Search NASA⌕ Search

SEARCH · Search NASA

Results for “tether force”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Electric Sail Propulsion for Deep Space Missions

Electrostatic Sail (E-sail) propulsion extracts momentum from the solar wind, which has minimal speeds of 400 km/sec, through electrostatic repulsion of the positively charged solar wind ions. This momentum exchange is accomplished by an array of multi-kilometer-length charged tethers biased to a high positive voltage, producing an electric field around the tethers that deflect the positively charged solar wind particles. This electric field grows in diameter as the spacecraft moves away from the sun, increasing the E-sail effective area. The growth of the E-sail effective area allows the created propulsive force to decrease at a rate closer to 1/r out to distances from the sun of up to 20 Astronomical Units (AU). This is unlike solar sail propulsion, where the thrust decreases at a rate of 1/r2 and is only effective out to distances of ~5 AU. The propulsive force is applied without expending any propellant. Although the thrust generated by an E-Sail is low, it can be applied continuously over a period of years (depending on the mission type), and can push a 500 kg spacecraft to tremendous velocities—as high as 12 AU per year—making the voyage to 600 AU in as few as 50 years after launch. The NASA Marshall Space Flight Center recently completed a NASA Innovative Advanced Concept (NIAC) study in which all of the major system- and subsystem-level aspects of an E-Sail-propelled vehicle were assessed and a maturation plan developed. If implemented, E-Sail propulsion could be realized and deployed as a viable option for space missions within a decade.

Interstellar Probe↗
NASA NTRS2004

8th Spacecraft Charging Technology Conference

The 8th Spacecraft Charging Technology Conference was held in Huntsville, Alabama, October 20-24, 2003. Hosted by NASA s Space Environments and Effects (SEE) Program and co-sponsored by the Air Force Research Laboratory (AFRL) and the European Space Agency (ESA), the 2003 conference saw attendance from eleven countries with over 65 oral papers and 18 poster papers. Presentation topics highlighted the latest in spacecraft charging mitigation techniques and on-orbit investigations, including: Plasma Propulsion and Tethers; Ground Testing Techniques; Interactions of Spacecraft and Systems With the Natural and Induced Plasma Environment; Materials Characterizations; Models and Computer Simulations; Environment Specifications; Current Collection and Plasma Probes in Space Plasmas; On-Orbit Investigations. A round-table discussion of international standards regarding electrostatic discharge (ESD) testing was also held with the promise of continued discussions in the off years and an official continuation at the next conference.

Minor, J. L.↗
DOE OSTI2024

How Precisely Can Individual Molecules Be Analyzed? A Case Study on Locally Quantifying Forces and Energies Using Scanning Probe Microscopy

Recent advances in scanning probe microscopy methodology have enabled the measurement of tip-sample interactions with picometer accuracy in all three spatial dimensions, thereby providing a detailed site-specific and distance-dependent picture of the related properties. This paper explores the degree of detail and accuracy that can be achieved in locally quantifying probe-molecule interaction forces and energies for adsorbed molecules. Toward this end, cobalt phthalocyanine (CoPc), a promising CO 2 reduction catalyst, was studied on Ag(111) as a model system using low-temperature, ultrahigh vacuum noncontact atomic force microscopy. Data were recorded as a function of distance from the surface, from which detailed three-dimensional maps of the molecule's interaction with the tip for normal and lateral forces as well as the tip-molecule interaction potential were constructed. The data were collected with a CO molecule at the tip apex, which enabled a detailed visualization of the atomic structure. Determination of the tip-substrate interaction as a function of distance allowed isolation of the molecule-tip interactions; when analyzing these in terms of a Lennard-Jones-type potential, the atomically resolved equilibrium interaction energies between the CO tethered to the tip and the CoPc molecule could be recovered. Interaction energies peaked at less than 160 meV, indicating a physisorption interaction. As expected, the interaction was weakest at the aromatic hydrogens around the periphery of the molecule and strongest surrounding the metal center. In conclusion, the interaction, however, did not peak directly above the Co atom but rather in pockets surrounding it.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An in situ shearing x-ray measurement system for exploring structures and dynamics at the solid–liquid interface

