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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Chemical specificity in polyzwitterion-polyelectrolyte coacervates: polycations vs polyanions

Aqueous solutions containing polyzwitterions and polyelectrolytes were studied to probe the effects of chemical specificity on the complexation among different types of chains and resulting liquid–liquid phase separation (coacervation). Two kinds of blends were studied. A polyzwitterion, poly(sulfobetaine methacrylate) (PSBMA), was blended with either (1) a polycation, poly(diallydimethylammonium chloride) (PDADMAC), or (2) a polyanion, sodium poly(styrene sulphonate) (NaPSS). Coacervation was observed in both blends after equilibration, while the freshly prepared blend solutions exhibited distinct behavior dependent on the mixing protocols. Mixing solutions of the polyzwitterions and the polycations led to coacervation almost instantaneously. In contrast, the blends containing the same polyzwitterions and the polyanions exhibited no such coacervation by following the same mixing protocol. However, blends prepared after dissolving a solid mixture containing the same polyzwitterions and the polyanions in water exhibited coacervation. Based on the small-angle X-ray scattering (SAXS), cryo-electron microscopy, and rheology measurements, complexation and coacervation in the polyzwitterion-polyelectrolyte blends is rationalized in terms of the entropy change associated with reorganization of solvent (water), which appears to be larger in the polyzwitterion-polycation case in comparison with the polyzwitterion-polyanion blends. These results highlight the importance of chemical specificity and mixing protocols leading to metastable structures in designing a new class of materials based on macromolecular complexation of polyzwitterions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Did the exposure of coacervate droplets to rain make them the first stable protocells?

Membraneless coacervate microdroplets have long been proposed as model protocells as they can grow, divide, and concentrate RNA by natural partitioning. However, the rapid exchange of RNA between these compartments, along with their rapid fusion, both within minutes, means that individual droplets would be unable to maintain their separate genetic identities. Hence, Darwinian evolution would not be possible, and the population would be vulnerable to collapse due to the rapid spread of parasitic RNAs. In this study, we show that distilled water, mimicking rain/freshwater, leads to the formation of electrostatic crosslinks on the interface of coacervate droplets that not only suppress droplet fusion indefinitely but also allow the spatiotemporal compartmentalization of RNA on a timescale of days depending on the length and structure of RNA. We suggest that these nonfusing membraneless droplets could potentially act as protocells with the capacity to evolve compartmentalized ribozymes in prebiotic environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Coacervate droplets, proteinoid microspheres, and the genetic apparatus

Differences between typical coacervate droplets and typical proteinoid microspheres are examined. It is pointed out that coacervate droplets are produced from polymers obtained from contemporary organisms. The microspheres considered are aggregates of proteinoid formed from monomeric amino acids under geologically relevant conditions. Aspects regarding the primordial sequence are discussed along with the origin of the genetic apparatus and the genetic code.

Fox, S. W.↗
NASA NTRS1975

Coacervate-like microspheres from lysine-rich proteinoid

Microspheres form isothermally from lysine-rich proteinoid when the ionic strength of the solution is increased with NaCl or other salts. Studies with different monovalent anions and with polymers of different amino acid composition indicate that charge neutralization and hydrophobic bonding contribute to microsphere formation. The particles also form in sea water, especially if heated or made slightly alkaline. The microspheres differ from those made from acidic proteinoid but resemble coacervate droplets in some ways (isothermal formation, limited stability, stabilization by quinone, uptake of dyes). Because the constituent lysine-rich proteinoid is of simulated prebiotic origin, the study is interpreted to add emphasis to and suggest an evolutionary continuity for coacervation phenomena.

Rohlfing, D. L.↗
DOE OSTI2024

Precision Loading and Delivery of Molecular Cargo by Size-Controlled Coacervation of Gold Nanoparticles Functionalized with Elastin-like Peptides

Thermoresponsive elastin-like peptides (ELPs) have been extensively investigated in biotechnology and medicine, but little attention has been paid to the process by which coacervation causes ELP-decorated particles to aggregate. Here, using gold nanoparticles (AuNPs) functionalized with a cysteine-terminated 96-repeat of the VPGVG sequence (V96-Cys), we show that the size of the clusters that reversibly form above the ELP transition temperature can be finely controlled in the 250 to 930 nm range by specifying the concentration of free V96-Cys in solution and using AuNPs of different sizes. We further find that the localized surface plasmon resonance peak of the embedded AuNPs progressively red-shifts with cluster size, likely due to an increase in particle–particle contacts. We exploit this fine control over size to homogeneously load precise amounts of the dye Nile Red and the antibiotic Tetracycline into clusters of different hydrodynamic diameters and deliver cargos near-quantitatively by deconstructing the aggregates below the ELP transition temperature. Beyond establishing a key role for free ELPs in the agglomeration of ELP-functionalized particles, our results provide a path for the thermally controlled delivery of precise quantities of molecular cargo. This capability might prove useful in combination photothermal therapies and theranostic applications, and to trigger spatially and temporally uniform responses from biological, electronic, or optical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate

