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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Exploring wave propagation in heterogeneous metastructures using the relaxed micromorphic model

Metamaterials are artificial structures that can manipulate and control sound waves in ways not possible with conventional materials. While much effort has been undertaken to widen the bandgaps produced by these materials through design of heterogeneities within unit cells, comparatively little work has considered the effect of engineering heterogeneities at the structural scale by combining different types of unit cells. In this paper, we use the relaxed micromorphic model to study wave propagation in heterogeneous metastructures composed of different unit cells. We first establish the efficacy of the relaxed micromorphic model for capturing the salient characteristics of dispersive wave propagation through comparisons with direct numerical simulations for two classes of metamaterial unit cells: namely phononic crystals and locally resonant metamaterials. We then use this model to demonstrate how spatially arranging multiple unit cells into metastructures can lead to tailored and unique properties such as spatially-dependent broadband wave attenuation, rainbow trapping, and pulse shaping. In the case of the broadband wave attenuation application, we show that by building layered metastructures from different metamaterial unit cells, we can slow down or stop wave packets in an enlarged frequency range, while letting other frequencies through. In the case of the rainbow-trapping application, we show that spatial arrangements of different unit cells can be designed to progressively slow down and eventually stop waves with different frequencies at different spatial locations. Finally, in the case of the pulse-shaping application, our results show that heterogeneous metastructures can be designed to tailor the spatial profile of a propagating wave packet. Collectively, these results show the versatility of the relaxed micromorphic model for effectively and accurately simulating wave propagation in heterogeneous metastructures, and how this model can be used to design heterogeneous metastructures with tailored wave propagation functionalities.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2001

Expression of heat shock protein 72 in atrophied rat skeletal muscles

Changes in the expression of heat shock protein 72 (HSP72) in response to atrophic-inducing perturbations of muscle involving chronic mechanical unloading and denervation were determined. Adult male Wistar rats were assigned randomly to a sedentary cage control (CON), hind limb unloading (HU, via tail suspension), HU plus tenotomy (HU + TEN), HU plus denervation (HU + DEN), or HU + TEN + DEN group. Tenotomy and DEN involved cutting the Achilles tendon and removing a segment of the sciatic nerve, respectively. After 5 days, HSP72 levels in the soleus of the HU + DEN and HU + TEN + DEN groups were 42 (P < 0.05) and 53% (P < 0.01) less than CON, respectively. Soleus weight decreased in both groups. Heat shock protein 72 levels in the plantaris of the HU + TEN, HU + DEN, and HU + TEN + DEN groups were 31, 25, and 30% lower than CON, respectively (P < 0.05). Plantaris weight decreased in the HU + DEN and HU + TEN + DEN, but not in the HU + TEN group. Hind limb unloading alone had little effect on the HSP72 level in either muscle. Reduced levels of HSP72 were associated with a decreased soleus (r=0.62, P < 0.01) and plantaris (r=0.78, P < 0.001) weight. These results indicate that the levels of HSP72 in both a slow and a fast rat plantarflexor are responsive to a chronic decrease in the levels of loading and/or activation and suggest that the neuromuscular activity level and the presence of innervation of a muscle are important factors that induce HSP72 expression.