Revealing interfacial structure and dynamics has been one of the essential thematic topics in material science and condensed matter physics. Synchrotron-based x-ray scattering techniques can deliver unique and insightful probing of interfacial structures and dynamics, in particular, in reflection geometries with higher surface and interfacial sensitivity than transmission geometries. We demonstrate the design and implementation of an in situ shearing x-ray measurement system, equipped with both inline parallel-plate and cone-and-plate shearing setups and operated at the advanced photon source at Argonne National Laboratory, to investigate the structures and dynamics of end-tethered polymers at the solid-liquid interface. With a precise lifting motor, a micrometer-scale gap can be produced by aligning two surfaces of a rotating upper shaft and a lower sample substrate. A torsional shear flow forms in the gap and applies tangential shear forces on the sample surface. The technical combination with nanoscale rheology and the utilization of in situ x-ray scattering allow us to gain fundamental insights into the complex dynamics in soft interfaces under shearing. In this work, we demonstrate the technical scope and experimental capability of the in situ shearing x-ray system through the measurements of charged polymers at both flat and curved interfaces upon shearing. Furthermore, through the in situ shearing x-ray scattering experiments integrated with theoretical simulations, we aim to develop a detailed understanding of the short-range molecular structure and mesoscale ionic aggregate morphology, as well as ion transport and dynamics in soft interfaces, thereby providing fundamental insight into a long-standing challenge in ionic polymer brushes with a significant technological impact.

36 MATERIALS SCIENCE↗
NASA NTRS1978

Tethered subsatellite as a tool for large body plasma flow interaction studies

It is shown that the qualitative scaling laws can be satisfied for some aspects of certain astrophysical plasma flow interactions by utilizing the Tethered Satellite System (TSS) to deploy and maintain bodies ranging from 50 to 150 m in radius. The stability of the TSS for such large bodies and the limits on body size are considered. The inflation of the bodies is discussed along with the dynamic and electrodynamic forces on the surface of the bodies.

Stone, N. H.↗
DOE OSTI2023

Ion Specificity Influences on the Structure of Zwitterionic Brushes

Zwitterionic brushes have a wide range of applications, including use as lubricating surfaces and antifouling membranes. In this study, densely end-tethered poly(cysteine methacrylate) (PCysMA) brushes were synthesized using surfaceinitiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET-ATRP). The structure of the PCysMA brushes was investigated using ellipsometry, X-ray reflectivity (XRR), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and atomic force microscopy (AFM). The results of these characterization techniques were used to study the effect of SO 4 2– , Cl – , NO 3 – , Br – , and SCN – anions, divalent Ca 2+ and Ba 2+ cations, and trivalent Y 3+ cations on the structure of the PCysMA brushes. The results showed that the PCysMA brushes in solution exhibit an “antipolyelectrolyte” effect to a certain degree, which inversely follows the Hofmeister series of anions. The introduction of divalent cations Ca 2+ and Ba 2+ had a modest impact on the dimensions of the PCysMA brushes, indicating that chelating interactions between the cations and zwitterion units work against the “antipolyelectrolyte” effect. The complexation was even stronger in the presence of trivalent Y 3+ cations, which caused the PCysMA brushes to shrink. These findings highlight the importance of ion specificity to the structure of zwitterionic brushes in aqueous solutions.

