SEARCH · Search NASA

Results for “structured model reduction”

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.

SourceResearch connectionFrom yearThrough year

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

At least 1,351 records · Page 75

All sources NASA NTRS DOE OSTI

DOE OSTI2017

Low-rank factorization of electron integral tensors and its application in electronic structure theory

In this letter, we introduce the reverse Cuthill-McKee (RCM) algorithm, which is often used for the bandwidth reduction of sparse tensors, to transform the two-electron integral tensors to their block diagonal forms. By further applying the pivoted Cholesky decomposition (CD) on each of the diagonal blocks, we are able to represent the high-dimensional two-electron integral tensors in terms of permutation matrices and low-rank Cholesky vectors. This representation facilitates the low-rank factorization of the high-dimensional tensor contractions that are usually encountered in post-Hartree-Fock calculations. In this letter, we discuss the second-order Møller-Plesset (MP2) method and linear coupled- cluster model with doubles (L-CCD) as two simple examples to demonstrate the efficiency of the RCM-CD technique in representing two-electron integrals in a compact form.

electronic structure theory↗

DOE OSTI2024

Options for Achieving Cost Reduction in Advanced Reactors through Open Architecture

A key contributor to high capital costs and schedule overruns for new nuclear power plants is lack of standardization, driven by site-specific customization and construction of multiple designs by competing vendors rather than commitment to a single standardized program. While advanced reactor vendors typically individually target repeat construction of standardized units, the many competing designs could exacerbate the problem. “Open Architecture”, the open specification of requirements and interfaces for structures, systems and components (SSCs), has been proposed as a means of promoting standardization, by facilitating existing non-nuclear suppliers to enter the industry and/or allowing SSCs to be configured for more than one reactor within the same technology type. Contracting mechanisms that facilitate information sharing and alignment of incentives between stakeholders may complement such an approach. A preliminary scheme is presented for selection of SSCs for which such strategies could be adopted, based on a vendor make/buy decision model and stakeholder interviews. SSCs are categorized according to number of suppliers and their contribution to the reactor’s competitive edge. SSCs with many potential suppliers and a high contribution to competitive edge may be attractive for widening the supply chain via open specification of system requirements and interfaces, e.g., SSCs in the power island. SSCs with few suppliers and low contribution to competitive edge may be potential avenues for common system specification between vendors, e.g., some of the auxiliary SSCs. Potential cost reductions from such strategies will depend upon the size of the build program and the reactor type.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2014

Strengthening Retrofit Markets for Comprehensive Savings in Multifamily Buildings (Interim Final Report)

