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QM Investigation of Rare Earth Ion Interactions with First Hydration Shell Waters and Protein-Based Coordination Models

Here, conventional methods for extracting rare earth metals (REMs) from mined mineral ores are inefficient, expensive, and environmentally damaging. Recent discovery of lanmodulin (LanM), a protein that coordinates REMs with high-affinity and selectivity over competing ions, provides inspiration for new REM refinement methods. Here, we used quantum mechanical (QM) methods to investigate trivalent lanthanide cation (Ln 3+ ) interactions with coordination systems representing bulk solvent water and protein binding sites. Energy decomposition analysis (EDA) showed differences in the energetic components of Ln 3+ interaction with representatives of solvent (water, H 2 O) and protein binding sites (acetate, CH 3 COO – ), highlighting the importance of accurate description of electrostatics and polarization in computational modeling of REM interactions with biological and bioinspired molecules. Relative binding free energies were obtained for Ln 3+ with coordination complexes originating from binding sites in PDB structures of a lanthanum binding peptide (PDB entry 7CCO) and LanM, with explicit consideration of the first hydration shell waters, according to quasi-chemical theory (QCT). Beyond the first shell, the bulk solvent environment was represented with an implicit continuum model. Ln 3+ interactions with (H 2 O) 9 and both binding site models became more favorable, moving down the periodic series. This trend was more pronounced with the protein binding site models than with water, resulting in affinity increasing with periodic number, except for the last REM, Lu 3+ , which bound less favorably than the preceding element, Yb 3+ . Using the truncated 7CCO binding site model, the magnitude and trend of the experimental Ln 3+ relative binding free energies for the whole 7CCO peptide were reproduced. Conversely, the previously reported experimental data for LanM show a preference for the earlier lanthanides; this is likely due to longer-range interactions and cooperative effects, which are not represented by the reduced models. Using the truncated 7CCO binding site model, the magnitude and trend of the experimental Ln 3+ relative binding free energies for the whole 7CCO peptide were reproduced. In contrast to the previously reported experimental data for LanM, the peptide preferentially binds the earlier lanthanides. This difference likely arises due to longer-range interactions and cooperative effects not represented by the peptide. Further investigation of Ln 3+ interactions with whole proteins using polarizable molecular mechanics models with explicit solvent is warranted to understand the influence of longer-ranged interactions, cooperativity, and bulk solvent. Nevertheless, the present work provides new insights into Ln 3+ interactions with biomolecules and presents an effective computational platform for designing specific single-site REM binding peptides more efficiently.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Mars exploration using biomorphic flyers

We will illustrate how autonomous biomorphic flyers will enable imagery and environmental measurements to be captured from extremely low altitudes and even inside terrain features.

biology bioinspired

Bioinspired Engineering of Exploration Systems (BEES) - its Impact on Future Missions

This paper describes an overview of our "Bioinspired Engineering of Exploration Systems for Mars" ( "BEES for Mars") project. The BEES approach distills selected biologically inspired strategies utilizing motion cues/optic flow, bioinspired pattern recognition, biological visual and neural control systems, bioinspired sensing and communication techniques, and birds of prey inspired search and track algorithmic systems. Unique capabilities so enabled, provide potential solutions to future autonomous robotic space and planetary mission applications. With the first series of tests performed in September 2003, August 2004 and September 2004, we have demonstrated the BEES technologies at the El Mirage Dry Lakebed site in the Mojave Desert using Delta Wing experimental prototypes. We call these test flyers the "BEES flyer", since we are developing them as dedicated test platform for the newly developed bioinspired sensors, processors and algorithmic strategies. The Delta Wing offers a robust airframe that can sustain high G launches and offers ease of compact stowability and packaging along with scaling to small size and low ReynOld's number performance for a potential Mars deployment. Our approach to developing light weight, low power autonomous flight systems using concepts distilled from biology promises to enable new applications, of dual use to NASA and DoD needs. Small in size (0.5 -5 Kg) BEES Flyers are demonstrating capabilities for autonomous flight and sensor operability in Mars analog conditions. The BEES project team spans JPL, NASA Ames, Australian National University (ANU), Brigham Young University(BYU), DC Berkeiey, Analogic Computers Inc. and other institutions. The highlights from our recent flight demonstrations exhibiting new Mission enabling capabilities are described. Further, this paper describes two classes of potential new missions for Mars exploration: (1) the long range exploration missions, and (2) observation missions, for real time imaging of critical ephemeral phenomena, that can be enabled by use of BEES flyers. For example, such flyers can serve as a powerful black-box for critical descent and landing data and enablers for improved science missions complementing and supplementing the existing assets like landers and rovers by providing valuable exploration and quick extended low-altitude aerial coverage of the sites of interest by imaging them and distributing instruments to them. Imaging done by orbiters allows broad surface coverage at limited spatial resolution. Low altitude air-borne exploration of Mars offers a means for imaging large areas, perhaps up to several hundred kilometers, quickly and efficiently, providing a close-up birds-eye view of the planetary terrain and close-up approach to constrained difficult areas like canyons and craters. A novel approach to low-mass yet highly capable flyers is enabled by small aircraft equipped using sensors and processors and algorithms developed using BEES technology. This project is focused towards showing the direct impact of blending the best of artificial intelligence attributes and bioinspiration to create a leap beyond existing capability for our future Missions.