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

Assembly of Building Blocks by Double-End-Anchored Polymers in the Dilute Regime Mediated by Hydrophobic Interactions at Controlled Distances

Hierarchical assembly of building blocks via competing, orthogonal interactions is a hallmark of many of nature’s composite materials that do not require highly specific ligand-receptor interactions. To mimic this assembly mechanism requires the development of building blocks capable of tunable interactions. In the present work, we explored the interplay between repulsive (steric and electrostatic) and attractive hydrophobic forces. The designed building blocks allow hydrophobic forces to effectively act at controlled, large distances, to create and tune the assembly of membrane-based building blocks under dilute conditions and affect their interactions with cellular membranes via physical cross-bridges. Specifically, we employed double-end-anchored poly(ethylene glycol)s (DEA-PEGs)—hydrophilic PEG tethers with hydrophobic tails on both ends. Using differential-interference-contrast optical microscopy, synchrotron small angle X-ray scattering (SAXS), and cryogenic electron microscopy, we investigated the ability of DEA-PEGs to mediate assembly in the dilute regime on multiple length scales and on practical time scales. The PEG length, anchor hydrophobicity, and molar fraction of DEA-PEG molecules within a membrane strongly affect the assembly properties. Additional tuning of the intermembrane interactions can be achieved by adding repulsive interactions via PEG-lipids (steric) or cationic lipids to the DEA-PEG-mediated attractions. Further, while the optical and electron microscope imaging methods provided qualitative evidence of the ability of DEA-PEGs to assemble liposomes, the SAXS measurements and quantitative line-shape analysis in dilute preparations demonstrated that the ensemble average of loosely organized liposomal assemblies maintains DEA-PEG concentration-dependent tethering on defined nanometer length scales. For cationic liposome–DNA nanoparticles (CL–DNA NPs), aggregation induced by DEA-PEGs decreased internalization of NPs by cells, but tuning the DEA-PEG-induced attractions by adding repulsive steric interactions via PEG-lipids limited aggregation and increased NP uptake. However, confocal microscopy imaging together with colocalization studies with Rab11 and LysoTracker as markers of intracellular pathways showed that modifying CL–DNA NPs with DEA-PEGs alters their interactions with the plasma and endosomal membranes.

- x-ray scattering↗
NASA NTRS1986

Tethered constellations

The studies that have been carried out on Tethered Constellations are briefly addressed. A definition of a tethered constellation is any number of masses/platforms greater that two connected by tethers in a stable configuration. Configurations and stability constraints are reviewed. Conclusions reached are: (1) The 1-D, horizontal, passively stabilized constellations have been ruled out; (2) Fishbone constellations have been also ruled out; (3) Alternative stable 2-D configurations have been devised such as the quadrangular configuration stabilized by electrodynamic forces (ESC), the quadrangular configuration stabilized by differential air drag (DSC), and the pseudo elliptical configuration stabilized by electrodynamic forces (PEC). Typical dimensions for these constellations are 10 km (horizontal) by 20 km (vertical) with balloon diameters around 100 m in the case of a DSC and a power consumption around 7 KW for an ESC or PEC.

Lorenzini, E.↗
NASA NTRS1997

Root cytoskeleton: its role in perception of and response to gravity

We have critically evaluated the possible functions of the plant cytoskeleton in root gravisensing and graviresponse and discussed the evidence that microtubules (MTs) and actin microfilaments (MFs) do not control differential cell growth during bending of roots. On the other hand, MF and MT networks are envisaged to participate in gravisensing because of the mechanical properties of the cytoskeletal structures that interconnect plant cell organelles with the plasma membrane. In restrained gravisensing, forces are suggested to be transmitted to membranes because large-scale gravity-dependent repositioning of organelles is effectively prevented due to the cytoskeleton-mediated anchorage of their envelopes at the plasma membrane. From the cytoskeletal point of view, we can also envisage an unrestrained gravity sensing when cytoskeletal tethers are not strong enough to preserve the tight control over distribution of organelles and the latter, if heavy enough, are allowed to sediment towards the physical bottom of cells. This situation obviously occurs in root cap statocytes because these uniquely organized cells are depleted of prominent actin MF bundles, endoplasmic MT arrays, and ER elements in their internal cytoplasm. Nevertheless, indirect evidence clearly indicates that sedimented root cap statoliths are enmeshed within fine but dynamic MF networks and that their behaviour is obviously under, at least partial, cytoskeletal control. The actomyosin-enriched domain among and around amyloplasts is proposed to increase the perception of gravity due to the grouping effect of sedimenting statoliths. Cytoskeletal links between myosin-rich statoliths, and cell peripheries well equipped with dense cortical MTs, membrane-associated cytoskeleton, as well as with ER elements, would allow efficient restrained gravisensing only at the statocyte cell cortex. As a consequence of cytoskeletal depletion in the internal statocyte cytoplasm and bulk sedimentation of large amyloplasts, restrained gravisensing is spatially restricted to the bottom of the statocyte irrespective of whether roots are vertical or horizontal. This spatial aspect allows for efficient gravisensing via amplification of gravity-induced impacts on the cellular architecture, a phenomenon which is unique to root cap statocytes.