Energy efficiency is vitally important in Maine. Nearly 70% of Maine households rely on fuel oil as their primary energy source for home heating, a higher share than in any other state. Coupled with the state's long, cold winters, Maine's dependence on oil renders homeowners particularly vulnerable to fluctuating fuel costs. With $\$$4.5 million in seed funding from the Energy Department's Better Buildings Neighborhood Program, the Governor's Energy Office (GEO), through Efficiency Maine Trust (the Trust), is spurring Maine landlords to lower their monthly energy bills and improve comfort for their tenants during the state's cold winter months and increasingly warmer summers. Maine's aging multifamily housing stock can be expensive to heat and costly to maintain. It is not unusual to find buildings with little or no insulation, drafty windows, and significant air leaks, making them ideal candidates for energy efficiency upgrades. Maine modeled its Multifamily Efficiency Program (MEP) after the state's highly successful Home Energy Savings Program (HESP) for single-family homes. HESP provided cash incentives and financing opportunities to owners of one-to four-unit structures, which resulted in thousands of energy assessments and whole-house energy upgrades in 225 communities. Maine's new MEP multifamily energy efficiency upgrade and weatherization initiative focuses on small to medium-sized (i.e., five to 20 units) apartment buildings. The program's energy efficiency upgrades will provide at least 20% energy savings for each upgraded multifamily unit. The Trust’s MEP relies on a network of approved program partners who help move projects through the pipeline from assessment to upgrade. MEP has two components: benchmarking and development of an Energy Reduction Plan (ERP). Using the ENERGY STAR® Portfolio Manager benchmarking tool, MEP provides an assessment of current energy usage in the building, establishes a baseline for future energy efficiency improvements, and enables tracking and monitoring of future energy usage at the building— all at no cost to the building owner. The ERP is developed by a program partner using either the Trust’s approved modeling or prescriptive tools; it provides detailed information about the current energy related conditions in the building and recommends energy efficiency, health, and safety improvements. The Trust's delivery contractor provides quality assurance and controls throughout the process. Through this effort, MEP's goal is to establish a self-sustaining, market-driven program, demonstrating the value of energy efficiency to other building owners. The increasing value of properties across the state will help incentivize these owners to continue upgrades after the grant period has ended. Targeting urban areas in Maine with dense clusters of multifamily units—such as Portland, Lewiston- Auburn, Bangor, and Augusta—MEP engaged a variety of stakeholder groups early on to design its multifamily program. Through direct emails and its website, program officials invited lending institutions, building professionals, engineering firms, equipment distributors, and local property owners associations to attend open meetings around the state to learn about the goals of the multifamily program and to help define its parameters. These meetings helped program administrators understand the diversity of the customer base: some owners are individuals with a single building, while other owners are groups of people or management companies with an entire portfolio of multifamily buildings. The diversity of the customer base notwithstanding, owners see MEP as an opportunity to make gains in their respective properties. Consistently high turnouts at stakeholder meetings fueled greater customer interest as awareness of the program spread through word of mouth. The program also gained traction by utilizing the program partner networks and building on the legacy of the Trust’s successful HESP for single-family residences. MEP offers significant incentives for building owners to participate in the upgrade program. Wholebuilding benchmarking services are available to most multifamily housing buildings free of charge. The service provides the building owner with an assessment of the building's current energy efficiency as compared to other multifamily buildings on a national scale, establishes a baseline to measure future improvements, and enables owners to track monthly energy consumption using the ENERGY STAR Portfolio Manager. Once the benchmarking process is complete, the program links building owners with approved program partners (e.g., energy professionals, home performance contractors) to identify and implement specific energy-saving opportunities in the building. Program partners can also provide project quotes with estimated financing incentives and payback period calculations that enable building owners to make informed decisions. What's more, the Trust provides two financial incentives for successful completion of program milestones. The first is a per-unit incentive for completion of an approved ERP (i.e., $\$$100 per unit if a prescriptive path is followed, and $\$$200 per unit for a modeled ERP). Upon final inspection of the installed project scope of work, an incentive of $\$$1,400 per unit or 50% of installed cost—whichever is less—is paid. The Trust originally established a $\$$1 million loan-loss reserve fund (LLRF) to further enhance financing opportunities for qualified multifamily building owners. This funding mechanism was designed to connect building owners with lenders that retain the mortgages for their properties and encourages the lenders to offer financing for energy efficiency improvements. However, there has been no interest in the LLRF and therefore the LLRF has been reduced. Ultimately, MEP plans to build an online tool for building owners to assess opportunities to make upgrades in their multifamily units. The tool will include a performance rating system to provide a way for building owners to more easily understand energy use in their building, and how it could be improved with energy efficiency upgrades. Prospective tenants will also be able to use the rating system to make informed decisions about where to rent. Furthermore, the rating can be incorporated into real estate listings as a way for prospective home buyers and the real estate financial community to evaluate a home's operating costs. The Trust’s MEP has identified the state's most experienced energy professionals, vendors, suppliers, and contractors that install energy efficiency equipment in the multifamily sector to be qualified program partners. To be eligible for partnership, energy assessment professionals and contractors are required to have demonstrated experience in the multifamily sector and hold associated professional certifications, such as Building Operator Certification (BOC), Certified Energy Manager (CEM), Professional Engineer (PE), or Building Performance Institute (BPI) Multifamily Building Analyst. Widespread program interest has enabled the Trust to redirect funds that might otherwise be needed for program promotion to building capacity through contractor training. In addition to boosting professional training and certification opportunities, MEP teaches its partners how to market the multifamily program to prospective multifamily homeowners.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2023

