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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Decomposition of Irganox 1010 in plastic bonded explosives

Abstract Degradation pathways of Irganox 1010 in aged plastic bonded explosive (PBX) 9501 were investigated using ultrahigh performance liquid chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC‐QTOF). Using a targeted approach, a total of 44 Irganox 1010 decomposition products were discovered. These decomposition products were formed through hydrolysis, scission, and/or oxidation of Irganox 1010. The hydrolytic decomposition of Irganox is a straightforward process resulting in the cleavage of the ester group(s) while oxidation and scission are more complicated and can happen at multiple locations on the Irganox 1010 molecule. Moreover, due to the symmetric nature of Irganox 1010, multiple decomposition reactions can occur. Indeed some decomposition products exhibited hydrolysis, oxidation, and scission. In order to probe any trends in the aged PBX 9501 samples, principal component analysis (PCA) was implemented. The greatest chemical differences between the aged PBX samples was hydrolysis of the ester functional groups on Irganox 1010. Despite the negative connotations of hydrolysis, the Irganox 1010 decomposition products are still able to function as a radical scavenger in PBX 9501 as intended.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterization of Heparin’s Conformational Ensemble by Molecular Dynamics Simulations and Nuclear Magnetic Resonance Spectroscopy

Heparin is a highly charged, polysulfated polysaccharide and serves as an anticoagulant. Heparin binds to multiple proteins throughout the body, suggesting a large range of potential therapeutic applications. Although its function has been characterized in multiple physiological contexts, heparin’s solution conformational dynamics and structure–function relationships are not fully understood. Molecular dynamics (MD) simulations facilitate the analysis of a molecule’s underlying conformational ensemble, which then provides important information necessary for understanding structure–function relationships. However, for MD simulations to afford meaningful results, they must both provide adequate sampling and accurately represent the energy properties of a molecule. The aim of this study is to compare heparin’s conformational ensemble using two well-developed force fields for carbohydrates, known as GLYCAM06 and CHARMM36, using replica exchange molecular dynamics (REMD) simulations, and to validate these results with NMR experiments. In this work, the anticoagulant sequence, an ultra-low-molecular-weight heparin, known as Arixtra (fondaparinux, sodium), was simulated with both parameter sets. The results suggest that GLYCAM06 matches experimental nuclear magnetic resonance three-bond J-coupling values measured for Arixtra better than CHARMM36. In addition, NOESY and ROESY experiments suggest that Arixtra is very flexible in the sub-millisecond time scale and does not adopt a unique structure at 25 C. Moreover, GLYCAM06 affords a much more dynamic conformational ensemble for Arixtra than CHARMM36.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Site-specific photo-crosslinking in a double crossover DNA tile facilitated by squaraine dye aggregates: advancing thermally stable and uniform DNA nanostructures

We investigated the role of dichloro-squaraine (SQ) dye aggregates in facilitating thymine–thymine interstrand photo-crosslinking within double crossover (DX) tiles, to develop thermally stable and structurally uniform two-dimensional (2D) DNA-based nanostructures. By strategically incorporating SQ modified thymine pairs, we enabled site-selective [2 + 2] photocycloaddition under 310 nm UV light. Strong dye–dye interactions, particularly through the formation of aggregates, facilitated covalent bond formation between proximal thymines. To evaluate the impact of dye aggregation on crosslinking efficiency, ten DX tile variants with varying SQ-modified thymine positions were tested. Our results demonstrated that SQ dye aggregates significantly enhanced crosslinking, driven by precise SQ-modified thymine dimer placement within the DNA tiles. Analytical techniques, including denaturing PAGE and UV-visible spectroscopy, validated successful crosslinking in DNA tiles with multiple SQ-modified thymine pairs. This non-phototoxic method offers a potential route for creating thermally stable, homogeneous higher-order DNA–dye assemblies with potential applications in photoactive and exciton-based fields such as optoelectronics, nanoscale computing, and quantum computing. Furthermore, the insights from this study establish a foundation for further exploration of advanced DNA–dye systems, enabling the design of next-generation DNA nanostructures with enhanced functional properties.