navigation

Biologically-inspired navigation and flight control for Mars flyer missions

Bioinspired Engineering Exploration Systems (BEES), is enabling new bioinspired sensors for autonomous exploration of Mars. The steps towards autonomy in development of these BEES flyers are described. A future set of Mars mission that are uniquely enabled by surch flyers are finally described.

bioinspired engineering Mars mission design flight

Bio-inspired interlocking metasurfaces

Interlocking metasurfaces (ILMs) are patterned arrays of mating features that enable the joining of bodies by constraining motion and transmitting force. They offer an alternative to traditional joining solutions such as mechanical fasteners, welds, and adhesives. This study explores the development of bio-inspired ILMs using a problem-driven bioinspired design (BID) framework. We develop a taxonomy of attachment solutions that considers both biological and engineered systems and derive conventional design principles for ILM design. We conceptualize two engineering implementations to demonstrate concept development using the taxonomy and ILM conventional design principle through the BID framework: one for rapidly assembled bridge truss members and another for modular microrobots. These implementations highlight the potential of BID to enhance performance, functionality, and tunability in ILMs.

attachment

Benefits to society of bioinspired flight capabilities

This paper highlights how in just about 100 years since the first successful flight took place at Kitty Hawk, our recent developments using inspiration from biology are enabling us to demonstrate flight capability for Mars exploration.

flight biology

Role of a Chemist in Modern Industries: Design and Development of Nanoengineered Multifunctional Materials

During the past fifteen years significant investment has been made for the applications of nanotechnology in almost every aspect of life. Almost every area of research has projected improvements including biotechnology, bioinspired electronic, optical and radiological sensors, or a promise for the emergence of some novel device technologies. For such applications major focus has been placed on research nanoparticles, nanotubes nanorods and two-dimensional structures similar to that of graphene. Some near- term applications of nano- particles and nanowires have produced very promising results for better synthesis of energy storage materials, design of biologically active composites like apatites, laser host crystals, photodetectors and sensor materials for radiation detection. To achieve desired morphologies, nanomaterials can be utilized some organic melt and orient the grains by the directional solidification method. The organic treated materials produce different characteristics than coarsened oxide materials. The focus is also understanding the morphology and performance function in human organs that occur because of aging or disease, and responses to interventions. We annealed to determine the changes in morphologies and hence effect of aging. In this presentation, we will discuss correlation between the designed composition, micromorphology and the performance parameters of nanomaterials. To understand the mechanism of formation of nanoparticles, nanoboloids, fibers experimental details and observations on the of multinary compounds will be presented. These observations on the transition of nanomorphology can highlight the mechanism of the phase transition in some oxides and selenides.

Singh, N. B.