Structural Design and Aeromechanical Analysis of Unconventional Blades for Future Mars Rotorcraft

The structural design for rotor blades with thin, unconventional airfoils for Earth-based testing is obtained using three-Dimensional (3D) aeromechanical analysis in support of the NASA ROAMX project. The outer mold line was provided by NASA, but the internal structural design was developed at the University of Maryland and is presented here along with a thorough aeromechanical analysis. The main objectives are to verify the structural integrity of the design and understand the unique aeroelastic behavior of the non-conventional airfoils designed for low-Reynolds number and high subsonic Mach number. Four different blade models are considered, with the pitch axis varied from quarter-chord to mid-chord to determine the effect of C.G. offset on natural frequencies, blade deformations, root loads, and 3D stresses. First, torsional stability is calculated for each of the designs – especially important due to the low Lock number on Mars. All four blade designs are studied under rotation in vacuum, and significant reductions in root loads and 3D stresses are achieved by moving the pitch axis closer to mid-chord to reduce the C.G. offset. Based on the vacuum analysis, the blade design with the pitch axis at 40% chord is selected for aeromechanical analysis. The blade control load, airloads, deformations, and 3D stresses are studied for steady hover. Dynamic control load and dynamic 3D stresses are studied for unsteady hover achieved using cyclic. Significant elastic twist is observed due to the trapeze effect and propeller moment, affecting the spanwise distribution of aerodynamic loads on the blades. The dynamic control load is found to increase significantly due to inertial coupling from the C.G. offset. The dynamic stresses also increase, although still have factors of safety greater than two for both tensile and compressive stress.

Structural Design↗

DOE OSTI2014

Mechanical property changes in porous low-k dielectric thin films during processing

The design of future generations of Cu-low-k dielectric interconnects with reduced electronic crosstalk often requires engineering materials with an optimal trade off between their dielectric constant and elastic modulus. This is because the benefits associated with the reduction of the dielectric constant by increasing the porosity of materials, for example, can adversely affect their mechanical integrity during processing. By using load-dependent contact-resonance atomic force microscopy, the changes in the elastic modulus of low-k dielectric materials due to processing were accurately measured. These changes were linked to alterations sustained by the structure of low-k dielectric films during processing. A two-phase model was used for quantitative assessments of the elastic modulus changes undergone by the organosilicate skeleton of the structure of porous and pore-filled dielectrics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2017

Elucidation of Iron Gettering Mechanisms in Boron-Implanted Silicon Solar Cells

To facilitate cost-effective manufacturing of boron-implanted silicon solar cells as an alternative to BBr 3 diffusion, we performed a quantitative test of the gettering induced by solar-typical boron-implants with the potential for low saturation current density emitters (< 50 fA/cm 2 ). We show that depending on the contamination level and the gettering anneal chosen, such boron-implanted emitters can induce more than a 99.9% reduction in bulk iron point defect concentration. The iron point defect results as well as synchrotron-based Nano-X-ray-fluorescence investigations of iron precipitates formed in the implanted layer imply that, with the chosen experimental parameters, iron precipitation is the dominant gettering mechanism, with segregation-based gettering playing a smaller role. We reproduce the measured iron point defect and precipitate distributions via kinetics modeling. First, we simulate the structural defect distribution created by the implantation process, and then we model these structural defects as heterogeneous precipitation sites for iron. Unlike previous theoretical work on gettering via boron- or phosphorus-implantation, our model is free of adjustable simulation parameters. The close agreement between the model and experimental results indicates that the model successfully captures the necessary physics to describe the iron gettering mechanisms operating in boron-implanted silicon. Furthermore, this modeling capability allows high-performance, cost-effective implanted silicon solar cells to be designed.

