Micropatterned Hydrogels with Highly Ordered Cellulose Nanocrystals for Visually Monitoring Cardiomyocytes.

Cardiac microphysiological systems are accurate in vitro platforms that reveal the biological mechanisms underlying cardiopathy, accelerating pharmaceutical research in this field. Current cardiac microphysiological devices and organs-on-chips consist of several layers prepared with complex, multi-step processes. Incorporating inorganic photonic crystals may cause long-term biocompatibility issues. Herein, micropatterned hydrogels with anisotropic structural colors are prepared by locking shear-oriented tunicate cellulose nanocrystals (TCNCs) in hydrogel networks through in situ polymerization, allowing the visualization and monitoring of cardiomyocytes. The anisotropic hydrogels are composed of highly ordered TCNCs with bright interference color and micro-grooved methacrylated gelatin with excellent biocompatibility. The microgroove patterns induce cardiomyocyte alignment and the autonomous beating of cardiomyocytes causes the hydrogels to deform, dynamically shifting the interference color. These micropatterned hydrogels could noninvasively monitor real-time changes of cardiomyocytes under pharmaceutical treatment and electrical stimulation through wavelength shifts in the transmittance spectra. This system provides a new way to detect the beat rate of cardiac tissue and it may contribute to high throughput develop.

Enzymatic Crosslinked Silk Fibroin Hydrogel for Biodegradable Electronic Skin and Pulse Waveform Measurements.

The development of a portable, controllable, and environmentally friendly electronic skin (e-skin) is highly desirable; however, it presents a major challenge. Herein, a biocompatible, biodegradable, and easily usable hydrogel was designed and fabricated as e-skin to enable the transmission of information regarding the spatial pressure distribution. Silk fibroin (SF) was used as the hydrogel skeleton, which endowed the hydrogel with intelligent mechanical sensitivity. During its conditioning in weakly acidic media, the density of the enzymatic crosslink increased and a dense network was formed due to the formation of covalent/hydrogen bonds. Additionally, a conductive SF/polyvinyl alcohol (PVA) hybrid film was molded as a flexible electrode after graphite deposition. The above SF sensing unit based on SF hydrogels and SF/PVA hybrid films showed high strain sensitivity (4.78), fast responsiveness (<0.1 s), good cycling stability (≥10,000), excellent biocompatibility, and biodegradability. Importantly, a coplanar 8 × 8 pixel SF-based e-skin array was successfully fabricated and applied for 3D signal transmission of the object. The SF-based e-skin was capable of precisely tracking the changes in the pulse pressure, the movement of the finger joint, and the vibrations of the vocal cord. Therefore, the current findings provide a solid foundation for future studies exploring the next generation of electronic devices.

High-Strength and Tough Cellulose Hydrogels Chemically Dual Cross-Linked by Using Low- and High-Molecular-Weight Cross-Linkers.

Hydrogels are the focus of extensive research interests due to their potential application in the fields of biomedical materials, biosensors, agriculture, and cosmetics. Natural polysaccharide is one of the good candidates of these hydrogels. However, weak mechanical properties of cellulose hydrogels greatly limit their practical application. Here, chemically dual-cross-linked cellulose hydrogels (DCHs) were constructed by sequential reaction of cellulose with low- and high-molecular-weight cross-linkers to obtain relatively short chains and long chains cross-linked networks. Both the distribution and density of the cross-linking domains in the hydrogel networks were monitored by three-dimensional Raman microscopic imaging technique. Interestingly, the ruptured stress of DCHs in tensile and compressive tests were 1.7 and 9.4 MPa, which were 26.3- and 83.9-fold larger than those of chemically single-cross-linked cellulose hydrogel. The reinforcement mechanism of DCH was proposed, as the breaking of the short-chain cross-linking in the networks effectively dissipated mechanical energy, and the extensibility of the relatively long-chain cross-linking maintained the elasticity of DCH. Therefore, both the strength and toughness of DCH was enhanced, and the dual networks consisting of short-chain and long-chain cross-linking played an important role in the improvement of the mechanical properties of the cellulose hydrogels. The application prospect of the robust cellulose hydrogels with bimodal network structure would be greatly broadened in the sustainable biopolymer fields.

