Fabrication of Sulfated Heterosaccharide/Poly (Vinyl Alcohol) Hydrogel Nanocomposite for Application as Wound Healing Dressing

Nowadays, natural polysaccharides-based hydrogels have achieved promising results as dressings to promote skin healing. In the present study, we prepared a novel hydrogel nanocomposite with poly(vinyl alcohol) (PVA) and sulfated heterosaccharide (UF), named UPH. The SEM results showed that the UPH had dense porous structures with a high porosity and a specific surface area. The UPH had a good swelling property, which can effectively adsorb exudate and keep the wound moist. The in vitro experiments results showed that the UPH was non-cytotoxic and could regulate the inflammatory response and promote the migration of fibroblasts significantly. The phenotypic, histochemistry, and Western blot analyses showed UPH treatment accelerated the wound healing and recovery of skin tissue at wound sites in a C57BL/6 mouse model. Furthermore, the UPH could promote the inflammation process to onset earlier and last shorter than that in a normal process. Given its migration-promoting ability and physicochemical properties, the UPH may provide an effective application for the treatment and management of skin wounds.     

Ultrastretchable and conductive core/sheath hydrogel fibers with multifunctionality

Conductive hydrogels with ionic compounds possess great potential for the development of soft smart devices. A dielectric scarfskin is typically required for these devices to prevent short circuiting, leading to devices with lower stretchability than the hydrogel. Henceforth, commonly used dielectric materials, such as PDMS and Ecoflex, cannot be largely stretched. Hydrogel devices with ultrastretchability are required to accommodate hostile application environments. Herein, we propose a hydrogel fiber coated with a dielectric layer that can be stretched to over 2000% of its initial length. The fiber remains conductive when stretched to ~1300%. In addition, the core/sheath hydrogel fiber can be endowed with a variety of functional properties, such as electroluminescence (EL), photoluminescence (PL), and magnetic‐responsiveness, demonstrating scalability of the resultant fiber. The present work can pave the way for numerous next‐generation soft devices, such as smart textiles and wearable electronics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 272–280     

Double‐crosslinked reversible redox‐responsive hydrogels based on disulfide–thiol interchange

We present novel redox‐responsive hydrogels based on poly(N‐isopropylacrylamide) or poly(acrylamide), consisting of a reversible disulfide crosslinking agent N,N′‐bis(acryloyl)cystamine and a permanent crosslinking agent N,N′‐methylenebisacrylamide for microfluidic applications. The mechanism of swelling/deswelling behavior starts with the cleavage and reformation of disulfide bonds, leading to a change of crosslinking density and crosslinking points. Raman and ultraviolet‐visible spectroscopy confirm that conversion efficiency of thiol–disulfide interchange up to 99%. Rheological analysis reveals that the E modulus of hydrogel is dependent on the crosslinking density and can be repeatedly manipulated between high‐ and low‐stiffness states over at least 5 cycles without significant decrease. Kinetic studies showed that the mechanical strength of the gels changes as the redox reaction proceeds. This process is much faster than the autonomous diffusion in the hydrogel. Moreover, cooperative diffusion coefficient (D_coop) indicates that the swelling process of the hydrogel is affected by the reduction reaction. Finally, this reversibly switchable redox behavior of bulky hydrogel could be proven in microstructured hydrogel dots through short‐term photopatterning process. These hydrogel dots on glass substrates also showed the desired short response time on cyclic swelling and shrinking processes known from downsized hydrogel shapes. Such stimuli‐responsive hydrogels with redox‐sensitive crosslinkers open a new pathway in exchanging analytes for sensing and separating in microfluidics applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2590–2601     

Anion‐Mediated Effects on the Size and Mechanical Properties of Enzymatically Crosslinked Suckerin Hydrogels

The suckerin family of proteins, identified from the squid sucker ring teeth assembly, offers unique mechanical properties and potential advantages over other natural biomaterials. In this study, a small suckerin isoform, suckerin‐12, is used to create enzymatically crosslinked, macro‐scale hydrogels. Upon exposure to specific salt conditions, suckerin‐12 hydrogels contracted into a condensed state where mechanical properties are found to be modulated by the salt anion present. The rate of contraction is found to correlate well with the kosmotropic arm of the Hofmeister anion series. However, the observed changes in hydrogel mechanical properties are better explained by the ability of the salt to neutralize charges in suckerin‐12 by deprotonization or charge screening. Thus, by altering the anions in the condensing salt solution, it is possible to tune the mechanical properties of suckerin‐12 hydrogels. The potential for suckerins to add new properties to materials based on naturally‐derived proteins is highlighted.     