NASA Discipline Plant Biology↗
NASA NTRS2002

Small Particle Response to Fluid Motion using Tethered Particles to Simulate Microgravity

This paper reports on ground based work conducted to support the Spaceflight Definition project SHIVA (Spaceflight Holography Investigation in a Virtual Apparatus). SHIVA will advance our understanding of the movement of a particle in a fluid. Gravity usually dominates the equations of motion, but in microgravity as well as on earth other terms can become important. Before two members of our team found an analytical solution of the equations, numerical methods and/or neglecting terms were required. The general solution predicts that the usually neglected history term becomes important when the characteristic viscous time is in the same order as the vibration period and peaks when the two times are equal. In this case three force terms, the Stokes drag, the added mass, and the history drag must all be included in predicting particle movement. We also developed diagnostic recording methods using holography to save all of the particle field data, allowing the experiment to essentially be transferred from space back to earth in what we call the "virtual apparatus". Using state-of-the-art methods in holography we will quantify the three-dimensional motion of sets of particles, allowing us to test and apply the new analytical solutions. The motion of particles up to 4 mm in diameter in a fluid that oscillates at frequencies up to 100 Hz with amplitudes up to 200 microns is being examined. Ground studies to support the flight development program have employed various schemes to simulate microgravity. One of the most reliable and meaningful methods uses spheres tethered to a fine hair suspended in the fluid. We have also investigated particles with nearly neutral buoyancy. Recordings are made at the peak amplitudes of vibration of the cell providing a measure of the ratio of fluid to particle amplitude. The experiment requires precise location of the particle at the time of recording. The hologram of the particle provides microscopic images of the particle that are used for finding the position with an accuracy of a few microns. To make the experiment more versatile, the spaceflight system will record holograms both on film and electronically. The electronic holograms can be downlinked providing real time data. Results of the ground experiments, the flight experiment design, and data analysis procedures are reported.

Trolinger, J. D.↗
NASA NTRS2002

Small Particle Response to Fluid Motion using Tethered Particles to Simulate Microgravity

This paper reports on ground based work conducted to support the Spaceflight Definition project SHIVA (Spaceflight Holography Investigation in a Virtual Apparatus). SHIVA will advance our understanding of the movement of a particle in a fluid. Gravity usually dominates the equations of motion, but in microgravity as well as on earth other terms can become important. Before two members of our team found an analytical solution of the equations, numerical methods and/or neglecting terms were required. The general solution predicts that the usually neglected history term becomes important when the characteristic viscous time is in the same order as the vibration period and peaks when the two times are equal. In this case three force terms, the Stokes drag, the added mass, and the history drag must all be included in predicting particle movement. We also developed diagnostic recording methods using holography to save all of the particle field data, allowing the experiment to essentially be transferred from space back to earth in what we call the "virtual apparatus". Using state-of-the-art methods in holography we will quantify the three-dimensional motion of sets of particles, allowing us to test and apply the new analytical solutions. The motion of particles up to 4 mm in diameter in a fluid that oscillates at frequencies up to 100 Hz with amplitudes up to 200 microns is being examined. Ground studies to support the flight development program have employed various schemes to simulate microgravity. One of the most reliable and meaningful methods uses spheres tethered to a fine hair suspended in the fluid. We have also investigated particles with nearly neutral buoyancy. Recordings are made at the peak amplitudes of vibration of the cell providing a measure of the ratio of fluid to particle amplitude. The experiment requires precise location of the particle at the time of recording. The hologram of the particle provides microscopic images of the particle that are used for finding the position with an accuracy of a few microns. To make the experiment more versatile, the spaceflight system will record holograms both on film and electronically. The electronic holograms can be downlinked providing real time data. Results of the ground experiments, the flight experiment design, and data analysis procedures are reported.

