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NASA NTRS2002

Trends in lignin modification: a comprehensive analysis of the effects of genetic manipulations/mutations on lignification and vascular integrity

A comprehensive assessment of lignin configuration in transgenic and mutant plants is long overdue. This review thus undertook the systematic analysis of trends manifested through genetic and mutational manipulations of the various steps associated with monolignol biosynthesis; this included consideration of the downstream effects on organized lignin assembly in the various cell types, on vascular function/integrity, and on plant growth and development. As previously noted for dirigent protein (homologs), distinct and sophisticated monolignol forming metabolic networks were operative in various cell types, tissues and organs, and form the cell-specific guaiacyl (G) and guaiacyl-syringyl (G-S) enriched lignin biopolymers, respectively. Regardless of cell type undergoing lignification, carbon allocation to the different monolignol pools is apparently determined by a combination of phenylalanine availability and cinnamate-4-hydroxylase/"p-coumarate-3-hydroxylase" (C4H/C3H) activities, as revealed by transcriptional and metabolic profiling. Downregulation of either phenylalanine ammonia lyase or cinnamate-4-hydroxylase thus predictably results in reduced lignin levels and impaired vascular integrity, as well as affecting related (phenylpropanoid-dependent) metabolism. Depletion of C3H activity also results in reduced lignin deposition, albeit with the latter being derived only from hydroxyphenyl (H) units, due to both the guaiacyl (G) and syringyl (S) pathways being blocked. Apparently the cells affected are unable to compensate for reduced G/S levels by increasing the amounts of H-components. The downstream metabolic networks for G-lignin enriched formation in both angiosperms and gymnosperms utilize specific cinnamoyl CoA O-methyltransferase (CCOMT), 4-coumarate:CoA ligase (4CL), cinnamoyl CoA reductase (CCR) and cinnamyl alcohol dehydrogenase (CAD) isoforms: however, these steps neither affect carbon allocation nor H/G designations, this being determined by C4H/C3H activities. Such enzymes thus fulfill subsidiary processing roles, with all (except CCOMT) apparently being bifunctional for both H and G substrates. Their severe downregulation does, however, predictably result in impaired monolignol biosynthesis, reduced lignin deposition/vascular integrity, (upstream) metabolite build-up and/or shunt pathway metabolism. There was no evidence for an alternative acid/ester O-methyltransferase (AEOMT) being involved in lignin biosynthesis.The G/S lignin pathway networks are operative in specific cell types in angiosperms and employ two additional biosynthetic steps to afford the corresponding S components, i.e. through introduction of an hydroxyl group at C-5 and its subsequent O-methylation. [These enzymes were originally classified as ferulate-5-hydroxylase (F5H) and caffeate O-methyltransferase (COMT), respectively.] As before, neither step has apparently any role in carbon allocation to the pathway; hence their individual downregulation/manipulation, respectively, gives either a G enriched lignin or formation of the well-known S-deficient bm3 "lignin" mutant, with cell walls of impaired vascular integrity. In the latter case, COMT downregulation/mutation apparently results in utilization of the isoelectronic 5-hydroxyconiferyl alcohol species albeit in an unsuccessful attempt to form G-S lignin proper. However, there is apparently no effect on overall G content, thereby indicating that deposition of both G and S moieties in the G/S lignin forming cells are kept spatially, and presumably temporally, fully separate. Downregulation/mutation of further downstream steps in the G/S network [i.e. utilizing 4CL, CCR and CAD isoforms] gives predictable effects in terms of their subsidiary processing roles: while severe downregulation of 4CL gave phenotypes with impaired vascular integrity due to reduced monolignol supply, there was no evidence in support of increased growth and/or enhanced cellulose biosynthesis. CCR and CAD downregulation/mutations also established that a depletion in monolignol supply reduced both lignin contents supply reduced both lignin contents and vascular integrity, with a concomitant shift towards (upstream) metabolite build-up and/or shunting.The extraordinary claims of involvement of surrogate monomers (2-methoxybenzaldehyde, feruloyl tyramine, vanillic acid, etc.) in lignification were fully disproven and put to rest, with the investigators themselves having largely retracted former claims. Furthermore analysis of the well-known bm1 mutation, a presumed CAD disrupted system, apparently revealed that both G and S lignin components were reduced. This seems to imply that there is no monolignol specific dehydrogenase, such as the recently described sinapyl alcohol dehydrogenase (SAD) for sinapyl alcohol formation. Nevertheless, different CAD isoforms of differing homology seem to be operative in different lignifying cell types, thereby giving the G-enriched and G/S-enriched lignin biopolymers, respectively. For the G-lignin forming network, however, the CAD isoform is apparently catalytically less efficient with all three monolignols than that additionally associated with the corresponding G/S lignin forming network(s), which can more efficiently use all three monolignols. However, since CAD does not determine either H, G, or S designation, it again serves in a subsidiary role-albeit using different isoforms for different cell wall developmental and cell wall type responses.The results from this analysis contrasts further with speculations of some early investigators, who had viewed lignin assembly as resulting from non-specific oxidative coupling of monolignols and subsequent random polymerization. At that time, though, the study of the complex biological (biochemical) process of lignin assembly had begun without any of the (bio)chemical tools to either address or answer the questions posed as to how its formation might actually occur. Today, by contrast, there is growing recognition of both sophisticated and differential control of monolignol biosynthetic networks in different cell types, which serve to underscore the fact that complexity of assembly need not be confused any further with random formation. Moreover, this analysis revealed another factor which continues to cloud interpretations of lignin downregulation/mutational analyses, namely the serious technical problems associated with all aspects of lignin characterization, whether for lignin quantification, isolation of lignin-enriched preparations and/or in determining monomeric compositions. For example, in the latter analyses, some 50-90% of the lignin components still cannot be detected using current methodologies, e.g. by thioacidolysis cleavage and nitrobenzene oxidative cleavage. This deficiency in lignin characterization thus represents one of the major hurdles remaining in delineating how lignin assembly (in distinct cell types) and their configuration actually occurs.

