Protein-Polyelectrolyte Complexes and Micellar Assemblies.

In this review, we highlight the recent progress in our understanding of the structure, properties and applications of protein-polyelectrolyte complexes in both bulk and micellar assemblies. Protein-polyelectrolyte complexes form the basis of the genetic code, enable facile protein purification, and have emerged as enterprising candidates for simulating protocellular environments and as efficient enzymatic bioreactors. Such complexes undergo self-assembly in bulk due to a combined influence of electrostatic interactions and entropy gains from counterion release. Diversifying the self-assembly by incorporation of block polyelectrolytes has further enabled fabrication of protein-polyelectrolyte complex micelles that are multifunctional carriers for therapeutic targeted delivery of proteins such as enzymes and antibodies. We discuss research efforts focused on the structure, properties and applications of protein-polyelectrolyte complexes in both bulk and micellar assemblies, along with the influences of amphoteric nature of proteins accompanying patchy distribution of charges leading to unique phenomena including multiple complexation windows and complexation on the wrong side of the isoelectric point

Phase stability and dynamics of entangled polymer-nanoparticle composites.

Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host

Tethered Nanoparticle – Polymer Composites: Phase Behavior, Structure, Dynamics And Rheology

Nanoparticle - polymer composites, or polymer nanocomposites, are ubiquitous in the modern world. Controlled dispersion of nanoparticles in nanocomposites is often a critical requirement and has lead to evolution of a variety of strategies for regulating nanoparticle interactions and assembly. This work focuses on one such technique wherein the nanoparticle surfaces are densely tethered with polymer chains. Complete screening of the interparticle interactions and steric repulsion among the tethered chains thus results in repulsive and stable nanoparticles across a range of polymer molecular weights and chemistries and nanoparticle volume fraction. These nanoparticles are found to be ideal for studying polymer nanocomposites, and a phase diagram constructed on the basis of nanoparticle arrangements is presented. Tethered nanoparticles, in the limit small tethered polymer chains, also serve as model systems for studying the properties of soft nanoparticles. Well-dispersed suspensions of these soft nanoparticles in oligomers exhibit unique properties across the jamming transition, including anomalous structural and dynamic trends typically associated with complex molecular fluids. In the jammed regime, these suspensions behave as typical soft glasses and allow for quantitative comparisons with the existing models for soft glasses. At the same time, the tethered chains facilitate relaxations even in the deeply jammed regime and thus lead to novel features including Newtonian behavior and terminal relaxations in the jammed suspensions. On the other end of the spectrum, studies of suspensions of these nanoparticles in extremely large polymer chains provide insights on the physical processes responsible for the atypical, negative non-Einsteinian deviations in the viscosity typically observed in blends of nanoparticles in large polymer hosts. We also explore the origins of atypical faster - than - diffusion relaxation mechanisms in soft materials through studying the relaxation mechanisms in these jammed suspensions as well as single-component tethered nanoparticle fluids. A simple theoretical framework is presented to account for the genesis of driving mechanisms in our systems, and comparisons between theoretical and experimental results provide strong support to the existing theory that hyperdiffusion in soft materials arises from the system's response to internal stresses; however, the origin of these internal stresses might vary considerably from one material to another

Polyelectrolyte Complex-Covalent Interpenetrating Polymer Network Hydrogels

Polyelectrolyte complex (PEC) hydrogels possess rich microstructural diversity and tunability of the shear response, self-healing attributes, and pH- and salt-responsiveness. Yet, their utility in biotechnology and biomedicine has been limited, owing to their weak mechanical strength and uncontrolled swelling. Here, we introduce a strategy to overcome these drawbacks of PEC hydrogels by interlacing the electrostatically crosslinked PEC network with a covalently crosslinked polymer network, creating polyelectrolyte complex-covalent interpenetrating polymer network (PEC-IPN) hydrogels. Structural and material characterizations of model PEC-IPN hydrogels composed of oppositely charged ABA triblock copolymers and photocrosslinkable 4-arm poly(ethylene oxide) (PEO) highlight the key advantages of our approach. Upon initial mixing of the three constituents, the PEC network self-assembles swiftly in aqueous environs, providing structural rigidity and serving as protective scaffoldings for the covalently crosslinkable PEO precursors. Photocrosslinking of the PEO chains creates a covalent network, providing structural reinforcement to the PEC network. The resulting PEC-IPN hydrogels possess significantly improved shear and tensile strengths, swelling characteristics, and mechanical stability in saline environments while preserving the intrinsic mesoscale structure of the PEC network and its salt-responsiveness. We envision that our approach to fabricating PEC-based IPN hydrogels will pave the way for the creation of self-assembled hybrid materials that harness the unique attributes of electrostatic self-assembly pathways, with broad applications in biomedicine

