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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Solid-phase Mn speciation in suspended particles along meltwater-influenced fjords of West Greenland

Manganese (Mn) is an essential micro-nutrient that can limit or, along with iron (Fe), co-limit phytoplankton growth in the ocean. Glacier meltwater is thought to be a key source of trace metals to high latitude coastal systems, but little is known about the nature of Mn delivered to glacially-influenced fjords and adjacent coastal waters. In this work, we combine in-situ dissolved Mn (dMn) measurements of surface waters with Mn K-edge X-ray absorption spectroscopy (XAS) data of suspended particles in four fjords of West Greenland. Data were collected from transects of up to 100 km in fjords with different underlying bedrock geology from 64 to 70°N. We found that dMn concentrations generally decreased conservatively with increasing salinity (from 80 to 120 nM at salinity < 8 to < 40 nM at salinities > 25). Dissolved Fe (dFe) trends in these fjords similarly declined with increasing distance from glacier outflows (declining from > 20 nM to < 8 nM). However, the dMn/dFe ratio increased rapidly likely due to the greater stability of dMn at intermediate salinities (i.e. 10–20) compared to rapid precipitation of dFe across the salinity gradient. The XAS data indicated a widespread presence of Mn(II)-rich suspended particles near fjord surfaces, with structures akin to Mn(II)-bearing phyllosilicates. However, a distinct increase in Mn oxidation state with depth and the predominance of birnessite-like Mn(IV) oxides was observed for suspended particles in a fjord with tertiary basalt geology. The similar dMn behaviour in fjords with different suspended particle Mn speciation (i.e., Mn(II)-bearing phyllosilicates and Mn(IV)-rich birnessite) is consistent with the decoupling of dissolved and particulate Mn and suggests that dMn concentrations on the scale of these fjords are controlled primarily by dilution of a freshwater dMn source rather than exchange between dissolved and particle phases. This work provides new insights into the Mn cycle in high latitude coastal waters, where small changes in the relative availabilities of dMn, dFe and macronutrients may affect the identity of the nutrient(s) proximally limiting primary production.

58 GEOSCIENCES↗
DOE OSTI2024

HERO WEC 2024 Hydraulic Configuration Deployment Data

The following submission includes raw and processed data from the in water deployment of NREL's Hydraulic and Electric Reverse Osmosis Wave Energy Converter (HERO WEC), in the form of parquet files, TDMS files, CSV files, bag files and MATLAB workspaces. This dataset was collected in March 2024 at the Jennette's pier test site in North Carolina. This submission includes the following: - Data description document (HERO WEC FY24 Hydraulic Deployment Data Descriptions.doc) - This document includes detailed descriptions of the type of data and how it was processed and/or calculated. - Processed MATLAB workspace - The processed data is provided in the form of a single MATLAB workspace containing data from the full deployment. This workspace contains data from all sensors down sampled to 10 Hz along with all array Value Added Products (VAPs). - MATLAB visualization scripts - The MATLAB workspaces can be visualized using the file "HERO_WEC_2024_Hydraulic_Config_Data_Viewer.m/mlx". The user simply needs to download the processed MATLAB workspaces, specify the desired start and end times and run this file. Both the .m and .mlx file format has been provided depending on the user's preference. - Summary Data - The fully processed data was used to create a summary data set with averages and important calculations performed on 30-minute intervals to align with the intervals of wave resource data reported from nearby CDIP ocean observing buoys located 20km East of Jennette's pier and 40km Northeast of Jennette's pier. The wave resource data provided in this data set is to be used for reference only due the difference in water depth and proximity to shore between the Jennette's pier test site and the locations of the ocean observing buoys. This data is provided in the Summary Data zip folder, which includes this data set in the form of a MATLAB workspace, parquet file, and excel spreadsheet. - Processed Parquet File - The processed data is provided in the form of a single parquet file containing data from all HERO WEC sensors collected during the full deployment. Data in these files has been down sampled to 10 Hz and all array VAPs are included. - Interim Filtered Data - Raw data from each sensor group partitioned into 30-minute parquet files. These files are outputs from an intermediate stage of data processing and contain the raw data with no Quality Control (QC) or calculations performed in a format that is easier to use than the raw data. - Raw Data - Raw, unprocessed data from this deployment can be found in the Raw Data zip folder. This data is provided in the form of TDMS, CSV, and bag files in the original format output by the MODAQ system. - Python Data Processing Script - This links to an NREL public github repository containing the python script used to go from raw data to fully processed parquet files. Additional documentation on how to use this script is included in the github repository. This data set has been developed by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided by the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy Water Power Technologies Office.