NASA Discipline Musculoskeletal↗
NASA NTRS2005

Predictive Interfaces for Long-Distance Tele-Operations

We address the development of predictive tele-operator interfaces for humanoid robots with respect to two basic challenges. Firstly, we address automating the transition from fully tele-operated systems towards degrees of autonomy. Secondly, we develop compensation for the time-delay that exists when sending telemetry data from a remote operation point to robots located at low earth orbit and beyond. Humanoid robots have a great advantage over other robotic platforms for use in space-based construction and maintenance because they can use the same tools as astronauts do. The major disadvantage is that they are difficult to control due to the large number of degrees of freedom, which makes it difficult to synthesize autonomous behaviors using conventional means. We are working with the NASA Johnson Space Center's Robonaut which is an anthropomorphic robot with fully articulated hands, arms, and neck. We have trained hidden Markov models that make use of the command data, sensory streams, and other relevant data sources to predict a tele-operator's intent. This allows us to achieve subgoal level commanding without the use of predefined command dictionaries, and to create sub-goal autonomy via sequence generation from generative models. Our method works as a means to incrementally transition from manual tele-operation to semi-autonomous, supervised operation. The multi-agent laboratory experiments conducted by Ambrose et. al. have shown that it is feasible to directly tele-operate multiple Robonauts with humans to perform complex tasks such as truss assembly. However, once a time-delay is introduced into the system, the rate of tele\ioperation slows down to mimic a bump and wait type of activity. We would like to maintain the same interface to the operator despite time-delays. To this end, we are developing an interface which will allow for us to predict the intentions of the operator while interacting with a 3D virtual representation of the expected state of the robot. The predictive interface anticipates the intention of the operator, and then uses this prediction to initiate appropriate sub-goal autonomy tasks.

Wheeler, Kevin R.↗
DOE OSTI2026

Creep in multi-principal element materials –– A review

The ongoing push towards enhanced energy efficiency and reduced emissions has necessitated the creation of materials with superior performance, especially under extreme conditions. Modern industries, such as aerospace, energy production, and nuclear power, rely heavily on materials that can withstand elevated temperatures without compromising structural integrity. At these heightened temperatures, materials, even when subjected to mechanical stresses well below their yield strength, may experience slow deformation leading to eventual rupture — a phenomenon known as creep. With the expansive design space that comes with the high entropy concept and their reported excellent high temperature strength, multi-principal element materials (MPEMs) have attracted interest in the scientific community for high-temperature applications. Here, this review offers a comprehensive examination of existing studies on creep in MPEMs, which includes multi-principal element−alloys, −bulk metallic glasses, −ceramics, and −superalloys, comparing published findings on MPEMs with pure elements, traditional alloys, bulk metallic glasses, and superalloys. The sub-topics covered include a comparison among different creep-testing methods, creep mechanisms, creep exponents, creep strain rates, activation volume, and creep-activation energy. Modeling efforts for predicting creep behavior of MPEMs are also reviewed. Methods for improving creep resistance by performing heat treatments and/or modifying microstructures are discussed. Overall, the current state of MPEMs has not yet surpassed the creep performance of commercial alloys. Finally, directions for future efforts are suggested, such as experimenting in various controlled environments, expanding the number of compositions tested, exploring advanced manufacturing techniques, and using machine-learning to predict creep properties based on compositions and microstructures.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Development of a software interface for optical disk archival storage for a new life sciences flight experiments computer

The current Life Sciences Laboratory Equipment (LSLE) microcomputer for life sciences experiment data acquisition is now obsolete. Among the weaknesses of the current microcomputer are small memory size, relatively slow analog data sampling rates, and the lack of a bulk data storage device. While life science investigators normally prefer data to be transmitted to Earth as it is taken, this is not always possible. No down-link exists for experiments performed in the Shuttle middeck region. One important aspect of a replacement microcomputer is provision for in-flight storage of experimental data. The Write Once, Read Many (WORM) optical disk was studied because of its high storage density, data integrity, and the availability of a space-qualified unit. In keeping with the goals for a replacement microcomputer based upon commercially available components and standard interfaces, the system studied includes a Small Computer System Interface (SCSI) for interfacing the WORM drive. The system itself is designed around the STD bus, using readily available boards. Configurations examined were: (1) master processor board and slave processor board with the SCSI interface; (2) master processor with SCSI interface; (3) master processor with SCSI and Direct Memory Access (DMA); (4) master processor controlling a separate STD bus SCSI board; and (5) master processor controlling a separate STD bus SCSI board with DMA.

Bartram, Peter N.↗
NASA NTRS2000

Interpreting Assemblages with Titanite (Sphene): It Does not have to be Greek to You.

