Search NASA⌕ Search

SEARCH · Search NASA

Results for “isotope labeling”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3

Exploration of the bio-analogous asymmetric C–C coupling mechanism in tandem CO 2 electroreduction

C–C coupling is a critical step of CO 2 fixation in constructing the carbon skeleton of value-added multicarbon products. The Wood–Ljungdahl pathway is an efficient natural process through which microbes transform CO 2 into methyl and carbonyl groups and subsequently couple them together. This asymmetric coupling mechanism remains largely unexplored in inorganic CO 2 electroreduction. Here we experimentally validate the asymmetric coupling pathway through isotope-labelled co-reduction experiments on a Cu surface where 13 CH 3 I and 12 CO are co-fed externally as the methyl and the carbonyl source, respectively. Isotope-labelled multicarbon oxygenates were detected, which confirms an electrocatalytic asymmetric coupling on the Cu surface. We further employed tandem Cu–Ag nanoparticle systems in which *CH x and *CO intermediates can be generated to achieve asymmetric C–C coupling for a practical CO 2 electroreduction. We found that the production of multicarbon oxygenates is correlated with the generation rate of two intermediate indicators, CH 4 and CO. By aligning their rates, the oxygenates generation rate can be maximized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Associative nitrogen fixation linked with three perennial bioenergy grasses in field and greenhouse experiments

Abstract Associative nitrogen (N 2 )‐fixation (ANF) by bacteria in the root‐zone of perennial bioenergy grasses has the potential to replace or supplement N fertilizer and support sustainable production of biomass, but its application in marginal ecosystems requires further evaluation. In this study, we first combined both greenhouse and field experiments, to explore the N 2 fixation effects of three temperate feedstocks Miscanthus × giganteus (giant miscanthus, Freedom), Panicum virgatum (switchgrass, Alamo), and Saccharum sp. (energycane, Ho 02‐147). In field studies across three growing seasons, plant and soil pools of candidate feedstocks were partially composed of N derived from the atmosphere (Ndfa). Energycane, giant miscanthus, and switchgrass were estimated to derive >30%, %Ndfa. Greenhouse studies were also performed to trace isotopically labeled 15 N 2 into plant biomass and soil pools. Evidence for Ndfa was detected in all three feedstock grasses (using reference 15 N of soil, chicory, and sorghum, δ 15 N~+7.0). Isotopically labeled 15 N 2 was traced into biomass (during grass elongation stage) and soil pools. Extrapolation of rates during the 24 hr labeling period to 50 days estimated 30%–55% of plant Ndfa, with the greatest Ndfa for energycane. The findings of the field natural abundance and greenhouse 15 N 2 feeding experiments provided complementary evidence that perennial bioenergy grasses have the potential to support relatively high rates of ANF, and accumulate diazotroph‐derived N into biomass when grown on non‐fertilized soil.

09 BIOMASS FUELS↗

Enabling quantitative analysis of complex polymer blends by infrared nanospectroscopy and isotopic deuteration

Atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) deciphers surface morphology of thin-film polymer blends and composites by simultaneously mapping physical topography and chemical composition. However, acquiring quantitative phase and composition information from multi-component blends can be challenging using AFM-IR due to the possible overlapping infrared absorption bands between different species. Isotope labeling one of the blend components introduces a new type of bond (carbon-deuterium vibration) that can be targeted using AFM-IR and responds at wavelengths sufficiently shifted toward unoccupied regions (around 2200 cm –1 ). In this project, AFM-IR was used to probe the surface morphology and chemical composition of three polymer blends containing deuterated polystyrene; each blend is expected to exhibit various degrees of miscibility. AFM-IR results successfully demonstrated that deuterium labeling prevents infrared spectral overlap and enables the visualization of blend phases that could not normally be distinguished by other scanning probe techniques. The nanoscale domain composition was resolved by fast infrared spectrum analysis. Overall, we presented isotope labeling as a robust approach for circumventing obstacles preventing the quantitative analysis of multiphase systems by AFM-IR.