2D DNA template↗
NASA NTRS1991

Heat transfer and core neutronics considerations of the heat pipe cooled thermionic reactor

The authors summarize the results of detailed neutronic and thermal-hydraulic evaluations of the heat pipe cooled thermionic (HPTI) reactor design, identify its key design attributes, and quantify its performance characteristics. The HPTI core uses modular, liquid-metal core heat transfer assemblies to replace the liquid-metal heat transport loop employed by in-core thermionic reactor designs of the past. The nuclear fuel, power conversion, heat transport, and heat rejection functions are all combined into a single modular unit. The reactor/converter assembly uses UN fuel pins to obtain a critical core configuration with in-core safety rods and reflector controls added to complete the subassembly. By thermally bonding the core heat transfer assemblies during the reactor core is coupled neutronically, thermally, and electrically into a modular assembly of individual power sources with cross-tied architecture. A forward-facing heat pipe radiator assembly extends from the reactor head in the shape of a frustum of a cone on the opposite side of the power system from the payload. Important virtues of the concept are the absence of any single-point failures and the ability of the core to effectively transfer the TFE waste heat load laterally to other in-core heat transfer assemblies in the event of multiple failures in either in-core and radiator heat pipes.

Determan, W. R.↗
DOE OSTI2023

Nucleation of cubic boron nitride on boron-doped diamond via plasma enhanced chemical vapor deposition

Cubic boron nitride (c-BN), with a small 1.4% lattice mismatch with diamond, presents a heterostructure with multiple opportunities for electronic device applications. However, the formation of c-BN/diamond heterostructures has been limited by the tendency to form hexagonal BN at the interface. In this study, c-BN has been deposited on free standing polycrystalline and single crystal boron-doped diamond substrates via electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD), employing fluorine chemistry. In situ x-ray photoelectron spectroscopy (XPS) is used to characterize the nucleation and growth of boron nitride (BN) films as a function of hydrogen gas flow rates during deposition. The PECVD growth rate of BN was found to increase with increased hydrogen gas flow. In the absence of hydrogen gas flow, the BN layer was reduced in thickness or etched. The XPS results show that an excess of hydrogen gas significantly increases the percent of sp2 bonding, characteristic of hexagonal BN (h-BN), particularly during initial layer growth. Reducing the hydrogen flow, such that hydrogen gas is the limiting reactant, minimizes the sp2 bonding during the nucleation of BN. TEM results indicate the partial coverage of the diamond with thin epitaxial islands of c-BN. The limited hydrogen reaction is found to be a favorable growth environment for c-BN on boron-doped diamond.

Physics↗
NASA NTRS1993

Voyager Photometry of Saturn's A Ring

Saturn's A Ring samples a wide range of dynamical environments, from the relatively unperturbed, optically thick inner region to the outer part of the ring, which contains numerous density waves. We analyze Voyager images of the A Ring to determine how the reflectivity of different radial regions varies with lighting and viewing geometry. We model our data with a classical radiative transfer code that includes the illumination of the rings by the Sun and Saturn. The particles in the inner and mid-A Ring have Bond albedos near 0.5 and are more backscattering than satellites of comparable albedo. The region outside the Encke Gap becomes progressively less backscattering with increasing radius. Particle properties change abruptly outside the Keeler Gap; particles here have an albedo near 0.6 and a Lambert-like phase function. In contrast with previous suggestions, the abundance of free, submicrometer "dust" is small throughout the entire A Ring; this conclusion holds even in the outermost A Ring, which is strongly perturbed by density waves. Models derived from low-phase data, assuming only macroscopic particles, correctly predict the highphase reflectivity of the outer A Ring and individual strong density waves in the mid-A Ring. However, the inner and mid-A Ring are typically darker at high phase by a factor of two than our models predict. This discrepancy may be due to the reduced multiple scattering from a layer in which the particles are more closely packed. We have also studied the quadrupole azimuthal brightness asymmetry of the A Ring. The asymmetry has a full amplitude of 35% in the mid-A Ring in low-phase Voyager 2 images. We present results on its behavior and possible implications for the structure of the rings. Finally, we compare our results with studies using other data sets to synthesize our current understanding of the nature of the A Ring.

