Intermolecular And Surface Forces

BACKGROUND Hydrogels are formed through the cross-linking of hydrophilic polymer chains within an aqueous microenvironment. The gelation can be achieved through a variety of mechanisms, spanning physical entanglement of polymer chains, electrostatic interactions, and covalent chemical cross-linking. The water-rich nature of hydrogels makes them broadly applicable to many areas, including tissue engineering, drug delivery, soft electronics, and actuators. Conventional hydrogels usually possess limited mechanical strength and are prone to permanent breakage. The lack of desired dynamic cues and structural complexity within the hydrogels has further limited their functions. Broadened applications of hydrogels, however, require advanced engineering of parameters such as mechanics and spatiotemporal presentation of active or bioactive moieties, as well as manipulation of multiscale shape, structure, and architecture. ADVANCES Hydrogels with substantially improved physicochemical properties have been enabled by rational design at the molecular level and control over multiscale architecture. For example, formulations that combine permanent polymer networks with reversibly bonding chains for energy dissipation show strong toughness and stretchability. Similar strategies may also substantially enhance the bonding affinity of hydrogels at interfaces with solids by covalently anchoring the polymer networks of tough hydrogels onto solid surfaces. Shear-thinning hydrogels that feature reversible bonds impart a fluidic nature upon application of shear forces and return back to their gel states once the forces are released. Self-healing hydrogels based on nanomaterial hybridization, electrostatic interactions, and slide-ring configurations exhibit excellent abilities in spontaneously healing themselves after damages. Additionally, harnessing techniques that can dynamically and precisely configure hydrogels have resulted in flexibility to regulate their architecture, activity, and functionality. Dynamic modulations of polymer chain physics and chemistry can lead to temporal alteration of hydrogel structures in a programmed manner. Three-dimensional printing enables architectural control of hydrogels at high precision, with a potential to further integrate elements that enable change of hydrogel configurations along prescribed paths. OUTLOOK We envision the continuation of innovation in new bioorthogonal chemistries for making hydrogels, enabling their fabrication in the presence of biological species without impairing cellular or biomolecule functions. We also foresee opportunities in the further development of more sophisticated fabrication methods that allow better-controlled hydrogel architecture across multiple length scales. In addition, technologies that precisely regulate the physicochemical properties of hydrogels in spatiotemporally controlled manners are crucial in controlling their dynamics, such as degradation and dynamic presentation of biomolecules. We believe that the fabrication of hydrogels should be coupled with end applications in a feedback loop in order to achieve optimal designs through iterations. In the end, it is the combination of multiscale constituents and complementary strategies that will enable new applications of this important class of materials.

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Advances in engineering hydrogels

With advances in tissue engineering, the possibility of regenerating injured tissue or failing organs has become a realistic prospect for the first time in medical history. Tissue engineering - the combination of bioactive materials with cells to generate engineered constructs that functionally replace lost and/or damaged tissue - is a major strategy to achieve this goal. One facet of tissue engineering is biofabrication, where three-dimensional tissue-like structures composed of biomaterials and cells in a single manufacturing procedure are generated. Cell-laden hydrogels are commonly used in biofabrication and are termed "bioinks". Hydrogels are particularly attractive for biofabrication as they recapitulate several features of the natural extracellular matrix and allow cell encapsulation in a highly hydrated mechanically supportive three-dimensional environment. Additionally, they allow for efficient and homogeneous cell seeding, can provide biologically-relevant chemical and physical signals, and can be formed in various shapes and biomechanical characteristics. However, despite the progress made in modifying hydrogels for enhanced bioactivation, cell survival and tissue formation, little attention has so far been paid to optimize hydrogels for the physico-chemical demands of the biofabrication process. The resulting lack of hydrogel bioinks have been identified as one major hurdle for a more rapid progress of the field. In this review we summarize and focus on the deposition process, the parameters and demands of hydrogels in biofabrication, with special attention to robotic dispensing as an approach that generates constructs of clinically relevant dimensions. We aim to highlight this current lack of effectual hydrogels within biofabrication and initiate new ideas and developments in the design and tailoring of hydrogels. The successful development of a "printable" hydrogel that supports cell adhesion, migration, and differentiation will significantly advance this exciting and promising approach for tissue engineering.