Assemblages with titanite, pyroxene(s), olivine, ilmenite, magnetite, and quartz can be used to constrain the intensive and compositional variables that operate during crystallization. Such assemblages are relatively rare in metamorphic rocks, but they are more common in igneous rocks and more frequently reported in plutonic than volcanic rocks. We used the program QUILF, enhanced with thermodynamic data for titanite, to compute stable reactions among titanite (CaTiOSiO4), Fe-Mg-Ti ilmenite and magnetite (hereafter ilmenite and magnetite), Ca-Mg-Fe pyroxenes and olivine, and quartz, and to evaluate some of the factors that control titanite stability. Calculations at 1, 3, and 6 Kbar and 650, 850, 1100 0 C, in the system CaO - MgO - FeO Fe2O3 - TiO2 - SiO2, suggest that the reactions: Augitc + Ilmenite = Titanite + Magnetite + Quartz and Augite + Ilmenite + Quartz = Titanite + Orthopyroxene, impose well defined fugacity of O2, alpha(sub SiO2), , and compositional restrictions to the assemblages: (1) Titanite + Magnetite + Quartz, (2) Titanite + Orthopyroxene, (3) Augite + Ilmenite, and consequently titanite stability. From our calculations in this system we can draw the following general conclusions: (1) The assemblage Titanite + Magnetite + Quartz is always a good indicator of relatively high fugacity of O2, and it is likely more common in relatively iron-rich bulk compositions and for decreasing temperature and pressure conditions. (2) At high temperatures (>= 650 C) titanite is not stable in quartz-saturated rocks that contain the assemblage Orthopyroxene + Augite + Ilmenite + Magnetite. (3) In quartz-saturated rocks the coexistence of titanite and magnetite with either orthopyroxene or olivine requires a confluence of conditions relating bulk composition, fugacity of O2, and slow cooling. Thus, such assemblages must be rare. (4) Regardless of T and fugacity of O2 conditions, and bulk-composition, titanite is not stable in quartz-absent rocks that contain Olivine + Orthopyroxene + Augite + Ilmenite + Magnetite. Decreasing temperature and pressure conditions appear to favor titanite crystallization, thus, it is not unsurprising that titanite is frequently observed in slowly cooled rocks, albeit, in association with amphibole. We argue that the titanite + amphibole association is likely favored by high water activity, regardless of oxygen fugacity. Because water activity increases during crystallization of a pluton, the association titanite + amphibole, and consequently titanite, is likely to be more common in plutonic rocks than in volcanic rocks.

Xirouchakis, Dimitrios M.↗
NASA NTRS2002

Effect of Wind Velocity on Flame Spread in Microgravity

A three-dimensional, time-dependent model is developed describing ignition and subsequent transition to flame spread over a thermally thin cellulosic sheet heated by external radiation in a microgravity environment. A low Mach number approximation to the Navier Stokes equations with global reaction rate equations describing combustion in the gas phase and the condensed phase is numerically solved. The effects of a slow external wind (1-20 cm/s) on flame transition are studied in an atmosphere of 35% oxygen concentration. The ignition is initiated at the center part of the sample by generating a line-shape flame along the width of the sample. The calculated results are compared with data obtained in the 10s drop tower. Numerical results exhibit flame quenching at a wind speed of 1.0 cm/s, two localized flames propagating upstream along the sample edges at 1.5 cm/s, a single line-shape flame front at 5.0 cm/s, three flames structure observed at 10.0 cm/s (consisting of a single line-shape flame propagating upstream and two localized flames propagating downstream along sample edges) and followed by two line-shape flames (one propagating upstream and another propagating downstream) at 20.0 cm/s. These observations qualitatively compare with experimental data. Three-dimensional visualization of the observed flame complex, fuel concentration contours, oxygen and reaction rate isosurfaces, convective and diffusive mass flux are used to obtain a detailed understanding of the controlling mechanism, Physical arguments based on lateral diffusive flux of oxygen, fuel depletion, oxygen shadow of the flame and heat release rate are constructed to explain the various observed flame shapes.