Block Polyelectrolyte Additives That Modulate the Viscoelasticity and Enhance the Printability of Gelatin Inks at Physiological Temperatures

We demonstrate the utility of block polyelectrolyte (bPE) additives to enhance viscosity and resolve challenges with the three-dimensional (3D) printability of extrusion-based biopolymer inks. The addition of oppositely charged bPEs to solutions of photocurable gelatin methacryloyl (GelMA) results in complexation-driven self-assembly of the bPEs, leading to GelMA/bPE inks that are printable at physiological temperatures, representing stark improvements over GelMA inks that suffer from low viscosity at 37 °C, leading to low printability and poor structural stability. The hierarchical microstructure of the self-assemblies (either jammed micelles or 3D networks) formed by the oppositely charged bPEs, confirmed by small-angle X-ray scattering, is attributed to the enhancements in the shear strength and printability of the GelMA/ bPE inks. Varying bPE concentration in the inks is shown to enable tunability of the rheological properties to meet the criteria of pre- and postextrusion flow characteristics for 3D printing, including prominent yielding behavior, strong shear thinning, and rapid recovery upon flow cessation. Moreover, the bPE self-assemblies also contribute to the robustness of the photo-cross- linked hydrogels; photo-cross-linked GelMA/bPE hydrogels are shown to exhibit higher shear strength than photo-cross-linked GelMA hydrogels. Last, the assessment of the printability of GelMA/bPE inks indicates excellent printing performance, including minimal swelling postextrusion, satisfactory retention of the filament shape upon deposition, and satisfactory shape fidelity of the various printed constructs. We envision this study to serve as a practical guide for the printing of bespoke extrusion inks where bPEs are used as scaffolds and viscosity enhancers that can be emulated in a range of photocurable precursors

Electrosteric Control Of The Aggregation And Yielding Behavior Of Concentrated Portlandite Suspensions

Portlandite (calcium hydroxide: CH: Ca (OH)2) suspensions aggregate spontaneously and form percolated fractal aggregate networks when dispersed in water. Consequently, the viscosity and yield stress of portlandite suspensions diverge at low particle loadings, adversely affecting their processability. Even though polycarboxylate ether (PCE)-based comb polyelectrolytes are routinely used to alter the particle dispersion state, water demand, and rheology of similar suspensions (e.g., ordinary portland cement suspensions) that feature a high pH and high ionic strength, their use to control portlandite suspension rheology has not been elucidated. This study combines adsorption isotherms and rheological measurements to elucidate the role of PCE composition (i.e., charge density, side chain length, and grafting density) in controlling the extent of PCE adsorption, particle flocculation, suspension yield stress, and thermal response of portlandite suspensions. We show that longer sidechain PCEs are more effective in affecting suspension viscosity and yield stress, in spite of their lower adsorption saturation limit and fractional adsorption. The superior steric hindrance induced by the longer side chain PCEs results in better efficacy in mitigating particle aggregation even at low dosages. However, when dosed at optimal dosages (i.e., a dosage that induces a dynamically equilibrated dispersion state of particle aggregates), different PCE-dosed portlandite suspensions exhibit identical fractal structuring and rheological behavior regardless of the side chain length. Furthermore, it is shown that the unusual evolution of the rheological response of portlandite suspensions with temperature can be tailored by adjusting the PCE dosage. The ability of PCEs to modulate the rheology of aggregating charged particle suspensions can be generally extended to any colloidal suspension with a strong screening of repulsive electrostatic interactions

