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NASA NTRS1990

Latest developments in the Advanced Photovoltaic Solar Array Program

In 1985, the Advanced Photovoltaic Solar Array (APSA) Program was established to demonstrate a producible array system with a specific power greater than 130 W/kg at a 10-kW (BOL) power level. The latest program phase completed fabrication and initial functional testing of a prototype wing representative of a full-scale 5-kW (BOL) wing (except truncated in length to about 1 kW), with weight characteristics that could meet the 130-W/kg (BOL) specific power goal using thin silicon solar cell modules and weight-efficient structural components. The wing configuration and key design details are reviewed, along with results from key component-level and wing-level tests. Projections for future enhancements that may be expected through the use of advanced solar cells and structural components are shown. Performance estimates are given for solar electric propulsion orbital transfer missions through the Van Allen radiation belts. The latest APSA program plans are presented.

Stella, Paul M.↗

DOE OSTI2017

Large Modulation of Charge Carrier Mobility in Doped Nanoporous Organic Transistors

Molecular doping of organic electronics has shown promise to sensitively modulate important device metrics. One critical challenge is the disruption of structure order upon doping of highly crystalline organic semiconductors, which significantly reduces the charge carrier mobility. This paper demonstrates a new method to achieve large modulation of charge carrier mobility via channel doping without disrupting the molecular ordering. Central to the method is the introduction of nanopores into the organic semiconductor thin films via a simple and robust templated meniscus-guided coating method. Using this method, the charge carrier mobility of C 8 -benzothieno[3,2-b]benzothiophene transistors is boosted by almost sevenfold. This paper further demonstrates enhanced electron transport by close to an order of magnitude in a diketopyrrolopyrrole-based donor–acceptor polymer. Combining spectroscopic measurements, density functional theory calculations, and electrical characterizations, the doping mechanism is identified as partial-charge-transfer induced trap filling. The nanopores serve to enhance the dopant/organic semiconductor charge transfer reaction by exposing the π-electrons to the pore wall.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Engineering the electronic and strained interface for high activity of PdM core @Pt monolayer electrocatalysts for oxygen reduction reaction

Alloyed nanoparticles with core-shell structures provide a favorable model to modulate interfacial interaction and surface structures at the atomic level, which is important for designing electrocatalysts with high activity and durability. Herein, core-shell structured Pd 3 M@Pt/C nanoparticles with binary PdM alloy cores (M = Fe, Ni, and Co) and a monolayer Pt shell were successfully synthesized with diverse interfaces. Among these, Pd 3 Fe@Pt/C exhibited the best oxygen reduction reaction catalytic performance, roughly 5.4 times more than that of the commercial Pt/C catalyst used as reference. The significantly enhanced activity is attributed to the combined effects of strain engineering, interfacial electron transfer, and improved Pt utilization. Density functional theory simulations and extended X-ray absorption fine structure analysis revealed that engineering the alloy core with moderate lattice mismatch and alloy composition (Pd 3 Fe) optimizes the surface oxygen adsorption energy, thereby rendering excellent electrocatalytic activity. Finally, future researches may use this study as a guide on the construction of highly effective core-shell electrocatalysts for various energy conversions and other applications.

25 ENERGY STORAGE↗

DOE OSTI2018

The folate-binding module of Thermus thermophilus cobalamin-dependent methionine synthase displays a distinct variation of the classical TIM barrel: a TIM barrel with a `twist'

Methyl transfer between methyltetrahydrofolate and corrinoid molecules is a key reaction in biology that is catalyzed by a number of enzymes in many prokaryotic and eukaryotic organisms. One classic example of such an enzyme is cobalamin-dependent methionine synthase (MS). MS is a large modular protein that utilizes an S N 2-type mechanism to catalyze the chemically challenging methyl transfer from the tertiary amine (N5) of methyltetrahydrofolate to homocysteine in order to form methionine. Despite over half a century of study, many questions remain about how folate-dependent methyltransferases, and MS in particular, function. Here, the structure of the folate-binding (Fol) domain of MS from Thermus thermophilus is reported in the presence and absence of methyltetrahydrofolate. It is found that the methyltetrahydrofolate-binding environment is similar to those of previously described methyltransferases, highlighting the conserved role of this domain in binding, and perhaps activating, the methyltetrahydrofolate substrate. These structural studies further reveal a new distinct and uncharacterized topology in the C-terminal region of MS Fol domains. Furthermore, it is found that in contrast to the canonical TIM-barrel β 8 α 8 fold found in all other folate-binding domains, MS Fol domains exhibit a unique β 8 α 7 fold. It is posited that these structural differences are important for MS function.