Prasad, Kuldeep↗
NASA NTRS2002

An Automated Method to Compute Orbital Re-Entry Trajectories with Heating Constraints

Determining how to properly manipulate the controls of a re-entering re-usable launch vehicle (RLV) so that it is able to safely return to Earth and land involves the solution of a two-point boundary value problem (TPBVP). This problem, which can be quite difficult, is traditionally solved on the ground prior to flight. If necessary, a nearly unlimited amount of time is available to find the "best" solution using a variety of trajectory design and optimization tools. The role of entry guidance during flight is to follow the pre-determined reference solution while correcting for any errors encountered along the way. This guidance method is both highly reliable and very efficient in terms of onboard computer resources. There is a growing interest in a style of entry guidance that places the responsibility of solving the TPBVP in the actual entry guidance flight software. Here there is very limited computer time. The powerful, but finicky, mathematical tools used by trajectory designers on the ground cannot in general be made to do the job. Nonconvergence or slow convergence can result in disaster. The challenges of designing such an algorithm are numerous and difficult. Yet the payoff (in the form of decreased operational costs and increased safety) can be substantial. This paper presents an algorithm that incorporates features of both types of guidance strategies. It takes an initial RLV orbital re-entry state and finds a trajectory that will safely transport the vehicle to a Terminal Area Energy Management (TAEM) region. During actual flight, the computed trajectory is used as the reference to be flown by a more traditional guidance method.

Zimmerman, Curtis↗
DOE OSTI2025

Structural and Dynamical Insights into the Formation Process of a Cross-Linked Polymer Network in Acrylic Adhesives During Thermal Curing

Many modern adhesives, sealants, and coatings rely on the controlled transition from a liquid to a solid state by forming a three-dimensional cross-linked polymer network, often referred to as curing. The curing process, which is initiated by the mixing of reactive components or an external trigger, defines the structure of a network and further controls the final mechanical properties of cured materials. However, the curing mechanism is not fully understood yet due to the lack of experimental tools capable of directly probing the structure and dynamics of a network over relevant time- and length scales. Here, in this paper, we report the curing process of a commercial two-component methyl methacrylate (MMA) adhesive using in operando X-ray photon correlation spectroscopy (XPCS), a method that closely simulates the target manufacturing environment of the adhesive. The results are then integrated with those obtained by rheology, differential scanning calorimetry (DSC), and transmission electron microscopy to establish the structure–dynamics–process–property relationship. The XPCS results identify four distinct stages in the curing process after the mixing, extrusion, and deposition of the acrylic adhesive: (i) At a cure time (or “aging time”, t age ) of less than 1 min, nanodomains of polymerized MMA are formed within a liquid monomeric MMA matrix. The average size is several nm and remains constant over t age , while the dynamics of the nanodomains are slowed down with t age due to an increase in the viscosity of the MMA matrix. (ii) After t age > 1 min, the size of the nanodomains increases with t age until the gel point (= 6.3 min after mixing as determined by rheology). The dynamics of the nanodomains also increase due to the heat generated by the exothermic reaction. (iii) At the gel point, the nanodomains begin to interconnect each other, resulting in a network structure with a characteristic length of about 100 nm. This characteristic network size does not change for the rest of the curing process up to t age = 500 min. The dynamics of the network structure, however, show a rapid slowing down with t age up to t age ≈ 12 min, corresponding to the onset of vitrification (as determined by rheology). (iv) At t age > 12 min, when the DSC and rheology data can no longer provide meaningful information, the XPCS data show a further slowing down of the network dynamics associated with vitrification. Our results provide rich and complex insights into the physics and material design of thermosets in commercially relevant processes, which are essential for future industrial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Model form and sensitivity analysis of CALPHAD-based nucleation models in b-stabilized Ti alloys