14 SOLAR ENERGY↗

DOE OSTI2025

Regime Characterization of Offshore Wind Resource Using Unsupervised Learning

Predictability of wind resource conditions is critical for offshore wind design and operations. While many studies of extreme wind conditions focus on specific events such as low-level jets or ramps, these rely on threshold definitions that limit generality. Here we present a data-driven framework that combines principal component analysis (PCA), self-organizing maps (SOM), and k-means clustering to classify wind resource conditions as typical and anomalous from climatological data. Anomalies are defined not by fixed thresholds but by flagging samples located far from SOM node centers inside the baseline SOM structure. This reframes extremes as rare ebents and hence, likely difficult to anticipate by numerical weather prediction models. We applied this approach to 23 years (2000–2022) of hourly profiles from the NOW-23 hindcast model at the Humboldt Wind Energy Area. Classification is conducted on a feature space consisting of 10 m wind speed and direction, bulk shear and veer across 30–270 m, and a low-level jet index. Dimensionality reduction is achieved through PC. A 2 × 3 OM lattice trained on the PCA vectors identified six baseline regimes spanning weak to strong flow states. High quantization-error profiles are identified and re-clustered into four anomalous regimes. The baseline regimes exhibited clear seasonal and diurnal cycles. Meanwhile, the anomalous regimes represented <10 % of all hours but showed distinct combinations of speed, shear, and veer, when compared to the baseline regimes. Anomalous regimes are typically short-lived (~few hours), yet their transitions can lead to hub-height wind changes of −18 to +9 m s -1 . For a representative 15 MW turbine, these shifts imply rapid swings in capacity factor from near-full output to negligible generation. Validation with lidar buoy data showed 51% agreement in SOM labels across ~6,000 overlapping hours, with most mismatches confined to adjacent speed classes. HRRR comparisons further revealed that anomalous regimes were disproportionately associated with forecast biases exceeding 5 m s -1 . Together, these results reframe extremes in offshore wind from absolute maxima or minima to weather states that are difficult to anticipate from models.

17 WIND ENERGY↗

DOE OSTI2020

DisasterAWARE – A Global Alerting Platform for Flood Events

The rising number of flooding events combined with increased urbanization is contributing to significant economic losses due to damages to structures and infrastructures. From a risk reduction and resilience perspective, it is not only essential to forecast flood risk and potential impacts, but also to disseminate the information to stakeholders on the ground for rapid implementation of mitigation and response measures. This paper provides (i) an introduction to DisasterAWARE®, a global alerting system, that is used to disseminate flood risk information to stakeholders across the globe, and (ii) a discussion of the models implemented using earth observation data (Synthetic Aperture Radar and optical imagery) for near real-time assessment of flood severity and potential flood impacts to infrastructures. While the models are still in their nascent stage, a case study implementation of the models for the 2020 flooding event in Africa is presented to showcase the model integration with DisasterAWARE®.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1987

Development of a high-performance cryogenic radiator with V-groove radiation shields

A feasibility demonstration model of a new-technology, high-performance, cryogenic radiative cooler has been successfully tested in a helium-cooled vacuum chamber. Thermal isolation of the radiator cold stage from the warm spacecraft and instrument is achieved by a novel arrangement of lightweight radiation shields which form large V-groove cavities, and by the use of low-conductance structural supports. The vacuum chamber experiments demonstrate the thermal isolation capability of the radiator design. Analytical model predictions are all within 1 K of the measured test temperatures. Utilization of this design enables reasonably sized radiative coolers (less than 0.3 sq m) to achieve operating temperatures below 60 K at earth, Mars, and beyond for useful cooling loads below 75 mW. The design can be scaled to accommodate larger heat loads. The reduction in operating temperature of over 15 K relative to any radiative cooler flown in the past will allow the V-groove isolation radiator to meet the challenging instrument cooling requirements of many future space missions.