Yamada, Kazuhiro (ORCID:0000000210068610)↗

NASA NTRS2006

A Novel, Free-Space Optical Interconnect Employing Vertical-Cavity Surface Emitting Laser Diodes and InGaAs Metal-Semiconductor-Metal Photodetectors for Gbit/s RF/Microwave Systems

Emerging technologies and continuing progress in vertical-cavity surface emitting laser (VCSEL) diode and metal-semiconductor-metal (MSM) photodetector research are making way for novel, high-speed forms of optical data transfer in communication systems. VCSEL diodes operating at 1550 nm have only recently become commercially available, while MSM photodetectors are pushing the limits of contact lithography with interdigitated electrode widths reaching sub micron levels. We propose a novel, free-space optical interconnect operating at about 1Gbit/s utilizing VCSEL diodes and MSM photodetectors. We report on development, progress, and current work, which are as follows: first, analysis of the divergent behavior of VCSEL diodes for coupling to MSM photodetectors with a 50 by 50 m active area and second, the normalized frequency response of the VCSEL diode as a function of the modulating frequency. Third, the calculated response of MSM photodetectors with varying electrode width and spacing on the order of 1 to 3 m as well as the fabrication and characterization of these devices. The work presented here will lead to the formation and characterization of a fully integrated 1Gbit/s free-space optical interconnect at 1550 nm and demonstrates both chip level and board level functionality for RF/microwave digital systems.

Savich, Gregory R.↗

DOE OSTI2014

Quantification of the transferability of a designed protein specificity switch reveals extensive epistasis in molecular recognition

Re-engineering protein–protein recognition is an important route to dissecting and controlling complex interaction networks. Experimental approaches have used the strategy of “second-site suppressors,” where a functional interaction is inferred between two proteins if a mutation in one protein can be compensated by a mutation in the second. Mimicking this strategy, computational design has been applied successfully to change protein recognition specificity by predicting such sets of compensatory mutations in protein–protein interfaces. To extend this approach, it would be advantageous to be able to “transplant” existing engineered and experimentally validated specificity changes to other homologous protein–protein complexes. Here, we test this strategy by designing a pair of mutations that modulates peptide recognition specificity in the Syntrophin PDZ domain, confirming the designed interaction biochemically and structurally, and then transplanting the mutations into the context of five related PDZ domain–peptide complexes. We find a wide range of energetic effects of identical mutations in structurally similar positions, revealing a dramatic context dependence (epistasis) of designed mutations in homologous protein–protein interactions. To better understand the structural basis of this context dependence, we apply a structure-based computational model that recapitulates these energetic effects and we use this model to make and validate forward predictions. The context dependence of these mutations is captured by computational predictions, our results both highlight the considerable difficulties in designing protein–protein interactions and provide challenging benchmark cases for the development of improved protein modeling and design methods that accurately account for the context.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1972

Excitation of Na D-line radiation in collisions of sodium atoms with internally excited H2, D2, and N2

Excitation of D-line radiation in collisions of Na atoms with vibrationally excited N2, H2 and D2 was studied in two modulated crossed beam experiments. In both experiments, the vibrational excitation of the molecules was provided by heating the molecular beam source to temperatures in the range of 2000 to 3000 K, which was assumed to give populations according to the Boltzmann expression. In the first experiment, a total rate coefficient was measured as a function of molecular beam temperature, with absolute calibration of the photon detector being made using the black body radiation from the heated molecular beam source. Since heating affects both the internal energy and the collisional kinetic energy, the first experiment could not determine the relative contributions of internal energy transfer versus collisional excitation. The second experiment achieved partial separation of internal versus kinetic energy transfer effects by using a velocity-selected molecular beam. Using two simple models for the kinetic energy dependence of the transfer cross section for a given change in vibrational quantum number, the data from both experiments were used to determine parameters in the models.