36 MATERIALS SCIENCE↗

Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

The ability to simultaneously monitor the flux of iron atoms within the solution and solid phases can provide considerable insight into mechanisms of iron oxide mineral transformations. The autocatalytic interaction between hematite and Fe(II)-oxalate has long been of interest for its environmental and industrial relevance. In this study we take advantage of iron isotopic labelling and mass-sensitive imaging at the single particle scale to determine how changes in solution composition correlate with the morphologic evolution of faceted, micrometer-sized hematite platelets. Net dissolution is confirmed through analyses of aqueous iron chemistry, as well as by quantitative atomic force microscopy. Isotopic mapping techniques show that Fe(II) readily adsorbs to (001) and (012) surfaces in the absence of oxalate, but when oxalate is present selective dissolution of the (001) surface prevails and 57Fe deposition via recrystallization is not observed. Comparison between particle microtopographies following reaction with Fe(II), oxalate, and Fe(II)-oxalate show substantially different behavior, consistent with distinct mechanisms of interaction with hematite surfaces. The extensive characterization conducted on the coupled solution/solid dynamics in this system provides new insight for distinguishing crystal growth, dissolution, and recrystallization processes.

Taylor, Sandra D. [BATTELLE (PACIFIC NW LAB)]↗

Hydrazinoacetic acid is a biosynthetic precursor of the bacterially produced nitramine, N -nitroglycine

Nitramines [R(R′)N–NO 2 ; R,R′=H or alkyl] are valuable synthetic products, but knowledge of the biosynthetic processes that generate these compounds is limited. This work sought to elucidate the biosynthesis of a nitramine natural product, N-nitroglycine (NNG) by Streptomyces noursei . Stable isotope studies showed that S. noursei cells supplemented with L-(ε- 15 N)lysine, ( 15 N)glycine, or ( 13 C)hydrazinoacetic acid (HAA) incorporated 67%, 88%, and 67% of the isotope label into NNG, respectively, indicating that these compounds are biosynthetic precursors of NNG. Liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) of 15 N-Lys-labeled NNG confirmed that the nitro nitrogen of NNG originates from Lys. Bioinformatics analysis of the S. noursei genome showed evidence for a biosynthetic gene cluster (BGC) that contained machinery for HAA biosynthesis ( nngKLM ), consistent with the results of the isotope labeling. In vitro reconstitution of the gene products produced HAA. The borders of this BGC were defined by cross-referencing the predicted BGC with previously published differential proteomics data. Furthermore, we show that azaserine is produced alongside NNG in S. noursei cultures, linking the two biosynthetic pathways via a proposed nitrosamine biosynthetic intermediate. Finally, the oxygen balance for NNG is −20.2% for the formation of carbon dioxide (CO 2 ), which is comparable to that of hexahydro-1,3,5- trinitro-1,3,5-triazene (common name: RDX; −21.6%). Crystal structure data of NNG indicate that the unit crystalizes as a pure material, not a hydrate, suggesting a favorable energetic crystallization phase. The combined results suggest a route that, with further development, could lead to sustainable production of energetic nitramines via synthetic biology or biocatalytic approaches.

