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At least 919 records · Page 51

Steric Modulation of Protein‐Mediated Nanoparticle Assembly: Controlling Cluster Size, Polydispersity, and FRET Responses by Rebalancing Short‐ and Long‐Range Interactions

Understanding and manipulating protein-nanoparticle interactions is of broad interest to fields ranging from nanomedicine to the biological fabrication of functional hierarchical materials. This study investigates how steric forces introduced by a pegylated derivative of superfolder green fluorescent protein (sfGFP) that is monofunctional for silica binding modulate the delicate interplay of long-range (electrostatic and van der Waals) and short-range (protein-mediated) interactions in pH-responsive silica nanoparticle (SiNP) assembly by bifunctional silica-binding sfGFP. Increasing the length of the PEG segment and pre-incubating SiNPs with increasing concentrations of pegylated proteins enables precise control over cluster size within the 800–1450 nm range with a sixfold decrease in polydispersity index to a remarkable 0.1 endpoint. Weakening short-range attractive interactions via mutagenesis extends this control to clusters in the 50–250 nm range and reveals that the Förster resonance energy transfer (FRET) efficiency of clusters scales linearly with cluster diameter below 230 nm but increases only by 15% as clusters grow to 1450 nm. Furthermore, these findings enable the development of a system that provides an optical readout to dynamic changes in solution conditions enacted by a combination of pH adjustment and ion charge screening.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing Molecular Assembly of Small Organic Molecules during Meniscus-Guided Coating Using Experimental and Molecular Dynamics Approaches

Evaporation-based thin-film coating processes are ubiquitous in fields such as organic electronics, dye coatings, and the pharmaceutical industry. Based on experimental observations of enhanced thin-film alignment during meniscus-guided coating (MGC), a molecular dynamics simulation was developed to describe the thin-film formation that occurs due to the interplay between evaporation and fluid dynamics. The process of solvent evaporation from solution is first examined, which leads to the formation of a solid thin film after evaporation is complete. Next, an MGC process was simulated by introducing a flow profile coupled with the evaporative system. In this work, we gain insights into how molecules respond and reorient in the presence of a flow profile. These results indicate that both the evaporation and the flow profile have an impact on orienting small molecules in a thin film during the MCG process. Combining experimental techniques with simulations helps enhance the understanding of the forces that are significant in directing molecular aggregation during coating processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ameloblastin binding to biomimetic models of cell membranes – A continuum of intrinsic disorder

A 37-residue amino acid sequence corresponding to the segment encoded by exon-5 of murine ameloblastin (Ambn), AB2 (Y67-Q103), has been implicated with membrane association, ameloblastin self-assembly, and amelogenin-binding. Here, our aim was to characterize, at the residue level, the structural behavior of AB2 bound to chemical mimics of biological membranes using NMR spectroscopy. To better define the structure of AB2 using NMR-based methods, recombinant 13 C- and 15 N-labelled AB2 (*AB2) was prepared and data collected free in solution and with deuterated dodecylphosphocholine (dPC) micelles, deuterated bicelles, and both small and large unilamellar vesicles. Amide chemical shift and intensity perturbations observed in 1 H- 15 N HSQC spectra of *AB2 in the presence of bicelles and dPC micelles suggest that a region of *AB2, S6-E36 (murine Ambn S68 – E98), associates with the membrane biomimetics. A CSI-3 analysis of the NMR chemical shift assignments for *AB2 free in solution and bound to dPC micelles indicated the peptide remains disordered except for the adoption of a short, 12-residue α-helix, F10-G21 (murine Ambn F72-G83). In dPC micelles, the NOE NMR data was void of patterns characteristic of long-lived helical structure indicating this helix was transient in nature. A continuum of intrinsic disorder in the membrane-bound state may be responsible for ameloblastin’s ability to dynamically interact with multiple partners at the same site during amelogenesis.