Trolinger, J. D.↗
DOE OSTI2021

Linearized modeling and optimization of shared mooring systems

Shared mooring systems, where adjacent platforms are tethered directly to each other, can reduce anchor quantities and mooring line lengths in a floating array but also introduce new modeling and design challenges. This paper presents and demonstrates a first-order approach to modeling and designing shared mooring systems that simplifies these challenges. We formulate a general, linearized model for the force-displacement response of shared mooring systems, including inter-platform couplings. Using this linearization, we realize significant simplifications to the shared mooring system design problem and propose a corresponding design optimization approach. Finally, we demonstrate the complete approach on a variety of shared-mooring floating wind farm layouts with generic design assumptions and constraints. Some fundamental observations about shared mooring systems can be made from the results. Polygonal array layouts with perpendicular anchor positions appear to maximize shared mooring system efficiency. Also, arrays with greater levels of sharing tend to exhibit larger deviations in offsets between platforms. Overall, the results show how the linearized approach can be applied to efficiently evaluate and systematically optimize preliminary shared mooring system designs.

17 WIND ENERGY↗
DOE OSTI2023

Validating a Tethered Balloon System and Optical Technologies for Marine Wildlife Detection and Tracking

The interactions between marine wildlife and marine energy devices are not well understood, leading to regulatory delays for device deployments and testing. Technologies that enable marine wildlife observations can help to fill data gaps and reduce uncertainties about animal–device interactions. A validation test conducted in Galveston Bay near La Porte, Texas, in December 2022 used a technology package consisting of a tethered balloon system and three independent sensor systems, including three-band visible, eight-band multispectral, and single-band thermal to detect three marine-mammal-shaped surrogates. The field campaign aimed to provide an initial step to evaluating the use of the TBS and the effectiveness of the sensor suite for marine wildlife observations and detection. From 2 December to 7 December 2022, 6 flights were conducted under varying altitudes and environmental conditions resulting in the collection of 5454 images. A subset of the images was classified and analyzed with two collection criteria including Beaufort wind force scale and TBS altitude to assess a range of observations of a surrogate from near-shore to offshore based on pixel count. The results of this validation test demonstrate the potential for using TBSs and imaging sensors for marine wildlife observations and offer valuable information for further development and application of this technology for marine energy and other blue economy sectors.

47 OTHER INSTRUMENTATION↗
NASA NTRS1979

System noise analysis of the dumbbell tethered satellite for gravity-gradient measurements

An analysis of the dumbbell gravity gradiometer concept for measuring short wavelength variations in the earth's gravity gradient is presented. Variations in the gradient are recorded by measuring tension variations in a vertically stabilized satellite consisting of heavy masses connected by a long wire or rod. Tension noise arises from the excitation of various mechanical oscillations of the system. The principal noise sources that were identified are fluctuations in atmospheric drag heating and drag force resulting from density variations and winds. Approximate analytical expressions are presented for the tension noise as a function of the system design parameters for various possible configurations. Computer simulations using numerical integration were performed to study the tension noise for several sample cases. Three designs consistent with Shuttle launch capabilities are discussed.

