Nanostructured, responsive hydrogels formed due to electrostatic interactions have promise for applications such as drug delivery and tissue mimics. These physically cross-linked hydrogels are composed of an aqueous solution of oppositely charged triblocks with charged end-blocks and neutral, hydrophilic mid-blocks. Due to their electrostatic interactions, the end-blocks microphase separate and form physical cross-links that are bridged by the mid-blocks. The structure of this system was determined using a new, efficient embedded fluctuation (EF) model in conjunction with self-consistent field theory. The calculations using the EF model were validated against unapproximated field-theoretic simulations with complex Langevin sampling and were found consistent with small angle X-ray scattering (SAXS) measurements on an experimental system. Using both the EF model and SAXS, phase diagrams were generated as a function of end-block fraction and polymer concentration. Several structures were observed including a body-centered cubic sphere phase, a hexagonally packed cylinder phase, and a lamellar phase. Finally, the EF model was used to explore how parameters that directly relate to polymer chemistry can be tuned to modify the resulting phase diagram, which is of practical interest for the development of new hydrogels.
The kinetics of formation and structural evolution of novel polyelectrolyte complex materials formed by the assembly of water-soluble di-and triblock copolymers, with one neutral block and one (or two) cationic or anionic blocks, have been investigated. Comparison was made between the assembly of ABA and AB′ copolymers in which A represents the ionic blocks and B and B′ are the neutral poly(ethylene oxide) blocks. The degree of polymerization of B was twice that of B′ and the ionic A blocks were of equal degrees of polymerization in all polymers. The mechanism and speed of the assembly process, and the organization of these domains, was probed using dynamic mechanical spectroscopy and small-angle X-ray scattering (SAXS). SAXS revealed that the equilibrium morphologies of both the diblock copolymer and the triblock copolymer materials were generally qualitatively the same with some apparent quantitative differences in phase boundaries, possibly attributable to lack of full equilibration. Slow kinetics and difficulties in reaching equilibrium phase structures, especially in triblock materials, is a principal message of this article. Detailed analysis of the SAXS data revealed that the triblock copolymer materials formed ordered phases via a nucleation and growth pathway and that the addition of small amounts (∼20%) of corresponding diblock copolymers increased the rate of structure formation and enhanced several key physical properties.
A complex coacervate is a fluid phase that results from the electrostatic interactions between two oppositely charged macromolecules. The nature of the coacervate core structure of hydrogels and micelles formed from complexation between pairs of diblock or triblock copolymers containing oppositely charged end-blocks as a function of polymer and salt concentration was investigated. Both ABA triblock copolymers of poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] and analogous poly[(allyl glycidyl ether)-b-(ethylene oxide)] diblock copolymers, which were synthesized to be nearly one-half of the symmetrical triblock copolymers, were studied. The poly(allyl glycidyl ether) blocks were functionalized with either guanidinium or sulfonate groups via postpolymerization modification. Mixing of oppositely charged block copolymers resulted in the formation of nanometer-scale coacervate domains. Small angle neutron scattering (SANS) experiments were used to investigate the size and spacing of the coacervate domains. The SANS patterns were fit using a previously vetted, detailed model consisting of polydisperse core-shell micelles with a randomly distributed sphere or body-centered cubic (BCC) structure factor. For increasing polymer concentration, the size of the coacervate domains remained constant while the spatial extent of the poly(ethylene oxide) (PEO) corona decreased. However, increasing salt concentration resulted in a decrease in both the coacervate domain size and the corona size due to a combination of the electrostatic interactions being screened and the shrinkage of the neutral PEO blocks. Additionally, for the triblock copolymers that formed BCC ordered domains, the water content in the coacervate domains was calculated to increase from approximately 16.8% to 27.5% as the polymer concentration decreased from 20 to 15 wt %.
We herein report the development of crosslinked polyether particles as a reactive platform for the preparation of functional microgels. Thiol-ene crosslinking of poly(allyl glycidyl ether) in miniemulsion droplets - stabilized by a surface active, bio-compatible polyethylene glycol block copolymer - resulted in colloidal gels with a PEG corona and an inner polymeric network containing reactive allyl units. The stability of the allyl groups allows the microgels to be purified and stored before a second, subsequent thiol-ene functionalization step allows a wide variety of pH- and chemically-responsive groups to be introduced into the nanoparticles. The facile nature of this synthetic platform enables the preparation of microgel libraries that are responsive to different triggers but are characterized by the same size distribution, surface functionality, and crosslinking density. In addition, the utilization of a crosslinker containing cleavable ester groups renders the resulting hydrogel particles degradable at elevated pH or in the presence of esterase under physiological conditions.
Well-defined microgel particles were prepared by combining coacervate-driven cross-linking of ionic triblock copolymers with the ability to control particle size and encapsulate functional cargos inherent in microfluidic devices. In this approach, the efficient assembly of PEO-based triblock copolymers with oppositely charged end-blocks allows for bioinspired cross-linking under mild conditions in dispersed aqueous droplets. This strategy enables the integration of charged cargos into the coacervate domains (e.g., the loading of anionic model compounds through electrostatic association with cationic end-blocks). Distinct release profiles can be realized by systematically varying the chemical nature of the payload and the microgel dimensions. This mild and noncovalent assembly method represents a promising new approach to tunable microgels as scaffolds for colloidal biomaterials in therapeutics and regenerative medicine.
Accurately tuning the macroscopic properties of biopolymer‐based hydrogels remains challenging due to the ill‐defined molecular architecture of the natural building blocks. Here, we report a biohybrid coacervate hydrogel, combining the biocompatibility and biodegradability of naturally occurring hyaluronic acid (HA) with the tunability of a synthetic polyethylene oxide (PEO) ‐based ABA‐triblock copolymer. Coacervation of the cationic ammonium or guanidinium‐functionalized copolymer A‐blocks with the anionic HA leads to hydrogel formation. Both mechanical properties and water content of the self‐healing hydrogels can be controlled independently by altering the copolymer structure. By controlling the strength of the interaction between the polymer network and small‐molecule cargo, both release rate and maximum release are controlled. Finally, we show that coacervation of HA and the triblock copolymer leads to increased biostability upon exposure to hyaluronidase. We envision that noncovalent crosslinking of HA hydrogels through coacervation is an attractive strategy for the facile synthesis of tunable hydrogels for biomedical applications.
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