Bard, Steven↗

NASA NTRS1987

Numerical arc segmentation algorithm for a radio conference-NASARC (version 2.0) technical manual

The information contained in the NASARC (Version 2.0) Technical Manual (NASA TM-100160) and NASARC (Version 2.0) User's Manual (NASA TM-100161) relates to the state of NASARC software development through October 16, 1987. The Technical Manual describes the Numerical Arc Segmentation Algorithm for a Radio Conference (NASARC) concept and the algorithms used to implement the concept. The User's Manual provides information on computer system considerations, installation instructions, description of input files, and program operating instructions. Significant revisions have been incorporated in the Version 2.0 software. These revisions have enhanced the modeling capabilities of the NASARC procedure while greatly reducing the computer run time and memory requirements. Array dimensions within the software have been structured to fit within the currently available 6-megabyte memory capacity of the International Frequency Registration Board (IFRB) computer facility. A piecewise approach to predetermined arc generation in NASARC (Version 2.0) allows worldwide scenarios to be accommodated within these memory constraints while at the same time effecting an overall reduction in computer run time.

Whyte, Wayne A., Jr.↗

NASA NTRS1994

Integrated active and passive control design methodology for the LaRC CSI evolutionary model

A general design methodology to integrate active control with passive damping was demonstrated on the NASA LaRC CSI Evolutionary Model (CEM), a ground testbed for future large, flexible spacecraft. Vibration suppression controllers designed for Line-of Sight (LOS) minimization were successfully implemented on the CEM. A frequency-shaped H2 methodology was developed, allowing the designer to specify the roll-off of the MIMO compensator. A closed loop bandwidth of 4 Hz, including the six rigid body modes and the first three dominant elastic modes of the CEM was achieved. Good agreement was demonstrated between experimental data and analytical predictions for the closed loop frequency response and random tests. Using the Modal Strain Energy (MSE) method, a passive damping treatment consisting of 60 viscoelastically damped struts was designed, fabricated and implemented on the CEM. Damping levels for the targeted modes were more than an order of magnitude larger than for the undamped structure. Using measured loss and stiffness data for the individual damped struts, analytical predictions of the damping levels were very close to the experimental values in the (1-10) Hz frequency range where the open loop model matched the experimental data. An integrated active/passive controller was successfully implemented on the CEM and was evaluated against an active-only controller. A two-fold increase in the effective control bandwidth and further reductions of 30 percent to 50 percent in the LOS RMS outputs were achieved compared to an active-only controller. Superior performance was also obtained compared to a High-Authority/Low-Authority (HAC/LAC) controller.

Voth, Christopher T.↗

NASA NTRS2012

Multiscale Modeling of Ultra High Temperature Ceramics (UHTC) ZrB2 and HfB2: Application to Lattice Thermal Conductivity

We are developing a multiscale framework in computational modeling for the ultra high temperature ceramics (UHTC) ZrB2 and HfB2. These materials are characterized by high melting point, good strength, and reasonable oxidation resistance. They are candidate materials for a number of applications in extreme environments including sharp leading edges of hypersonic aircraft. In particular, we used a combination of ab initio methods, atomistic simulations and continuum computations to obtain insights into fundamental properties of these materials. Ab initio methods were used to compute basic structural, mechanical and thermal properties. From these results, a database was constructed to fit a Tersoff style interatomic potential suitable for atomistic simulations. These potentials were used to evaluate the lattice thermal conductivity of single crystals and the thermal resistance of simple grain boundaries. Finite element method (FEM) computations using atomistic results as inputs were performed with meshes constructed on SEM images thereby modeling the realistic microstructure. These continuum computations showed the reduction in thermal conductivity due to the grain boundary network.

Lawson, John W.↗

NASA NTRS2012

Multiscale Modeling of UHTC: Thermal Conductivity

Lawson, John W.↗

NASA NTRS2020

Polyvinyl Alcohol and Medium Density Polyethylene Composite Materials for Neutron Radiation Shielding