Dones, Luke↗
DOE OSTI2022

A Simulation-based Method for Correcting Mode Coupling in CMB Angular Power Spectra

Modern cosmic microwave background (CMB) analysis pipelines regularly employ complex time-domain filters, beam models, masking, and other techniques during the production of sky maps and their corresponding angular power spectra. However, these processes can generate couplings between multipoles from the same spectrum and from different spectra, in addition to the typical power attenuation. Within the context of pseudo-C ℓ based, MASTER-style analyses, the net effect of the time-domain filtering is commonly approximated by a multiplicative transfer function, F ℓ , that can fail to capture mode mixing and is dependent on the spectrum of the signal. To address these shortcomings, we have developed a simulation-based spectral correction approach that constructs a two-dimensional transfer matrix, ${J}_{{\ell }{\ell }^{\prime} }$, which contains information about mode mixing in addition to mode attenuation. We demonstrate the application of this approach on data from the first flight of the Spider balloon-borne CMB experiment.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2011

Design, Development and Test Challenges: Separation Mechanisms for the Orion Pad Abort-1 Flight Test

On May 6, 2010, NASA launched the first successful integrated flight test, Pad Abort-1, of the Orion Project from the White Sands Missile Range in Las Cruces, New Mexico. This test demonstrated the ability to perform an emergency pad abort of a full-scale 4.8 m diameter, 8200 kg crew capsule. During development of the critical separation mechanisms for this flight test, various challenges were overcome related to environments definition, installation complications, separation joint retraction speed, thruster ordnance development issues, load path validation and significant design loads increases. The Launch Abort System retention and release (LAS R&R) mechanism consisted of 6 discrete structural connections between the LAS and the crew module (CM) simulator, each of which had a preloaded tension tie, Superbolt torque-nut and frangible nut. During the flight test, the frangible nuts were pyrotechnically split, permitting the CM to separate from the LAS. The LAS separation event was the driving case in the shock environment for many co-located hardware items. During development testing, it was necessary to measure the source shock during the separation event so the predicted shock environment could be validated and used for certification testing of multiple hardware items. The Lockheed Martin test team measured the source separation shock due to the LAS R&R function, which dramatically decreased the predicted environment by 90% at 100 Hz. During development testing a hydraulic tensioner was used to preload the joint; however, the joint relaxation with the tensioner proved unsatisfactory so the design was modified to include a Superbolt torque-nut. The observed preload creep during lab testing was 4% after 30 days, with 2.5% occurring in the first 24 hours. The conversion of strain energy (preload) to kinetic energy (retraction) was measured to be 50-75%. Design features and careful monitoring of multiple strain gauges on each tension tie allowed a pure tensile load to be applied after stacking at the launch pad. Following installation, preload in each joint was monitored for 24 hours. Due to unforeseen complications and the influence of temperature on the portable data acquisition system, the team encountered difficulty in tracking the joint relaxation. In some cases, bond-line failure of the strain gauges occurred.