biosynthesis↗

Elucidation of Aromatic Catabolic Pathways in White-Rot Fungi

This project aims to investigate the hypothesis that white-rot fungi can simultaneously depolymerize lignin extracellularly and catabolize depolymerization products intracellularly as carbon and energy sources. Evaluating this hypothesis will provide deeper understanding of the role of white-rot fungi in facilitating carbon sequestration in Nature. Additionally, identifying the most promising fungal strains for lignin turnover and catabolism will catalyze future efforts in genetic tool development to enable metabolic engineering in white-rot fungi for lignin bioconversion to bioproducts. Lignin is the second most abundant plant-based biopolymer on Earth and represents up to 40% of the energy density of lignocellulosic biomass. Even though lignin is a massive natural carbon and energy reservoir, only a small group of basidiomycete fungi, namely white-rot fungi (WRF), have evolved the ability to efficiently depolymerize and mineralize lignin to CO2 and H2O. Considerable research efforts have been undertaken to understand how WRF depolymerize lignin but the biochemical reactions that convert lignin into CO2 have been largely neglected. In fact, it is unclear if WRF intracellularly catabolize lignin-derived aromatic compounds to utilize them as a carbon and energy source, or rather if lignin is depolymerized and mineralized extracellularly merely to facilitate access to cellulose and hemicellulose for use as a primary carbon source. To date, we have employed 13C-isotope labeling, systems biology approaches, and in vitro enzyme assays to definitively demonstrate that two WRF, Trametes versicolor and Gelatoporia (Ceriporiopsis) subvermispora, funnel carbon from lignin-derived aromatic compounds into central carbon metabolism via intracellular catabolic pathways [1]. Specifically, 13C-isotopic labeling approaches showed that these WRF utilize poplar-derived aromatic compounds (e.g. 4-hydroxybenzoic acid (4-HBA)) as a carbon source. In silico genome analysis led us to hypothesize a complete catabolic pathway for 4-HBA and identify multiple homologous sequences for enzymes with putative oxidative decarboxylase, hydroxylase, and ring-opening dioxygenase activities, which are among the main biochemical reactions acting on aromatic compounds. Spatial and differential proteomic and metabolomic analyses supported the proposed catabolic pathways and showed alternative catabolic steps in T. versicolor that were not present in G. subvermispora. Based on the in silico, proteomics, and transcriptomics results, we down-selected enzymes for further in vitro characterization, and we have assigned a function to six fungal enzymes (including oxidative decarboxylases, hydroxylases, and ring-opening dioxygenases). Interestingly, even though we selected homologous enzyme pairs from both WRF with similar -omics trends, in a few cases only one of the studied fungi showed activity for the proposed substrate. Based on all the observations from this study [1], we hypothesized that 4-HBA preferentially undergoes oxidative decarboxylation to hydroquinone and subsequent hydroxylation to 1,2,4-benzenetriol in G. subvermispora before ring cleavage, whereas 4-HBA would preferentially undergo hydroxylation to protocatechuate and further oxidative decarboxylation to 1,2,4-benzenetriol in T. versicolor. Examining additional decarboxylases and hydroxylases as well as enzymes from other protein families that can perform the same or similar oxidative reactions, such as cytochromes P450 with aromatic hydroxylation activity, will also be key for elucidating enzyme preferences for specific substrates. Overall, this work forms the foundation of a new research area based on lignin catabolism by WRF, which could be further exploited to convert the undervalued biopolymer lignin into value-added compounds.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Extracellular electron transfer across bio-nano interfaces for CO 2 electroreduction

Acetogenic bacteria represent a class of organisms capable of converting reducing equivalents and carbon dioxide into products with carbon–carbon bonds. Materials-based bio-electrochemical approaches are attractive for supplying biological organisms directly with grid-supplied electrons to convert carbon dioxide to value-added chemicals. Carbon nanotube-modified biocathodes have emerged as promising candidates for microbial electrosynthesis with high yields of carbon product formation, but a fundamental understanding of extracellular charge transfer at this electrode-biofilm interface is still lacking. Here, we utilize solid-state interfaces between semiconducting single-walled carbon nanotubes (s-SWCNT) and a model acetogenic bacterium for mechanistic studies of electro-catalytic CO 2 conversion to acetate. Studies of bacteria/s-SWCNT interactions in a transistor-based device suggest direct extracellular electron transfer (EET) at the bio-nano interface. Deuterium isotope labeling experiments confirmed that the availability of electrochemically produced H 2 as a redox mediator does not limit the efficiency of EET and CO 2 electro-reduction for C. ljungdahlii biofilms, suggesting the primary reducing equivalents are the electrons delivered across the electrode/bacterium interface or involvement of biological redox mediators. Additional isotope labeling studies demonstrate high Faradaic efficiency for CO 2 electro-reduction at the SWCNT/bacterium interface. These results provide important information about EET across the bacterium/material interface in a model biocathode.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Data from Improved Annotation of Untargeted Metabolomics Data through Buffer Modifications That Shift Adduct Mass and Intensity