Krause, H. F.↗

DOE OSTI2012

Structural characterization of human Uch37

Uch37 is a deubiquitylating enzyme (DUB) that is functionally linked with multiple protein complexes and signal transduction pathways. Uch37 associates with the 26S proteasome through Rpn13 where it serves to remove distal ubiquitin moeities from polyubiquitylated proteins. Uch37's proteasome associated activity was shown to liberate proteins from destruction. However, Uch37 may also specifically facilitate the destruction of inducible nitric oxide synthase and I{kappa}B-{alpha} at the proteasome. Wicks et al. established Uch37's potential to modulate the transforming growth factor-{beta}(TGF-{beta}) signaling cascade, through tis interaction with SMAD7. Yao et al. demonstrated that Uch37 also associates with the Ino80 chromatin-remodeling complex (Ino80 complex), which is involved in DNA repair and transcriptional regulation. Uch37's importance in metazoan development was underscored recently as Uch37 knockouts in mice result in prenatal lethality, where mutant embryos had severe defects in brain development. Protein ubiquitylation is an ATP-dependent post-translational modification that serves to signal a wide variety of cellular processes in eukaryotes. A protein cascade, generally comprising three enzymes, functions to activate, transport and specifically transfer ubiquitin to the targeted protein, culminating in an isopeptide linkage between the {epsilon}-amino group of a target protein's lysysl residue and the ubiquitin's terminal carboxylate. Monoubiquitination plays an important role in histone regulation, endocytosis, and viral budding. Further processing of the target protein may be accomplished by ubiquitylation of the protein on a different lysine, or through the formation of polyubiquitin chains, where the best-characterized outcome is destruction of the polyubiquitin-labeled protein in the proteasome. DUBs catalyze the removal of ubiquitin from proteins. This activity serves to reverse the effects of ubiquitination, permit ubiquitin recycling, or liberate free ubiquitin after translation. Uch37, is a cysteine protease from the ubiquitin C-terminal hydrolase (UCH) family. The catalytic domain of UCH enzymes has a central, six-stranded, antiparallel {beta}-sheet that is flanked on each side by {alpha}-helices. Like picornain 3C, UCH family proteins contain a catalytic triad comprising the side chains of cysteine, histidine, and aspartate. in picornain 3C, the aspartate's carboxylate side chain acts to position histidine's imidazole group for general base catalysis, which activates cysteine for nucleophilic attack. UCH enzymes also contain a glutamine, which may serve to stabilize the tetrahedral transition state. The UCH family can be divided into two distinct groups, that is, enzymes solely composed of the globular UCH fold, or enzymes comprising the UCH domain and a C-terminal extension. The latter group can be subdivided based on the composition of the C-terminal extension. Uch37 carries a C-terminal extension. Until now, the structure of a full-length UCH from this structural class has not been reported.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2014

New insights on the nature of two-dimensional polarons in semiconducting polymers: Infrared absorption in poly(3-hexylthiophene)

Infrared absorption of positively charged polarons in conjugated polymer chains and π-stacked aggregates is investigated theoretically, employing a Holstein-based Hamiltonian which treats electronic coupling, electron-vibrational coupling, and disorder on equal footing. The spectra evaluated from the Hamiltonian expressed in a one- and two-particle basis set are essentially exact, insofar as the main, aromatic-quinoidal vibrational mode is treated fully nonadiabatically. Diagonal and off-diagonal (“paracrystalline”) disorder are resolved along the polymer axis (x) and the aggregate stacking axis (y). Disorder along the polymer axis selectively attenuates the x-polarized spectrum, which is dominated by the polaron peak P{sub 1}. Disorder along the stacking axis selectively attenuates the y-polarized spectrum, which is dominated by the lower-energy charge-transfer peak, DP{sub 1}. Calculated spectra are in excellent agreement with the measured induced-absorption and charge-modulation spectra, reproducing the peak positions and relative peak intensities within a line shape rich in vibronic structure. Our nonadiabatic approach predicts the existence of a weak, x-polarized peak P{sub 0}, slightly blueshifted from DP{sub 1}. The peak is intrinsic to single polymer chains and appears in a region of the spectrum where narrow infrared active vibrational modes have been observed in nonaggregated conjugated polymers. The polaron responsible for P{sub 0} is composed mainly of two-particle wave functions and cannot be accounted for in the more conventional adiabatic treatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2013

Robotics On-Board Trainer (ROBoT)