59 BASIC BIOLOGICAL SCIENCES↗

Structure–Function Insights into Thermoresponsive Copolymers as Lanthanide Precipitants

The synthetic toolbox for stimuli-responsive polymers has broadened to include many tunable variables, making these materials applicable in diverse technologies. However, unraveling the key composition–structure–function relationships to facilitate ground-up design remains a challenge due to the inherent dispersity in sequence and conformations for synthetic polymers. We here present a systematic study of these relationships using a model system of copolymers with a thermoresponsive (N-isopropylacrylamide) backbone in addition to metal-chelating (acrylic acid) and hydrophobic structural comonomers and evaluate their efficiency at isolating technologically critical lanthanide ions. The efficiency of lanthanide ion extraction by precipitation was quantitated with a metallochromic dye to reveal trends relating copolymer hydrophobicity to improved separations. Further, we examined the role of different hydrophobic comonomers in dictating the solution-phase conformation of the polymer in the presence and absence of lanthanide ions, and we correlated key features of the hydrophobic comonomer to extraction efficiency. Lastly, we identified how the local proximity of thermoresponsive, chelating, and hydrophobic subunits facilitates metal extraction by manipulating the copolymer sequence with multiblock polymerization. Through mechanistic analysis, we propose a binding-then-assembly process through which metal ions are coprecipitated with macromolecular chelators.

Copolymers↗

Crystal structure and catalytic mechanism of drimenol synthase, an unusual bifunctional terpene cyclase–phosphatase

Drimenol synthase fromAquimarina spongiae(AsDMS) is a highly unusual chimera that integrates two distinct, sequential isoprenoid processing activities within a single polypeptide chain. AsDMS catalyzes the class II cyclization of farnesyl diphosphate (FPP) to form drimenyl diphosphate, which then undergoes enzyme-catalyzed hydrolysis to yield drimenol, a bioactive sesquiterpene alcohol with antifungal and anticancer properties. Here, we report the X-ray crystal structures of AsDMS and its complex with a sesquiterpene thiol. The AsDMS structure exhibits a didomain architecture consisting of a terpene cyclase β domain and a haloacid dehalogenase-like phosphatase domain, with two distinct active sites located on opposite sides of the protein. Mechanistic studies show that dephosphorylation of the drimenyl diphosphate intermediate proceeds through stepwise hydrolysis such that two equivalents of inorganic phosphate rather than inorganic pyrophosphate are coproducts of the reaction sequence. When the AsDMS reaction is performed in H 2 18 O, 18 O is not incorporated into drimenol, indicating that the hydroxyl oxygen of drimenol originates from the prenyl oxygen of FPP rather than a water molecule from bulk solution. These results correct a mechanistic proposal previously advanced by another group. Surprisingly, AsDMS exhibits substrate promiscuity, catalyzing the conversion of the slowly reactive substrate mimic farnesyl-S-thiolodiphosphate into cyclic and linear sesquiterpene products. Structural and mechanistic insights gained from AsDMS illustrate the functional diversity of terpene biosynthetic enzymes and provide a foundation for engineering “designer cyclase” assemblies capable of generating a wide variety of terpenoid products.

Science & Technology - Other Topics↗

Channel Wall Nozzle Manufacturing Technology Advancements for Liquid Rocket Engines

A regeneratively-cooled nozzle is a critical component for expansion of the hot gases to enable high temperature and performance liquid rocket engines systems. Channel wall nozzles are a design solution used across the propulsion industry as a simplified method to fabricate the nozzle structure with internal coolant passages. The scale and complexity of the channel wall nozzle (CWN) design is challenging to fabricate leading to extended lead times and higher costs. Some of these challenges include: 1) unique and high temperature materials, 2) Tight tolerances during manufacturing and assembly to contain high pressure propellants, 3) thin-walled features to maintain adequate wall temperatures, and 4) Unique manufacturing process operations and tooling. The United States (U.S.) National Aeronautics and Space Administration (NASA) along with U.S. specialty manufacturing vendors are maturing modern fabrication techniques to reduce complexity and decrease costs associated with channel wall nozzle manufacturing technology. Additive Manufacturing (AM) is one of the key technology advancements being evaluated for channel wall nozzles. Much of additive manufacturing for propulsion components has focused on powder bed fusion, but the scale is not yet feasible for application to large scale nozzles. NASA is evolving directed energy deposition (DED) techniques for nozzles including arc-based deposition, blown powder deposition, and Laser Wire Direct Closeout (LWDC). There are different approaches being considered for fabrication of the nozzle and each of these DED processes offer unique process steps for rapid fabrication. The arc-based and blown powder deposition techniques are being used for the forming of the CWN liner. A variety of materials are being demonstrated including Inconel 625, Haynes 230, JBK-75, and NASA HR-1. The blown powder DED process is also being demonstrated for forming an integral channel nozzle in a single operation in similar materials. The LWDC process is a method for closing out the channels within the liner and forming the structural jacket using a localized laser wire deposition technique. Identical materials mentioned above have been used for this process in addition to bimetallic closeout (C-18150–SS347, and C-18150–Inconel 625). NASA has completed process development, material characterization, and hot-fire testing on a variety of these channel wall nozzle fabrication techniques. This paper will present an overview of the various processes and materials being evaluated and the results from the hot-fire testing. Future development and technology focus areas will also be discussed relative to channel wall nozzle manufacturing.