Manned spacecraft venturing beyond the Earth’s Van Allen Belts will be subjected to high levels of radiation from both energetic particles emanating from the sun and from galactic atomic events, such as supernovae. The metal shell of a spacecraft offers some protection from gamma radiation and high energy particles originating from both the sun and cosmic sources. The interaction of these high energy particles and radiation with the spacecraft hull create secondary radiation and neutrons, additional hazards for astronauts and electronic systems. Shielding of neutrons is the most challenging of the high energy radiation, since neutrons have zero charge and are least affected by electrical fields, magnetic fields, and atomic forces. Previous studies showed that polyethylene is an effective neutron shielding material, due to its high hydrogen content. High energy neutrons are slowed to thermal neutrons through multiple collisions with the hydrogen atoms, increasing the effectiveness of neutron capture by boron-10 atoms. This study discusses the fabrication and testing of polyvinyl alcohol (PVOH) samples as a neutron shielding material, with comparison to medium density polyethylene (MDPE) composite samples to be used for neutron shielding for spacecraft. PVOH, an aqueous polymer, was chosen for hydrogen content and for enabling the use of organic reinforcement such as cellulose for secondary structural composites. OLTARIS (On-Line Tool for the Assessment of Radiation in Space) was used for radiation shielding simulation and compared with experimental data. Modeling indicates that the most effective shielding from radiation was in an aluminum layer backed by a polymer layer, either MDPE or PVOH. Cross-linked PVOH was also included in the OLTARIS modeling. All 3 polymer cases showed shielding improvement over aluminum alone, with similar dose equivalent reduction for galactic cosmic radiation(GCR)and for radiation from a solar particle event (SPE). Fourier Transform Infrared (FTIR) Spectroscopy was used to confirm the cross-linking in the PVOH sample and to determine the uniformity through the thickness. PVOH, cross-linked PVOH, and MDPE samples were tested for neutron shielding effectiveness using a 1 curie Americium-Beryllium neutron source. Test results indicated the most shielding in the cross-linked PVOH, followed by the pristine PVOH, and MDPE. Neutron testing suggests that polyvinyl alcohol is a good alternative to polyethylene for neutron shielding. The neutron shielding materials, PVOH and cross-linked PVOH developed under this research will enable the safe operation of spacecraft beyond the Earth’s protective Van Allen Radiation Belts. It will be crucial for NASA’s manned missions to the Moon or Mars to protect the health of astronauts and equipment from the harmful effects of excessive radiation.

neutron, shielding, radiation, polyvinyl alcohol, ↗

DOE OSTI2018

Periodic Material-Based Seismic Base Isolators for Small Modular Reactors

Important structures such as nuclear power plants should experience very little vibrations in order to maintain the safety of the nuclear facilities during seismic events. Protection of these structures by seismic isolators requires the isolators to provide seismic isolation irrespective of the direction of excitations and to develop a stable response without rocking. Conventional seismic isolation systems, however, can only fulfill partial requirements for the seismic protection. This study adopts the principle of periodic materials for seismic isolation. These materials exhibit unique properties of frequency band gaps, where incoming waves with frequencies falling inside the frequency band gaps are forbidden. The new isolation systems, known as periodic foundations, function both as a structural foundation to support the gravitational weight of the superstructure and also as a seismic isolator. The isolation mechanism, hypothetically, can easily fulfill all the requirements for seismic protection of the critical facilities. This study focuses on the design of one-dimensional (1D) and three-dimensional (3D) periodic foundations for seismic isolation of small modular reactor (SMR) buildings. The theoretical study was first conducted to reveal the fundamental behavior of periodic foundations. Then global sensitivity analysis was utilized to study the effect of design parameters on the frequency band gaps. In addition, simple straight-forward design equations based on the sensitivity analysis are proposed for the design of periodic foundations. Utilizing the proposed equations, prototypes of 1D and 3D periodic foundations were designed to isolate an SMR building. Scaled models were fabricated and experimentally tested to validate the hypothesis and design. The periodic foundation structural systems were tested under various input waves, including seismic waves, in the horizontal and vertical directions and the torsional mode. The shake table test results show that the periodic foundations can reduce the acceleration response of the SMR building up to 90% in the horizontal direction and the torsional mode. As much as a 40% response reduction in the vertical direction is also observed. Moreover, the periodic foundation-isolated structure exhibited stable response with negligible rocking on the structure. This study proved the capability of periodic foundations to enhance the seismic safety of critical structures.