Review, Academic↗

NASA NTRS2019

Overview of Heatshield for Extreme Entry Environment Technology (HEEET)

The objective of the Heatshield for Extreme Entry Environment Technology (HEEET) projects is to mature a 3-D Woven Thermal Protection System (TPS) to Technical Readiness Level (TRL) 6 to support future NASA missions to destinations such as Venus and Saturn. Destinations that have extreme entry environments with heat fluxes > 3500 W/cm2 and pressures up to 5 atmospheres, entry environments that NASA has not flown since Pioneer-Venus and Galileo. The scope of the project is broad and can be split into roughly four areas, Manufacturing/Integration, Structural Testing and Analysis, Thermal Testing and Analysis and Documentation. Manufacturing/Integration covers from raw materials, piece part fabrication to final integration on a 1-meter base diameter 45-degree sphere cone Engineering Test Unit (ETU). A key aspect of the project was to transfer as much of the manufacturing technology to industry in preparation to support future mission infusion. The forming, infusion and machining approaches were transferred to Fiber Materials Inc. and FMI then fabricated the piece parts from which the ETU was manufactured. The base 3D-woven material consists of a dual layer weave with a high-density outer layer to manage recession in the system and a lower density, lower thermal conductivity inner layer to manage the heat load. At the start of the project it was understood that due to weaving limitations the heat shield was going to be manufactured from a series of tiles. And it was recognized that the development of a seam solution that met the structural and thermal requirements of the system was going to be the most challenging aspect of the project. It was also recognized that the seam design would drive the final integration approach and therefore the integration of the ETU was kept in-house within NASA. A final seam concept has been successfully developed and implemented on the ETU. The structural testing and analysis covers from characterization of the different layers of the infused material as functions of weave direction and temperature to sub-component level testing such as 4pt bend testing at sub-ambient and elevated temperature and culminates in testing of the ETU results from which will validate the structural models developed using the element and sub-component level tests. Given the seam has to perform both structurally and aerothermally during entry a novel 4pt bend test fixture was developed allowing articles to be tested while the front surface is heated with a laser. These tests are being utilized to establish the systems structural capability during entry.A broad range of aerothermal tests (arcjet tests) were performed to develop material response models for predicting the required TPS thickness to meet a missions needs and to evaluate failure modes and establish the capability of the system. The final aspect of the project is to develop a comprehensive Design and Data Book such that a future mission will have the information necessary to adopt the technology. This presentation will provide an overview for each of these areas and argue that HEEET has successfully achieved TRL 6.