Colombo, G.↗
NASA NTRS2003

Small Particle Response to Fluid Motion Using Tethered Particles to Simulate Microgravity

This paper reports on ground based work conducted to support the Spaceflight Definition project SHIVA (Spaceflight Holography Investigation in a Virtual Apparatus). SHIVA will advance our understanding of the movement of a particle in a fluid. Gravity usually dominates the equations of motion, but in microgravity as well as on earth other terms can become important. Through an innovative application of fractional differential equations, two members of our team produced the first analytical solution of a fundamental equation of motion, which had only been solved numerically or by approximation before. The general solution predicts that the usually neglected history term becomes important in particle response to a sinusoidal fluid movement when the characteristic viscous time is in the same order as the fluid oscillation period and peaks when the two times are equal. In this case three force terms, the Stokes drag, the added mass, and the history drag must all be included in predicting particle movement. We have developed diagnostic recording methods using holography to save all of the particle field data, allowing the experiment to essentially be transferred from space back to earth in what we call the virtual apparatus for on-earth microgravity experimentation. We can quantify precisely the three-dimensional motion of sets of particles, allowing us to test and apply the new analytical solutions. We are examining the response of particles up to 2 mm radius to fluid oscillation at frequencies up to 80 Hz with amplitudes up to 200 microns. Ground studies to support the flight development program have employed various schemes to simulate microgravity. One of the most reliable and meaningful methods uses spheres tethered to a fine hair suspended in the fluid. We have also investigated particles with nearly neutral buoyancy. Recordings are made at the peak amplitudes of vibration of the cell providing a measure of the ratio of fluid to particle amplitude. The experiment requires precise location of the particle to within microns during recording, and techniques for achieving this are one of the project challenges. Focused microscopic images and diffraction patterns are used. To make the experiment more versatile, the spaceflight system will record holograms both on film and electronically. A cross correlation procedure enables sub pixel accuracies for electronic recordings, partially accommodating the lower spatial resolution of CCDs. The electronic holograms can be down linked providing real time data. Results of the ground experiments, the flight experiment design, and data analysis procedures are reported.

Trolinger, James↗
DOE OSTI2024

Influence of Antarctic and Greenland Continental Shelf Circulation on High‐Latitude Oceans in E3SM

The science objectives of this project are to simulate and understand the impacts of both deep-basin warm-water intrusions and land-ice melt on the continental shelf circulations and sea-ice distributions around the margins of Greenland and Antarctica. As well, the role of subsurface ocean heat from the Atlantic on declining sea-ice cover in the Arctic is explored. Mesoscale processes and fine bathymetry are implicated in cross-shelf property transports around both Greenland and Antarctica. Therefore, we configured and ran an atmospheric reanalysis-forced global ocean/sea-ice simulation on a grid that reduces from 8 km at the Equator to 2 km at the poles (UH8to2) with 60 vertical levels. It was produced using the Energy Exascale Earth System Model ‘‘HiLAT’’ code (E3SMv0-HiLAT) that uses the Parallel Ocean Program (POP) and CICE5 as its ocean and sea-ice components, respectively. Two main UH8to2 simulations were carried out: one for 1975-2009 and the other for July 2016-2020 after it was initialized from a 1/25° data-assimilative ocean/sea-ice prediction system ocean/sea-ice state. The UH8to2 is not coupled to an active land-ice model. Rather, land-ice melt is represented by observationally informed freshwater fluxes (FWFs). Short (multi-year) UH8to2 simulations were conducted to understand sensitivities when Greenland ice sheet (GrIS) melt is released only at the ocean surface or when it is distributed over the upper water column in accordance with fjord melt plume behavior; these cases were compared with a no GrIS melt case. West Greenland continental shelf currents were fastest in the vertical distribution case and an increase in baroclinic conversion at the shelf break associated with increased eddy kinetic energy was found relative to the surface release case. Further, salinity is lower and meltwater volume greater in the eastern Labrador Sea in the vertical distribution case. For the Arctic, the veracity of the UH8to2 was evaluated for 2017-2020 using available observations. Simulated seasonal sea-ice thickness and concentration are realistic, but the ice is unrealistically thin in the central and eastern Arctic in the fall. Comparisons of vertical sections of ocean temperature, salinity, and buoyancy collected from Ice-Tethered Profilers (ITPs) in the eastern Arctic in the fall and winter of 2019/2020 and co-located/concurrent UH8to2 fields show the stratification over the top 100 m of the water column is too low in the model, the simulated mixed layer too deep, and the simulated subsurface Atlantic Water (AW) too warm; these biases may contribute to the sea-ice biases. A model intercomparison study using the UH8to2 and a forced 1/25° regional Arctic ocean/sea-ice (uses the HYbrid Coordinate Ocean Model and CICE5) simulation further investigates the relationship between AW and sea-ice in the eastern Arctic. The models show a mesoscale-rich pulse of Atlantic Water extending into the eastern basin that reaches maximum intensity in late winter of 2018, after which it decreases in strength. Concurrent and co-located sea-ice melt or the inhibition of sea-ice growth is seen and is attributed to halocline mesoscale eddies doming into the mixed layer with convection bringing this heat into the vicinity of the sea-ice.