Accurate prediction of α-phase nucleation and growth in β-stabilized titanium alloys is crucial for designing heat treatments to optimize mechanical properties in additively manufactured lightweight components. Ideally, predictions of nucleation and growth would incorporate both top-down observations of past experimental heat treatments and bottom-up modeling of phase transformations; however, the appropriate method of combining these information sources is not self-evident. Combining top-down and bottom-up information requires a unified form of model that can connect between spatiotemporal scales, as well as sets of fitting parameters that can be identified by each data source. The selection of which parameters to fit to which data source can be made based on expert opinion, or by performing a sensitivity analysis. In solid-solid nucleation, direct observation of the nucleation and growth process is challenging. Most data on the heat treatment-controlled phase transformations are not in-situ. To predict the process and outcome of the nucleation, growth and coarsening of precipitates, theoretical models of the nucleation pathway are used to bridge the gap. Many sources of uncertainty affect the modeling of this nucleation process. It can be influenced by small variations in the thermomechanical processing history, chemical composition, and initial microstructure. If molecular dynamics (MD) simulations are used to determine thermodynamic quantities and inform CALPHAD modeling, additional uncertainty can be introduced and accounted for using Bayesian methods. Top-down uncertainties require additional steps to quantify. The influence of nucleation model form on the sensitivity of predictions to input parameters and physical conditions is the focus of this study. Classical nucleation theory (CNT) allows modeling to formulate the nucleation as homogeneous or, more commonly, heterogeneous. Non-classical nucleation models are also increasingly explored as a means of reconciling top-down and bottom-up data. In this study, the sensitivity of the intragranular nucleation of α in a β-annealed, slow-cooled aging (BASCA) heat treatment of β-stabilized Ti5553 alloy is explored using CNT and both heterogeneous and homogeneous assumptions. The Kampmann-Wagner Numerical model of precipitate nucleation and growth is employed. Using open-source tools (pyCalphad and thermodynamic modeling of TiMo as a surrogate system, a sensitivity analysis is performed to measure variations in key parameters, including chemical driving force, interfacial energy, and diffusivity, as they relate to predictions of precipitate number density. The inclusion of top-down and bottom-up data in selection of nucleation model form is discussed.

Rodriguez Negron, A. M.↗
NASA NTRS2002

An Automated Method to Compute Orbital Re-entry Trajectories with Heating Constraints

Determining how to properly manipulate the controls of a re-entering re-usable launch vehicle (RLV) so that it is able to safely return to Earth and land involves the solution of a two-point boundary value problem (TPBVP). This problem, which can be quite difficult, is traditionally solved on the ground prior to flight. If necessary, a nearly unlimited amount of time is available to find the 'best' solution using a variety of trajectory design and optimization tools. The role of entry guidance during flight is to follow the pre- determined reference solution while correcting for any errors encountered along the way. This guidance method is both highly reliable and very efficient in terms of onboard computer resources. There is a growing interest in a style of entry guidance that places the responsibility of solving the TPBVP in the actual entry guidance flight software. Here there is very limited computer time. The powerful, but finicky, mathematical tools used by trajectory designers on the ground cannot in general be converted to do the job. Non-convergence or slow convergence can result in disaster. The challenges of designing such an algorithm are numerous and difficult. Yet the payoff (in the form of decreased operational costs and increased safety) can be substantiaL This paper presents an algorithm that incorporates features of both types of guidance strategies. It takes an initial RLV orbital re-entry state and finds a trajectory that will safely transport the vehicle to Earth. During actual flight, the computed trajectory is used as the reference to be flown by a more traditional guidance method.