HEEET↗

NASA NTRS2018

Overview of Heatshield for Extreme Entry Environment Technology (HEEET) Project

The objective of the Heatshield for Extreme Entry Environment Technology (HEEET) projects is to mature a 3-D Woven Thermal Protection System (TPS) to Technical Readiness Level (TRL) 6 to support future NASA missions to destinations such as Venus and Saturn. Destinations that have extreme entry environments with heat fluxes up to 5000 watts per square centimeter and pressures up to 5 atmospheres, entry environments that NASA has not flown since Pioneer-Venus and Galileo. The scope of the project is broad and can be split into roughly four areas, Manufacturing/Integration, Structural Testing and Analysis, Thermal Testing and Analysis and Documentation. Manufactruing/Integration covers from raw materials, piece part fabrication to final integration on a 1-meter base diameter 45-degree sphere cone Engineering Test Unit (ETU). A key aspect of the project was to transfer as much of the manufacturing technology to industry in preparation to support future mission infusion. The forming, infusion and machining approaches were transferred to Fiber Materials Inc. and FMI then fabricated the piece parts from which the ETU was manufactured. The base 3D-woven material consists of a dual layer weave with a high density outer layer to manage recession in the system and a lower density, lower thermal conductivity inner layer to manage the heat load. At the start of the project it was understood that due to weaving limitations the heat shield was going to be manufactured from a series of tiles. And it was recognized that the development of a seam solution that met the structural and thermal requirements of the system was going to be the most challenging aspect of the project. It was also recognized that the seam design would drive the final integration approach and therefore the integration of the ETU was kept in-house within NASA. A final seam concept has been successfully developed and implemented on the ETU and will be discussed. The structural testing and analysis covers from characterization of the different layers of the infused material as functions of weave direction and temperature, to sub-component level testing such as 4-pt bend testing at sub-ambient and elevated temperature. ETU test results are used to validate the structural models developed using the element and sub-component level tests. Given the seam has to perform both structurally and aerothermally during entry a novel 4-pt bend test fixture was developed allowing articles to be tested while the front surface is heated with a laser. These tests are intended to establish the system's structural capability during entry. A broad range of aerothermal tests (arcjet tests) are being performed to develop material response models for predicting the required TPS thickness to meet a mission's needs and to evaluate failure modes. These tests establish the capability of the system and assure robustness of the system during entry. The final aspect of the project is to develop a comprehensive Design and Data Book such that a future mission will have the information necessary to adopt the technology. This presentation will provide an overview and status of the project and describe the status of the tehnology maturation level for the inner and outer planet as well as earth entry sample return missions.

Ellerby, Don↗

NASA NTRSDate not supplied

Solid-state Architecture Batteries for Enhanced Rechargeability and Safety for Electric Aircraft

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria. The performance metrics for eVTOL craft are at least 2 times greater than those of electric automobiles. Furthermore, safety is essential for operation of commercial electric aerovehicles. Preliminary systems level analysis has indicated that there are five key properties which must be optimized for successful implementation of battery systems. Those five key criteria are: safety, energy density, power, packaging design and scalability. Current state-of-the-art (SOA) lithium-ion batteries meet or exceed the requirements for electric aviation in the areas of power and scalability, yet are insufficient in the key performance criteria of energy, safety and packaging design. The SABERS concept proposes a battery that meets all five key performance criteria through development of a solid-state architecture battery utilizing high energy density and power density sulfur-selenium cathode with a lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. This cathode will be developed by implementing NASA patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte will be used as a safe, non-flammable replacement to the highly flammable liquid organic electrolytes currently used in SOA lithium-ion batteries. This solid-state lithium-sulfur-selenium cell will be designed into a serial stacking configuration to enable dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, reducing the amount of interfaced connections for the cell, and minimizing the cooling requirements for the cell. Lastly, optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures from 0 °C to 150 °C which provides the required energy density, discharge rates, and inherent safety to meet the strict aerospace performance criteria. This presentation will show initial results that demonstrate the SABERS Team has developed a composite carbon-sulfur cathode which exceeds 1100 Wh/kg at a discharge rate of 0.4C, and 804 Wh/kg at a discharge rate of 1C. Additionally, this presentation will show the SABERS Team multiscale computational modeling approach and has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM is on the 1-10 µm scale and provides electromechanical and grain interactions for predictive design guidelines for the experimental team to follow.

