssNMR). Multidimensional correlation experiments have become a standard method for obtaining sufficient spectral resolution to determine the polymorphic structure of carbohydrates and address biochemical questions regarding the supramolecular organization of cell walls. Here, using plant cellulose and matrix polysaccharides as examples, we will review how the multifaceted complexity of polysaccharide structure is impeding the resonance assignment process and assess the available biochemical and spectroscopic approaches that could circumvent this barrier. We will emphasize the ineffectiveness of the current methods in reconciling the ever-growing dataset and deriving structural information. We will evaluate the protocols for achieving efficient and homogeneous hyperpolarization across the cell wall material using magic-angle spinning dynamic nuclear polarization (MAS-DNP). Critical questions regarding the line-broadening effects of cell wall molecules at cryogenic temperature and by paramagnetic biradicals will be considered. Finally, the MAS-DNP method will be placed into a broader context with other structural characterization techniques, such as cryo-electron microscopy, to advance ssNMR research in carbohydrate and cell wall biomaterials.

09 BIOMASS FUELS↗
DOE OSTI2020

Structural and Proteomic Studies of the Aureococcus anophagefferens Virus Demonstrate a Global Distribution of Virus-Encoded Carbohydrate Processing

Viruses modulate the function(s) of environmentally relevant microbial populations, yet considerations of the metabolic capabilities of individual virus particles themselves are rare. We used shotgun proteomics to quantitatively identify 43 virus-encoded proteins packaged within purified Aureococcus anophagefferens Virus (AaV) particles, normalizing data to the per-virion level using a 9.5-Å-resolution molecular reconstruction of the 1900-Å (AaV) particle that we generated with cryogenic electron microscopy. This packaged proteome was used to determine similarities and differences between members of different giant virus families. We noted that proteins involved in sugar degradation and binding (e.g., carbohydrate lyases) were unique to AaV among characterized giant viruses. To determine the extent to which this virally encoded metabolic capability was ecologically relevant, we examined the TARA Oceans dataset and identified genes and transcripts of viral origin. Our analyses demonstrated that putative giant virus carbohydrate lyases represented up to 17% of the marine pool for this function. In total, our observations suggest that the AaV particle has potential prepackaged metabolic capabilities and that these may be found in other giant viruses that are widespread and abundant in global oceans.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Environmental Metrics of Ethanol Production Improve with Increased Biomass Yield and Carbohydrate Content in Populus Trichocarpa

When selecting economically and environmentally advantageous genotypes for domestication in a biofuel supply chain, variability of cell-wall composition within a feedstock population and its impact on biorefinery metrics must be understood. We performed a life cycle assessment (LCA) on a poplar-to-ethanol supply chain to quantify global warming potential and cumulative energy demand as affected by variable carbohydrate content in a large representative natural variant population of Populus trichocarpa. The results showed that both environmental metrics decrease with increasing tree size and with increasing biomass carbohydrate content. These trends parallel prior economic results and provide clear direction to breeders or genetic engineers when improving poplar cultivars.

09 BIOMASS FUELS↗
DOE OSTI2020

Carbohydrate‐binding domains facilitate efficient oligosaccharides synthesis by enhancing mutant catalytic domain transglycosylation activity

Abstract Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers.

Bandi, Chandra Kanth↗
DOE OSTI2026

Divergent trait controls on soluble sugars and starch underlie global strategies of tree carbohydrate storage

