Cellulose Nanocrystal-Based Gradient Hydrogel Actuators with Controllable Bending Properties.

Stimuli-responsive hydrogel actuators are being increasingly used in microtechnology, but typical bilayer hydrogel actuators have significant drawbacks due to weak adhesive interface between the two layers. In this study, thermoresponsive single-layer hydrogel actuators are produced by generating a gradient distribution of cellulose nanocrystals (CNCs) in a poly(N-isopropylacrylamide) (PNIPAAm) hydrogel network by electrophoresis. Tunable bending properties of the composite hydrogels, such as the thermoresponsive bending speed and angle, are realized by varying the electrophoresis time, applied voltage, and CNC concentration. By varying these conditions, the gradient distribution of the CNCs can be optimized, leading to fast bending and large bending angles of the hydrogels. Bending properties are attributed to the gradient distribution of CNCs causing different deswelling rates across the hydrogel network owing to reinforcing effects. Bending ability is also influenced by differences in the CNC dimensions based on the sources of cellulose, which determine the rigidity of the CNC-rich layer of the polymer composite. It is thus shown that thermoresponsive single-layer gradient hydrogels with tunable bending properties can be realized.

Actuation of Hydrogel Architectures Prepared by Electrophoretic Adhesion of Thermoresponsive Microgels.

Owing to their unique properties, hydrogels may be used for preparing soft actuators. Soft actuators are expected to respond quickly; however, the response speed of gels is slow. To study this issue and overcome it, thermoresponsive soft actuators were prepared by the electrophoretic adhesion of cationic and anionic thermoresponsive microgels, comprising poly(diallyldimethylammonium chloride) and poly(styrenesulfonate) sodium salt, respectively. The kinetics of the prepared hydrogel architectures in response to temperature depended on the microgel diameter instead of the architecture size. We also prepared bilayered hydrogel architectures by adhesion of thermoresponsive and/or nonthermoresponsive microgels. These bent rapidly in response to temperature because these architectures consisted of microgel assemblies. In addition, specific bending motion was demonstrated by the adhesion of microgel layers of different sizes. The present study provides not only a guideline for the design of hydrogel actuators with quick response but also presents a method for the free-form fabrication of functional hydrogel materials that undergo complex motions in response to stimuli.

Travelling Wave Generation of Wrinkles on the Hydrogel Surfaces.

The dynamic and static properties of structured surfaces have important functions in nature. In particular, wrinkles have important static roles, for example, increasing surface area, but dynamic roles of wrinkles remain poorly understood. Specifically, to understand and utilize the dynamic functions of wrinkles, it is necessary to observe wrinkle formation directly. In this study, a polyion complex (PIC) is formed on a hydrogel surface by electrophoresis, and the process of wrinkle formation through a transparent electrode is directly observed. By quantitative analysis of the wavelength and amplitude of wrinkles, it is found that the wrinkles move randomly in a wavy pattern in the initial stage of growing process. Furthermore, the direction of wavy motion of wrinkles is controlled by the compression of hydrogels in the in-plane direction. The present study provides important insights into the fabrication of wrinkled surfaces with a controlled flow direction; opening the possibility for active wrinkles used in the development of functional surface structures as actuators that are capable of transporting small objects in water.

Formation of Single Double-Layered Coacervate of Poly(N,N-diethylacrylamide) in Water by a Laser Tweezer.

We demonstrate liquid-liquid phase separation involving both coacervation and coil-to-globule phase transition of a thermoresponsive polymer. By focusing a near-infrared laser beam into an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM), a single phase-separated polymer microdroplet can be formed and stably trapped at the focal point. Such droplet formation is induced by a local elevation in temperature (induced by a photothermal effect) and an optical force. The technique allows us to selectively analyze a single polymer droplet trapped at the focal point. In this study, we applied this technique to poly(N,N-diethylacrylamide) (PDEA) in water and generated a double-layered PDEA droplet. Such an inhomogeneous and complex microstructure has not been previously observed both in steady-state heating of a PDEA solution and in the PNIPAM system. Moreover, we used micro-Raman spectroscopy to clarify that PDEA underwent dehydration due to a coil-to-globule phase transition. Despite this, the polymer concentration (Cpoly) of the trapped PDEA droplet was very low and was around 30 wt %. Cpoly depended on the molecular weight of PDEA and the laser power that regulates the temperature elevation. These results strongly indicate that PDEA undergoes coacervation in addition to a coil-to-globule phase transition. This study will help provide us with a fundamental understanding of the phase separation mechanisms of thermoresponsive polymers.