Cellulose nanocrystals-based optical organohydrogel fiber with customizable iridescent colors for strain and humidity response.

Stimuli-responsive optical hydrogels are widely used in various fields including environmental sensing, optical encryption, and intelligent display manufacturing. However, these hydrogels are susceptible to water losses when exposed to air, leading to structural damage, significantly shortened service lives, and compromised durability. This study presents mechanically robust, environmentally stable, and multi-stimuli responsive optical organohydrogel fibers with customizable iridescent colors. These fibers are fabricated by incorporating tunicate cellulose nanocrystals, alginate, and acrylamide in a glycerol-water binary system. The synthesized fibers exhibit high strength (1.38 MPa), moisture retention capabilities, and elastic properties. Furthermore, a sensor based on these fibers demonstrates high- and low-temperature resistance along with stimuli-responsive characteristics, effectively detecting changes in environmental humidity and strains. Moreover, the fiber sensor demonstrates continuous, repeatable, and quantitatively predictable moisture discoloration responses across a humidity range of 11 % and 98 %. During strain sensing, the optical-organohydrogel-based sensor demonstrates a large working strain (50 %) and excellent cycling stability, underscoring its potential for effectively monitoring a wide range of intricate human motions. Overall, the synthesized fibers and their simple fabrication method can elicit new avenues for numerous related applications including the large-scale implementation of advanced wearable technology.

pH-triggered polydopamine-decorated nanocellulose membranes for continuously selective separation of organic dyes.

Membrane separation technology has emerged as a powerful tool to separate organic dyes from industrial wastewater. However, continuously selective separation of organic dyes with similar molecular weight remains challenging. Herein, we presented a pH-triggered membrane composed of polydopamine-decorated tunicate-derived cellulose nanofibers (PDA@TCNFs) for selective separation of organic dyes. Such self-supporting membranes with nanoporous structure were fabricated by facile vacuum-assisted filtration of PDA@TCNF suspension. The incorporation of polydopamine not only enhanced the stability of the membranes, but also endowed membranes with excellent pH sensitivity, facilitating the continuously selective separation of organic dyes. These pH-triggered PDA@TCNF membranes could selectively separate Methyl Orange (MO) and Rhodamine B (RB) from the MO/RB mixed solution by switching the pH values. The continuously selective separation of the MO/RB mixed solution was demonstrated, where both MO and RB recovery ratios maintained at ∼99 % during 50 repeated cycles. This work provides a new strategy to develop a pH-triggered sustainable nanocellulose-based membrane for continuously selective separation of mixed dyes.

Spray-assisted LBL assembly of chitosan/nanocellulose as coatings of commercial membranes for oil-in-water emulsion separation.

Owing to the limitation of their wettability and pore size, lab filter membranes could not separate oil/water emulsions. Herein, we present surface modification of commercial membranes with chitosan/nanocellulose coatings via a spray-assisted layer-by-layer (LBL) assembly technology. By alternate spraying chitosan (CS) solution and TEMPO-oxidized tunicate cellulose nanofiber (TCNF) suspension, (CS/TCNF)n multilayers were obtained, where n denotes the number of bilayers. The (CS/TCNF)6 coated membrane possessed superhydrophilicity, underwater superoleophobicity, and outperforming anti-oil-fouling properties, which could effectively separate various oil-in-water emulsions. Importantly, the (CS/TCNF)6 coated membrane not only had stable permeate flux with nearly 100 % recovery ratio for the separation of pump oil-in-water emulsion, but also exhibited good harsh-environment-tolerant property. This work provided a novel strategy for designing and preparing stable anti-oil-fouling membranes for oily wastewater treatment.