Dinsel, Alison↗
NASA NTRS1994

Characterization of Damage Progression in SCS-6/timetal 21S (0)4 Under Thermomechanical Fatigue Loadings

A detailed experimental investigation was performed at a single maximum cyclic stress (sigma max) level to physically characterize the progression of thermomechanical fatigue (lW) damage in continuously reinforced (0 deg) SCS-6/Timetal 21S, a titanium matrix composite. In-phase (IP) and out of-phase (OP) loadings were investigated at sigma max = 1000 MPa with a temperature cycle from 150 to 6500 C. Damage progression, in terms of macroscopic property degradation, was experimentally quantified through an advanced TMF test methodology which incorporates explicit measurements of the isothermal static moduli at the TMF temperature extremes and the coefficient of thermal expansion (CTE) as functions of the TMF cycles. Detailed characterization of the physical damage progression at the microstructural level was performed by interrupting multiple TMF tests at various stages of mechanical property degradation and analyzing the microstructure through extensive destructive metallography. Further, the extent of damage was also quantified through residual static strength measurements. Results indicated that damage initiation occurred very early in cyclic life (N less than 0.1Nf) for both the IP and OP TMF loadings. IP TMF damage was found to be dominated by fiber breakage with a physical damage progression in the microstructure which was difficult to quantify. OP TMF loadings produced matrix cracking exclusively associated with surface initiations. Here, damage progression was easily distinguished in terms of both the number of cracks and their relative inward progressions toward the outer fiber rows with increased cycling. The point at which the leading cracks reached the outer fiber rows (when localized fiber/matrix de-bonding and matrix crack bridging occurred) appeared to be reflected in the macroscopic property degradation curves.

Castelli, Michael G.↗
DOE OSTI2025

Structural Changes in Metal Chalcogenide Nanoclusters Associated with Single Heteroatom Incorporation

Atomically precise nanoclusters (NCs) are promising building blocks for designing materials and interfaces with unique properties. By incorporating heteroatoms into the core, the electronic and magnetic properties of NCs can be precisely tuned. To accurately predict these properties, density functional theory (DFT) is often employed, making the rigorous benchmarking of DFT results particularly important. In this study, we present a benchmarking approach based on metal chalcogenide NCs as a model system. We synthesized a series of bimetallic, iron-cobalt chalcogenide NCs [Co 6-x Fe x S 8 (PEt 3 ) 6 ] + (x = 0-6) (PEt = triethyl phosphine) and investigated the effect of heteroatoms in the octahedral metal chalcogenide core on their size and electronic properties. Using ion mobility-mass spectrometry (IM-MS), we observed a gradual increase in the collision cross section (CCS) with an increase in the number of Fe atoms in the core. DFT calculations combined with trajectory method CCS simulations successfully reproduced this trend, revealing that the increase in cluster size is primarily due to changes in metal-ligand bond lengths, while the electronic properties of the core remain largely unchanged. Moreover, this method allowed us to exclude certain multiplicity states of the NCs, as their CCS values were significantly different from those predicted for the lowest-energy structures. Here, this study demonstrates that gas-phase IM-MS is a powerful technique for detecting subtle size differences in atomically precise NCs, which are often challenging to observe using conventional NC characterization methods. Accurate CCS measurements are established as a benchmark for comparison with theoretical calculations. The excellent correspondence between experimental data and theoretical predictions establishes a robust foundation for investigating structural changes of transition metal NCs of interest to a broad range of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

..beta..-Ketoadipic Acid Production in P. putida for Performance-Advantaged Nylons

Biomass derived chemicals can possess extended functionality, often in the form of heteroatoms like oxygen and nitrogen, that can enable performance advantaged properties in emergent materials. One illustrative example of this concept is ..beta..-ketoadipic acid (..beta..KA), a C6 dicarboxylic acid with a ketone in its backbone. ..beta..KA can be obtained via biological cultivation from aromatic compounds, sugars, and even waste plastics. When ..beta..KA is implemented into polymers, namely nylons, in place of adipic acid the overall material properties are increased. Specifically, the glass transition temperature (which is the measurement at which temperature a plastic softens) is increased by 69 degrees C and the water permeability is reduced by 20%. Molecular dynamic (MD) simulations reveal that the ..beta..-ketone in ..beta..KA leads to restricted movement across multiple backbone carbons when compared to adipic acid. Furthermore, MD simulations reveal that the ..beta..-ketone, when compared to no-ketone or an a-ketone, can lead to an increase in hydrogen bonding between neighboring chains. Both phenomena may help explain the molecular origin of the increases in polymer performance. Aside from performance advantages in thermomechanical performance, the production of ..beta..KA also is advantaged in its manufacturing. Although estimates for the minimum selling price (MSP) of ..beta..KA exceed adipic acid the manufacture of ..beta..KA would reduce supply chain energy and GHG emissions by >50% and >30% respectively. Further TEA analysis reveals that the MSP of ..beta..KA is primarily driven by the feedstock cost while the capital expenditures are driven largely by fermentation costs. Overall, the work presented within will be illustrative of how biomass derived molecules, namely ..beta..KA, can manifest performance advantages across multiple benchmarks and may enable a path to market for biomass-derived materials.