Geometry Control of Wrinkle Structures Aligned on Hydrogel Surfaces.

Surface geometries in nature such as wrinkle structures have various functions. Attention has been paid to the fabrication method of the geometry and geometry control by external stimuli. This is because surface geometries as an active interface are able to contribute to the control of interactions with the external environment. In this study, aligned wrinkles were fabricated on the surface of stretched hydrogels in aqueous conditions by the electrophoretic formation of a polyion complex layer. The geometry of wrinkles was controlled by the stretching ratio and Young's modulus of hydrogels, and hierarchical wrinkle structures were fabricated after unloading the stretched hydrogels. Therefore, it can be a new wrinkle-formation method capable of transferring the initial elastic anisotropy of the substrate material to the wrinkle structure. Creation of thermoresponsive wrinkles that can transform their geometrical configuration reversibly was achieved by fabrication of aligned wrinkles on the surface of thermoresponsive hydrogels.

Supramolecular Biocomposite Hydrogels Formed by Cellulose and Host-Guest Polymers Assisted by Calcium Ion Complexes.

Hydrogels are biocompatible polymer networks; however, they have the disadvantage of having poor mechanical properties. Herein, the mechanical properties of host-guest hydrogels were increased by adding a filler and incorporating other noncovalent interactions. Cellulose was added as a filler to the hydrogels to afford a composite. Citric acid-modified cellulose (CAC) with many carboxyl groups was used instead of conventional cellulose. The preparation began with mixing an acrylamide-based αCD host polymer (p-αCD) and a dodecanoic acid guest polymer (p-AADA) to form supramolecular hydrogels (p-αCD/p-AADA). However, when CAC was directly added to p-αCD/p-AADA to form biocomposite hydrogels (p-αCD/p-AADA/CAC), it showed weaker mechanical properties than p-αCD/p-AADA itself. This was caused by the strong intramolecular hydrogen bonding (H-bonding) within the CAC, which prevented the CAC reinforcing p-αCD/p-AADA in p-αCD/p-AADA/CAC. Then, calcium chloride solution (CaCl2) was used to form calcium ion (Ca2+) complexes between the CAC and p-αCD/p-AADA. This approach successfully created supramolecular biocomposite hydrogels assisted by Ca2+ complexes (p-αCD/p-AADA/CAC/Ca2+) with improved mechanical properties relative to p-αCD/p-AADA hydrogels; the toughness was increased 6-fold, from 1 to 6 MJ/m3. The mechanical properties were improved because of the disruption of the intramolecular H-bonding within the CAC by Ca2+ and subsequent complex formation between the carboxyl groups of CAC and p-AADA. This mechanism is a new approach for improving the mechanical properties of hydrogels that can be broadly applied as biomaterials.

Dimensionally Stable and Mechanically Adaptive Polyelectrolyte Hydrogel.