Zimmerman, Curtis↗
NASA NTRS1999

Early root cap development and graviresponse in white clover (Trifolium repens) grown in space and on a two-axis clinostat

White clover (Trifolium repens) was germinated and grown in microgravity aboard the Space Shuttle (STS-60, 1994; STS-63, 1995), on Earth in stationary racks and in a slow-rotating two-axis clinostat. The objective of this study was to determine if normal root cap development and early plant gravity responses were dependent on gravitational cues. Seedlings were germinated in space and chemically fixed in orbit after 21, 40, and 72 h. Seedlings 96 h old were returned viable to earth. Germination and total seedling length were not dependent on gravity treatment. In space-flown seedlings, the number of cell stories in the root cap and the geometry of central columella cells did not differ from those of the Earth-grown seedlings. The root cap structure of clinorotated plants appeared similar to that of seedlings from microgravity, with the exception of three-day rotated plants, which displayed significant cellular damage in the columella region. Nuclear polarity did not depend on gravity; however, the positions of amyloplasts in the central columella cells were dependent on both the gravity treatment and the age of the seedlings. Seedlings from space, returned viable to earth, responded to horizontal stimulation as did 1 g controls, but seedlings rotated on the clinostat for the same duration had a reduced curvature response. This study demonstrates that initial root cap development is insensitive to either chronic clinorotation or microgravity. Soon after differentiation, however, clinorotation leads to loss of normal root cap structure and plant graviresponse while microgravity does not.

manned↗
DOE OSTI2025

Evaluating inkjet dispenser/liquid vortex capture-mass spectrometry for single-cell metabolomics in Hep G2 steatosis caused by tamoxifen

Single-cell mass spectrometry (MS) is advancing our understanding of metabolic pathways in heterogeneous cell populations; however, many techniques are slow or require disruptive sample preparations. This study evaluated coupling a modified HP D100 single-cell inkjet dispenser with liquid vortex capture-mass spectrometry (D100/LVC-MS). The D100 is a single-cell inkjet dispenser capable of titrating solutions and isolating single cells via disposable cassettes equipped with microfluidic channels and an impedance sensor. The LVC-MS enables high-throughput capture, lysis, and ionization of analytes for mass spectrometric analysis. The D100/LVC-MS system was characterized through titration and single-cell experiments. Propranolol titration demonstrated linearity across a broad concentration range using the D100/LVC-MS system. Additionally, Hep G2 hepatocarcinoma cells and Chlamydomonas reinhardtii algae were used to showcase the D100’s high-throughput or low-buffer-volume single-cell dispensing strategies. The D100/LVC-MS system’s performance was validated by evaluating tamoxifen-induced steatosis in Hep G2 cells. Tamoxifen, associated with nonalcoholic fatty liver disease in breast cancer patients following long-term use, was tested in Hep G2 cells at 20 µM for 72 h against DMSO-treated controls. High-throughput analysis of 500 cells per condition, completed in 25 min per run, demonstrated the system’s efficiency. The D100/LVC-MS system simultaneously quantified tamoxifen and measured triglycerides and phosphatidylcholines. Triglycerides were upregulated in the tamoxifen-treated cells and the results indicated two distinct cell populations, differing in tamoxifen and phosphatidylcholines levels, suggesting heterogeneity within the treated population. In conclusion, these findings highlight the D100/LVC-MS system as a cost-effective, high-throughput platform for single-cell metabolomics and lipidomics, with significant potential for evaluating metabolic alterations.

Chromatography↗
NASA NTRS1994

Pickup protons and pressure-balanced structures: Voyager 2 observations in merged interaction regions near 35 AU