16 TIDAL AND WAVE POWER↗
DOE OSTI2025

Review: Recent advances of ToF-SIMS for environmental analysis and imaging

Background: Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful surface analysis technique, initially developed and applied in inorganic materials and semiconductors. In past decades, ToF-SIMS has attracted more attention in its analysis capabilities of organic materials, with increased applications in biology, medical, and health development. It has also become a versatile and effective tool in environmental analysis due to its high mass resolution, mass accuracy, and depth profiling. Results: In this review, we first give an overview of the principle of ToF-SIMS and follow with recent ToF-SIMS applications in exemplary environmental study cases, including atmospheric aerosol, soil, water, plant, and organic solvent analysis. Moreover, sample preparation techniques are summarized in relation to corresponding environmental applications. Specifically, we call attention to ToF-SIMS investigations showcasing studies in surface chemical compositions, images, and depth profile analysis. These findings emphasize the important role of interfacial chemistry in environmental processes and provide valuable insights into dynamic processes, such as chemical transformation, particle formation, plant biology, and microbial inspired biotechnology development. The mass spectral imaging results acquired by ToF-SIMS offer a deeper understanding of intermediate stages and transient phases for environmental specimens. Significance: In situ and operando imaging offer new possibilities in studying phenomena in real time with high spatial resolution. Furthermore, it is anticipated that more research groups will use ToF-SIMS in environmental research given recent advances in measurement capabilities and surging needs in chemical mapping of complex analytes and systems.

Aerosol↗
DOE OSTI2023

A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation

High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e., the key kinetically limiting half-reaction in several electrochemical energy conversion technologies, including green hydrogen generation. We compare the activity of the (001) facet of LaCr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 O 3-δ with the parent compounds (single B-site in the ABO 3 perovskite). While the single B-site perovskites roughly follow the expected volcano-type activity trends, the HEO clearly outperforms all of its parent compounds with 17 to 680 times higher currents at a fixed overpotential. As all samples were grown as an epitaxial layer, our results indicate an intrinsic composition–function relationship, avoiding the effects of complex geometries or unknown surface composition. In-depth X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during the adsorption of reaction intermediates. The surprisingly high OER activity demonstrates that HEOs are a highly attractive, earth-abundant material class for high-activity OER electrocatalysts, possibly allowing the activity to be fine-tuned beyond the scaling limits of mono- or bimetallic oxides.

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

More Realistic Intermediate Depth Dry Firn Densification in the Energy Exascale Earth System Model (E3SM)

Abstract Earth system models account for seasonal snow cover, but many do not accommodate the deeper snowpack on ice sheets (aka firn) that slowly transforms to ice under accumulating snowfall. To accommodate and resolve firn depths of up to 60 m in the Energy Exascale Earth System Model's land surface model (ELM), we add 11 layers to its snowpack and evaluate three dry snow compaction equations in multi‐century simulations. After comparing results from ELM simulations (forced with atmospheric reanalysis) with empirical data, we find that implementing into ELM a two‐stage firn densification model produces more accurate dry firn densities at intermediate depths of 20–60 m. Compared to modeling firn using the equations in the (12 layer) Community Land Model (version 5), switching to the two‐stage firn densification model (with 16 layers) significantly decreases root‐mean‐square errors in upper 60 m dry firn densities by an average of 41 kg m −3 (31%). Simulations with three different firn density parameterizations show that the two‐stage firn densification model should be used for applications that prioritize accurate upper 60 m firn air content (FAC) in regions where the mean annual surface temperature is greater than roughly −31°C. Because snow metamorphism, firn density, and FAC are major components in modeling ice sheet surface albedo, melt water retention, and climatic mass balance, these developments advance broader efforts to simulate the response of land ice to atmospheric forcing in Earth system models.

