Saloplastic Macroporous Polyelectrolyte Complexes: Cartilage Mimics.
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ABSTRACT:
SUBMITTER: Hariri HH
PROVIDER: S-EPMC2994323 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Polyelectrolyte complexes (PEC) are formed by mixing the solutions of oppositely charged polyelectrolytes, which were hitherto deemed "impossible" to process, since they are infusible and brittle when dry. Here, we describe the process of fabricating free-standing micro-patterned PEC films containing array of hollow or filled microchambers by one-step casting with small applied pressure and a PDMS mould. These structures are compared with polyelectrolyte multilayers (PEM) thin films having array of hollow microchambers produced from a layer-by-layer self-assembly of the same polyelectrolytes on the same PDMS moulds. PEM microchambers "cap" and "wall" thickness depend on the number of PEM bilayers, while the "cap" and "wall" of the PEC microchambers can be tuned by varying the applied pressure and the type of patterned mould. The proposed PEC production process omits layering approaches currently employed for PEMs, reducing the production time from ~2 days down to 2?hours. The error-free structured PEC area was found to be significantly larger compared to the currently-employed microcontact printing for PEMs. The sensitivity of PEC chambers towards aqueous environments was found to be higher compared to those composed of PEM.
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Project description:Precipitates of polyelectrolyte complexes were transformed into rugged shapes suitable for bioimplants by ultracentrifugation in the presence of high salt concentration. Salt ions dope the complex, creating a softer material with viscous fluid-like properties. Complexes that were compacted under the centrifugal field (CoPECs) were made from poly(diallyldimethyl ammonium), PDADMA, as polycation, and poly(styrene sulfonate), PSS, or poly(methacrylic acid), PMAA, as polyanion. Dynamic mechanical testing revealed a rubbery plateau at lower frequencies for PSS/PDADMA with moduli that decreased with increasing salt concentration, as internal ion pair cross-links were broken. CoPECs had significantly lower modulii compared to similar polyelectrolyte complexes prepared by the "multilayering" method. The difference in mechanical properties was ascribed to higher water content (located in micropores) for the former and, more importantly, to their nonstoichiometric polymer composition. The modulus of PMAA/PDADMA CoPECs, under physiological conditions, demonstrated dynamic mechanical properties that were close to those of the nucleus pulposus in an intervertebral disk.
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Project description:Articular cartilage has a limited healing capacity that complicates the treatment of joint injuries and osteoarthritis. Newer repair strategies have focused on the use of cells and biomaterials to promote cartilage regeneration. In the present study, we developed and characterized bioinspired materials designed to mimic the composition of the cartilage extracellular matrix. Chondroitin sulfate (CS) and chitosan (CH) were used to form physically cross-linked macromolecular polyelectrolyte complexes (PEC) without the use of additional crosslinkers. A single-step water-in-oil emulsification process was used to either directly embed mesenchymal stem cells (MSC) in PEC particles created with a various concentrations of CS and CH, or to co-embed MSC with PEC in agarose-based microbeads. Direct embedding of MSC in PEC resulted in high cell viability but irregular and large particles. Co-embedding of PEC particles with MSC in agarose (Ag) resulted in uniform microbeads 80-90 ?m in diameter that maintained high cell viability over three weeks in culture. Increased serum content resulted in more uniform PEC distribution within the microbead matrix, and both high and low CS:CH ratios resulted in more homogeneous microbeads than 1:1 formulations. Under chondrogenic conditions, expression of sulfated GAG and collagen type II was increased in 10:1 CS:CH PEC-Ag microbeads compared to pure Ag beads, indicating a chondrogenic influence of the PEC component. Such PEC-Ag microbeads may have utility in the directed differentiation and delivery of progenitor cell populations for cartilage repair.
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Project description:The ionic assembly of oppositely charged polyelectrolyte-surfactant complexes (PESCs) is often done with the aim of constructing more functional colloids, for instance as advanced delivery systems. However, PESCs are often not easily loaded with a solubilisate due to intrinsic restrictions of such complexes. This question was addressed from a different starting point: by employing microemulsion droplets as heavily loaded surfactant systems and thereby avoiding potential solubilisation limitations from the beginning. We investigated mixtures of cationic oil-in-water (O/W) microemulsion droplets and oppositely charged sodium polyacrylate (NaPA) and determined structure and phase behaviour as a function of the mixing ratio for different droplet sizes and different M w (NaPA). Around an equimolar charge ratio an extended precipitate region is present, which becomes wider for larger droplets and with increasing M w of the NaPA. Static and dynamic light scattering (SLS and DLS) and small-angle neutron scattering (SANS) show the formation of one-dimensional arrangements of microemulsion droplets for polyelectrolyte excess, which become more elongated with increasing M w (NaPA) and less so with increasing NaPA excess. What is interesting is a marked sensitivity to ionic strength, where already a modest increase to ?20 mM leads to a dissolution of the complexes. This work shows that polyelectrolyte/microemulsion complexes (PEMECs) are structurally very versatile hybrid systems, combining the high solubilisate loading of microemulsions with the larger-scale structuring induced by the polymer, thereby markedly extending the concept of conventional PESCs. This type of system has not been described before and is highly promising for future applications where high payloads are to be formulated.
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Project description:A poly(7-oxanorbornene-2-carboxylate) polymer containing pendent triethyleneglycol (TEG) chains of 2.8 MDa ("2.8M TEG") was synthesized and evaluated for long-term lubrication and wear reduction of ex vivo bovine cartilage as well as for synovitis in rats and dogs after intra-articular administration. Bovine cartilage surfaces were tested under torsional friction for 10,080 rotations while immersed in either saline, bovine synovial fluid (BSF), or 2.8M TEG. For each solution, coefficient of friction (?), changes in surface roughness, and lost cartilage glycosaminoglycan were compared. To directly compare 2.8M TEG and BSF, additional samples were tested sequentially in BSF, BSF, 2.8M TEG, and then BSF. Finally, another set of samples were tested twice in saline to induce surface roughness and then tested in BSF, Synvisc, or 2.8M TEG to determine each treatment's effect on worn cartilage. Next, male Lewis rats were injected in one knee with 2.8M TEG or saline and evaluated for effects on gait, and female beagles were injected with either 2.8M TEG or saline in one knee, and their synovial tissues analyzed for inflammation by H&E staining. Treatment with 2.8M TEG lowers ?, lessens surface roughness, and minimizes glycosaminoglycan loss compared to saline. The 2.8M TEG also reduces ? compared to BSF in pairwise testing and on worn cartilage surfaces. Injection of 2.8M TEG in rat or beagle knees gives comparable effects to treatment with saline, and does not cause significant synovitis.
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Project description:Polyelectrolyte complexation is critical to the formation and properties of many biological and polymeric materials, and is typically initiated by aqueous mixing followed by fluid-fluid phase separation, such as coacervation. Yet little to nothing is known about how coacervates evolve into intricate solid microarchitectures. Inspired by the chemical features of the cement proteins of the sandcastle worm, here we report a versatile and strong wet-contact microporous adhesive resulting from polyelectrolyte complexation triggered by solvent exchange. After premixing a catechol-functionalized weak polyanion with a polycation in dimethyl sulphoxide (DMSO), the solution was applied underwater to various substrates whereupon electrostatic complexation, phase inversion, and rapid setting were simultaneously actuated by water-DMSO solvent exchange. Spatial and temporal coordination of complexation, inversion and setting fostered rapid (?25?s) and robust underwater contact adhesion (Wad ? 2?J?m(-2)) of complexed catecholic polyelectrolytes to all tested surfaces including plastics, glasses, metals and biological materials.
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