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Results for “complex coacervation”

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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26 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Leveraging Hydration Forces for Size-Specific Nanoparticle Enrichment with a Redox-Responsive Silica-Binding Elastin-Like Polypeptide

Elastin-like polypeptides (ELPs) are low-complexity proteins that coacervate above a characteristic lower critical solution temperature (LCST). While the thermoresponsiveness of ELPs has been widely exploited in the biomedical and biomaterials fields, their ability to mediate nanoparticle assembly below their transition temperature remains largely unexplored. Here, we show that unmodified ELPs induce the reversible flocculation of silica nanoparticles (SiNPs) by forming backbone hydrogen bonds with surface silanols. Interparticle bridging is modulated by ELP length and concentration and by the presence of N- and C-terminal anchoring groups such as a cysteine residue and a Car9 silica-binding peptide. Using a redox-responsive fusion protein consisting of disulfide-bonded ELP domains terminated by Car9 segments, we stabilize 20 nm SiNPs under oxidizing conditions while triggering particle flocculation upon addition of reductant. We find that SiNP sedimentation under reducing conditions exhibits a sharp dependency on particle size that arises from the curvature-dependent structure of surface silanols. While the isolated silanols of SiNPs smaller than 30 nm are efficiently engaged by the ELP domains of Car9-anchored proteins, repulsion forces associated with the presence of a layer of molecular water together with increased electrostatic repulsion preclude efficient engagement of H-bonded silanols displayed on the surface of SiNPs larger than 60 nm. We harness these findings to selectively enrich SiNPs based on size and expand the concept to titania (TiO2) by demonstrating that rutile nanoparticles can be stabilized or sedimented with solid-binding ELPs by adjusting the solution pH to promote or discourage the formation of a hydration layer. These strategies should prove broadly useful for the separation of other oxides and their polymorphs and provide a tunable strategy for nanoparticle assembly and bioinspired colloidal design.

ELP↗
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 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↗
DOE OSTI2023

Bioinspired mineralizing microenvironments generated by liquid-liquid phase coexistence

Biominerals such as bones, teeth and shells exhibit improved mechanical properties and intricate morphologies not seen in nonbiologically-produced minerals of ostensibly the same composition. These remarkable properties of biogenic minerals are thought to arise due to precise local control over the mineral deposition process, including organic and inorganic inclusions. Understanding how Biology controls the local reaction environment during formation of these materials to control their composition, structure, and properties is a grand challenge that promises to enable new routes to high-performance materials. This project developed multi-compartment bioinspired microreactors as artificial mineralizing vesicles, and used them to understand and control formation of inorganic/organic composite solid materials. A major emphasis was on developing all-aqueous emulsions in which each droplet was a structured microreactor with two or more adjacent phases. This approach provided local control over reaction environment including availability of inclusions such as polypeptides and metal ions, while being sufficiently simple to produce large populations of essentially identical multiphase reactor droplets simultaneously within a batch. Organic/inorganic composite materials could be produced with very high organic content that stabilized the inorganic portions as amorphous materials (e.g., amorphous calcium carbonate) by preventing the typical conversion to more thermodynamically crystalline forms (e.g., calcite). These stabilized amorphous composites could be stored indefinitely and converted to crystalline forms later by removal of the organic inclusions via, for example, heating. Compositional gradients in the organic and inorganic components were embedded during synthesis due to the evolution of the reaction microenvironment, and despite the complexity of this process it occurred similarly across the population of reactive droplets and was hence encoded into the population of resulting composite particles. The approach developed here allows pre-structuring of reactive microenvironments to control the spatiotemporal reaction environment, which is an important step towards rational design and on-demand production of complex functional materials with desired composition, optical properties, and mechanical response.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Induced Chirality in QDs Using Thermoresponsive Elastin-like Polypeptides

Circular dichroism (CD) spectroscopy has emerged as a potent tool for probing chiral small-molecule ligand exchange on natively achiral quantum dots (QDs). In this study, we report a novel approach to identifying QD–biomolecule interactions by inducing chirality in CdS QDs using thermoresponsive elastin-like polypeptides (ELPs) engineered with C-terminal cysteine residues. Our method is based on a versatile two-step ligand exchange process starting from monodisperse oleate-capped QDs in nonpolar media and proceeding through an easily accessed achiral glycine-capped QD intermediate. Successful conjugation of the ELPs onto the QDs is confirmed by the diagnostic CD response corresponding to the QD electronic transitions in the visible range. The resulting ELP:CdS conjugates demonstrate thermally reversible coacervation, as observed through dynamic light scattering, small-angle X-ray scattering, and electron microscopy. Furthermore, this research provides a foundation for using induced chirality in QD electronic transitions to probe QD conjugation to complex peptides and proteins, opening pathways for designing dynamic, stimuli-responsive hybrid nanomaterials.

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