58 GEOSCIENCES↗
DOE OSTI2023

Spatial Study 2022: Water Column, Sediment, and Total Ecosystem Respiration Rates across the Yakima River Basin, Washington, USA (v2)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin and is associated with the manuscript “Sediment-associated processes account for most of the spatial variation in ecosystem respiration in the Yakima River basin” submitted to Nature Communications Earth & Environment (Garayburu-Caruso et al., in review). The dataset provides ecosystem metabolism estimates generated from streamMetabolizer (Appling et al.; 2018) using data collected during the same five-week period at 48 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Additionally, it includes the scripts used for the analysis and producing the figures in the manuscript. The contents include streamMetabolizer inputs and outputs and additional relevant data needed to generate the main manuscript results. The data included are: total ecosystem respiration, water respiration, calculated sediment-associated respiration, gross primary production outputs from the river corridor model for the Yakima River Basin, median grain size (d50), depth, dissolved oxygen, water temperature, pressure, and annual oxygen consumption. The associated GitHub repository can be found at https://github.com/river-corridors-sfa/SSS_metabolism. Samples collected during this study were labeled as “Second Spatial Study” or “SSS.” Raw time series sensor data, total suspended solids, and depth data from SSS were published at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1969566. A subset of data from the SSS samples were published in the contiguous United States (CONUS)-Scale Model-Sample (CM) study data package available at https://data.ess-dive.lbl.gov/view/doi:10.15485/1923689 that presents data from across the CONUS. They include dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC), total nitrogen (TN), grain size, aerobic sediment respiration, dissolved oxygen (DO), and temperature. Parent IDs and Site IDs are consistent between the SSS and CM data packages, and they can be mapped directly so data across packages can be used together. Field metadata for the samples in this da This dataset is comprised of one main data folder with four subfolders. The main data folder contains of (1) file-level metadata; (2) data dictionary; (3) total/water column/sediment respiration; (4) gross primary production (GPP); (5) median grain size (d50); and (6) annual oxygen consumption. The “Figures” subfolder contains the figures used in the paper and all intermediate files (including geospatial files). The “Published_Data” contains a readme directing the user to download the public data to reproduce analyses and figures. The “Scripts” folder contains all scripts used in the analyses that were not part of running StreamMetabolizer. Lastly, the “Stream_Metabolizer” folder contains all files associated with running StreamMetabolizer including (1) model input files, (2) model output files, (3) processing scripts, (4) histogram plots of the outputs, and (5) an R project. All files are .csv, .pdf, .R, .Rmd, .Rproj, .html, .png, .txt, .qgz, .cpg, .dbf, .prj, .shp, .shp.ea.iso.xml, .shp.iso.xml, .shx, .sbn. ta package can be found at either link. We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Oxygen Evolution on Iron Oxide Nanoparticles: The Impact of Crystallinity and Size on the Overpotential

The oxygen evolution reaction (OER) is a critical reaction in electrolysis and photoelectrolysis of water to generate and store clean energy. Therefore, the development of low-cost and efficient electrocatalysts for the OER is of great scientific and technological importance. Although promising iron oxide-based electrocatalysts have been recently developed for the OER, an in-depth experimental and theoretical analysis of the OER mechanism on iron oxide-based electrocatalysts is still needed to provide guidelines to optimize the performance of iron oxide-based electrocatalysts further. To address this need, we synthesized a series of monodisperse iron oxide nanoparticles to analyze their intrinsic OER activities. Using nanoparticles of the same size but different crystallinity, we show that amorphous iron oxide nanoparticles have better OER activity than crystalline ones. The size effect studies further revealed that the edge/defect sites are the active sites for the OER. Density functional theory calculations demonstrated that the edge/defect sites provide bridge sites to adsorb OER intermediates, resulting in low OER overpotential. These calculations confirm that the high OER activity of amorphous nanoparticles results from a high concentration of defect sites on their surface. These results provide novel strategies to increase the performance of iron oxide-based and likely other oxide-based OER electrocatalysts.

Electrochemistry↗
DOE OSTI2020

Pervasive low-velocity layer atop the 410-km discontinuity beneath the northwest Pacific subduction zone: Implications for rheology and geodynamics

Regional triplication waveforms of five intermediate-depth events are modeled to simultaneously obtain the compressional (P) and shear (SH) wave velocity structure beneath northwestern Pacific subduction zone. Both the P- and SH-wave velocity models for three different sub-regions show a low-velocity layer (LVL) with a thickness of ~55-80 km lying above the 410-km discontinuity with a ~900 km lateral extent from the Japan Sea to the northeastern Asian continental margin. With the dihedral angle approaching to zero around 400 km, a minute amount of melt atop the 410-km discontinuity caused by the hydrous slab might completely wet olivine grain boundaries and result in a low seismic velocity layer in this specific subduction zone. This mechanism suggests that the 410-LVL is a low viscosity zone that would partially decouple the upper mantle from the transition zone. We infer that the widespread 410-LVL provides evidence for a water-bearing mantle transition zone beneath the western Pacific subduction zone.