Urban Air Mobility (UAM) Vehicles↗

NASA NTRSDate not supplied

Computational Modeling Development of Solid-state Architecture Batteries for Enhanced Rechargeability and Safety for Electric Aircraft

Urban Air Mobility (UAM) Vehicles↗

NASA NTRS2024

Flight Mechanics Modeling and Simulation of the Earth Entry System

Introduction: The Mars Sample Return (MSR) Campaign being planned by NASA and ESA has the ambitious goal to return Mars samples back to Earth. This international collaboration had developed a concept of operations that included a ESA-designed Earth Return Orbiter (ERO) and NASA-designed Capture, Containment, and Return System (CCRS). The Earth Entry System (EES), consisting of a protective aeroshell that houses the samples as well as sample containment vessels, would conduct entry, descent, and landing (EDL) on a direct Earth trajectory. The EES would enter on a spin-stabilized ballistic trajectory with the goal to passively achieve aerodynamic stability throughout all regions of flight. The EDL sequence would end with the EES impacting the soft playa soil of the Utah Test and Training Range (UTTR). As of the submission of this abstract, the MSR campaign is undergoing a re-architecture leading to a pause in EES development. However, the novel approaches developed in flight mechanics modeling and simulation can significantly benefit the greater IPPW community in the development of Earth return vehicles. This paper will present the latest state of EES flight mechanics modeling and simulation. The paper will highlight the simulation architecture developed and key lessons learned from understanding of EDL trajectory sensitivities. Modeling and Simulation: Figure 1 provides a high-level concept of operations for the approach, entry, descent, and landing (AEDL) phase of the CCRS-portion of MSR. The objective of EES flight mechanics is to model and simulate the EES trajectory from ERO separation to ground impact at UTTR. A variety of flight mechanics simulation models were utilized to model both exo-atmopsheric and atmospheric portions of flight. 42, a 6-DOF simulation developed at Goddard Space Flight Center, is utilized for propagating the attitude of EES during exo-atmospheric flight. 42 allows for a variety of spin eject mechanism scenarios to be simulated for analysis. 10 minutes prior to entry, the 42 states are handed off to the EDL sims. The prime EDL sim utilized by EES is the Program to Optimize Simulated Trajectories II (POST2), a 6-DOF sim developed at Langley Research Center, and the independent verification and validation EDL sim utilized is DSENDS, a 6-DOF sim developed at Jet Propulsion Laboratory. Figure 2 provides a visualization of the flight mechanics simulation model flow through various points in the AEDL phase. Due to the existence of a variety of sim models, the EES flight mechanics team developed processes for data hand-off. These processes included the development of a centralized coordinate frame document, utilization of a single, centralized simulation input document for all sims to reference, and hand-off files containing both the technical data to be ingested by other flight mechanics sims as well as annotations of modeling assumptions utilized to generate the data. Figure~\ref{fig:post2simarchitecture} provides an overview of the POST2 sim architecture wherein POST2 ingests numerous subsystem models and input files. The dispersed state file generated by MONTE provides the position/velocity state of the trajectory while the 42 Handoff file provides the attitude. The aerodynamics database, delivered by the EES aeroscience team, is utilized to simulate the aerodynamic forces and moments experienced during EDL. A custom atmosphere model, developed by EES atmosphere team, is utilized to simulate the anticipated atmosphere environment around the region of Earth through which the EES trajectory flys. These inputs and subsystem models can be varied depending on the AEDL flight mechanics scenario being simulated. Monte Carlo simulations are utilized to generate statistical AEDL performance metrics in the form of scorecards and violin plots. Furthermore, outputs from the POST2 simulation are utilized for follow-on analyses including aerothermal and landing performance. \section{Flight Mechanics Lessons Learned} Though the EES flight mechanics team uncovered a variety of lessons learned through the analysis conducted to support CCRS through preliminary design review, this paper will highlight the most important lessons. A key AEDL performance goal is to ensure the landing footprint of EES remains on the UTTR south range. A common modeling strategy used in EDL analysis is One-Variable-At-a-Time (OVAT). OVAT analysis provides insight into the key drivers that affect AEDL performance metrics. Figure 3 shows the landing ellipses for single dispersion sources as compared to the baseline aggregate of all dispersions. The figure shows that atmosphere winds alone dominate the size of the footprint ellipse (note: EES does not use a parachute unlike previous Earth-return missions and is in wind-driven free fall for ~5min). The significance of the wind led the EES flight mechanics team to pursue the development of a Custom Atmosphere Model [4], in lieu of EarthGRAM [1], built on actual radiosonde wind measurements around the UTTR-region. This decision was driven by the realism in the generated footprint ellipses and lessons-learned from Stardust [5]. These findings will be invaluable for future Earth-return missions in providing an early understanding of the key drivers affecting footprint size and modeling considerations for which to account. Another lesson learned is tied to the AEDL performance goal of achieving passive stability throughout all regions of flight. It is well understood that blunt-body aeroshells are less stable as they transition from supersonic to subsonic. Eliminating a backshell does help improvestability; however, other phenomena such as roll-induced instability during terminal descent can still arise. The EES flight mechanics team developed stability metrics as tools to better understand the causes of and better predict the onset of dynamic instability. These tools were built upon analytical models developed by Jaffe [3] and Murphy [2]. The tools were shown to both be very accurate in correlation with actual unstable cases and useful in developing stability margin policies based on the vehicle design and simulation considerations (e.g. sphere-cone angle change, mass change, wind turbulence). These tools allowed for the current EES design to demonstrate the ability to achieve passive stability and can be an invaluable tool for consideration in the design of parachute-less Earth-return vehicles.