Ultrafast Stiffening of Concentrated Thermoresponsive Mineral Suspensions

Extrusion-based 3D printing with rapidly hardening polymeric materials is capable of building almost any conceivable structure. However, concrete, one of the most widely used materials for large-scale structural components, is generally based on inorganic binder materials like Portland cement. Unlike polymeric materials, a lack of precise control of the extent and rate of solidification of cement-based suspensions is a major issue that affects the ability to 3D-print geometrically complex structures. Here, we demonstrate a novel method for controllable-rapid solidification of concentrated mineral suspensions that contain a polymer binder system based on epoxy and thiol precursors as well as one or more mineral fillers like quartz and calcite. The thermally triggered epoxy-thiol condensation polymerization induces rapid stiffening of the hybrid suspensions (0.30 ≤ ϕ ≤ 0.60), at trigger temperatures ranging between 50 °C and 90 °C achieving average stiffening rates up to 400 Pa/s. The use of nucleophilic initiators such as 1-methylimidazole provides control over the activation temperature and curing rate, thereby helping to achieve an adjustable induction period and excellent thermal latency. By using multiple techniques, we provide guidelines to create designer compositions of mineral suspensions that utilize thermal triggers to achieve thermal latency and ultrafast stiffening – prerequisite attributes for 3D-manufacturing of topologically-optimized structural components

Dissolution Amplification by Resonance and Cavitational Stimulation at Ultrasonic and Megasonic Frequencies

Acoustic stimulation offers a green pathway for the extraction of valuable elements such as Si, Ca, and Mg via solubilization of minerals and industrial waste materials. Prior studies have focused on the use of ultrasonic frequencies (20-40 kHz) to stimulate dissolution, but mega sonic frequencies (≥1 MHz) offer benefits such as matching of the resonance frequencies of solute particles and an increased frequency of cavitation events. Here, based on dissolution tests of a series of minerals, it is found that dissolution under resonance conditions produced dissolution enhancements between 4x-to-6x in Si-rich materials (obsidian, albite, and quartz). Cavitational collapse induced by ultrasonic stimulation was more effective for Ca- and Mg-rich carbonate precursors (calcite and dolomite), exhibiting a significant increase in the dissolution rate as the particle size was reduced (i.e. available surface area was increased), resulting in up to a 70x increase in the dissolution rate of calcite when compared to unstimulated dissolution for particles with d50\u3c 100 μm. Cavitational collapse induced by mega sonic stimulation caused a greater dissolution enhancement than ultrasonic stimulation (1.5x vs 1.3x) for amorphous class F fly ash, despite its higher Si content because the hollow particle structure was susceptible to breakage by the rapid and high number of lower-energy mega sonic cavitation events. These results are consistent with the cavitational collapse energy following a normal distribution of energy release, with more cavitation events possessing sufficient energy to break Ca-O and Mg-O bonds than Si-O bonds, the latter of which has a bond energy approximately double the others. The effectiveness of ultrasonic dissolution enhancement increased exponentially with decreasing stacking fault energy (i.e., resistance to the creation of surface faults such as pits and dislocations), while, in turn, the effectiveness of mega sonic dissolution increased linearly with the stacking fault energy. These results give new insights into the use of acoustic frequency selections for accelerating elemental release from solutes by the use of acoustic perturbation

Thermal Jamming of a Colloidal Glass

We investigate the effect of temperature on structure and dynamics of a colloidal glass created by tethering polymers to the surface of inorganic nanoparticles. Contrary to the conventional assumption, an increase in temperature slows down glassy dynamics of the material, yet causes no change in its static structure factor.We show that these findings can be explained within the soft glassy rheology framework if the noise temperature X of the glass phase is correlated with thermodynamic temperature.This publication was based on work supported in part by the National Science Foundation, No. DMR-1006323 and by No. KUS-C1-018-02, made by King Abdullah University of Science and Technology (KAUST). Facilities available through the Cornell Center for Materials Research (CCMR) were also used for this study