Five pressure-balanced structures, each with a scale of the order of a few hundredths of an astonomical unit (AU), were identified in two merged interaction regions (MIRs) near 35 AU in the Voyager 2 plasma and magnetic field data. They include a tangential discountinuity, simple and complex magnetic holes, slow correlated variations among the plasma and magnetic field parameters, and complex uncorrelated variations among the parameters. The changes in the magnetic pressure in these events are balanced by changes in the pressure of interstellar pickup protons. Thus the pickup protons probably play a major role in the dynamics of the MIRs. The solar wind proton and electron pressures are relatively unimportant in the MIRs at 35 AU and beyond. The region near 35 AU is transition region: the Sun is the source of the magnetic field, but the interstellar medium in source of pickups protons. Relative to the solar wind proton guyroadius, the thicknesses of the discontinuities and simple magnetic holes observed near 35 AU are at least an order of magnitude greater than those observed at 1 AU. However, the thicknesses of the tangential discontinuity and simple magnetic holes observed near 35 AU (in units of the pickup proton Larmor radius) are comparable to those observed at 1 AU (in units of the solar wind proton gyroradius). Thus the gyroradius of interstellar pickup protons controls the thickness of current sheets near 35 AU. We determine the interstellar pickup proton pressure in the PBSs. Using a model for the pickup proton temperature, we estimate that the average interstellar pickup proton pressure, temperature, and density in the MIRs at 35 AU are (0.53 +/- 0.14) x 10(exp -12) erg/cu cm, (5.8 +/- 0.4) x 10(exp 6) K and (7 +/- 2) x 10(exp -4)/cu cm.

Burlaga, L. F.↗
DOE OSTI2022

Controlling Symmetry Breaking Charge Transfer in BODIPY Pairs

Symmetry breaking charge transfer (SBCT) is a process in which a pair of identical chromophores absorb a photon and use its energy to transfer an electron from one chromophore to the other, breaking the symmetry of the chromophore pair. This excited state phenomenon is observed in photosynthetic organisms where it enables efficient formation of separated charges that ultimately catalyze biosynthesis. SBCT has also been proposed as a means for developing photovoltaics and photocatalytic systems that operate with minimal energy loss. It is known that SBCT in both biological and artificial systems is in part made possible by the local environment in which it occurs, which can move to stabilize the asymmetric SBCT state. However, how environmental degrees of freedom act in concert with steric and structural constraints placed on a chromophore pair to dictate its ability to generate long-lived charge pairs via SBCT remain open topics of investigation. In this work we compare a broad series of dipyrrin dimers that are linked by distinct bridging groups to discern how the spatial separation and mutual orientation of linked chromophores and the structural flexibility of their linker each impact SBCT efficiency. Across this material set, we observe a general trend that SBCT is accelerated as the spatial separation between dimer chromophores decreases, consistent with the expectation that the electronic coupling between these units varies exponentially with their separation. However, one key observation is that the rate of charge recombination following SBCT was found to slow with decreasing interchromophore separation, rather than speed up. This stems from an enhancement of the dimers’ structural rigidity due to increasing steric repulsion as the length of their linker shrinks. This rigidity further inhibits charge recombination in systems where symmetry has already enforced zero HOMO-LUMO overlap. Additionally, for the forward transfer the active torsion is shown to increase LUMO-LUMO coupling, allowing for faster SBCT within bridging groups. Further, by understanding trends for how rates of SBCT and charge recombination depend on a dimer’s internal structure and their environment, we identify design guidelines for creating artificial systems for driving sustained light-induced charge separation. Such systems can find application in solar energy technologies and photocatalytic applications but can serve as a model for light-induced charge separation in biological systems.

14 SOLAR ENERGY↗
DOE OSTI2024

Nano-Plasticity of an Electrified Ionic Liquid/Electrode Interface: Uncovering Hard–Soft Structuring via Controlled Metal Fill Factor