The linear viscoelastic response, LVR, of a hydrated polyelectrolyte complex coacervate, PEC, was evaluated over a range of frequencies, temperatures, and salt concentrations. The PEC was a nearly stoichiometric blend of a quaternary ammonium poly([3-(methacrylamido)propyl]trimethylammonium chloride), PMAPTAC, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt), PAMPS, an aliphatic sulfonate, selected because they remain fully charged over the conditions of use. Narrow molecular weight distribution polyelectrolytes were prepared using fractionation techniques. A partially deuterated version of PMAPTAC was incorporated to determine its coil radius of gyration, R g , within PECs using small-angle neutron scattering. Chain dimensions were determined to be Gaussian with a Kuhn length of 2.37 nm, which remained constant from 25 to 65 °C. The LVR for a series of matched molecular weight PECs, mostly above the entanglement threshold, exhibited crossovers of modulus versus frequency classically attributed to the reptation time, relaxation between entanglements, and the relaxation of a Kuhn length of units (the “monomer” time). The scaling for zero shear viscosity, η 0 , versus chain length, N, was η 0 ~ N 3.1 , in agreement with “sticky reptation” theory. The lifetime and activation energy, E p , of a pair between polyanion and polycation repeat units, Pol + Pol – , were determined from diffusion coefficients of salt ions within the PEC. The activation energy for LVR of salt-free PECs was 2E p , showing that the key mechanism limiting the dynamics of undoped PECs is pair exchange. An FTIR technique was used to distinguish whether SCN– acts as a counterion or a co-ion within PECs. Doping of PECs with NaSCN breaks Pol + Pol – pairing efficiently, which decreases effective cross-linking and decreases viscosity. Finally, an equation was derived that quantitatively predicts this effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1967

Coacervates

Coacervates obtained from aqueous colloidal solutions of proteins

BIOGENESIS↗
DOE OSTI2023

A Coacervate-Based Mixed-Conducting Binder for High-Power, High-Energy Batteries

Polymer binders add crucial structural integrity to lithium ion battery composite cathodes, but industry standard binders, such as polyvinylidene fluoride (PVDF), are insulating to ions and electrons, detrimentally adding resistance to the overall system. In this work, we use electrostatics to stabilize a blend of a charged conjugated polymer with an oppositely charged polyelectrolyte, providing a processable, stable binder with high ionic and electronic conduction. Using LiFePO4 cathodes as a model system, we show significant improvement in rate capability and stability, with the conducting binder enabling a 39% utilization at 6C compared to 1.6% when PVDF is the binder. Additionally, the conducting binder affords a 63% capacity retention over 400 C/2 cycles, compared to only a 6% retention over 400 cycles when PVDF is the binder. These results show that electrostatically stabilized complexation is a promising strategy to integrate both electronic and ionic conductivity into a binder, while simultaneously maintaining stability and processability.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Genetic control of morphological transitions in a coacervating protein template

Nature routinely exploits liquid–liquid phase separation (LLPS) of proteins to control the assembly and mineralization of hybrid materials. Here, we show that fusion of the Car9 silica-binding peptide to an elastin-like polypeptide (ELP) yields temperature- and sequence-programmable soft matter templates for the synthesis of silicified architectures ranging in size from nanometers to micrometers. Specifically, we demonstrate unprecedented control over the diameter of silica nanoparticles (SiNP) in the 30–60 nm range with 4 nm precision, show that a single arginine residue (R4) in the Car9 sequence underpins the transition from micelles to proteinosomes, and find that substitutions in other basic residues modulate electrostatic repulsion and solvation to enable access to kinetically trapped species. These structures, which include interconnected micelles, small (∼200 nm) and large (>5 µm) vesicles, are readily visualized by SEM imaging following silicification. Molecular dynamics (MD) simulations and AlphaFold predictions reveal that mutations in positively charged residues alter interfacial packing, hydration, and conformational freedom of the silica-binding segments. Overall, our results establish sequence and thermal energy as synergistic levers for morphological control across length scales using solid-binding ELPs and establish mineralization as a powerful tool to visualize the structure of dynamic soft matter assemblies.