Annotation of untargeted high-resolution full-scan LC-MS metabolomics data remains challenging due to individual metabolites generating multiple LC-MS peaks arising from isotopes, adducts, and fragments. Adduct annotation is a particular challenge, as the same mass difference between peaks can arise from adduct formation, fragmentation, or different biological species. To address this, here we describe a buffer modification workflow (BMW) in which the same sample is run by LC-MS in both liquid chromatography solvent with 14NH3–acetate buffer and in solvent with the buffer modified with 15NH3–formate. Buffer switching results in characteristic mass and signal intensity changes for adduct peaks, facilitating their annotation. This relatively simple and convenient chromatography modification annotated yeast metabolomics data with similar effectiveness to growing the yeast in isotope-labeled media. Application to mouse liver data annotated both known metabolite and known adduct peaks with 95% accuracy. Overall, it identified 26% of ∼27 000 liver LC-MS features as putative metabolites, of which ∼2600 showed HMDB or KEGG database formula match. This workflow is well suited to biological samples that cannot be readily isotope labeled, including plants, mammalian tissues, and tumors.

Conversion↗

Improved Annotation of Untargeted Metabolomics Data through Buffer Modifications That Shift Adduct Mass and Intensity

Annotation of untargeted high-resolution full-scan LC-MS metabolomics data remains challenging due to individual metabolites generating multiple LC-MS peaks arising from isotopes, adducts and fragments. Adduct annotation is a particular challenge, as the same mass difference between peaks can arise from adduct formation, fragmentation, or different biological species. To address this, here we describe a Buffer Modification Workflow (BMW), in which the same sample is run by LC-MS in both liquid chromatography solvent with 14 NH 3 -acetate buffer, and in solvent with the buffer modified with 15 NH 3 -formate. Buffer switching results in characteristic mass and signal intensity changes for adduct peaks, facilitating their annotation. This relatively simple and convenient chromatography modification annotated yeast metabolomics data with similar effectiveness to growing the yeast in isotope-labeled media. Application to mouse liver data annotated both known metabolite and known adduct peaks with 95% accuracy. Altogether, it identified 26% of ~ 27,000 liver LC-MS features as putative metabolites, of which ~ 2600 showed HMDB or KEGG database formula match. This workflow is well-suited to biological samples that cannot be readily isotope labeled, including plants, mammalian tissues, and tumors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Daylength variation affects growth, photosynthesis, leaf metabolism, partitioning, and metabolic fluxes

Abstract Daylength, a seasonal and latitudinal variable, exerts a substantial impact on plant growth. However, the relationship between daylength and growth is nonproportional, suggesting the existence of adaptive mechanisms. Thus, our study aimed to comprehensively investigate the adaptive strategies employed by plants in response to daylength variation. We grew false flax (Camelina sativa) plants, a model oilseed crop, under long-day (LD) and short-day (SD) conditions and used growth measurements, gas exchange measurements, and isotopic labeling techniques, including 13C, 14C, and 2H2O, to determine responses to different daylengths. Our findings revealed that daylength influences various growth parameters, photosynthetic physiology, carbon partitioning, metabolic fluxes, and metabolite levels. SD plants employed diverse mechanisms to compensate for reduced CO2 fixation in the shorter photoperiod. These mechanisms included enhanced photosynthetic rates and reduced respiration in the light (RL), leading to increased shoot investment. Additionally, SD plants exhibited reduced rates of the glucose 6-phosphate (G6P) shunt and greater partitioning of sugars into starch, thereby sustaining carbon availability during the longer night. Isotopic labeling results further demonstrated substantial alterations in the partitioning of amino acids and TCA cycle intermediates between rapidly and slowly turning over pools. Overall, the results point to multiple developmental, physiological, and metabolic ways in which plants adapt to different daylengths to maintain growth.