Mechanically adaptive hydrogels with reversible cross-links can change their mechanical characteristics to adapt to the external environment. However, inevitable swelling/shrinkage occurs with the mechanical property change, which impedes the applications of these hydrogels. In this study, mechanical adaptivity with high dimensional stability is achieved in alginate-based polyelectrolyte hydrogels by introducing an opposite swelling mechanism. The dually crosslinked alginate-polystyrene sulfonate (Alg-PSS) hydrogels are constructed through the copolymerization of alginate-methacrylate (Alg-MA) and sodium p-styrene sulfonate (NaSS), as well as Ca2+ crosslinking. In the Alg-PSS hydrogel network, the reversible Ca2+ -carboxylate and Ca2+ -sulfonate cross-links can be disrupted by Na+ and soften the hydrogels. Moreover, the PSS chains crosslinked in the hydrogel network undergo the coil-globule transition in concentrated NaCl solutions to suppress hydrogel swelling during softening. The optimized Alg-PSS hydrogel (Alg5 -PSS0.75 -MBAA2.5 ) shows a dramatic tensile modulus change from 191.3 kPa in deionized water (DIW) to 15.1 kPa in 2.0 mol L-1 NaCl solution with a negligible volume increase ratio of only 0.6%. The Alg-PSS hydrogels may find applications in artificial valves or soft robotics, where high dimensional stability and invariable volume are required for smart hydrogels.

Electrophoretic Adhesion of Conductive Hydrogels.

For the development of next-generation wearable and implantable devices that connect the human body and machines, the adhesion of a conductive hydrogel is required. In this study, a conductive hydrogel is adhered using an electrophoretic approach through polyion complex formation at the interface of the hydrogels. Cationic and anionic conductive hydrogels adhere to anionic and cationic hydrogels, respectively. Moreover, the cationic and anionic conductive hydrogels adhere strongly to each other and the adhered conductive hydrogels exhibit conductivity. De-adhesion is possible by adding a salt and re-adhesion is demonstrated under aqueous conditions. It is believed that this innovative adhesion strategy for conductive hydrogels will be a fundamental technology for the connecting "soft" people and "hard" machines.

Hydrogel Adhesion by Wrinkling Films.

A novel adhesion control method for hydrogels utilizing swelling-induced wrinkling gel films is developed. Structures such as flat, crease, and wrinkle at the interface of adhered gels are controlled by swelling ratio of gel films. The role of microstructures at the gel-gel interface is investigated by adhesive strength measurement. Aligned wrinkles are fabricated with anisotropic swelling films. The adhesive strength of hydrogels with wrinkles parallel to tensile direction is larger than that with perpendicular wrinkles. Adhered gels detach without damage to their surfaces when the wrinkle structures are disrupted by peeling of the wrinkled film. Moreover, thermoresponsive film is used to control wrinkle structures at the adhered interface by temperature. The adhered interface is stable in cold water because of the existence of wrinkles; however, they detach in hot water due to wrinkle deformation. By using wrinkle structure at adhesive interfaces, both strong adhesion and easy detachment of hydrogels are achieved.

Fabrication of Hybrid Capsules via CaCO3 Crystallization on Degradable Coacervate Droplets.

Organic-inorganic CaCO3 capsules were prepared by crystallization of CaCO3 on Pickering emulsion prepared using coacervate droplets made from thermoresponsive and degradable poly(2-methylene-1,3-dioxepane- co-2-hydroxyethyl acrylate) (poly(MDO- co-HEA)) in sole aqueous medium. The diameters of CaCO3-based Pickering emulsion could be controlled by varying several parameters: diameter of CaCO3 powders, initial polymer concentration, and copolymer composition. The CaCO3 Pickering emulsion was able to load low-molecular-weight hydrophobic substances at temperatures above the lower critical solution temperature (LCST) due to formation of polymer-concentrated phases, i.e., coacervate droplets. The diameter of CaCO3 capsules prepared by crystallization also depended on the diameter of the CaCO3 Pickering emulsion. The CaCO3 shell was composed of calcite-type crystals, the most stable polymorph among known CaCO3 crystals. The facially prepared CaCO3 capsules are valuable for use in functional biomaterials, such as drug delivery carriers and cell culture scaffolds for noninvasive bone-regenerative medicine.

Dynamics of the Phase Separation in a Thermoresponsive Polymer: Accelerated Phase Separation of Stereocontrolled Poly( N, N-diethylacrylamide) in Water.