Tough all-polysaccharide hydrogels with uniaxially/planarly oriented structure.

Considering that the poor mechanical performances of polysaccharide hydrogels always limit their practical applications, herein, we design and fabricate tough all-polysaccharide hydrogels by incorporating uniaxially/planarly oriented tunicate cellulose nanocrystals in physically cross-linked alginate networks. Firstly, alginate chains were loosely cross-linked by surface quaternized tunicate cellulose nanocrystals (Q-TCNCs) and Ca2+ through electrostatic interaction. Secondly, the loosely cross-linked hydrogel was pre-stretched and immersed into CaCl2 solution, obtaining uniaxially oriented hydrogel, whose tensile strength was 31.6 MPa along the pre-stretching direction. After biaxial stretching, the orientation of TCNCs in hydrogel networks converted from dominantly uniaxially oriented structure to planarly oriented structure. The tensile strength, elastic modulus, and toughness of the planarly oriented hydrogels were about 6.6-, 44- and 3.3-folds of those of isotropic Q-TCNC/alginate hydrogel. This work provided a facile and efficient strategy for developing tough hydrogels with uniaxially/planarly oriented structure from biodegradable polymers.

Antibacterial nanocellulose membranes coated with silver nanoparticles for oil/water emulsions separation.

The superhydrophilic/underwater superoleophobic nanocellulose-based membranes show great potential in oil/water emulsion separation. However, nanocellulose composed of polysaccharides inevitably suffered from bacterial erosion during use or storage, resulting in structural damage or reduced separation efficiency. In this work, silver nanoparticles (AgNPs) as effective bactericidal materials are uniformly deposited on tunicate cellulose nanocrystals (TCNCs) by in situ hydrothermal reduction of silver nitrate. TCNCs not only act as reducing agents for silver ions, but also work as dispersant and stabilizers of AgNPs. Nanocomposite membranes are fabricated by vacuum-assisted filtrating of AgNPs@TCNC suspension, which exhibit nanoporous structure, superhydrophilicity, and underwater superoleophobicity. These membranes could efficiently separate oil/water microemulsion with water flux (>324 L m-2 h-1 bar-1) and oil rejection (>99%). Importantly, these membranes show excellent antibacterial efficacy against E. coli and S. aureus, benefiting to their long-term use and storage.

Bioinspired Shape Memory Hydrogel Artificial Muscles Driven by Solvents.

Although hydrogels containing large amounts of water are similar to natural muscles, they are a challenge to be used in artificial muscles because of their poor mechanical properties and low work capacities. The current paper describes the design and fabrication of tendril-inspired hydrogel artificial muscles via a consecutive shaping process. Tunicate cellulose nanocrystals (TCNCs) are incorporated into polymeric networks via host-guest interactions to reinforce the hydrogel. Tendril-inspired hydrogels are obtained by treating the TCNC-reinforced hydrogels with a consecutive stretching, twisting, and coiling process and locking the shaped structure through Fe3+/-COO- ionic coordination. These hydrogel muscles exhibit a high actuation rate, large actuation strain, and shape memory property in response to solvents. The actuation performances of hydrogel muscles are affected by their chirality, twist density, applied stress, and temporary shape. Moreover, a homochiral hydrogel muscle with temporary shape II shows comparable contractile work capacity with a natural muscle, which can be applied as the engine to actuate the movement of a car model. This work demonstrates a simple and effective strategy for the fabrication of hydrogel artificial muscles that have great potential for biomedical application as a result of their comparable water content and contractile work capacity with natural muscles.

Injectable chitin hydrogels with self-healing property and biodegradability as stem cell carriers.