Nonstructural carbohydrate (NSC) stores buffer tree metabolism, osmotic regulation, and defense, thereby mediating tolerance and survival under climate extremes. Yet, the functional and evolutionary determinants of interspecific variation in NSC remain elusive, limiting understanding and prediction of forest carbon allocation and mortality under global change. Here, we present a cross-species synthesis of NSC concentrations across multiple organs for 281 woody species from 102 mixed forest communities worldwide, where we quantified species-specific deviations from community means to disentangle intrinsic trait effects from environmental and methodological variation. We found phylogenetic signals in NSC deviations, with coniferous gymnosperms and evergreen species consistently maintaining lower stem soluble sugars and starch concentrations than co-occurring angiosperms and deciduous species, respectively. A global pattern emerged where greater stomatal sensitivity to leaf water potential was associated with declines in the relative concentrations of both sugars and starch. In contrast, xylem hydraulic safety traits showed weak and organ-dependent relationships with NSC concentrations. Sugars increased with photosynthetic capacity and declined with wood density, whereas starch showed the reverse pattern, which aligned with the distinct functional-metabolic roles of sugars and starch. By integrating trait-based ecology with a community-centered framework, our study provides global evidence that stomatal regulation, photosynthetic capacity, specific leaf area, and wood density jointly govern interspecific NSC variation, through contrasting effects on sugars and starch. These are among the most broadly measured traits globally, thus the emergent carbohydrate–trait relationships can have broad applications toward understanding and predicting forest growth and survival under climate change.

tropic system↗
DOE OSTI2021

Adaptive variation and plasticity in non‐structural carbohydrate storage in a temperate tree species

Abstract Trees' total amount of non‐structural carbohydrate (NSC) stores and the proportion of these stores residing as insoluble starch are vital traits for individuals living in variable environments. However, our understanding of how stores vary in response to environmental stress is poorly understood as the genetic component of storage is rarely accounted for in studies. Here, we quantified variation in NSC traits in branch samples taken from over 600 clonally transplanted black cottonwood ( Populus trichocarpa) trees grown in two common gardens. We found heritable variation in both total NSC stores and the proportion of stores in starch (H 2 TNC = 0.19, H 2 PropStarch = 0.31), indicating a substantial genetic component of variation. In addition, we found high amounts of plasticity in both traits in response to cold temperatures and significant genotype‐by‐environment (GxE) interactions in the total amount of NSC stored (54% of P is GxE). This finding of high GxE indicates extensive variation across trees in their response to environment, which may explain why previous studies of carbohydrate stores' responses to stress have failed to converge on a consistent pattern. Overall, we found high amounts of environmental and genetic variation in NSC storage concentrations, which may bolster species against future climate change.

Blumstein, Meghan↗
DOE OSTI2023

RNAseq analysis of Cellvibrio japonicus during starch utilization differentiates between genes encoding carbohydrate active enzymes controlled by substrate detection or growth rate

ABSTRACT Bacterial utilization of starch is increasingly of interest as the importance and contributions of animal gut microbiomes become more defined. Consequently, identifying and characterizing the bacterial enzymes responsible for the degradation, transport, and metabolism of starch will enable developments in pharmaceutical, biotechnological, and culinary industries searching for novel prebiotics, carrier molecules, and low glycemic index sweeteners. The current challenge is that bacteria proficient at starch utilization often have hundreds of carbohydrate active enzymes, and it is unclear which are essential for starch utilization using only homology-based bioinformatics or computational methods. Complementary experimental data are also needed, especially to understand the regulation of bacterial starch utilization. We have completed an RNAseq analysis of the Gram-negative bacterium Cellvibrio japonicus and found that it has sophisticated regulation that includes substrate sensing and growth rate components for genes that encode starch-degrading enzymes. Among the 22 genes predicted to encode starch-active enzymes, C. japonicus has 10 alpha-amylases, 4 alpha-glucosidases, 2 pullulnases, and 2 cyclomaltodextrin glucanotransferases, 15 of which were up-regulated during exponential growth on starch and 8 up-regulated in stationary phase. Growth analyses with an enzyme secretion deficient mutant of C. japonicus suggested that secreted amylases are essential for this bacterium to degrade starch. Our approach of coupling a physiological growth assay with transcriptomic data provides a platform to identify targets for further genetic or biochemical analysis that can be broadly applied to other starch-utilizing bacteria. IMPORTANCE Understanding the bacterial metabolism of starch is important as this polysaccharide is a ubiquitous ingredient in foods, supplements, and medicines, all of which influence gut microbiome composition and health. Our RNAseq and growth data set provides a valuable resource to those who want to better understand the regulation of starch utilization in Gram-negative bacteria. These data are also useful as they provide an example of how to approach studying a starch-utilizing bacterium that has many putative amylases by coupling transcriptomic data with growth assays to overcome the potential challenges of functional redundancy. The RNAseq data can also be used as a part of larger meta-analyses to compare how C. japonicus regulates carbohydrate active enzymes, or how this bacterium compares to gut microbiome constituents in terms of starch utilization potential.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Catalytic Upgrading of Carbohydrates in Waste Streams to Hydrocarbons: Paper Sludge to Fuel Project (PStF)