58 GEOSCIENCES↗
NASA NTRS1978

Interactions of a tethered satellite system with the ionosphere

The Tethered Satellite System will be the first large structure deployed in space. It will react strongly with the magneto-ionic medium of the Earth's ionosphere and will thus be valuable experimental tool. Experiments planned for the structure are discussed. Emphasis is placed on the structures ability to excite a large variety of wave phenomena in the ionosphere using its electromotive force.

Grossi, M. D.↗
DOE OSTI2023

Hindered segmental dynamics in associative protein hydrogels studied by neutron spin-echo spectroscopy

Transient binding between associating macromolecules can cause qualitative changes to chain dynamics, including modes of conformational relaxation and diffusion, through tethering effects imparted by long-range connectivity. Here, in this work, the role of binding on short-time segmental dynamics in associative polymer gels is investigated by neutron spin-echo (NSE) measurements on a class of model artificial coiled-coil proteins with a systematically varied architecture, probing timescales of 0.1–130 ns, and length scales close to the molecular radius of gyration. The results illustrate effects of transient cross-linking on chain dynamics on different timescales, manifested in changes in segmental relaxation behavior with variations in strand length, chain concentration, and sticker distribution (endblock- vs midblock-functionalized). In all gels, a short-time cooperative diffusion mode is seen over all wave vectors, analogous to a semidilute solution, with no transitions seen at any known structural length scale. However, the diffusion coefficients are found to decrease with increasing junction density across all gels, with the strand length and number of stickers per chain in each gel appearing to play a relatively minor role. The slowing of cooperative diffusion with junction density contrasts with classical predictions of a greater restoring force for fluctuation dissipation due to the increased elasticity, suggesting additional effects of the coiled-coil junctions such as an enhancement in local viscosity that slows dynamics. Notably, the relaxation rates for all gels can be rescaled by the interjunction spacing inferred from small-angle neutron scattering, where they collapse onto a master curve suggestive of self-similar dynamics even in networks with different strand lengths and chain architectures. On long timescales (but shorter than the junction exchange time), a slowing of network relaxation is observed, resulting in a nondecaying plateau in the spin-echo amplitude attributed to a freezing of chain dynamics due to tethering. A characteristic length scale corresponding to the extent of dynamic fluctuations is estimated for each gel, which appears to be smaller than the interjunction spacing but similar to the correlation blob size of the overlapping strands. The results indicate an important role of transient binding on molecular-scale dynamics in associative polymer gels, even on timescales shorter than the junction exchange time, in addition to its effects on long-range self-diffusion previously observed.

36 MATERIALS SCIENCE↗