To meet the demands of various therapeutic tasks, injectable hydrogels with tunable mechanical properties and degradability are highly desired. Herein, we developed an injectable chitin hydrogel system with well-manipulated mechanical properties and degradability through dynamic acylhydrazone crosslinking catalyzed by 4-amino-DL-phenylalanine (Phe-NH2). The mechanical properties and degradability of the hydrogels could be easily adjusted by varying the solid content, while their gelation time could be maintained at a constant level (∼130 s) by altering Phe-NH2 content, thereby ensuring the good injectability of hydrogels. Moreover, the chitin hydrogels showed excellent self-healing capacity with a healing efficiency up to 95 %. Owing to their superior biocompatibility and biodegradability, the chitin hydrogels could support the proliferation and multi-potent differentiations of rat bone marrow-derived stem cells, serving as a beneficial 3D scaffold for stem cell encapsulation and delivery. This work provides a promising injectable delivery vehicle of therapeutic drugs or cells for tissue regenerative medicine.

Biocompatible cellulose-based supramolecular nanoparticles driven by host-guest interactions for drug delivery.

To extend the applications of natural products in nanomedicine, novel cellulose-based supramolecular nanoparticles (SNPs) were fabricated via a host-guest driven self-assembly strategy here. The adamantane-grafted carboxyethyl hydroxyethyl cellulose and ß-cyclodextrin-grafted glycerol ethoxylate were synthesized to self-assemble into the SNPs. Furthermore, doxorubicin (DOX)-functionalized ß-cyclodextrin was encapsulated into SNPs via an in situ co-assembly process to generate DOX-loaded SNPs (DOX-SNPs). The SNPs exhibited a quasi-spherical morphology with an average diameter of ∼25 nm. The DOX-SNPs with relatively larger diameter possessed a high DOX loading efficiency (∼94 %) and the pH-responsive drug release behaviors, which made them suitable as a drug delivery system. In vitro cytotoxicity assays demonstrated the excellent cytocompatibility of SNPs and the efficient inhibition of Hela cell proliferation of DOX-SNPs. Moreover, the DOX-SNPs could effectively enter Hela cells via endocytosis and release DOX under endo/lysosome pH. Thus, this nanocarrier has promising translational potential in cancer therapy and personalized nanomedicine.

X-ray shielding structural and properties design for the porous transparent BaSO4/cellulose nanocomposite membranes.

Since effective shielding of X-rays was required in medical, aviation and nuclear fields, a novel X-ray shielding BaSO4/cellulose nanocomposite membrane (BSCM) material with porous transparent structure has been designed. The effects of carboxylated nano-BaSO4 (BS) addition on the physical and morphological properties of the cellulose membrane (CM) were investigated. Meanwhile, the influence of X-ray shielding capacity was studied by different layers of composite membranes and the shielding mechanism of the X-ray was also discussed. Scanning electron microscopy (SEM) images displayed the aggregations of BS in the cellulose surface. Fourier transform infrared spectroscopy (FTIR) showed that the incorporation of BS into CM caused molecular interactions between CM and BS. Brunauer-Emmett-Teller (BET) indicated that the load of BS contributed little to the specific surface area and pore size. Meanwhile, the water vapor transmission rates (WVTR) also stayed at the same level before and after the binding of BS. The swelling ratios, weight loss ratios and mechanical property were decreased along with the addition of BS. The radiation shielding ability was enhanced. Therefore, this work was regarded as a possible example that the BSCM was designed as X-ray radiation shielding material or sandwich filler material in the implication of radiation shielding glass.

Hydrogels prepared from unsubstituted cellulose in NaOH/urea aqueous solution.

Novel cellulose hydrogels were synthesized through a "one-step" method from cellulose, which was dissolved directly in NaOH/urea aqueous solution, by using epichlorohydrin as crosslinker. Structure and properties of the hydrogels were characterized by using SEM, NMR, and water absorption testing. The hydrogels are fully transparent and display macroporous inner structure. The equilibrium swelling ratios of the hydrogels in distilled water at 25 degrees C are in the range from 30 to 60 g H(2)O/g dry hydrogel. Moreover, the reswelling water uptake of the hydrogels could be achieved to more than 70% compared with their initial swelling states. This work provided a simple and fast method for preparing eco-friendly hydrogels from unsubstituted cellulose.