59 BASIC BIOLOGICAL SCIENCES↗

Tuning the reactivity of carbon surfaces with oxygen-containing functional groups

Oxygen-containing carbons are promising supports and metal-free catalysts for many reactions. However, distinguishing the role of various oxygen functional groups and quantifying and tuning each functionality is still difficult. Here we investigate the role of Brønsted acidic oxygen-containing functional groups by synthesizing a diverse library of materials. By combining acid-catalyzed elimination probe chemistry, comprehensive surface characterizations, 15N isotopically labeled acetonitrile adsorption coupled with magic-angle spinning nuclear magnetic resonance, machine learning, and density-functional theory calculations, we demonstrate that phenolic is the main acid site in gas-phase chemistries and unexpectedly carboxylic groups are much less acidic than phenolic groups in the graphitized mesoporous carbon due to electron density delocalization induced by the aromatic rings of graphitic carbon. The methodology can identify acidic sites in oxygenated carbon materials in solid acid catalyst-driven chemistry.

Zhou, Jiahua↗

Large fluxes of fatty acids from membranes to triacylglycerol and back during N-deprivation and recovery in Chlamydomonas

Abstract Microalgae accumulate triacylglycerol (TAG) during nutrient deprivation and break it down after nutrient resupply, and these processes involve dramatic shifts in cellular carbon allocation. Due to the importance of algae in the global carbon cycle, and the potential of algal lipids as feedstock for chemical and fuel production, these processes are of both ecophysiological and biotechnological importance. However, the metabolism of TAG is not well understood, particularly the contributions of fatty acids (FAs) from different membrane lipids to TAG accumulation and the fate of TAG FAs during degradation. Here, we used isotopic labeling time course experiments on Chlamydomonas reinhardtii to track FA synthesis and transfer between lipid pools during nitrogen (N)-deprivation and resupply. When cells were labeled before N-deprivation, total levels of label in cellular FAs were unchanged during subsequent N-deprivation and later resupply, despite large fluxes into and out of TAG and membrane lipid pools. Detailed analyses of FA levels and labeling revealed that about one-third of acyl chains accumulating in TAG during N-deprivation derive from preexisting membrane lipids, and in total, at least 45% of TAG FAs passed through membrane lipids at one point. Notably, most acyl chains in membrane lipids during recovery after N-resupply come from TAG. Fluxes of polyunsaturated FAs from plastidic membranes into TAG during N-deprivation were particularly noteworthy. These findings demonstrate a high degree of integration of TAG and membrane lipid metabolism and highlight a role for TAG in storage and supply of membrane lipid components.

Plant Sciences↗

A Systems Biology Approach to Energy Flow in H 2 Producing Microbial Communities: Microbial Mats