Rohan Deshmukh↗

NASA NTRSDate not supplied

Solid-state Architecture Batteries for Enhanced Rechargeability and Safety (SABERS) for Extended Deep Space Applications

Extended duration deep space missions as well as permanent space habitats face numerous technical challenges, key among them is energy generation and energy storage. There are considerable monetary and technical barriers to the generation of power in space. Therefore, it is important to store and be able to access power in an efficient and safe manner over a large number of cycles. Energy storage and in particular, batteries, are vital to the operation of next-generation extraterrestrial shuttles, rovers, habitats and extravehicular activity (EVA) space suits. The performance metrics for extended duration space missions are at least 2 times greater than those set for terrestrial applications such as electric automobiles. Furthermore, safety is essential for operation of space missions particularly involving astronauts such as shuttles, habitats and EVA space suits. Preliminary systems level analysis has indicated that there are five key properties which must be optimized for successful implementation of battery systems. Those five key criteria are: safety, energy density, power, packaging design and scalability. Current state-of-the-art (SOA) lithium-ion batteries can meet or exceed the requirements for certain space applications in the areas of power and scalability, yet are insufficient in the key performance criteria of energy, safety and packaging design. The SABERS concept proposes a battery that meets all five key performance criteria through development of a solid-state architecture battery utilizing high capacity sulfur-selenium cathode and lithium metal anode. The combination of sulfur and selenium offers a balanced energy-to-power density ratio, which can be tailored to the specific application by altering the stoichiometric ratios of sulfur to selenium. This hybrid cathode will be developed by implementing NASA patented holey graphene technology as a highly conductive, ultra-lightweight electrode scaffold. A solid-state electrolyte will be used as a safe, non-flammable replacement to the highly flammable liquid organic electrolytes currently used in SOA lithium-ion batteries. This solid-state lithium-sulfur/selenium cell will be designed into a serial stacking configuration to enable dense packaging of the battery cells. The serial stacking configuration is termed a bipolar stack, which has the advantages of reducing overall cell weight, simplifying the interfaced connections for the cell, and minimizing the cooling requirements for the cell. Lastly, optimization of battery components will occur through a robust and rigorous combination of various computational modeling techniques covering multiple length scales. The expected result will be a fully solid-state battery with operational temperatures up to 150 °C which provides the required energy density, discharge rates, and inherent safety to meet the strict space mission performance criteria. In particular, the wide operational temperature window is required for the large temperature ranges which are experienced across a broad range of potential space missions. This presentation will show initial results that demonstrate the SABERS team has developed a composite carbon-sulfur cathode which exceeds 1100 Wh/kg at a discharge rate of 0.4C, and 804 Wh/kg at a discharge rate of 1C. Additionally, this presentation will show the SABERS team multiscale computational modeling approach and has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM is on the 1-10 µm scale and provides electromechanical and grain interactions for predictive design guidelines for the experimental team to follow.

Urban Air Mobility (UAM) Vehicles↗