ROBoT is an on-orbit version of the ground-based Dynamics Skills Trainer (DST) that astronauts use for training on a frequent basis. This software consists of two primary software groups. The first series of components is responsible for displaying the graphical scenes. The remaining components are responsible for simulating the Mobile Servicing System (MSS), the Japanese Experiment Module Remote Manipulator System (JEMRMS), and the H-II Transfer Vehicle (HTV) Free Flyer Robotics Operations. The MSS simulation software includes: Robotic Workstation (RWS) simulation, a simulation of the Space Station Remote Manipulator System (SSRMS), a simulation of the ISS Command and Control System (CCS), and a portion of the Portable Computer System (PCS) software necessary for MSS operations. These components all run under the CentOS4.5 Linux operating system. The JEMRMS simulation software includes real-time, HIL, dynamics, manipulator multi-body dynamics, and a moving object contact model with Tricks discrete time scheduling. The JEMRMS DST will be used as a functional proficiency and skills trainer for flight crews. The HTV Free Flyer Robotics Operations simulation software adds a functional simulation of HTV vehicle controllers, sensors, and data to the MSS simulation software. These components are intended to support HTV ISS visiting vehicle analysis and training. The scene generation software will use DOUG (Dynamic On-orbit Ubiquitous Graphics) to render the graphical scenes. DOUG runs on a laptop running the CentOS4.5 Linux operating system. DOUG is an Open GL-based 3D computer graphics rendering package. It uses pre-built three-dimensional models of on-orbit ISS and space shuttle systems elements, and provides realtime views of various station and shuttle configurations.

Johnson, Genevieve↗

DOE OSTI2025

Functional Connectivity of Red Chlorophylls in Cyanobacterial Photosystem I Revealed by Fluence-Dependent Transient Absorption

External stressors modulate the oligomerization state of photosystem I (PSI) in cyanobacteria. The number of red chlorophylls (Chls), pigments lower in energy than the P700 reaction center, depends on the oligomerization state of PSI. Here, we use ultrafast transient absorption spectroscopy to interrogate the effective connectivity of the red Chls in excitonic energy pathways in trimeric PSI in native thylakoid membranes of the model cyanobacterium Synechocystis sp. PCC 6803, including emergent dynamics, as red Chls increase in number and proximity. Fluence-dependent dynamics indicate singlet–singlet annihilation within energetically connected red Chl sites in the PSI antenna but not within bulk Chl sites on the picosecond time scale. These data support picosecond energy transfer between energetically connected red Chl sites as the physical basis of singlet–singlet annihilation. The time scale of this energy transfer is faster than predicted by Förster resonance energy transfer calculations, raising questions about the physical mechanism of the process. Our results indicate distinct strategies to steer excitations through the PSI antenna; the red Chls present a shallow reservoir that direct excitations away from P 700 , extending the time to trapping by the reaction center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Energy Transfer Mechanisms in Large Low-Bandgap Polymers from Time-Resolved Experiments and Nonadiabatic Molecular Dynamics Calculations

Conjugated polymers offer unprecedented chemical tunability for modulating energy transfer in a multitude of infrared light applications. In this work, we use a combination of time-resolved spectroscopic experiments and nonadiabatic molecular dynamics calculations to probe the photochemistry and nonradiative transitions in a recently synthesized narrow bandgap donor–acceptor conjugated polymer based on alternating cyclopentadithiophene and electronegative benzothiadiazole heterocycles. Using large-scale semi-empirical nonadiabatic molecular dynamics, which can treat a large 260-atom hexamer, we calculate an S 5 → S 1 lifetime of 34.75 fs, which is consistent with our time-resolved spectroscopic data. Our simulations suggest that vibronic motions of the central carbons in the cyclopentadithiophene functional groups are predominantly involved in the nonradiative transitions, and the excitation becomes more localized on a monomer fragment over time. The combined use of time-resolved experiments and nonadiabatic molecular dynamics calculations in this work provides mechanistic insight into chemical functionalities that can be tuned to enhance energy transfer in other prospective low-bandgap polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRSDate not supplied

Eleven Countries, an Integrated Spacecraft: the Story of International Collaboration that Built the Orion Spacecraft and Powered the Success of the Artemis I Mission