This report describes the results of work conducted at NASA Ames Research Center, in collaboration with investigators at Lawrence Livermore National Laboratory, during the time period 12/15/2014 to 12/15/2017. The work was an extension of a collaboration with LLNL that began in 2008. Work this reporting period focused primarily on tasks related to microbial mats from both the Elkhorn Slough and Baja California field sites, including the analysis and publication of data produced prior to 12/15/2014. During this reporting period, in addition to the microbial mat work, we also conducted a series of experiments with a particular algal-bacterial association (C. sorokiniana and A. brasilense). A number of aspects of this well-characterized algal-bacterial association enabled us not only to further our understanding of interactions between these particular organisms, but to apply that knowledge and techniques to our collection of microorganisms isolated from microbial mats. Microbial mat experiments focused both on intact mat communities and on cultures of organisms isolated from the mats (the Microbial Mat Living Library). In a series of co-culture experiments, we documented both positive and negative interactions amongst heterotrophic and autotrophic isolates of microbial mat microorganisms. One particularly important and novel mat cyanobacterium (ESFC-1) was studied in detail. We developed techniques to pursue an investigation of functional redundancy (the idea that closely related organisms perform identical roles in a community) in cyanobacterial autotrophs in the Elkhorn Slough microbial mat. In those experiments, we documented numerous instances of increases in growth rate between co-cultures of two organisms (relative to their growth rate in isolation) performing what would seem to be identical functional roles. Simplified microbial mat communities consisting of organisms from the Microbial Mat Living Library were constructed and studied in laboratory experiments. The “constructed mats” were grown in standard laboratory glassware and plasticware, but cultures were also combined with artificial materials in an effort to re-create the three-dimensional structure of naturally occurring microbial mats. These constructed mats re-created a number of functions attributable to natural microbial mats (N-fixation, H2-production) and simplified their study using molecular ecological techniques due to the smaller number of microbial “species” present. Cyanobacteria which migrated in response to vertical variations in light intensity (irradiance) obtained characteristic positions in constructed mats that were similar to their positions in natural mats. A detailed investigation of nitrogen cycling in both the Baja California and Elkhorn Slough microbial mats was initiated during this reporting period. The nitrogen cycle in the microbial mats has not been studied in depth, despite the fact that nitrogen usually limits growth in marine environments. The organisms conducting nitrogen cycling in both microbial mats were studied using the genomes available from earlier work on these mats, as well as with a targeted approach using molecular ecological methods developed here. Quantitative measurements of rates of nitrogen transformations were made using stable isotopically labeled nitrogen. The processes quantified and examined using molecular ecological methods included: nitrogen fixation, ammonification, ammonium and nitrate assimilation, denitrification, anaerobic oxidation of ammonium, and dissimilatory nitrate reduction to ammonium. In a series of experiments designed to examine a potential application for microbial mats, we demonstrated that both Elkhorn Slough and Baja California microbial mats were very effective in removing large quantities of both nitrate and ammonium from waste streams containing these compounds at levels where they would be considered to be pollutants. Considerable effort was expended during this reporting period to analyze, and prepare for publication, metagenomes and metatranscriptomes collected from two experimental manipulations of microbial mats. The first, a diel study, was conducted in November 2011, while the second, an investigation of the effects of sulfate on community composition, was conducted during this reporting period. For the earlier study, reference-based and reference-free methods were used to assess microbial ecology and genetic partitioning in these complex microbial systems, and that work is available as a pre-print. Four metagenomes from the same experiment were published. In the second, longer (nearly 200 day) manipulation, rRNA iTag libraries for cDNA and DNA were analyzed to determine the effects of sulfate concentration on microbial mat community composition over the course of the experiment. Work on the algal-bacterial association (Chlorella sorokiniana and Azospirillum brasilense) focused initially on demonstrating the transfer of carbon and nitrogen between the partners, using stable isotopic labeling and the LLNL NanoSIMS. Subsequently, the potential role of diazotrophy (nitrogen fixation) by the bacterial partner in supporting the growth of the association was assessed in a series of experiments. It appears to be the case that, although the bacterial partner demonstrably increases the fitness of the algae under nitrogen limitation, and cells of C. sorokiniana receive nitrogen originally fixed from atmospheric nitrogen by A. brasilense, the amount of nitrogen obtained by diazotrophy is too small to explain the increase in fitness.

08 HYDROGEN↗

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗

D-Band EPR and ENDOR Spectroscopy of 15 N-Labeled Photosystem I

For billions of years, nature has optimized the photosynthetic machinery that converts light energy into chemical energy. Key primary reactions of photosynthesis occur in large membrane protein-cofactor complexes. The light-induced sequential electron transfer reactions occur through a chain of donor/acceptor cofactors embedded in the protein matrix resulting in a long-lived transmembrane charge-separated state. EPR is the method of choice to study electron transfer and the interaction of protein environment with redox-active cofactors. However, the spectra of organic cofactor radicals typically are not fully resolved and severely overlap at conventional X-band EPR. Even at Q-band EPR, this overlap is present and often a serious problem. As a result, there is a large variation of the reported EPR data and limited understanding of electronic structures of several redox-active cofactors. These serious problems can often be overcome by the excellent spectral resolution provided by high-frequency EPR (HF EPR). In this work, we study the electronic structure of the primary electron donor P 700 and the secondary electron acceptor A 1 of Photosystem I (PSI) using 130 GHz (D-band) EPR and Electron-Nuclear-Double-Resonance (ENDOR) spectroscopy. PSI was isotopically labeled with 15 N (I = $\frac{1/2}$) to avoid quadrupolar interactions in the most abundant nitrogen isotope 14 N (I = 1) and simplify the ENDOR spectra. ENDOR spectroscopy is central for determining the hyperfine coupling of nitrogen atoms of the two chlorophyll molecules comprising oxidized P 700 and the involvement of protein nitrogen atoms with reduced A 1 . While HF ENDOR of A 1 - allows identification of two nitrogen atoms, HF ENDOR of P 700 + still does not permit unique assignment of the recorded hyperfine couplings.

