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.

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.

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.

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.

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.

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.

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.

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.

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.

Facile synthesis of a three-dimensional hydroxyapatite monolith for protein adsorption.

Hydroxyapatite (HA) shows promising applications in the clinical treatment of bone defects owing to its excellent physicochemical properties, such as biocompatibility, bioactivity, and osteoconductivity. However, it is difficult to maintain a porous structure in HA materials because of processing difficulties. In this study, a hard template method was developed to prepare a porous HA monolith with a hierarchical pore structure and high porosity. The cellulose monolith template was prepared from cellulose acetate using a thermally induced phase separation method. The cellulose monoliths were then immersed into the HA slurry to form a cellulose_HA composite monolith, which was converted to an HA monolith by burning in air to remove the cellulose monolith. Owing to the hierarchically porous structure of the cellulose monolith template, the obtained HA monolith demonstrated a hierarchically porous structure. Furthermore, the HA monolith was explored to study the adsorption and release properties of bovine serum albumin (BSA), which indicated that the HA monolith had a high adsorption capacity (388.6 mg g-1) and sustained release from the BSA-loaded HA monolith. Thus, HA monoliths have potential applications in the field of protein purification and biomaterials.

Facile Preparation of Hierarchically Porous Monolith with Optical Activity Based on Helical Substituted Polyacetylene via One-Step Synthesis for Enantioselective Crystallization.

The present study reported the flexible and highly efficient one-step synthesis of chiral hierarchical porous monoliths via cross-linking and polymerization-induced phase separation using substituted acetylene and cross-linker in the presence of porogenic solvent (tetrahydrofuran and methanol) in which the complex doping and complicated procedures were not required. It was demonstrated that hierarchical pore structure with through-pore and high surface area existed in the monoliths, which provides more chiral sites and space for interaction between monolithic materials and the solution. The porous structures and pore size can be adjusted by changing the conditions of phase separation. Moreover, the prepared monoliths exhibited good optical activity, thermal stability and mechanical properties. Therefore, the hierarchically porous monoliths with optical activity were applied in enantioselective crystallization and showed good performance.

Fabrication of Inorganic Oxide Fiber Using a Cigarette Filter as a Template.

Inorganic oxides with unique physical and chemical properties have attracted much attention because they can be applied in a wide range of fields. Herein, recycled cigarette filters are deacetylated to cellulose filters (CFs), which are then applied as templates to prepare fiber-like inorganic oxides (titanium dioxide, TiO2, and silicon dioxide, SiO2). Inorganic oxides are prepared using CF as a template by a typical sol-gel reaction of metal alkoxides. Owing to the fibrous structure of the CF template, the prepared inorganic oxides (TiO2 and SiO2) show similar fibrous structures, which was confirmed by scanning electron microscopy and nitrogen adsorption-desorption analysis. Moreover, the prepared inorganic oxides (TiO2 and SiO2) show high surface areas and pore volumes. Furthermore, the TiO2 fiber-like materials are evaluated for their photocatalytic properties by analyzing the methylene blue (MB) and methyl orange (MO) degradation. In this study, we provide a clean method, which can convert cellulose acetate-based waste into useful templates to prepare inorganic oxides with relatively simple steps, and the prepared inorganic oxides can be applied in water treatment.

Optically Transparent and Toughened Poly(methyl methacrylate) Composite Films with Acylated Cellulose Nanofibers.

In this work, nanocomposites of poly(methyl methacrylate) (PMMA) with cellulose nanofiber (CNF) were prepared by a solution casting technique. CNF was modified by propionic anhydride (PA) to form surface-propionylated CNF (CNFp) to improve its compatibility with the PMMA matrix. CNF, CNFp, and acetylated CNF were compared with respect to their influence as fillers in PMMA composite films by ultraviolet-visible transmittance, haze values, tensile strength testing, and water contact angle measurement. It was demonstrated that 1 wt % of CNFp has good compatibility and uniform dispersion in the PMMA matrix, as demonstrated by the formation of a smooth surface composite film with good transparency, enhanced tensile properties, improved toughness, and lower wettability. Therefore, PMMA/CNFp composite films have great potential for use in several applications such as lightweight transparent materials, window substitutes, and see-through packaging.

Effects of Acid-Anhydride-Modified Cellulose Nanofiber on Poly(Lactic Acid) Composite Films.

In this study, we investigated the effect of the addition of cellulose nanofiber (CNF) fillers on the performance of poly(lactic acid) (PLA). Modification of the hydroxyl group of cellulose to the acyl group by acid anhydrides changed the compatibility of the CNF with PLA. CNF was modified by acetic anhydride, propionic anhydride, and butyric anhydride to form surface-modified acetylated CNF (CNFa), propionylated CNF (CNFp), and butyrylated CNF (CNFb), respectively, to improve the compatibility with the PLA matrix. The effects of the different acid anhydrides were compared based on their rates of reaction in the acylation process. PLA with modified cellulose nanofiber fillers formed smoother surfaces with better transparency, mechanical, and wettability properties compared with the PLA/CNF composite film. The effects of CNFa, CNFp, and CNFb on the PLA matrix were compared, and it was found that CNFp was the best filler for PLA.

Injectable poly(γ-glutamic acid)-based biodegradable hydrogels with tunable gelation rate and mechanical strength.