Here, ionic liquids (ILs) nanostructuring at electrified interfaces is of both fundamental and practical interest as these materials are increasingly gaining prominence in energy storage and conversion processes. However, much remains unresolved about IL potential-controlled (re)organization under highly polarized interfaces, mostly due to the difficulty of selectively probing both the distal and proximal surface layers of adsorbed ions. In this work, the structural dynamics of the innermost layer (<10 nm from the surface) were independently interrogated from that of the ionic layers in the sub-surface region (>100 nm from the surface), using an infrared (IR) spectroscopy approach. By tuning the metal fill factor of gold films deposited on conductive metal oxide-modified IR internal reflection elements, the charge-driven (re)structuring of the inner and distal layers of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate is unveiled. Within a relatively wide potential region (~±1 V) bounding the potential of zero charges, the ionic liquid is shown to undergo a reversible (i.e., soft) reorganization whereby the innermost layer of anions (cations) is exchanged by a layer of cations (anions). Kinetically unhindered changes in the number density of constituent cations and anions largely follow electrostatic expectations in the subsurface region, whereas the innermost layer exhibits a pronounced hysteresis and very slow relaxation. Under larger negative potential bias, IL restructuring is characterized by a highly irreversible (i.e., hard) and intense interfacial densification of the BMPy + cations, consistent with the formation of nanoscale segregated liquids. The outcomes of this work reveal a plastic IL nanostructuring under a strong electric field.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Characterization of long-term extension of isolated cell walls from growing cucumber hypocotyls

Walls from frozen-thawed cucumber (Cucumis sativus L.) hypocotyls extend for many hours when placed in tension under acidic conditions. This study examined whether such "creep" is a purely physical process dependent on wall viscoelasticity alone or whether enzymatic activities are needed to maintain wall extension. Chemical denaturants inhibited wall creep, some acting reversibly and others irreversibly. Brief (15 s) boiling in water irreversibly inhibited creep, as did pre-incubation with proteases. Creep exhibited a high Q10 (3.8) between 20 degrees and 30 degrees C, with slow inactivation at higher temperatures, whereas the viscous flow of pectin solutions exhibited a much lower Q10 (1.35). On the basis of its temperature sensitivity, involvement of pectic gel-sol transitions was judged to be of little importance in creep. Pre-incubation of walls in neutral pH irreversibly inactivated their ability to creep, with a half-time of about 40 min. At 1 mM, Cu2+, Hg2+ and Al3+ were strongly inhibitory whereas most other cations, including Ca2+, had little effect. Sulfhydryl-reducing agents strongly stimulated creep, apparently by stabilizing wall enzyme(s). The physical effects of these treatments on polymer interactions were examined by Instron and stress-relaxation analyses. Some treatments, such as pH and Cu2+, had significant effects on wall viscoelasticity, but others had little or no apparent effect, thus implicating an enzymatic creep mechanism. The results indicate that creep depends on relatively rugged enzymes that are firmly attached to or entangled in the wall. The sensitivity of creep to SH-reducing agents indicates that thiol reduction of wall enzymes might provide a control mechanism for endogenous cell growth.

NASA Program Space Biology↗
DOE OSTI2025

High‐Performance Al–S Batteries by Spin Polarization Modulation via Catalytic Ni‐MoS 2 Nanosheets

Aluminum–sulfur (Al–S) batteries catalysts with adsorption and catalytic capabilities can effectively improve the slow redox kinetics, but the current research often ignores the effect of optimizing the electronic structure of the catalyst on improving charge transfer and adsorption. Here, in this study, Ni-doped monolayer MoS 2 nanosheets are synthesized and used as a catalytic additive for the sulfur cathode. The addition of Ni promotes spin splitting of 4d orbital of Mo, thereby affecting polarization degree of the basal plane sulfur and making it change from a low spin state to a high spin one. This high spin configuration raises the electron energy level and provides an active electron state to react with aluminum polysulfides (AlPSs), which optimizes the adsorption energy. At the same time, it accelerates electron transfer and lowers the energy barrier for the overall conversion of the polysulfides. Benefiting from these features, Al–S batteries based on rationally designed S@Ni-MoS 2 /C cathodes exhibit a high initial capacity (1603.0 mAh g −1 at 0.5 A g −1 ) and extraordinary cycling stability (0.035% capacity decay rate during 2000 cycles). This study showcases a spin-polarized electronic structure control strategy to enhance catalytic activity, providing a viable approach for developing efficient catalysts for practical Al–S batteries.

Aluminum-sulfur batteries↗