58 GEOSCIENCES↗
DOE OSTI2020

Thermocatalytic Heat Pipes for Geothermal Resource Recovery

Heat pipes are an important technology that allow orders of magnitude faster heat transfer than simple conduction. However, operating principles in heat pipes place fundamental bounds on their performance (critical heat flux and efficiency). Conventional heat pipe functionality is inherently tied to vaporization and condensation of the working fluid charged in the heat pipe. These fluids each have different operating temperature ranges based on the capillary, entrainment, sonic, and boiling limits of the heat pipe design. These limits, typically the capillary limit, dictate the maximum heat flux a heat pipe can carry, and most importantly for geothermal systems, the distance over which the pipes can operate (100 to 200 m maximum under optimum conditions). A thermocatalytic heat pipe breaks the inherent limitations of phase change thermo- and hydrodynamics and can transform heat pipe technology as a potentially more efficient means of extracting heat from a geothermal resource. The thermocatalytic heat pipe uses a working fluid to transport both sensible and chemical heat. An endothermic chemical reaction at depth removes heat from the reservoir and produces reactive intermediates, which are transported to the surface and used to run a reverse exothermic reaction that releases heat for use in power generation or other useful purposes. This technology offers two distinct advantages over conventional geothermal heat recovery technologies: (1) lower heat loss to the rock outside of the geothermal reservoir, and (2) higher heat transfer rates to the well field within the geothermal reservoir. Both advantages offer opportunity to reduce risks and lower costs of geothermal energy recovery. In this report, we discuss an initial effort to assess the efficacy and limitations of this technology for extracting heat from both porous/permeable and nominally impermeable geothermal reservoirs. Numerical simulation capabilities of the STOMP-GT code were enhanced to enable simulations of thermochemical heat pipes traversing geothermal reservoirs. An array of potential thermochemical reaction systems was evaluated and screened. Of these, an ethanol dehydration reaction was most promising in the vapor-liquid reaction set. A solid-phase dehydration reaction (CuSO4·5H2O) showed the highest reaction enthalpy per unit volume but would require development of a nonaqueous carrier fluid to implement it in a heat pipe. Subsurface reservoir simulations predicted long-term performance of the heat pipes for each geothermal reservoir type. The performance of U-shaped wells and coaxial wells was evaluated for a suite of reactions for both hydrothermal and hot dry rock reservoirs and was compared with a baseline case of simply pumping water through the wells. The heat pipe technology was additionally evaluated for an enhanced geothermal system (EGS) with an injection borehole, production borehole, and intervening hydraulically conductive fracture. All reservoir types showed significant improvement in heat recovered over a 20-year operating period ranging from a 1.8X increase for the hot dry rock case to more than 2.5X more energy recovered for the EGS case.

15 GEOTHERMAL ENERGY↗
DOE OSTI2024

Water foraging with dynamic roots in E3SM; The role of roots in terrestrial ecosystem memory on intermediate timescales (Final Technical Report)