Polypeptide-based hydrogels have potential applications in polymer therapeutics and regenerative medicine. However, designing reliable polypeptide-based hydrogels with a rapid injection time and controllable stiffness for clinical applications remains a challenge. Herein, a class of injectable poly(γ-glutamic acid) (PGA)-based hydrogels were constructed using furfurylamine and tyramine-modified PGA (PGA-Fa-Tyr) and the crosslinker dimaleimide poly(ethylene glycol) (MAL-PEG-MAL), through a facile strategy combining enzymatic crosslinking and Diels-Alder (DA) reaction. The injectable hydrogels could be quickly gelatinized and the gelation time, ranging from 10 to 95 s, could be controlled by varying the hydrogen peroxide (H2O2) concentration. Compared with hydrogels formed by single enzymatic crosslinking, the compressive stress and strain of the injectable hydrogels were remarkably enhanced because of the occurrence of the subsequent DA reaction in the hydrogels, suggesting the DA network imparted an outstanding toughening effect on the hydrogels. Furthermore, the mechanical strength, swelling ratio, pore size, and degradation behavior of the injectable hydrogels could be easily controlled by changing the molar ratios of H2O2/Tyr or furan/maleimide. More importantly, injectable hydrogels encapsulating bovine serum albumin exhibited sustained release behavior. Thus, the developed hydrogels hold great potential for applications in biomedical fields, such as tissue engineering and cell/drug delivery.

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.

Facile preparation of multi-stimuli-responsive degradable hydrogels for protein loading and release.

Functional materials that can recognize the tumor microenvironment, characterized by acidic or reducing conditions, are needed for the designing of drug delivery carriers for cancer treatment. Hydrogels are potential protein drug carriers because they contain a large amount of water and stimuli-responsive functions can easily be introduced in them. However, it is difficult to introduce multi-stimuli-responsive functions and degradability at the same time. Here, we synthesized thermo- and pH-responsive hydrogels via a coupling reaction between poly(ethylene glycol) diglycidyl ether (PEGDE) and cystamine (CA). The prepared hydrogels showed lower critical solution temperature-type thermoresponsive behavior and pH-responsive swelling changes due to the protonation of secondary and/or tertiary amino groups arising from the crosslinking agent CA. Under reducing conditions, the hydrogels were degraded via the thiol exchange reaction in the presence of dithiothreitol or glutathione. The loading and release properties of FITC-labeled model proteins from the hydrogels were investigated. The loaded amount of the protein increased with decreasing molecular weight or hydrodynamic radius, which is based on the size of the network structure of the hydrogels. Notably, loaded proteins in the hydrogels were released only under reducing conditions, which mimic the tumor microenvironment. Thus, the prepared multi-responsive degradable hydrogels are expected to be used as functional drug delivery carriers for cancer treatment.

Mechano-Responsive Hydrogels Driven by the Dissociation of a Host-Guest Complex.

We developed a mechano-responsive hydrogel that is driven by the dissociation of a host-guest complex. The hydrogel comprised a thermoresponsive linear polymer with adamantane as a guest molecule in its side chain and a nonthermoresponsive network structure with ß-cyclodextrin as a host molecule. Immobilization of the thermoresponsive polymer in the hydrogel via host-guest interaction resulted in a partial restriction of its phase transition, even above its lower critical solution temperature (LCST). The hydrogel demonstrated a decrease in transmittance when mechanical stress was applied at a temperature above its LCST, indicating that the phase transition of the thermoresponsive polymer was induced by the dissociation of the host-guest complex under mechanical stress. Moreover, this mechano-responsive behavior was repeatable by cooling the hydrogel to redissolve the thermoresponsive polymer. The strategy of the mechano-responsive phase transition will be useful for various applications that demand the control of desired functions by applied stress.

Fused sphere carbon monoliths with honeycomb-like porosity from cellulose nanofibers for oil and water separation.

Carbon monoliths with a unique hierarchical surface structure from carbonized cellulose nanofibers were synthesized in pursuit of developing carbon materials from sustainable natural resources. Through a 2-step hydrothermal - carbonization method, TEMPO-oxidized cellulose nanofibers were turned into carbon-rich hydrochar embedded with polystyrene latex as template for 80 nm-sized pores in a honeycomb pattern, while the triblock copolymer Pluronic F-127 was used for a dual purpose not reported before: (1) an interface between the cellulose nanofibers and polystyrene particles, as well as (2) act as a secondary template as ∼1 µm micelles that form hollow carbon spheres. The use of nanofibers allowed more contact between the carbon spheres to coalesce into a working monolith while optimizing the pore structure. Oil-water separation studies have shown that carbon monoliths have high adsorption capacity due to surface area and hydrophobicity. Testing against commercially available activated carbon pellets show greater performance due to highly-developed macropores.

Palladium nanoparticle loaded ß-cyclodextrin monolith as a flow reactor for concentration enrichment and conversion of pollutants based on molecular recognition.

This study reports pollutant remediation by a catalyst-loaded, ß-cyclodextrin cross-linked polymer monolith. The monolith enabled removal of the pollutant to a residual concentration with no environmental effect and conversion of the adsorbed pollutant into useful compounds with enriched concentration, allowing for the adsorption capacity regeneration.