15N↗

Is the Kok effect a respiratory phenomenon? Metabolic insight using 13 C labeling in Helianthus annuus leaves

The Kok effect is a well-known phenomenon in which the quantum yield of photosynthesis changes abruptly at low light. This effect has often been interpreted as a shift in leaf respiratory metabolism and thus used widely to measure day respiration. However, there is still no formal evidence that the Kok effect has a respiratory origin. Here, both gas exchange and isotopic labeling were carried out on sunflower leaves, using glucose that was 13 C-enriched at specific C-atom positions. Position-specific decarboxylation measurements and NMR analysis of metabolites were used to trace the fate of C-atoms in metabolism. Decarboxylation rates were significant at low light (including above the Kok break point) and increased with decreasing irradiance below 100 µmol photons m –2 s –1 . The variation in several metabolite pools such as malate, fumarate or citrate, and flux calculations suggest the involvement of several decarboxylating pathways in the Kok effect, including the malic enzyme. Our results show that day respiratory CO 2 evolution plays an important role in the Kok effect. Furthermore, the increase in the apparent quantum yield of photosynthesis below the Kok break point is also probably related to malate metabolism, which participates in maintaining photosynthetic linear electron flow.

54 ENVIRONMENTAL SCIENCES↗

An automated workflow that generates atom mappings for large‐scale metabolic models and its application to Arabidopsis thaliana

SUMMARY Quantification of reaction fluxes of metabolic networks can help us understand how the integration of different metabolic pathways determines cellular functions. Yet, intracellular fluxes cannot be measured directly but are estimated with metabolic flux analysis (MFA), which relies on the patterns of isotope labeling of metabolites in the network. The application of MFA also requires a stoichiometric model with atom mappings that are currently not available for the majority of large‐scale metabolic network models, particularly of plants. While automated approaches such as the Reaction Decoder Toolkit (RDT) can produce atom mappings for individual reactions, tracing the flow of individual atoms of the entire reactions across a metabolic model remains challenging. Here we establish an automated workflow to obtain reliable atom mappings for large‐scale metabolic models by refining the outcome of RDT, and apply the workflow to metabolic models of Arabidopsis thaliana . We demonstrate the accuracy of RDT through a comparative analysis with atom mappings from a large database of biochemical reactions, MetaCyc. We further show the utility of our automated workflow by simulating 15 N isotope enrichment and identifying nitrogen (N)‐containing metabolites which show enrichment patterns that are informative for flux estimation in future 15 N‐MFA studies of A. thaliana . The automated workflow established in this study can be readily expanded to other species for which metabolic models have been established and the resulting atom mappings will facilitate MFA and graph‐theoretic structural analyses with large‐scale metabolic networks.

59 BASIC BIOLOGICAL SCIENCES↗

Hyperspectral Light Sheet Raman Imaging of Leaf Metabolism (Final Report)

This final technical report details the accomplishment and findings of a project that developed technology related to imaging metabolic processes in plants. The report gives technical details of the design, construction and characterization of a Raman microscope system capable of identifying chemical species using the wavelength shifts of scattered excitation light. Some of the unique aspects of the design include: use of a Bessel beam excitation source, which allow long excitation lines that are resistant to scattering in complex media such as plants; excitation at 785 nm to avoid fluorescence emission that can occur in photosynthetic organisms; and a flat optical design that makes construction and alignment significantly simpler. This project also used stable isotope labeling to look at photorespiratory flux in the leaves of three different types of plants that have different photosynthesis pathways. Gas chromatography–mass spectrometry was used to look at which metabolites and amino acids had altered oxygen, carbon and hydrogen uptake under various conditions of environmental oxygen. This generated a rich data set that is being further analyzed to understand metabolic pathways in plants. This project also used the natural fluorescence in sorghum and rice to conduct an extensive experiment across different developmental stages. Spectral differences were identified at most of the developmental stages and these can be attributed to differential pigment and pigment-protein complexes present in different relative abundances as the plant develops.

09 BIOMASS FUELS↗