beta-ketoadipic acid↗
DOE OSTI2021

Factors Governing Oxygen Vacancy Formation in Oxide Perovskites

The control of oxygen vacancy (V O ) formation is critical to advancing multiple metal-oxide-perovskite-based technologies. In this work, we report the construction of a compact linear model for the neutral V O formation energy in ABO 3 perovskites that reproduces, with reasonable fidelity, Hubbard-U-corrected density functional theory calculations based on the state-of-the-art, strongly constrained and appropriately normed exchange-correlation functional. We obtain a mean absolute error of 0.45 eV for perovskites stable at 298 K, an accuracy that holds across a large, electronically diverse set of ABO 3 perovskites. Our model considers perovskites containing alkaline-earth metals (Ca, Sr, and Ba) and lanthanides (La and Ce) on the A-site and 3d transition metals (Ti, V, Cr, Mn, Fe, Co, and Ni) on the B-site in six different crystal systems (cubic, tetragonal, orthorhombic, hexagonal, rhombohedral, and monoclinic) common to perovskites. Physically intuitive metrics easily extracted from existing experimental thermochemical data or via inexpensive quantum mechanical calculations, including crystal bond dissociation energies and (solid phase) reduction potentials, are key components of the model. Beyond validation of the model against known experimental trends in materials used in solid oxide fuel cells, the model yields new candidate perovskites not contained in our training data set, such as (Bi,Y)(Fe,Co)O 3 , which we predict may have favorable thermochemical water-splitting properties. The confluence of sufficient accuracy, efficiency, and interpretability afforded by our model not only facilitates high-throughput computational screening for any application that requires the precise control of V O concentrations but also provides a clear picture of the dominant physics governing V O formation in metal-oxide perovskites.

08 HYDROGEN↗
NASA NTRS2013

An Offload NIC for NASA, NLR, and Grid Computing

This work addresses distributed data management and access dynamically configurable high-speed access to data distributed and shared over wide-area high-speed network environments. An offload engine NIC (network interface card) is proposed that scales at nX10-Gbps increments through 100-Gbps full duplex. The Globus de facto standard was used in projects requiring secure, robust, high-speed bulk data transport. Novel extension mechanisms were derived that will combine these technologies for use by GridFTP, bandwidth management resources, and host CPU (central processing unit) acceleration. The result will be wire-rate encrypted Globus grid data transactions through offload for splintering, encryption, and compression. As the need for greater network bandwidth increases, there is an inherent need for faster CPUs. The best way to accelerate CPUs is through a network acceleration engine. Grid computing data transfers for the Globus tool set did not have wire-rate encryption or compression. Existing technology cannot keep pace with the greater bandwidths of backplane and network connections. Present offload engines with ports to Ethernet are 32 to 40 Gbps f-d at best. The best of ultra-high-speed offload engines use expensive ASICs (application specific integrated circuits) or NPUs (network processing units). The present state of the art also includes bonding and the use of multiple NICs that are also in the planning stages for future portability to ASICs and software to accommodate data rates at 100 Gbps. The remaining industry solutions are for carrier-grade equipment manufacturers, with costly line cards having multiples of 10-Gbps ports, or 100-Gbps ports such as CFP modules that interface to costly ASICs and related circuitry. All of the existing solutions vary in configuration based on requirements of the host, motherboard, or carriergrade equipment. The purpose of the innovation is to eliminate data bottlenecks within cluster, grid, and cloud computing systems, and to add several more capabilities while reducing space consumption and cost. Provisions were designed for interoperability with systems used in the NASA HEC (High-End Computing) program. The new acceleration engine consists of state-ofthe- art FPGA (field-programmable gate array) core IP, C, and Verilog code; novel communication protocol; and extensions to the Globus structure. The engine provides the functions of network acceleration, encryption, compression, packet-ordering, and security added to Globus grid or for cloud data transfer. This system is scalable in nX10-Gbps increments through 100-Gbps f-d. It can be interfaced to industry-standard system-side or network-side devices or core IP in increments of 10 GigE, scaling to provide IEEE 40/100 GigE compliance.