We studied the dependence on tacticity of the dynamic phase separation behavior of thermoresponsive poly( N, N-diethylacrylamide) (PDEA) in an aqueous solution. Using a laser temperature-jump technique combined with transient photometry, we determined the time constants of the phase separation and found that both atactic and isotactic-rich PDEAs had fast and slow phase separation processes (τfast and τslow). The fast process (τfast) was independent of the tacticity, irrespective of the concentration. On the other hand, the slow process had a strong dependence on the tacticity. We found the slow phase separation process got considerably faster with increasing isotacticity in dilute solutions. This effect due to the tacticity of the PDEA is totally different from that of poly( N-isopropylacrylamide) and can be explained on the basis of the difference between the hydrophobicity of atactic PDEA and that of isotactic-rich PDEA.

Surface-Functionalized Biodegradable Nanoparticles Consisting of Amphiphilic Graft Polymers Prepared by Radical Copolymerization of 2-Methylene-1,3-Dioxepane and Macromonomers.

Biodegradable polyester-based nanoparticles were prepared by the precipitation of amphiphilic graft copolymers, which were prepared by the ring-opening radical copolymerization of 2-methylene-1,3-dioxepane (MDO) and amphiphilic macromonomers. The diameter of the nanoparticles was controlled by the degree of grafting and the molecular weight of the grafting oligomer. PMDO-g-poly(ethylene glycol) nanoparticles were degraded by the alkaline hydrolysis of the polyester backbone. Although the colloidal stability of nanoparticles was retained due to the reorientation of the PEG chains during hydrolysis, the size of the nanoparticles decreased with increasing hydrolysis time. We also prepared PMDO-g-poly(N-isopropylacrylamide) nanoparticles, which show aggregation in response to increasing temperature.

Thermoresponsive nanospheres with a regulated diameter and well-defined corona layer.

In the present work, we prepared core-corona-type nanospheres bearing a thermoresponsive polymer with a controlled chain length on their surface. The corona layers were composed of poly(N-isopropylacrylamide) (PNIPAAm) chains (Mn = 3000-18,000) with a narrow polydispersity index prepared by atom-transfer radical polymerization (ATRP). Nanospheres were prepared by dispersion copolymerization of styrene with the PNIPAAm macromonomer in a polar solvent. The obtained nanospheres were monodisperse in diameter. The diameter of the nanospheres was regulated either by the number or chain length of the PNIPAAm macromonomers. In fact, the nanosphere diameter was regulated from ca. 100 to 1000 nm. When two types of PNIPAAm macromonomers are used, the obtained nanospheres have two different kinds of PNIPAAm on their surface. The surface of the nanospheres was observed to be thermoresponsive nanosphere in 0, 50, 100 mmol L(-1) NaCl aqueous solution. The nanosphere diameter and the surface-grafted polymer were concurrently adjusted for use in biomedical applications.

Rapid self-healable poly(ethylene glycol) hydrogels formed by selective metal-phosphate interactions.

Rapid self-healable and biocompatible hydrogels were prepared using the selective formation of metal-ligand interactions between selected metal ions and phosphate end groups of poly(ethylene glycol) (PEG). The phosphate-terminated branch of PEG was synthesized via a substitution reaction of the hydroxyl end groups using phosphoryl chloride. The gelation and gel properties including rheological properties can be tuned by the careful selection of metal ions, branch numbers, and temperature. Especially, the gels rapidly formed by trivalent metal ions such as Fe(3+), V(3+), Al(3+), Ti(3+), and Ga(3+) have relatively small ionic radii. The ligand substitution rates also affected the repeatable autonomic healing ability. We have also demonstrated a gel-sol/sol-gel transition by switching the redox states of Fe(3+)/Fe(2+) ions. Learning from biological systems, the proposed phosphate-metal ion based self-healable hydrogels could become an attractive candidate for various biomedical and environmental applications.

Fabrication of chitin monoliths with controllable morphology by thermally induced phase separation of chemically modified chitin.