This research, funded by the Department of Energy Bioenergy Technologies Office (DOE BETO), aims to understand the barriers and assess opportunities for transforming carbohydrates in paper sludge, a solid lignocellulosic residue from the pulp and paper industry. The goal is to turn the paper sludge into a liquid hydrocarbon product that can be blended into jet fuel, both economically and sustainably. Research groups at North Carolina State University, National Renewable Energy Laboratory, and Yale University collaborated synergistically, leveraging their expertise in pulp and paper operations, biomass deconstruction, and catalytic upgrading to propose a pathway that efficiently captures the energy in paper sludge. Findings from this study could potentially contribute to advancing biomass conversion technologies, aligning with the efforts of the U.S. DOE BETO. This report documents the experimental and simulation results of a biochemical and catalytic pathway designed to transform paper sludge into a liquid hydrocarbon product. The process involves a sequence of seven steps, including ash removal, carbohydrate enzymatic hydrolysis, sugar dehydration, solvent recovery, aldol-condensation between furans and ketone, hydrogenation, and hydrodeoxygenation to obtain a hydrocarbon blend in the ~C10 range. The experimental efforts from the initiation of the project were guided by techno-economic analysis (TEA) and sensitivity analysis results including around seventy-eight operational parameters. This methodology facilitated the efficient use of resources over time. This study relies on detailed process simulations and TEA to determine the minimum fuel selling price (MFSP) for the hydrocarbon fuel product. Preliminary TEA results led to the evaluation of eight case studies considering alternative dehydration co-solvents, operational settings, and biorefinery layouts. Finally, the life cycle assessment of twenty-eight scenarios, comparing various dehydration co-solvents, fuel sources, chemical feedstock sources, side product utilization, and other process settings, was conducted. Landfilling scenarios with and without landfill gas recovery were also estimated, analyzed, and compared.

09 BIOMASS FUELS↗
DOE OSTI2025

Enhanced Production of Algae Lipids and Carbohydrates for Fuel and Polyurethane Precursors

This Final Technical Report summarizes the goals, approach, and outcomes of the project “Enhanced Production of Algae Lipids and Carbohydrates for Fuel and Polyurethane Precursors”. The project addressed the challenge of improving microalgae biomass productivity and simultaneously producing valuable polyurethane precursors (PUPs), from both lipids and carbohydrates, that can be converted into renewable biofuels and bio-based polyurethane (PU) products. By integrating advanced genetic engineering, traditional breeding, high-throughput screening, pilot cultivation, and chemical conversion technologies, the team achieved significant advancements in algae biotechnology.

09 BIOMASS FUELS↗
DOE OSTI2023

Mixed-Linkage Glucan Is the Main Carbohydrate Source and Starch Is an Alternative Source during Brachypodium Grain Germination

Seeds of the model grass Brachypodium distachyon are unusual because they contain very little starch and high levels of mixed-linkage glucan (MLG) accumulated in thick cell walls. It was suggested that MLG might supplement starch as a storage carbohydrate and may be mobilised during germination. In this work, we observed massive degradation of MLG during germination in both endosperm and nucellar epidermis. The enzymes responsible for the MLG degradation were identified in germinated grains and characterized using heterologous expression. By using mutants targeting MLG biosynthesis genes, we showed that the expression level of genes coding for MLG and starch-degrading enzymes was modified in the germinated grains of knocked-out cslf6 mutants depleted in MLG but with higher starch content. Our results suggest a substrate-dependent regulation of the storage sugars during germination. These overall results demonstrated the function of MLG as the main carbohydrate source during germination of Brachypodium grain. More astonishingly, cslf6 Brachypodium mutants are able to adapt their metabolism to the lack of MLG by modifying the energy source for germination and the expression of genes dedicated for its use.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Microorganisms that co-consume glucose with non-glucose carbohydrates and methods of use