Gradl, Paul R.↗

Liquid crystals of neat boron nitride nanotubes and their assembly into ordered macroscopic materials

Boron nitride nanotubes (BNNTs) have attracted attention for their predicted extraordinary properties; yet, challenges in synthesis and processing have stifled progress on macroscopic materials. Recent advances have led to the production of highly pure BNNTs. Here we report that neat BNNTs dissolve in chlorosulfonic acid (CSA) and form birefringent liquid crystal domains at concentrations above 170 ppmw. These tactoidal domains merge into millimeter- sized regions upon light sonication in capillaries. Cryogenic electron microscopy directly shows nematic alignment of BNNTs in solution. BNNT liquid crystals can be processed into aligned films and extruded into neat BNNT fibers. This study of nematic liquid crystals of BNNTs demonstrates their ability to form macroscopic materials to be used in high- performance applications.

Cedric J. Simonsen Ginestra↗

Cation selectivities in zwitterion grafted nanopores: effect of zwitterion architecture

Selective separation of monovalent cations is a critical challenge in applications such as water purification and lithium recovery from salt brines. Cross-linked zwitterionic amphiphilic copolymer (ZAC-X) membranes have gained attention for their exceptional anion permselectivity, attributed to self-assembled zwitterion-lined nanodomains that interact preferentially with anions according to their hydrated radii r hyd . However, these membranes show minimal selectivity among monovalent cations, despite significant differences in their hydration structures, motivating studies on the underlying mechanisms of cation transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the zwitterionic (ZI) ligands on cation diffusivities, partitioning, and permeabilities. To this end, we examined two contrasting ZI ligand architectures: Motif A (surface–cation–anion, S–ZI + –ZI − ) and Motif B (surface–anion–cation, S–ZI − –ZI + ). Our results show that in Motif A, the sulfonate groups of the ZI ligands are localized near the pore center radially, leading to strong electrostatic interactions with small bare cations (Mg 2+ and Li + ). This configuration results in high cation partitioning but low cation diffusion, maintaining solution-diffusion tradeoff typical of functionalized membranes. In contrast, Motif B show that sulfonate groups shift radially toward the mid-region of the pore. This shift, especially for small bare cations, introduces steric constraints that weaken their interactions with the sulfonate groups, thereby enhancing hydration and lowering partitioning, while still maintaining their low self-diffusivity. These findings establish zwitterion dipole orientation as a powerful design lever for tuning cation selectivity in membrane systems and offer molecular-level insights for engineering next-generation ion separation materials.

Morishita, Kazuya [Univ. of Texas, Austin, TX (Uni↗

Payload transportation at KSC

Cargo ground processing at John F. Kennedy Space Center (KSC) involves either a horizointal or vertical mode of assembly and processing of the STS payloads. Consequently, cargos are commonly referred to as horizontal or vertical payloads. The process flow for each mode requires different facilities and transportation requirements. Occasionally, a mixed mission cargo containing both horizontal and vertical payload elements will require a combination of horizontal and vertical transportation between facilities. Some of the engineering challenges and innovative solutions to satisy the unique on-site payload transportation requirements at KSC. In particular, some of the more demanding design requirements of the multiuse mission support equipment are presented, and the resulting engineering designs and unique solutions are outlined.

Donahue, M. E.↗

On the apparent insignificance of the randomness of flexible joints on large space truss dynamics

Deployable periodic large space structures have been shown to exhibit high dynamic sensitivity to period-breaking imperfections and uncertainties. These can be brought on by manufacturing or assembly errors, structural imperfections, as well as nonlinear and/or nonconservative joint behavior. In addition, the necessity of precise pointing and position capability can require the consideration of these usually negligible and unknown parametric uncertainties and their effect on the overall dynamic response of large space structures. This work describes the use of a new design approach for the global dynamic solution of beam-like periodic space structures possessing parametric uncertainties. Specifically, the effect of random flexible joints on the free vibrations of simply-supported periodic large space trusses is considered. The formulation is a hybrid approach in terms of an extended Timoshenko beam continuum model, Monte Carlo simulation scheme, and first-order perturbation methods. The mean and mean-square response statistics for a variety of free random vibration problems are derived for various input random joint stiffness probability distributions. The results of this effort show that, although joint flexibility has a substantial effect on the modal dynamic response of periodic large space trusses, the effect of any reasonable uncertainty or randomness associated with these joint flexibilities is insignificant.