As a natural polymer, chitin has excellent biological properties such as biodegradability and immunological, antibacterial, and wound-healing activities and has numerous applications in cosmetics, drug delivery, and pharmaceuticals. Organic polymer monoliths have also drawn significant attention, owing to their high permeability, large surface area, and high mechanical strength. They are usually applied to separation, ion exchange, catalysis, and chromatography. We have previously prepared cellulose monoliths using biopolymers; however, because chitin possesses amide groups on its side chain, it is superior to cellulose for further chemical modification and applications. However, the utilization of chitin is restricted by its insolubility in water and common organic solvents. In this study, for the first time, a monolith was prepared by chemical modification of chitin using a thermally induced phase separation (TIPS) method. First, we prepared dibutyrylchitin (DBC) as a starting polymer that is soluble in organic solvents. To prepare the monolith, DBC was dissolved completely in dimethyl sulfoxide (DMSO) while heating, and deionized water was added to the solution. It was then cooled at 20 °C to form a monolith via phase separation. The porous morphology of the DBC monolith was altered by regulating the DBC concentration, DMSO/H2O ratio, and aging temperature. The DBC monolith was converted to a chitin monolith by the alkaline hydrolysis of butyryl ester. The successful hydrolysis of butyryl ester was confirmed by the disappearance of the peak at 1735 cm-1 in the FT-IR spectra, which is related to the ester moiety of DBC. The chitin monolith has the potential to be utilized under water flow for catalysis, metal capture from wastewater, dye sorption, and drug delivery systems.

Porosity-Induced Improvement in KOH Activation of Chitin Nanofiber-Based Porous Carbon Leading to Ultrahigh Specific Capacitance.

The applicability of chitin-based carbon as a supercapacitor electrode material was investigated by adjusting its pore structure through polystyrene latex templating, without significant N doping. 2,2,6,6-tetramethylpiperidinyloxy (TEMPO)-oxidized chitin nanofibers were mixed with polystyrene latex, hydrothermally treated at 220 °C, carbonized, and activated using KOH at 800 °C, yielding activated hierarchical porous carbon. The variation of both polystyrene latex amount and carbonization temperature resulted in changes in the surface area and pore structure, which dictated the degree of pore uniformity and activation efficiency. The pore structure affected activation by allowing the selective removal of amorphous carbon, exposing the basal plane carbon, resulting in higher specific capacitance. By making activated hierarchical porous carbon more conducive to activation, specific capacitance of 567 F g-1 at 0.5 A g-1 was achieved, with no loss in performance after 10000 charge-discharge cycles.

Design of Injectable Poly(γ-glutamic acid)/Chondroitin Sulfate Hydrogels with Mineralization Ability.

Biocompatible hydrogels are considered promising agents for application in bone tissue engineering. However, the design of reliable hydrogels with satisfactory injectability, mechanical strength, and a rapid biomineralization rate for bone regeneration remains challenging. Herein, injectable hydrogels are fabricated using hydrazide-modified poly(γ-glutamic acid) and oxidized chondroitin sulfate by combining acylhydrazone bonds and ionic bonding of carboxylic acid groups or sulfate groups with calcium ions (Ca2+). The resulting hydrogels display a fast gelation rate and good self-healing ability due to the acylhydrazone bonds. The introduction of Ca2+ at a moderate concentration enhances the mechanical strength of the hydrogels. The self-healing capacity of hydrogels is improved, with a healing efficiency of 87.5%, because the addition of Ca2+ accelerates the healing process of hydrogels. Moreover, the hydrogels can serve as a robust template for biomineralization. The mineralized hydrogels with increasing Ca2+ concentration exhibit rapid formation and high crystallization of apatite after immersion in simulated body fluid. The hydrogels containing the aldehyde groups possess good bioadhesion to the bone and cartilage tissues. With these superior properties, the developed hydrogels demonstrate potential applicability in bone tissue engineering.

Stimuli-responsive composite hydrogels with three-dimensional stability prepared using oxidized cellulose nanofibers and chitosan.