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25th Anniversary Article: Engineering Hydrogels for Biofabrication

It is a challenge to synthesize materials that possess the properties of biological muscles-strong, elastic and capable of self-healing. Herein we report a network of poly(dimethylsiloxane) polymer chains crosslinked by coordination complexes that combines high stretchability, high dielectric strength, autonomous self-healing and mechanical actuation. The healing process can take place at a temperature as low as -20 °C and is not significantly affected by surface ageing and moisture. The crosslinking complexes used consist of 2,6-pyridinedicarboxamide ligands that coordinate to Fe(III) centres through three different interactions: a strong pyridyl-iron one, and two weaker carboxamido-iron ones through both the nitrogen and oxygen atoms of the carboxamide groups. As a result, the iron-ligand bonds can readily break and re-form while the iron centres still remain attached to the ligands through the stronger interaction with the pyridyl ring, which enables reversible unfolding and refolding of the chains. We hypothesize that this behaviour supports the high stretchability and self-healing capability of the material.

A highly stretchable autonomous self-healing elastomer

Naturally derived cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are emerging nanomaterials that display high strength, high surface area, and tunable surface chemistry, allowing for controlled interactions with polymers, nanoparticles, small molecules, and biological materials. Industrial production of nanocelluloses is increasing rapidly with several companies already producing on the tons-per-day scale, intensifying the quest for viable products across many sectors. While the hydrophilicity of the nanocellulose interface has posed a challenge to the use of CNCs and CNFs as reinforcing agents in conventional plastics, it is a significant benefit for creating reinforced or structured hydrogel composites (or, when dried, aerogels) exhibiting both mechanical reinforcement and a host of other desirable properties. In this context, this Review describes the quickly growing field of hydrogels and aerogels incorporating nanocelluloses; over 200 references are summarized in comprehensive tables ...

http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.7b00531

Review of Hydrogels and Aerogels Containing Nanocellulose

Hydrogels attract great attention as biomaterials as a result of their soft and wet nature, similar to that of biological tissues. Recent inventions of several tough hydrogels show their potential as structural biomaterials, such as cartilage. Any given application, however, requires a combination of mechanical properties including stiffness, strength, toughness, damping, fatigue resistance and self-healing, along with biocompatibility. This combination is rarely realized. Here, we report that polyampholytes, polymers bearing randomly dispersed cationic and anionic repeat groups, form tough and viscoelastic hydrogels with multiple mechanical properties. The randomness makes ionic bonds of a wide distribution of strength. The strong bonds serve as permanent crosslinks, imparting elasticity, whereas the weak bonds reversibly break and re-form, dissipating energy. These physical hydrogels of supramolecular structure can be tuned to change multiple mechanical properties over wide ranges by using diverse ionic combinations. This polyampholyte approach is synthetically simple and dramatically increases the choice of tough hydrogels for applications.

https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/56662/1/Gong-Manuscript-1.pdf

Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity

https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/49224/1/Pol53-9_1805-1822.pdf

Super tough double network hydrogels and their application as biomaterials

[∗] Dr. T. Kurokawa , Prof. J. P. Gong Faculty of Advanced Life Science Graduate School of Science Hokkaido University Sapporo, 060–0810 (Japan) E-mail: gong@sci.hokudai.ac.jp Dr. T. Kurokawa Creative Research Initiative Sousei Hokkaido University Sapporo, 001–0021 (Japan) M. A. Haque , G. Kamita Division of Biological Sciences Graduate School of Science Hokkaido University Sapporo, 060–0810 (Japan) Prof. K. Tsujii , Nanotechnology Research Center Research Institute for Electronic Science Hokkaido University (Retired) Sapporo, 001–0021 (Japan)

Unidirectional Alignment of Lamellar Bilayer in Hydrogel: One‐Dimensional Swelling, Anisotropic Modulus, and Stress/Strain Tunable Structural Color

https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/55147/1/Manuscript_final.pdf

Brittle–ductile transition of double network hydrogels: Mechanical balance of two networks as the key factor

In this work, we report a rubberlike elastic hydrogel containing microdomains of bilayers periodically stacked into the polymer network that satisfy the Bragg’s law of diffraction. The rubberlike elastic hydrogel has been synthesized by applying double network principle into a viscoelastic hydrogel containing single-domain macroscopic lamellar bilayer. The hydrogel is able to tune the magnificent structural color reversibly over the entire wavelength range of visible spectrum as fast as the uniaxial tensile stretching and compressive deformation are applied and released. Owing to the strength, softness, and rubberlike elastic deformability, the tunable hydrogel can be used extensively to design a new class of soft tactile sensor as an advanced stress sensor that is able to detect a local deformation of a complicated force field.

Md. Anamul Haque

Papers

Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity

Super tough double network hydrogels and their application as biomaterials

Unidirectional Alignment of Lamellar Bilayer in Hydrogel: One‐Dimensional Swelling, Anisotropic Modulus, and Stress/Strain Tunable Structural Color

Brittle–ductile transition of double network hydrogels: Mechanical balance of two networks as the key factor

Rapid and Reversible Tuning of Structural Color of a Hydrogel over the Entire Visible Spectrum by Mechanical Stimulation