Awrach, James↗
DOE OSTI2021

Controlling Amphiphilic Polymer Folding beyond the Primary Structure with Protein-Mimetic Di(Phenylalanine)

While methods for polymer synthesis have proliferated, their functionality pales in comparison to natural biopolymers–strategies are limited for building the intricate network of noncovalent interactions necessary to elicit complex, protein-like functions. Using a bioinspired di(phenylalanine) acrylamide (FF) monomer, we explored the impact of various noncovalent interactions in generating ordered assembled structures. Amphiphilic copolymers were synthesized that exhibit β-sheet-like local structure upon collapsing into single-chain assemblies in aqueous environments. Here, the systematic analysis of a series of amphiphilic copolymers illustrated that the global collapse is primarily driven by hydrophobic forces. Hydrogen-bonding and aromatic interactions stabilize local structure, as β-sheet-like interactions were identified via circular dichroism and thioflavin T fluorescence. Similar analysis of phenylalanine (F) and alanine-phenylalanine acrylamide (AF) copolymers found that distancing the aromatic residue from the polymer backbone is sufficient to induce β-sheet-like local structure akin to the FF copolymers; however, the interactions between AF subunits are less stable than those formed by FF. Further, hydrogen-bond donating hydrophilic monomers disrupt internal structure formed by FF within collapsed assemblies. Collectively, these results illuminate design principles for the facile incorporation of multiple facets of protein-mimetic, higher-order structure within folded synthetic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Controlling the corrosion resistance of multi-principal element alloys

Multi-principal element alloys (MPEAs) offer the possibility of many degrees of freedom in the choice of alloying elements to produce either single phase solid solutions or more complex multiphase microstructures. Large ranges of material properties have been observed for MPEAs and mastery of the selection of elements and their compositions can enable novel combinations of properties not possible in traditional alloys. From the aqueous corrosion perspective, optimization of phase stability, control of heterogeneities, passive film identity and its protectiveness, as well as substrate properties such as metal-metal bond strength and activation energy associated with dissolution, can all be controlling factors governed by alloy composition and structure. These factors can mediate the electrochemical reactions controlling spontaneous corrosion. The quest for superior properties based on well-informed element choice is suggested as a path forward guiding MPEA formulations for corrosion performance. However, gaps in fundamental knowledge exist regarding (a) the specific functions of each element, (b) the behavior of elements in unusual combinations, and (c) the formation of complex protective oxides. These issues currently hold back progress in optimization of corrosion properties.