Stimuli-responsive hydrogels have garnered the attention of the hydrogel industry, as they are able to change their physical and chemical properties based on changing external stimuli such as pH, temperature, ionic strength, electromagnetic fields, and light. However, stimuli-responsive hydrogel applications are hindered due to their inevitable swelling and shrinkage. Bacterial cellulose (BC), a natural hydrogel with tightly packed cellulose nanofibers (CNFs) was oxidized into dialdehyde BC (DABC) and was composited with chitosan (CS), a readily available natural polymer, to develop a mechanically adaptive hydrogel composite under different pH conditions. Composites exhibit pH sensitivity by presenting higher mechanical properties under acidic conditions and lower mechanical properties under basic conditions owing to the protonation of amino groups of the chitosan chains. Osmotic pressure is built up under acidic conditions, increasing the mechanical strength of the composites. The good three-dimensional stability of composites enables them to consistently maintain their volume when exposed to acidic or basic conditions.

Facile Fabrication of Hierarchically Porous Boronic Acid Group-Functionalized Monoliths With Optical Activity for Recognizing Glucose With Different Conformation.

At present, various materials based on helical polymers are nanoparticle or microsphere, which is not ease of use in practical application. Accordingly, facile preparation hierarchically porous monolith based on helical polymer needs to be developed. Herein, hierarchically porous boronic acid group-functionalized monoliths that exhibited optical activity were fabricated with a facile method based on crosslinking and polymerization-induced phase separation (CPIPS). Chiral substituted acetylene and achiral substituted acetylene with a boronic acid group were used as monomers. By regulating the composition of the pre-polymerization solution, the permeability and macropore size of the porous structure could be controlled. The hierarchically porous structure and large surface area were confirmed by scanning electron microscopy and nitrogen gas adsorption/desorption isotherms. In particular, the boronic acid functional group that can interact with a cis-diol group was successfully introduced on the skeleton surface of the monoliths. Further, the main chain of the copolymer that constituted the monoliths exhibited a high cis content and tacticity, and the monoliths showed good optical activity. Thus, the present study established a facile method to synthesize hierarchically porous boronic acid group-functionalized monoliths with optical activity via CPIPS, and the monoliths showed potential in recognition, separation, and adsorption of compound with chirality and cis-diol groups.

Robust Dual-Biomimetic Titanium Dioxide-Cellulose Monolith for Enrichment of Phosphopeptides.

Metal oxide affinity chromatography (MOAC) is considered to be one of the most effective methods for phosphopeptide enrichment. However, most of the materials used in the method are powder; frequent centrifugation is necessitated during the enrichment process, and potential risks of loss of peptides and materials and clogging of the column employed for liquid chromatography-mass spectrometry (LC-MS) arise. Moreover, the reusability of these materials to achieve sustainability was hardly investigated. To overcome these limitations, herein, inorganic titanium dioxide (TiO2) was coated onto the skeletal surface of the organic cellulose monolith (CM) material with a coral-like structure via a sol-gel method. This produced an organic-inorganic hybrid TiO2-CM material, which contained a combination of organic and inorganic substances, making it mimic the mollusk shell in terms of composition. The prepared TiO2-CM material as monolith exhibited excellent mechanical strength and did not break during the enrichment process; thus, the tedious implementation of multiple centrifugation cycles was prevented, thereby streamlining the experimental procedure and avoiding the loss of peptides and materials. Moreover, a large amount of TiO2 was introduced onto the surface of the CM material, and thus, the resultant TiO2-CM material exhibited a large surface area. As a result, the fabricated TiO2-CM material was successfully applied to the enrichment of phosphopeptides obtained from the tryptic digests of a BSA/ß-casein (mass ratio, 500/1) mixture. The results were superior to those achieved for commercial TiO2 beads, confirming that TiO2-CM has excellent selectivity for phosphopeptides and reusability. Furthermore, 9287 unique phosphopeptides derived from the 2661 phosphoproteins were successfully identified from two milligrams of tryptic digests of Hela cell exosomes obtained through five independent replications after enriching using the TiO2-CM material. The results indicated that the material has good application prospects in the analysis of protein phosphorylation. Furthermore, TiO2-CM consists of green and cheap cellulose as the skeleton, and its synthesis process is environment-friendly, simple, and inexpensive.