Bio-Inspired Engineering of Exploration Systems

The multidisciplinary concept of "bioinspired engineering of exploration systems" (BEES) is described, which is a guiding principle of the continuing effort to develop biomorphic explorers as reported in a number of articles in the past issues of NASA Tech Briefs. The intent of BEES is to distill from the principles found in successful nature-tested mechanisms of specific crucial functions that are hard to accomplish by conventional methods but that are accomplished rather deftly in nature by biological organisms. The intent is not just to mimic operational mechanisms found in a specific biological organism but to imbibe the salient principles from a variety of diverse bio-organisms for the desired crucial function. Thereby, we can build explorer systems that have specific capabilities endowed beyond nature, as they will possess a combination of the best nature-tested mechanisms for that particular function. The approach consists of selecting a crucial function, for example, flight or some selected aspects of flight, and develop an explorer that combines the principles of those specific attributes as seen in diverse flying species into one artificial entity. This will allow going beyond biology and achieving unprecedented capability and adaptability needed in encountering and exploring what is as yet unknown. A classification of biomorphic flyers into two main classes of surface and aerial explorers is illustrated in the figure, with examples of a variety of biological organisms that provide the inspiration in each respective subclass. Such biomorphic explorers may possess varied mobility modes: surface-roving, burrowing, hopping, hovering, or flying, to accomplish surface, subsurface, and aerial exploration. Preprogrammed for a specific function, they could serve as one-way communicating beacons, spread over the exploration site, autonomously looking for/at the targets of interest. In a hierarchical organization, these biomorphic explorers would report to the next level of exploration mode (say, a large conventional lander/rover) in the vicinity. A widespread and affordable exploration of new/hazardous sites at lower cost and risk would thus become possible by utilizing a faster aerial flyer to cover long ranges and deploying a variety of function- specific, smaller biomorphic explorers for distributed sensing and local sample acquisition. Several conceptual biomorphic missions for planetary and terrestrial exploration applications have been illustrated in "Surface-Launched Explorers for Reconnaissance/ Scouting" (NPO-20871), NASA Tech Briefs, Vol. 26, No. 4 (April, 2002), page 69 and "Bio-Inspired Engineering of Exploration Systems," Journal of Space Mission Architecture, Issue 2, Fall 2000, pages 49-79.

Thakoor, Sanita

EPR and 31 P ENDOR Characterization of Pseudo-Jahn–Teller Dynamics and N 2 Activation in Functional Nitrogenase Models, P 3 E M(N 2 ) (M = Fe, Co; E = Si, B, C)

Here, the nominally trigonal, pseudo-Jahn-Teller (PJT)-active, S = ½ N 2 -bound transition-metal complexes, P 3 E M(N 2 ), M = Fe, Co, with three in-plane phosphine-ligands and axial donors, E = Si, B, C, include functional nitrogenase models that catalyze reduction of N 2 to NH 3 . We applied EPR, 31 P ENDOR spectroscopy and DFT computations to characterize the PJT-induced distortions of four selected P 3 E M(N 2 ), revealing how the metal-ion and axial ligand E together tune both PJT dynamics and N 2 activation for reduction. Comparisons reveal an unrecognized correlation between PJT distortion, M-E bond elasticity, and N 2 activation, providing guidelines for designing bioinspired N 2 -reduction catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Actions, Observations, and Decision-Making: Biologically Inspired Strategies for Autonomous Aerial Vehicles

This paper details the development and demonstration of an autonomous aerial vehicle embodying search and find mission planning and execution srrategies inspired by foraging behaviors found in biology. It begins by describing key characteristics required by an aeria! explorer to support science and planetary exploration goals, and illustrates these through a hypothetical mission profile. It next outlines a conceptual bio- inspired search and find autonomy architecture that implements observations, decisions, and actions through an "ecology" of producer, consumer, and decomposer agents. Moving from concepts to development activities, it then presents the results of mission representative UAV aerial surveys at a Mars analog site. It next describes hardware and software enhancements made to a commercial small fixed-wing UAV system, which inc!nde a ncw dpvelopnent architecture that also provides hardware in the loop simulation capability. After presenting the results of simulated and actual flights of bioinspired flight algorithms, it concludes with a discussion of future development to include an expansion of system capabilities and field science support.