Tunicate cellulose nanocrystals reinforced nanocomposite hydrogels comprised by hybrid cross-linked networks.

Cellulose nanocrystals are considered as promising biomass nanofillers for polymeric hydrogels, but poor interface compatibility between cellulose nanocrystals and hydrogel matrix usually reduces their reinforcement effect. Here, we reported a novel interface compatible nanocomposite hydrogel prepared by introducing quaternized tunicate cellulose nanocrystals (Q-TCNCs) into chemically cross-linked poly (acrylic acid) (PAA) networks. Q-TCNCs acted as both nanofillers and physical cross-linkers in the PAA networks, and the electrostatic interaction between the positive charges of Q-TCNCs and negative charges of PAA chains improved their interface compatibility. The nanocomposite hydrogels exhibited controllable swelling ratio and pH-sensitive swelling behaviors. The mechanical properties of hydrogels significantly increased after incorporation of Q-TCNCs. Moreover, the nanocomposite hydrogels exhibited partly recoverable ability due to the presence of reversible electrovalent bonds in the hydrogel networks.

Structural characterization of fluoride species in shark teeth.

In shark teeth we have identified the species fluorapatite, hydroxyfluorapatite and its defect site, calcium fluoride, and potassium fluoride. Their relative amounts in teeth at different development stages have been quantified. Calcium fluoride and potassium fluoride may be associated with the fluoridation mechanism in shark teeth.

Biocompatible cellulose-based superabsorbent hydrogels with antimicrobial activity.

Current superabsorbent hydrogels commercially applied in the disposable diapers have disadvantages such as weak mechanical strength, poor biocompatibility, and lack of antimicrobial activity, which may induce skin allergy of body. To overcome these hassles, we have developed novel cellulose based hydrogels via simple chemical cross-linking of quaternized cellulose (QC) and native cellulose in NaOH/urea aqueous solution. The prepared hydrogel showed superabsorbent property, high mechanical strength, good biocompatibility, and excellent antimicrobial efficacy against Saccharomyces cerevisiae. The presence of QC in the hydrogel networks not only improved their swelling ratio via electrostatic repulsion of quaternary ammonium groups, but also endowed their antimicrobial activity by attraction of sections of anionic microbial membrane into internal pores of poly cationic hydrogel leading to the disruption of microbial membrane. Moreover, the swelling properties, mechanical strength, and antibacterial activity of hydrogels strongly depended on the contents of quaternary ammonium groups in hydrogel networks. The obtained data encouraged the use of these hydrogels for hygienic application such as disposable diapers.

Hydrogen-bond-induced inclusion complex in aqueous cellulose/LiOH/urea solution at low temperature.

It was puzzling that cellulose could be dissolved rapidly in 4.6 wt % LiOH/15 wt % urea aqueous solution precooled to -12 degrees C, whereas it could not be dissolved in the same solvent without prior cooling. To clarify this important phenomenon, the structure and physical properties of LiOH and urea in water as well as of cellulose in the aqueous LiOH/urea solution at different temperatures were investigated by means of laser light scattering, 13C NMR spectroscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and transmission electron microscopy (TEM). The results reveal that a hydrogen-bonded network structure between LiOH, urea, and water can occur, and that it becomes more stable with decreasing temperature. The LiOH hydrates cleave the chain packing of cellulose through the formation of new hydrogen bonds at low temperatures, which result in a relatively stable complex associated with LiOH, water clusters, and cellulose. A channel inclusion complex (IC) hosted by urea could encage the cellulose macromolecule in LiOH/urea solution with prior cooling and therefore provide a rationale for forming a good dispersion of cellulose. TEM observations, for the first time, showed the channel IC in dry form. The low-temperature step played an important role in shifting hydrogen bonds between cellulose and small molecules, leading to the dissolution of macromolecules in the aqueous solution.