Hydrogel Microchambers Integrated with Organic Electrodes for Efficient Electrical Stimulation of Human iPSC‐Derived Cardiomyocytes

A hydrogel‐based microchamber with organic electrodes for efficient electrical stimulations of human induced pluripotent stem cell‐derived cardiomyocytes (hiPSC‐CMs) is described. The microchamber is made from molecularly permeable, optically transparent, and electrically conductive polyvinyl alcohol (PVA) hydrogel and highly capacitive carbon electrode modified with poly(3,4‐ethylenedioxythiophene) (PEDOT). Spheroids of hiPSC‐CMs are cultured in microchambers, and electrically stimulated by the electrode for maturation. The large interfacial capacitance of the electrodes enables several days of electrical stimulation without generation of cytotoxic bubbles even when the electrodes are placed near the spheroids. The spheroids can be cultivated in the closed microchambers because of the permeated nutrients through the hydrogel, thus the spheroids are stably addressable and the culture medium around the sealed microchambers can be simply exchanged. Synchronized beating of the spheroids can be optically analyzed in situ, which makes it possible to selectively collect electrically responsive cells for further use. As the hydrogel is electrically conductive, the amount of electrical charge needed for maturing the spheroids can be reduced by configuring electrodes on the top and the bottom of the microchamber. The bioreactor will be useful for efficient production of matured hiPSC‐CMs for regenerative medicine and drug screening.     

Effect of polymer and ion concentration on mechanical and drug release behavior of gellan hydrogels using factorial design

Developing optimized hydrogel products requires an in-depth understanding of the mechanisms that drive hydrogel tunability. Here, we performed a full 4 × 4 factorial design study investigating the impact of gellan, a naturally derived polysaccharide (1%, 2%, 3%, or 4% w/v) and CaCl₂ concentration (1, 3, 7, or 10 mM) on the viscoelastic, swelling, and drug release behavior of gellan hydrogels containing a model drug, vancomycin. These concentrations were chosen to specifically provide insight into gellan hydrogel behavior for formulations utilizing polymer and salt concentrations expanding beyond those commonly reported by previous studies exploring gellan. With increasing gellan and CaCl₂ concentration, the hydrogel storage moduli (0.1–100 kPa) followed a power-law relationship and on average these hydrogels had higher liquid absorption capability and greater total drug release over 6 days. We suggest that the effects of gellan and CaCl₂ concentration and their interactions on hydrogel properties can be explained by various phenomena that lead to increased swelling and increased resistance to network expansion.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Precipitated droplets in-situ cross-linking polymerization and its applications

A novel, green and effective approach to fabricate uniform functional spherical polymer particles remains a huge challenge. Herein, we present a novel one-pot approach superior to traditional precipitation polymerization, called precipitated droplets in-situ cross-linking (PDIC) polymerization, by which uniform particles are fabricated on large scale without any toxic organic solvents or stabilizers. With this approach, functional spherical polymer particles can be fabricated continuously only relying on gravity, and the preparation process is thus super-fast. For example, polyacrylic acid (PAA) hydrogel particles with ultra-high adsorption capacity are fabricated within only 60 s. Moreover, we have successfully fabricated different functional hydrogel particles, including anticoagulant, reinforced and bactericidal particles, based on the monomers of 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylamide (AM) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (DMC), respectively. This approach has several advantages: (i) the technology is green; (ii) the size and porosity of the particles can be well-controlled; (iii) various functional spherical hydrogel particles can be fabricated by using corresponding monomers. More importantly, this approach fits the commercialization of functional hydrogel particles on demand.     

Cell‐Laden Hydrogels for Multikingdom 3D Printing

Living materials are created through the embedding of live, whole cells into a matrix that can house and sustain the viability of the encapsulated cells. Through the immobilization of these cells, their bioactivity can be harnessed for applications such as bioreactors for the production of high‐value chemicals. While the interest in living materials is growing, many existing materials lack robust structure and are difficult to pattern. Furthermore, many living materials employ only one type of microorganism, or microbial consortia with little control over the arrangement of the various cell types. In this work, a Pluronic F127‐based hydrogel system is characterized for the encapsulation of algae, yeast, and bacteria to create living materials. This hydrogel system is also demonstrated to be an excellent material for additive manufacturing in the form of direct write 3D‐printing to spatially arrange the cells within a single printed construct. These living materials allow for the development of incredibly complex, immobilized consortia, and the results detailed herein further enhance the understanding of how cells behave within living material matrices. The utilization of these materials allows for interesting applications of multikingdom microbial cultures in immobilized bioreactor or biosensing technologies.     

Bilayer Cylindrical Conduit Consisting of Electrospun Polycaprolactone Nanofibers and DSC Cross‐Linked Sodium Alginate Hydrogel to Bridge Peripheral Nerve Gaps

Herein, a bilayer cylindrical conduit (P‐CA) is presented consisting of electrospun polycaprolactone (PCL) nanofibers and sodium alginate hydrogel covalently cross‐linked with N,N′‐disuccinimidyl carbonate (DSC). The bilayer P‐CA conduit is developed by combining the electrospinning and outer–inner layer methods. Using DSC, as a covalent crosslinker, increases the degradation time of the sodium alginate hydrogel up to 2 months. The swelling ratio of the hydrogel is also 503% during the first 8 h. The DSC cross‐linked sodium alginate in the inner layer of the conduit promotes the adhesion and proliferation of nerve cells, while the electrospun PCL nanofibers in the outer layer provide maximum tensile strength of the conduit during surgery. P‐CA conduit promotes the migration of Schwann cells along the axon in a rat model based on functional and histological evidences. In conclusion, P‐CA conduit will be a promising construct for repairing sciatic nerves in a rat model.