Microorganisms that co-consume glucose with non-glucose carbohydrates, such as xylose, and methods of using same. The microorganisms comprise modifications that reduce or ablate the activity of a phosphoenolpyruvate (PEP):carbohydrate phosphotransferase system (PTS) protein or modifications that reduce or ablate the activity of a phosphoglucose isomerase and a GntR. The PTS protein may be selected from an enzyme I (EI), an HPr, an FPr, and an enzyme IIGlc (EIIGlc). Additional modifications include reduction or ablation of the activity of a pyruvate formate lyase, a lactate dehydrogenase, and a fumarate reductase and inclusion of recombinant pyruvate decarboxylase and alcohol dehydrogenase genes. The microorganisms are particularly suited to co-consuming glucose and xylose in media containing these substrates and producing ethanol therefrom.

Reed, Jennifer L.↗
DOE OSTI2023

Evidence for Lignin–Carbohydrate Complexes from Studies of Transgenic Switchgrass and a Model Lignin–Pectin Composite

Lignin–carbohydrate complexes (LCCs) form through interactions of lignin with plant cell wall polysaccharides and are thought to be a significant source of biomass recalcitrance. In this work, we investigated LCCs formed between lignin and pectin homogalacturonan (HG). The structural changes in HG deficient transgenic switchgrass (GAUT4-knockdown, GAUT4-KD) after hot water pretreatment were compared to wild-type plants using small-angle neutron scattering (SANS), which showed that there were ~2.2-fold more lignin aggregates in GAUT4-KD biomass compared to the wild type. This demonstrated that decreased pectin resulted in more lignin redistribution and suggested that interactions between lignin and HG restrict lignin mobility in plant cell walls. To better understand the types of interactions between lignin and pectin, a model composite was prepared by polymerizing either protiated or partially deuterated coniferyl alcohol to form a dehydrogenation polymer (DHP) in the presence of HG. Small-angle X-ray scattering (SAXS) showed that the DHP and HG form a highly interconnected network structure that is not observed in a physical mixture of the individual polymers. Contrast matching SANS revealed the structure of DHP and HG in the composite and showed that the HG forms a swollen interconnected polymer network (power-law exponent, P = 1.5) interspersed with DHP particles (radius of gyration, Rg, 264 Å) that are composed of solvent-accessible DHP polymers (P = 2.3). Fourier transform infrared spectroscopy showed a unique ester absorption band in the DHP/HG composites. Solid-state nuclear magnetic resonance (NMR) analysis also supports interactions between DHP and HG. Overall, this study provides new insights into the relationship between primary and secondary cell wall polymers during cell wall synthesis and how LCCs formed between pectin and lignin could represent a previously unrecognized source of biomass recalcitrance. This knowledge may help develop new approaches to modulate cell wall properties to improve biofuel and bioproduct production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Leaf nonstructural carbohydrate residence time, not concentration, correlates with leaf functional traits following the leaf economic spectrum in woody plants

Nonstructural carbohydrate (NSC) concentrations might reflect the strategies described in the leaf economic spectrum (LES) due to their dependence on photosynthesis and respiration. Here, we examined if NSC concentrations correlate with leaf structure, chemistry, and physiology traits for 114 species from 19 sites and 5 biomes around the globe. Total leaf NSC concentrations varied greatly from 16 to 199 mg g -1 dry mass and were mostly independent of leaf gas exchange and the LES traits. By contrast, leaf NSC residence time was shorter in species with higher rates of photosynthesis, following the fast-slow strategies in the LES. An average leaf held an amount of NSCs that could sustain one night of leaf respiration and could be replenished in just a few hours of photosynthesis under saturating light, indicating that most daily carbon gain is exported. Our results suggest that NSC export is clearly linked to the economics of return on resource investment.

59 BASIC BIOLOGICAL SCIENCES↗