Scully, John R.↗
DOE OSTI2026

Binuclear Acetoniminato Derivatives of Iron and Chromium Carbonyls: A Theoretical Study

The structures and energetics of binuclear acetoniminato metal carbonyl derivatives of the types (Me 2 C═N) 2 Fe 2 (CO) n and (Me 2 C═N) 2 Cr 2 (CO) n have been investigated by density functional theory. The (Me 2 C═N) 2 Fe 2 (CO) 6 structure, with bridging Me 2 C═N ligands using only their nitrogen atoms to bridge an Fe═Fe bond related to experimentally known species, as well as a related (Me 2 C═N) 2 Cr 2 (CO) 8 structure, appear to be energetically preferred. Among carbonyl-richer systems, the iron system energetically prefers a {Me 2 C═NC(O)} 2 Fe 2 (CO) 6 structure with bridging Me 2 C═NC(O) ligands, whereas the chromium system energetically prefers a structure with a 2,3-diazabutadiene ligand having each nitrogen atom bonded to a Cr(CO) 5 moiety. Preferred structures for systems with fewer CO groups include the tetracarbonyl (Me 2 C═N) 2 Fe 2 (CO) 4 in which one of the bridging Me 2 C═N uses its C═N double bond to bond to an iron atom, as well as (Me 2 C═N)2Cr 2 (CO) n (n = 7, 6) structures with chromium–chromium multiple bonds bridged by Me2C═N groups.

Carbonyls↗
DOE OSTI2020

Constructing protein polyhedra via orthogonal chemical interactions

Many proteins exist naturally as symmetrical homooligomers or homopolymers. The emergent structural and functional properties of such protein assemblies have inspired extensive efforts in biomolecular design2–5. As synthesized by ribosomes, proteins are inherently asymmetric. Therefore, they must acquire multiple surface patches that selectively associate to generate the different symmetry elements needed to form higher-order architectures—a daunting task for protein design. Here we address this problem using an inorganic chemical approach, whereby multiple modes of protein–protein interactions and symmetry are simultaneously achieved by selective, ‘one-pot’ coordination of soft and hard metal ions. We show that a monomeric protein (protomer) appropriately modified with biologically inspired hydroxamate groups and zinc-binding motifs assembles through concurrent Fe 3+ and Zn 2+ coordination into discrete dodecameric and hexameric cages. Our cages closely resemble natural polyhedral protein architectures and are, to our knowledge, unique among designed systems in that they possess tightly packed shells devoid of large apertures. At the same time, they can assemble and disassemble in response to diverse stimuli, owing to their heterobimetallic construction on minimal interprotein-bonding footprints. With stoichiometries ranging from [2 Fe:9 Zn:6 protomers] to [8 Fe:21 Zn:12 protomers], these protein cages represent some of the compositionally most complex protein assemblies—or inorganic coordination complexes—obtained by design.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Less Is More: Oligomer Extraction and Hydrothermal Annealing Increase PDMS Adhesion Forces for Materials Studies and for Biology-Focused Microfluidic Applications

Cues in the micro-environment are key determinants in the emergence of complex cellular morphologies and functions. Primary among these is the presence of neighboring cells that form networks. For high-resolution analysis, it is crucial to develop micro-environments that permit exquisite control of network formation. This is especially true in cell science, tissue engineering, and clinical biology. We introduce a new approach for assembling polydimethylsiloxane (PDMS)-based microfluidic environments that enhances cell network formation and analyses. We report that the combined processes of PDMS solvent-extraction and hydrothermal annealing create unique conditions that produce high-strength bonds between solvent-extracted PDMS (E-PDMS) and glass—properties not associated with conventional PDMS. Extraction followed by hydrothermal annealing removes unbound oligomers, promotes polymer cross-linking, facilitates covalent bond formation with glass, and retains the highest biocompatibility. Herein, our extraction protocol accelerates oligomer removal from 5 to 2 days. Resulting microfluidic platforms are uniquely suited for cell-network studies owing to high adhesion forces, effectively corralling cellular extensions and eliminating harmful oligomers. We demonstrate the simple, simultaneous actuation of multiple microfluidic domains for invoking ATP- and glutamate-induced Ca 2+ signaling in glial-cell networks. These E-PDMS modifications and flow manipulations further enable microfluidic technologies for cell-signaling and network studies as well as novel applications.

36 MATERIALS SCIENCE↗