Pisanich, Greg

Bioinspired engineering of exploration systems for NASA and DoD

A new approach called bioinspired engineering of exploration systems (BEES) and its value for solving pressing NASA and DoD needs are described. Insects (for example honeybees and dragonflies) cope remarkably well with their world, despite possessing a brain containing less than 0.01% as many neurons as the human brain. Although most insects have immobile eyes with fixed focus optics and lack stereo vision, they use a number of ingenious, computationally simple strategies for perceiving their world in three dimensions and navigating successfully within it. We are distilling selected insect-inspired strategies to obtain novel solutions for navigation, hazard avoidance, altitude hold, stable flight, terrain following, and gentle deployment of payload. Such functionality provides potential solutions for future autonomous robotic space and planetary explorers. A BEES approach to developing lightweight low-power autonomous flight systems should be useful for flight control of such biomorphic flyers for both NASA and DoD needs. Recent biological studies of mammalian retinas confirm that representations of multiple features of the visual world are systematically parsed and processed in parallel. Features are mapped to a stack of cellular strata within the retina. Each of these representations can be efficiently modeled in semiconductor cellular nonlinear network (CNN) chips. We describe recent breakthroughs in exploring the feasibility of the unique blending of insect strategies of navigation with mammalian visual search, pattern recognition, and image understanding into hybrid biomorphic flyers for future planetary and terrestrial applications. We describe a few future mission scenarios for Mars exploration, uniquely enabled by these newly developed biomorphic flyers.

Space Flight

Equilibrium-gated pattern formation: How molecular dissociation thermodynamics drive emergent behavior in dissipative polymeric systems

Emergent patterns in biological systems arise through dissipative processes that balance reaction and transport phenomena, producing highly functional properties from self-regulating mechanisms. Synthetic fabrication, by contrast, often relies on user-controlled, multistep methods that lack the self-organizing capabilities of natural systems. Inspired by nature, we sought chemical systems that integrate strongly coupled reaction and transport phenomena, identifying frontal ring-opening metathesis polymerization (FROMP) as a method capable of creating diverse forms and functions through reactive processing. By employing discrete molecular initiators, FROMP allows precise control of key reaction steps—inhibition, initiation, and propagation. Using an integrated computational and experimental framework, we uncover how near-equilibrium inhibition dynamics, coupled with far-from-equilibrium reaction kinetics, drive pattern formation in frontally polymerized synthetic materials. We propose the concept of equilibrium-gated pattern formation, demonstrating how initiator chemistry can be tuned to achieve programmable macroscale properties. Our study reveals a surprising insight: Emergent behavior in FROMP systems arises from the inhibition-dominated regime of resin composition, expanding prior observations that such behavior is confined to a narrow compositional space near the boundary between front quenching and uniform front propagation. We identify a broader compositional window, far from the quenching regime, where emergent behavior reliably manifests. This expanded design space significantly enhances the operational flexibility of reactive systems and their capacity for self-organization. Furthermore, these insights provide a roadmap for designing bioinspired materials with self-organizing capabilities, unlocking possibilities in synthetic manufacturing.

Architected Polymers

Stimulus-Responsive Modulation of Solvation Environments in Solid Catalysts

Liquid environments play a crucial role in the biological processes occurring in living organisms as well as in many human-made processes involving electrochemistry, photo-, and thermocatalysis. In the majority of these systems, aqueous phases are ubiquitous due to water’s natural abundance. Water molecules, however, can exert large changes in the chemical environment of catalytically active sites, altering the reaction rates, selectivity, and catalyst stability. These solvation effects induced by water molecules near catalytic sites can drastically change the energy landscape and unlock unique reaction pathways with far more favorable kinetics. In nature, living organisms couple these complex interactions with detection, communication, and actuation mechanisms to induce self-regulatory behavior, ensuring stability of the system and thus long-term durability. Extrapolating this behavior to heterogeneous catalysis is desirable because the resulting “smart materials” can potentially unlock new chemical conversion processes with higher atom efficiency, rates, and stability. The combination of polymer chemistry and heterogeneous catalysis has introduced versatile approaches for creating materials that can respond to cues in the reaction medium that alter the accessibility, intrinsic activity, and selectivity of the catalyst. To achieve this, one could combine stimulus-responsive polymers, which undergo a large volumetric phase transition in response to an external stimulus, with a solid catalyst. This chemo-mechanical response has been employed to create a variety of nanoreactor vessels with stimulus-responsive character that turn on- and off- depending on the reaction conditions. In this Account, we focus on the impact of these polymer coatings on the solvation environment around the active site and the implications of these effects on the reaction energy landscape, molecular arrangement of the solvent, electric fields at the catalyst–liquid interface, binding energy, and mobility of surface reaction intermediates. These seemingly subtle changes in solvent molecules induced by the presence of polymers can have a tremendous impact on the development of bioinspired heterogeneous catalysts, reliable chemical clocks, micro/nanoreactors, and robots. The large library of polymer chemistries offers a plethora of combinations of stimulus-responsive mechanisms (e.g., temperature, pH, light, magnetic field, solvent composition), providing the possibility of creating homeostatic catalysts à la carte.