Terrestrial ecosystems can show sustained responses to stress events that may last for years after the initial perturbation. This phenomenon is referred to as legacy or memory and it emerges from a set of ecosystem processes that are poorly captured by Earth System and Land Surface Models. Consequently, these models struggle to predict the impact that extreme climate events have on surface energy, carbon and hydrological exchange once a stressor such as drought has relaxed or in response to repeated exposure to stress. In this project, we set out to test how the addition of dynamic root profiles in land surface models impact the capacity for Earth System Models, such as the Department of Energy’s E3SM, to capture realistic legacy effects. Observations have shown that vegetation shifts their root profiles during stress events to forage for water and these altered root profiles may take years to relax back to the initial state. We hypothesized that the alteration of the belowground root structures may be a source of terrestrial ecosystem legacy that is missing from models. To test this idea we undertook three core activities. (1) We developed a global-scale analysis of the impact of dynamic roots on ecosystem legacy building from a recently developed dynamic root module. (2) We developed new root dynamics in the DOE’s Energy Land Model (ELM) that allowed not only root profiles to shift their profile but also simultaneously alter carbon allocation to fine root pools. We then tested the impact of these new dynamics with intensive sensitivity analysis at four long-term AmeriFlux sites. (3) We undertook detailed isotopic analysis of tree rings from these AmeriFlux sites to assess ecophysiological and ecohydrological legacy to stress events that can be used to benchmark the sensitivity experiments with ELM. From these core activities, we report the following key findings. Firstly, on a global scale, the addition of dynamic roots led to chronically water-stressed ecosystems recovering faster to climate stress while wetter ecosystem showed enhanced legacy. This is because across ecosystems, stress events were almost universally associated with water shortages that led to the development of deeper root profiles. These deeper root profiles proved beneficial for recovery from drought stress. While the root dynamics did not universally improve the modeled representation of legacy it showed complex transient dynamics that emerge from the addition of dynamic roots. Secondly, the sensitivity analysis illustrated long term shifts in rooting depths away from the prescribed default profile suggesting that initializing of root profiles could benefit from spin-up simulations that converge on locally optimized root profiles. In addition, by enabling dynamic allocation some of the sites predicted unrealistically low allocation to roots (and high allocation to leaves). While these changes did not dramatically alter modeled gross primary productivity, they illustrated that without more sophisticated root processes in models, there is little penalty to dramatically disinvest in roots. Thirdly, the isotopic analysis of tree rings showed highly distinct legacy responses across species and sites. For example, T. canadensis showed reduced transpiration the year after stress events illustrated by sustained elevated $\delta^{18}$O. In contrast, A saccharum displayed elevated $\delta^{13}$C associated with reduced stomatal conductance in response to the previous years’ stress event. These geochemical signatures of legacy were present despite tree growth returning to normal the year after the stress. The results show the importance of species-level dynamics in legacy that are absent in modeling that assumes common traits within plant functional types. In summary, the work here established new avenues to explore root dynamics in models while illustrating how additional root processes are needed before dynamic carbon allocation can be implemented. Lastly, this project provided mentorship to a postdoctoral fellow, training for an early career scientist and multiple undergraduate students recruited from a minority serving institution.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Influence of covariance of aerosol and meteorology on co-located precipitating and non-precipitating clouds over the Indo-Gangetic Plain

Aerosol–cloud–precipitation interaction (ACPI) plays a pivotal role in the global and regional water cycle and the earth's energy budget; however, it remains highly uncertain due to the different underlying physical mechanisms. Therefore, this study aims to systematically analyze the effects of aerosols and meteorological factors on ACPI in the co-located precipitating clouds (PCs) and non-precipitating clouds (NPCs) in winter and summer seasons by employing the long-term (2001–2021) retrievals from the Moderate Resolution Imaging Spectroradiometer (MODIS) and Tropical Rainfall Measuring Mission (TRMM) coupled with the National Center for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis-II datasets over the Indo-Gangetic Plain (IGP). The results exhibit a decadal increase in aerosol optical depth (AOD) over Lahore (5.2 %), Delhi (9 %), Kanpur (10.7 %), and Gandhi College (22.7 %) and a decrease over Karachi (-1.9 %) and Jaipur (-0.5 %). The most stable meteorology with high values of lower-tropospheric stability (LTS) is found in both seasons over Karachi. In the summer season, the occurrence frequency of clouds is high (74 %) over Gandhi College, 60 % of which are PCs. Conversely, the lowest number of PCs is found over Karachi. Similarly, in the winter season, the frequency of cloud occurrence is low over Karachi and high over Lahore and Gandhi College. The analysis of cloud top pressure (CTP) and cloud optical thickness (COT) indicates high values of cloud fraction (CF) for thick and high-level clouds over all study areas except Karachi. The microphysical properties such as cloud effective radius (CER) and cloud droplet number concentration (CDNC) bear high values (CER ≳ 15 µm and CDNC ≳ 50 cm -3 ) for both NPCs and PCs in summer. The AOD–CER correlation is good (weak) for PCs (NPCs) in winter. Similarly, the sensitivity value of the first indirect effect (FIE) is high (ranging from 0.2 ± 0.13 to 0.3 ± 0.01 in winter and from 0.19 ± 0.03 to 0.32 ± 0.05 in summer) for PCs and low for NPCs. The sensitivity value for the second indirect effect (SIE) is relatively higher (such as 0.6 ± 0.14 in winter and 0.4 ± 0.04 in summer) than FIE. Sensitivity values of the aerosol-cloud interaction (ACI) are low (i.e., -0.06 ± 0.09) for PCs in summer. Furthermore, the precipitation rate (PR) exhibits high values in the summer season, primarily due to the significant contribution from optically thick clouds with lower CDNC (≲ 50 cm -3 ) and larger CER and the intermediate contribution from optically thick clouds with higher CDNC ( ≳ 50 cm -3 ).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