The quest to return humans to the Moon in the next step towards humanity's exploration of space is more alive than ever. After a great deal of achievements, failures, and lessons learned, the Artemis I mission set o to the Moon on November 16, 2022, with the goal of testing a new rocket, the Space Launch System, and a new spacecraft, Orion: designed, assembled, and tested across two continents, and 11 countries. Behind this mission, decades of experience with the International Space Station, Autonomous Transfer Vehicle operations, and many other program collaborations built the know-how on how to succeed together in the toughest environment | deep space. The Artemis I mission proved to be an incredible success, meeting 161 total mission objectives, including 21 developed during the flight based on outperforming spacecraft. It was also a case-study in international collaboration, given that ESA, NASA, and industry partners Airbus and Lockheed Martin for the first time had to design, build, test, and fly a fully integrated human-rated spacecraft, with most critical functions dependent and interconnected across U.S. and European systems. The U.S.-built Orion Crew Module and Crew Module Adapter and European-built European Service Module (ESM) shared critical interfaces and commodities, from propulsion, avionics, active/passive thermal, electrical power generation, storage and distribution to the software that managed it all. In this paper, we will describe relevant aspects of the integrated spacecraft design, providing context for the challenges that the team faced in all phases required to get Orion ready to fly, and provide a direct account of how the joint team formed, trained, and supported the operations of the successful Artemis I mission. We will also explore the evolution of the partnerships, given that these allow a multi-national e ort to sustain the program production, share costs, leverage a broader base of engineering expertise, and build more diverse capabilities over the long haul to support the Artemis goals and objectives. Lastly, we will cover critical lessons learned and how the Orion Program has implemented these in preparation of the next Artemis missions to repeat the success of Artemis I. The purpose of this paper is to document knowledge we gained and lessons we learned through the development of an integrated Orion spacecraft, since it is imperative we build on this now, at the dawn of the Artemis Program, an international endeavor to push human space exploration.

Deep Space Exploration↗

DOE OSTI2025

Structure–Function Relationships in Sequence-Controlled Copolymers for Rare Earth Element Chelation

The ability to tune material function through primary sequence is a defining feature of biological macromolecules, allowing precise control over structure and target interactions in complex aqueous environments. However, translating sequence–structure–function relationships to synthetic macromolecules is challenging due to their dispersity in sequence, conformation, and composition. Here, we report systematic studies of amphiphilic polymer chelators designed to probe how composition and patterning influence binding affinity and selectivity for rare earth elements (REEs), a series of technologically relevant metals with challenging separation profiles. A library of copolymers varying hydrophobic monomer composition and patterning was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization, spanning statistical, gradient, and block architectures. REE binding was quantified using a high-throughput colorimetric assay, and reconstruction of polymer ensembles using kinetic stochastic simulations enabled quantitative comparisons of sequence heterogeneity, linking local monomer colocalization to emergent REE binding. Further, we investigated the role of different hydrophobic comonomers in tuning metal coordination, with binding trends linked to structural features that influence binding site desolvation. Complementary dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements showed that both polymer and monomer architecture modulate metal-induced conformational changes, and that multichain assembly behavior emerges beyond critical hydrophobic thresholds. Sequence control also altered REE selectivity, with nonmonotonic differences observed across compositionally identical polymers with different sequence architectures. Together, these findings establish design principles that connect polymer sequence and structure to binding performance, guiding the design of macromolecular chelators with enhanced affinity and selectivity for applications in separations, sensing, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2018

Variability in Galactic Cosmic Radiation- Induced DNA Damage Response in Inbred Mice Is Modulated by Genetics

In radiation biology, the ability to predict cancer risk associated with exposure to low doses of high-LET (Linear Energy Transfer) ionizing radiation remains a challenge. Epidemiological methods lack the sensitivity and power to provide detailed risk estimates for cancer and ignore individual sensitivity. We have hypothesized that DNA repair capacity is the primary factor differentiating peoples radiation sensitivity. We previously showed in immortalized human cell lines that characterizing the dose and time dependence of p53-binding protein 1 (53BP1) foci formation in the nucleus following X-rays exposure is sufficient to predict DNA repair response to any other LET in the same cell line. We now tested this hypothesis across a population of mice with different genetic background. Fibroblast cells were extracted and cultivated from 76 individual mice from 15 different strains and exposed to HZE (high (H) atomic number (Z) and energy (E) galactic cosmic ray particles) particles and X-rays. Individual radiation sensitivities were investigated by high throughput measurement of DNA repair kinetics that evaluated 53bp1 foci numbers as a surrogate for DNA double-strand breaks at various times post-irradiation. Instead of just counting foci which can be hard to distinguish for high-LET or high doses, we also took into account the track structure of high-LET particles to compute the remaining number of unrepaired tracks as a function of time post-irradiation. As expected, the percentage of unrepaired track over a 48 hours follow-up period increased with LET. In addition, repair rate was modulated by genetics, with animals from the same strain showing small variance while large rate differences were observed between strains. Radiation strain sensitivity ranking was estimated based on repair rates from exposure to each LET evaluated in this work, and ranking for high-LET correlated better with ranking from high dose of X-ray, not low dose. At the in-vivo level, drops in T-cells and B-cells number measured 24 hours after 0.1 Gy (Gray) X-ray exposure, correlated with slower DNA repair kinetic in fibroblast cells of the same strains of mice. At the genomic level, mouse genome wide association (GWA) analysis identified seven significant genetic loci on chromosomes 2, 3, 7, 10, 11, 13 and 19 with different significance depending on the LET. Interestingly, for the two highest LET, a common locus on Chromosome 10 was identified with high enrichment for DNA repair associated genes.Overall, this work suggests that repair kinetics of primary skin fibroblasts is a good surrogate marker for in-vivo radiation sensitivities in other tissues and that this response is modulated by genetics. Our study also confirms that DNA repair kinetics following high doses of X-ray can be used to predict radiation sensitivity to high-LET.