42 ENGINEERING↗

NASA NTRS2003

Structural Basis for Flip-Flop Action of Thiamin Pyrophosphate-Dependent Enzymes Revealed by Human Pyruvate Dehydrogenase

Thiamin pyrophosphate (TPP), the biologically active form of vitamin BI, is a cofactor of enzymes catalyzing reactions involving the cleavage of a carbon-carbon bond adjacent to an oxo group. TPP-dependent enzymes show a common mechanism of TPP activation by: (1) forming the ionic N-H...O(sup -) hydrogen bonding between the N1' atom of the aminopirymidine ring of the coenzyme and intrinsic gamma-carboxylate group of glutamate and (2) imposing an "active" V-conformation that brings the N4' atom of the aminopirymidine to the distance required for the intramolecular C-H.. .N hydrogen bonding with the thiazolium C2 atom. Within these two hydrogen bonds that rapidly exchange protons, protonation of the N1' atom is strictly coordinated with the deprotonation of the 4' -amino group and eventually abstraction of the proton from C2. The human pyruvate dehydrogenase Elp, component of human pyruvate dehydrogenase complex, catalyzes the irreversible decarboxylation of the pyruvate followed by the reductive acetylation of the lipoyl group of dihydrolipoyl acyltransferase. Elp is alpha(sub 2)beta(sub2)-heterotetrameric with a molecular mass of I54 kDa, which has two catalytic sites, each providing TPP and magnesium ion as cofactors and each formed on the interface between the PP and PYR domains. The dynamic nonequivalence of two otherwise chemically equivalent catalytic sites has been observed and the flip-flop mechanism was suggested, according to which two active sites affect each other and in which different steps of the catalytic reaction are performed in each of the sites at any given moment. Based on specific futures of human pyruvate dehydrogenase including rigid and flexible connections between domains that bind the cofactor we propose a mechanistic model for the flip-flop action of this enzyme. We postulate that the dynamic protein environment drives the exchange of tautomers in the 4' -aminopyrimidine ring of the cofactor through a concerted shuttl-like motion of tightly connected domains. The dynamic exchange of those tautomers, in turns, is required during the reactions of pyruvate decarboxylation and reductive acetylation of lipoamide. Thus the shuttle-like motion of the domains is coordinated with the reactions of decarboxylation and acetylation, which are carried out in each of the cofactor sites resulting in a flip-flop action of the enzyme. The structure-derived mechanism of action of human pyruvate dehydrogenase may be likely common for other TPP-dependent enzymes.

Dominiak, Paulina↗

DOE OSTI2016

Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

Moonshiram, Dooshaye↗

DOE OSTI2023

Projection pursuit adaptation on polynomial chaos expansions

Here, the present work addresses the issue of accurate stochastic approximations in high-dimensional parametric space using tools from uncertainty quantification (UQ). The basis adaptation method and its accelerated algorithm in polynomial chaos expansions (PCE) were recently proposed to construct low-dimensional approximations adapted to specific quantities of interest (QoI). The present paper addresses one difficulty with these adaptations, namely their reliance on quadrature point sampling, which limits the reusability of potentially expensive samples. Projection pursuit (PP) is a statistical tool to find the “interesting” projections in high-dimensional data and thus bypass the curse-of-dimensionality. In the present work, we combine the fundamental ideas of basis adaptation and projection pursuit regression (PPR) to propose a novel method to simultaneously learn the optimal low-dimensional spaces and PCE representation from given data. While this projection pursuit adaptation (PPA) can be entirely data-driven, the constructed approximation exhibits mean-square convergence to the solution of an underlying governing equation and thus captures the supports and probability distributions associated with the physics constraints. The proposed approach is demonstrated on a borehole problem and a structural dynamics problem, demonstrating the versatility of the method and its ability to discover low-dimensional manifolds with high accuracy with limited data. In addition, the method can learn surrogate models for different quantities of interest while reusing the same data set.

97 MATHEMATICS AND COMPUTING↗