hierarchy↗
DOE OSTI2025

Propulsion of synthetic protocells and coacervates driven by biochemical catalysis

An important area in the design of biomolecular materials is the mimicry of cellular function through the assembly of molecular components into synthetic cells, or protocells. Through compartmentalization and subsequent evolution, biological cells have achieved the goals of specificity, amplification, and response. By assembling cell-like structures that mimic the organization and size of a natural cell but that incorporate novel components and respond to synthetic triggers, we can extend their capabilities beyond what is currently achievable in biology. For applications in energy, these include the ability to convert chemical to mechanical energy, and to enable the response of sensors and responders once a threshold has been reached. This technical report summarizes progress made on this project as of Dec 31, 2023.

36 MATERIALS SCIENCE↗
DOE OSTI2023

HP1-driven phase separation recapitulates the thermodynamics and kinetics of heterochromatin condensate formation

The spatial segregation of pericentromeric heterochromatin (PCH) into distinct, membrane-less nuclear compartments involves the binding of Heterochromatin Protein 1 (HP1) to H3K9me2/3-rich genomic regions. While HP1 exhibits liquid–liquid phase separation properties in vitro, its mechanistic impact on the structure and dynamics of PCH condensate formation in vivo remains largely unresolved. Here, using a minimal theoretical framework, we systematically investigate the mutual coupling between self-interacting HP1-like molecules and the chromatin polymer. We reveal that the specific affinity of HP1 for H3K9me2/3 loci facilitates coacervation in nucleo and promotes the formation of stable PCH condensates at HP1 levels far below the concentration required to observe phase separation in purified protein assays in vitro. These heterotypic HP1–chromatin interactions give rise to a strong dependence of the nucleoplasmic HP1 density on HP1-H3K9me2/3 stoichiometry, consistent with the thermodynamics of multicomponent phase separation. The dynamical cross talk between HP1 and the viscoelastic chromatin scaffold also leads to anomalously slow equilibration kinetics, which strongly depend on the genomic distribution of H3K9me2/3 domains and result in the coexistence of multiple long-lived, microphase-separated PCH compartments. The morphology of these complex coacervates is further found to be governed by the dynamic establishment of the underlying H3K9me2/3 landscape, which may drive their increasingly abnormal, aspherical shapes during cell development. These findings compare favorably to 4D microscopy measurements of HP1 condensate formation in live Drosophila embryos and suggest a general quantitative model of PCH formation based on the interplay between HP1-based phase separation and chromatin polymer mechanics.

3D genomics↗
NASA NTRS1977

Chemical Evolution and the Origin of Life: Bibliography 1975

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

West, Martha W.↗
DOE OSTI2023

Effects of Salt on Phase Behavior and Rheological Properties of Alginate–Chitosan Polyelectrolyte Complexes

Oppositely charged polyelectrolytes often form polyelectrolyte complexes (PECs) due to the association through electrostatic interactions. Obtaining PECs using natural, biocompatible polyelectrolytes is of interest in the food, pharmaceutical, and biomedical industries. In this work, PECs were prepared from two biopolymers, positively charged chitosan and negatively charged alginate. We investigate the changes in the structure and properties of PECs by adding sodium chloride (salt doping) to the system. The shear modulus of PECs can be tuned from ~10 to 10 4 Pa by changing the salt concentration. The addition of salt led to a decrease in the water content of the complex phase with increasing shear modulus. However, at a very high salt concentration, the shear modulus of the complex phase decreased but did not lead to the liquid coacervate formation, typical of synthetic polyelectrolytes. This difference in phase behavior has likely been attributed to the hydrophobicity of chitosan and long semiflexible alginate and chitosan chains that restrict the conformational changes. Large amplitude oscillatory shear experiments captured nonlinear responses of PECs. The compositions of the PECs, determined as a function of salt concentration, signify the preferential partitioning of salt into the complex phase. Small-angle X-ray scattering of the salt-doped PECs indicates that the Kuhn length and radius of the alginate–chitosan associated structure qualitatively agree with the captured phase behavior and rheological data. This study provides insights into the structure–property as a function of salt concentration of natural polymer-based PECs necessary for developing functional materials from natural polyelectrolytes.

59 BASIC BIOLOGICAL SCIENCES↗