Koch, R. M.↗

Design and Flight Testing of an Inflatable Sunshield for the NGST

The Next Generation Space Telescope (NGST) mission is scheduled to launch in 2007 and be stationed at L2 for a mission life of ten years. The large aperture mirror and optical detectors aboard NGST require shielding from the constant solar energy seen at this orbit. The government reference NGST design, called the Yardstick, baselined a sunshield using an inflation deployment system. During the formulation phase, NGST is spending approximately 25% of the overall budget to foster the development of new technology. The goal is to develop and demonstrate enabling or enhancing technology and provide innovative solutions for the design of the NGST observatory. Inflatable technology falls in the category of enhancing technology due to its advantages in weight, stowed volume and cost. The Inflatable Sunshield in Space (ISIS) flight experiment will provide a realistic space flight demonstration of an inflatable sunshield. The supporting technology development program will provide an information base for the design, manufacture, assembly and testing of large thin membranes and inflatable structural elements for space structures. The ISIS experiment will demonstrate the feasibility of using inflatable technology to passively cool optical systems for NGST and provide correlation between analytical predictions and on orbit results. The experiment will be performed on a Hitchhiker/Space Shuttle mission in late 2001. The ISIS mission is an effort to address several major technical challenges of the NGST inflatable sunshield, namely controlled inflation deployment, plenarity and separation of large stretched membranes, space rigidization of inflatable booms, and dynamic modeling and simulation. This paper will describe the design of the flight experiment and the testing to be performed on-orbit.

Adams, Michael L.↗

Method for making a microporous membrane

A method for making a microporous membrane comprises the steps of: providing a plurality of carbon nanotubes having a hollow interior diameter of 20 Angstroms or less; sonicating the plurality of carbon nanotubes utilizing a solution comprising deionized, distilled water and a surfactant that coats at least one of the plurality of carbon nanotubes; collecting the coated carbon nanotubes; forming a matrix that supports the plurality of carbon nanotubes; embedding the coated carbon nanotubes into the matrix; rinsing the coated nanotubes to remove at least a portion of the surfactant; curing the nanotube-matrix assembly; and cutting the nanotube-matrix assembly to a particular thickness so as to open the ends of the embedded nanotubes. The hollow interiors of the plurality of embedded carbon nanotubes comprise the pores of the microporous membrane.

Gavalas, Lillian Susan↗

Work Term Assignment Spring 2017

My tour in the Engineering Robotics directorate exceeded my expectations. I learned lessons about Creo, manufacturing and assembly, collaboration, and troubleshooting. During my first tour, last spring, I used Creo on a smaller project, but had limited experience with it before starting in the Dynamic Systems Test branch this spring. I gained valuable experience learning assembly design, sheet metal design and designing with intent for manufacturing and assembly. These skills came from working both on the hatch and the floor. I also learned to understand the intent of other designers on models I worked with. While redesigning the floor, I was modifying an existing part and worked to understand what the previous designer had done to make it fit with the new model. Through working with the machine shop and in the mock-up, I learned much more about manufacturing and assembly. I used a Dremel, rivet gun, belt sander, and countersink for the first time. Through taking multiple safety training for different machine shops, I learned new machine shop safety skills specific to each one. This semester also gave me new collaborative opportunities. I collaborated with engineers within my branch as well as with Human Factors and the building 10 machine shop. This experience helped me learn how to design for functionality and assembly, not only for what would be easiest in my designs. In addition to these experiences, I learned many lessons in troubleshooting. I was the first person in my office to use a Windows 10 computer. This caused unexpected issues with NASA services and programs, such as the Digital Data Management Server (DDMS). Because of this, I gained experience finding solutions to lockout and freeze issues as well as Creo specific settings. These will be useful skills to have in the future and will be implemented in future rotations. This co-op tour has motivated me more to finish my degree and pursue my academic goals. I intend to take a machining Career Gateway Elective in the Fall to improve my skills in building as well as designing with manufacturing intent. I am also inspired to take more mechatronics CGE courses before I graduate to learn more about the crossover between mechanical and electrical engineering. This semester, I worked on multiple projects and had the opportunity to learn from engineers of different disciplines. I became proficient in Creo 2.0, a program I had not used significantly before. I finished modifying the hatch for 3D print and made sizeable modifications to the nose floor support design. I also gained hands-on experience that will be useful in my engineering career in the future. I would consider all of these major achievements from this spring semester. Lastly, I learned to ask more questions and to search for the right people to find answers which I know will be a valuable skill in the future. This summer, I will be completing my last rotation in the Flight Operations Directorate at Ellington Air Field. After this last tour, I will be returning to school for the Fall, Spring and Summer. I will graduate in August of 2018. I am looking forward to learning more about the different jobs available to engineers. This division works directly with many different types of aircrafts and I am excited to learn more about this focus of engineering. The Aircraft Operations Division values team work greatly and I intend to improve my interpersonal skills by working with them this summer.