catalysts

Cooperative Lander-Surface/Aerial Microflyer Missions for Mars Exploration

Concepts are being investigated for exploratory missions to Mars based on Bioinspired Engineering of Exploration Systems (BEES), which is a guiding principle of this effort to develop biomorphic explorers. The novelty lies in the use of a robust telecom architecture for mission data return, utilizing multiple local relays (including the lander itself as a local relay and the explorers in the dual role of a local relay) to enable ranges ~10 to 1,000 km and downlink of color imagery. As illustrated in Figure 1, multiple microflyers that can be both surface or aerially launched are envisioned in shepherding, metamorphic, and imaging roles. These microflyers imbibe key bio-inspired principles in their flight control, navigation, and visual search operations. Honey-bee inspired algorithms utilizing visual cues to perform autonomous navigation operations such as terrain following will be utilized. The instrument suite will consist of a panoramic imager and polarization imager specifically optimized to detect ice and water. For microflyers, particularly at small sizes, bio-inspired solutions appear to offer better alternate solutions than conventional engineered approaches. This investigation addresses a wide range of interrelated issues, including desired scientific data, sizes, rates, and communication ranges that can be accomplished in alternative mission scenarios. The mission illustrated in Figure 1 offers the most robust telecom architecture and the longest range for exploration with two landers being available as main local relays in addition to an ephemeral aerial probe local relay. The shepherding or metamorphic plane are in their dual role as local relays and image data collection/storage nodes. Appropriate placement of the landing site for the scout lander with respect to the main mission lander can allow coverage of extremely large ranges and enable exhaustive survey of the area of interest. In particular, this mission could help with the path planning and risk mitigation in the traverse of the long-distance surface explorer/rover. The basic requirements of design and operation of BEES to implement the scenarios are discussed. Terrestrial applications of such concepts include distributed aerial/surface measurements of meteorological events, i.e., storm watch, seismic monitoring, reconnaissance, biological chemical sensing, search and rescue, surveillance, autonomous security/ protection agents, and/or delivery and lateral distribution of agents (sensors, surface/subsurface crawlers, clean-up agents). Figure 2 illustrates an Earth demonstration that is in development, and its implementation will illustrate the value of these biomorphic mission concepts.

Thakoor, Sarita

A bioinspired approach for adaptive solid-solid phase change material coatings with optimized surface features for passive thermal regulation

The necessity to reduce global energy consumption calls for innovative strategies in building thermal management. Passive thermal regulation, particularly through bio-inspired designs, offers a promising avenue by mimicking nature's efficient control of optical properties. This research introduces a novel, climate-responsive coating that integrates optimized bio-inspired surface features with a solid-solid phase change material (SS-PCM) to dynamically manage solar absorptivity without adding additional thickness, enabling both heating and cooling as needed. Drawing on the photonic architectures of the Saharan silver ant and Morpho Didius butterfly, we employed a modeling and multi-objective optimization framework to tailor these surface features. Simulations reveal that surface texture, rather than the intrinsic phase transition of the SS PCM, dominates optical control. Relative to a flat SS PCM coating, optimized isotropic random roughness and broader range features yielded the highest passive heating power increase of about 144 % and 319 % respectively suitable for cold climates. Saharan ant-inspired features enhanced passive cooling for hot climates, achieving a 21.8 % improvement. For moderate climates, Butterfly-wing-inspired surface features provided a balanced enhancement of 19 % for heating and 7 % for cooling. Across all cases, the optimized surface features reduced combined heating and cooling energy demand more effectively than the baseline coating, while preserving material thickness. These findings demonstrate that climate-adaptive, optimized bio-inspired surface features can unlock the full potential of SS PCM coatings, providing a versatile pathway to significant energy savings in buildings and other applications. The methodology establishes a framework for designing next-generation adaptive envelopes that leverage natural photonic principles for high-impact, low-cost thermal regulation.

36 MATERIALS SCIENCE