High-LET Radiation↗

NASA NTRS1996

Galactic cosmic radiation model and its applications

A model for the differential energy spectra of galactic cosmic radiation as a function of solar activity is described. It is based on the standard diffusion-convection theory of solar modulation. Estimates of the modulation potential based on fitting this theory to observed spectral measurements from 1954 to 1989 are correlated to the Climax neutron counting rates and to the sunspot numbers at earlier times taking into account the polarity of the interplanetary magnetic field at the time of observations. These regression lines then provide a method for predicting the modulation at later times. The results of this model are quantitatively compared to a similar Moscow State University (MSU) model. These model cosmic ray spectra are used to predict the linear energy transfer spectra, differential energy spectra of light (charge less than or = 2) ions, and single event upsets rates in memeory devices. These calculations are compared to observations made aboard the Space Shuttle.

Badhwar, G. D.↗

DOE OSTI2013

Protein Conformational Populations and Functionally Relevant Substates

Functioning proteins do not remain fixed in a unique structure, rather they sample a range of conformations facilitated by motions within the protein. Even in the native state, a protein exists as a collection of interconverting conformations driven by thermodynamic fluctuations. Motions on the fast time scale allow a protein to sample conformations in the nearby area of its conformational landscape, while motions on slower time scales give it access to conformations in distal areas of the landscape. Emerging evidence indicates that protein landscapes contain conformational substates with dynamic and structural features that support the designated function of the protein. Nuclear magnetic resonance (NMR) experiments provide information about conformational ensembles of proteins. X-ray crystallography allows researchers to identify the most populated states along the landscape, and computational simulations give atom-level information about the conformational substates of different proteins. This ability to characterize and obtain quantitative information about the conformational substates and the populations of proteins within them is allowing researchers to better understand the relationship between protein structure and dynamics and the mechanisms of protein function. In this Account, we discuss recent developments and challenges in the characterization of functionally relevant conformational populations and substates of proteins. In some enzymes, the sampling of functionally relevant conformational substates is connected to promoting the overall mechanism of catalysis. For example, the conformational landscape of the enzyme dihydrofolate reductase hasmultiple substates, which facilitate the binding and the release of the cofactor and substrate and catalyze the hydride transfer. For the enzyme cyclophilin A, computational simulations reveal that the long time scale conformational fluctuations enable the enzyme to access conformational substates that allow it to attain the transition state, therefore promoting the reaction mechanism. Long-term, this emerging view of proteins with conformational substates has broad implications for improving our understanding of enzymes, enzyme engineering, and better drug design. Researchers have already used photoactivation to modulate protein conformations as a strategy to develop a hypercatalytic enzyme. Furthermore, the alteration of the conformational substates through binding of ligands at locations other than the active site provides the basis for the design of new medicines through allosteric modulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Evidence of a purely electronic two-dimensional lattice at the interface of TMD/Bi 2 Se 3 heterostructures

When 2D materials are vertically stacked, new physics emerges from interlayer orbital interactions and charge transfer modulated by the additional periodicity of interlayer atomic registry (moiré superlattice). Surprisingly, relatively little is known regarding the real-space distribution of the transferred charges within this framework. In this paper we provide the first experimental indications of a real-space, non-atomic lattice formed by interlayer coupling induced charge redistribution in vertically stacked Bi 2 Se 3 /transition metal dichalcogenide (TMD) 2D heterostructures. Robust enough to scatter 200 keV electron beams, this non-atomic lattice generates selected area diffraction patterns that correspond excellently with simulated patterns from moiré superlattices of the parent crystals suggesting their location at sites of high interlayer atomic registry. Density functional theory (DFT) predicts concentrated charge pools reside in the interlayer region, located at sites of high nearest-neighbor atomic registry, suggesting the non-atomic lattices are standalone, reside in the interlayer region, and are purely electronic.

2D materials↗