Sico, Mallory↗

SpiderFab: Process for On-Orbit Construction of Kilometer-Scale Apertures

The SpiderFab effort has investigated the value proposition and feasibility of radically changing the way we build and deploy spacecraft by enabling space systems to fabricate and integrate key components on-orbit. In this Phase II effort, we have focused on developing and demonstrating tools and processes to enable robotic systems to manufacture and assemble high performance structural elements that will serve as the support structures for components such as antennas and solar arrays. Through testing of these technologies in the laboratory environment,these efforts have established the technical feasibility of the key capabilities required for in-space manufacture of large apertures such as antennas, solar arrays, and optical systems,maturing prototype technical solutions for these capabilities to TRL-4. The SpiderFab effort has resulted in successful post-NIAC transition of the technology, first to SBIR-funded development of a technology for in-space manufacture (ISM) of truss structures, and then to a NASA/STMD Tipping Point Technologies funded effort to prepare a flight demonstration of ISM of a structure for a GEO communications satellite.

Manufacturing↗

Investigation of Ring-heterogeneous Geometry Approximation for Efficient and Practical SFR Analysis

A novel geometry approximation scheme named ring-heterogeneous approximation for intermediate resolution multiphysics analysis of SFRs is presented. This approach particularly targets neutronics coupled with thermo-mechanics feedback, which dominate the passive safety of SFR designs. The ring-heterogeneous approximation casts an array of pins into volume-preserving bands of materials that constitute the pins. It allows to efficiently simulate SFRs with an unstructured mesh and also to explicitly consider the deformation of each material by retaining their heterogeneity. Verification results with single assembly and core problems of the ABTR benchmark demonstrated that the ring-heterogeneous approximation is a reasonable approximation for SFRs. For a 2D full core problem, the ring-heterogeneous approximation significantly reduced the number of elements by at least a factor of 70 from a fully-heterogeneous mesh while almost exactly preserving the reference fully-heterogeneous solutions with the RMS error of only 0.02% in the ring-wise fission reaction rate.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Mesoporous optically clear heat insulators for sustainable building envelopes

Mesoporous materials exhibit highly controlled nanoscale structures, often templated by liquid crystalline assemblies of surfactants, with emergent and often designable physical properties. However, scaling their fabrication to be suitable for uses like envelopes of buildings is challenging. Here we describe fabrication of flexible square-meter-sized films and multi-centimeter-thick slabs made of three-dimensional spatial graphs of mesopore tubes having all structural features under 50 nanometers. Solution-based kinetic fabrication process templates growing networks of cylindrical surfactant micelles with thin tubes of polysiloxane forming gel networks and, upon replacing surfactants and solvents with air, yields lightweight materials with >99% visible-range optical transparency and ~10 mW K-1m-1 thermal conductivity. Such predesigned metamaterials enable transparent thermal barriers for wall-grade insulated glass units, square-meter window retrofits and unconcentrated solar thermal energy harnessing.

14 SOLAR ENERGY↗

Assembly induced delaminations in composite structures

Experimental and analytical studies of the development of delaminations around fastener holes in composite structures are presented. This type of delamination is known to occur in composite skins that are mechanically fastened to a poorly mating substructure. Results of an experimental study to determine the resistance of laminates to the initiation of assembly induced delaminations and the residual strength of assembly damaged coupons are presented for AS4/3501-6, IM7/8551-7A, and AS4/PEEK material systems. A survey of existing analytical models for predicting the residual strength and stability of delaminations is presented, and the development of a new model for predicting the initiation of delaminations around a fastener hole is outlined. The fastener hole damage initiation model utilizes a finite element based Fourier series solution, and is validated through comparisons of analytical and experimental results.

Goering, J.↗