Tunicate Cellulose Nanocrystals Research Articles

Tunicate cellulose nanocrystal reinforced multifunctional hydrogel with super flexible, fatigue resistant, antifouling and self-adhesive capability for effective wound healing

Hydrogels as skin wound dressings have been extensively studied owing to their good flexibility and biocompatibility. Nevertheless, the mechanical performance, adhesive capability, antifouling and antibacterial properties of conventional hydrogels are still unsatisfactory, which hinder the application of hydrogel for cutaneous healing. Here, we developed a novel biocompatible multifunctional hydrogel with super flexible, fatigue resistant, antifouling and self-adhesive capability for effective wound healing, where naturally rigid polymers including quaternized chitosan (QCS) and Tunicate cellulose nanocrystals (TCNCs) are used as bioactive cross-linkers and reinforcers to endow the hydrogel with excellent mechanical and antibacterial property, and the synergistic contributions from the poly(acrylic acid/methacrylate anhydride dopamine/sulfobetaine methacrylate) (poly(AA/DMA/SBMA)) chains and QCS endow the hydrogel with excellent adhesive property, antioxidant, antifouling and pH-responsive sustained drug release capabilities. The optimized hydrogel exhibited high tensile strength (77.69 KPa), large tensile strain (889.9 %), large toughness (307.51KJ.m−3), high adhesive strength (35.57 KPa) and ideal compressive property. The in vivo infected full-thickness skin model demonstrated that the hydrogel with vanvomycin sustained release ability efficiently improved the granulation tissue formation, facilitating collagen deposition and reducing inflammatory expression, thus effectively accelerating wound healing. This superiorly skin-adhesive antibacterial biocompatible hydrogel appears to be a promising candidate for wound therapy.

Hydration Programmable, Shape Memorable Artificial Muscles for Antagonistic Movements

AbstractShape memory polymers (SMPs) capable of generating various deformations from anisotropic temporary shapes to permanent shapes have been emerging as soft robots. However, traditional SMPs cannot imitate the antagonistic movement of human skeletal muscles due to their modulus limitations in shape programming and recovery process. Herein, hydration programmable shape memory polymer (HP‐SMP)‐based fibers that can undergo reversible actuation by assembling antagonistic pairs are reported, where the shape programming of the antagonist muscle relies on the contraction of agonist muscle. HP‐SMP fibers are composed of tunicate cellulose nanocrystals (TCNCs) reinforced semi‐interpenetrating polymer networks. Leveraging their distinctive structure and hydration programmability, the HP‐SMP fibers exhibit large actuation strain (−60%) and high work capacity (751 J kg−1), allowing for reversible actuation under constant stress. Most significantly, the continuous antagonistic movements of HP‐SMP fibers assembled into artificial limbs are demonstrated to realize humanoid motion. This work provides new possibilities for replicating a series of lifelike human movements through the biomimetic design of antagonistic pairs of artificial muscles, utilizing renewable and sustainable biosourced materials.

Preparation and characterization of a novel high barrier mulching film with tunicate cellulose nanocrystals/sodium alginate/alkali lignin

In this study, the base film (CSL) was prepared by blending tunicate cellulose nanocrystals (TCNCs) extracted from tunicate shells, with sodium alginate (SA) and alkali lignin (AL). Then, the mulching film (CSL-WK) was prepared using water-borne polyurethane (WPU) as binder to install low-energy Kaolin on the surface of CSL film. The influences of composition with different concentrations on mechanical properties were studied. The tensile strength and elongation at break of CSL-WK film could reach 86.58 MPa and 50.49 %, respectively. The mulching films were characterized by degradability test, SEM, FTIR, and TGA. TCNCs had good compatibility with SA and AL, and a rough structure was formed on the surface of the film to improve the hydrophobicity. The barrier properties, including ultraviolet resistance, water contact angle, water vapor permeability, water retention, and flame retardancy, were tested. The results showed that CSL-WK films could block 97 % of ultraviolet light, reduce about 25 % of soil water loss, and self-extinguish within 7 s of open flame ignition. Note that the secondary spraying method significantly improved the barrier property of films. This study lays a foundation for the preparation of ecologically friendly, biodegradable, and high barrier mulching film, and expands the application of marine resources.

Di-aldehyde tunicate cellulose nanocrystal (D-tCNC) aerogels for drug delivery: Effect of D-tCNC composition on aerogel structure and release properties

Aerogels as drug carriers have the characteristics of a large specific surface area, high porosity and an elastic skeleton structure. Compared with traditional drug carriers, the use of aerogels as drug carriers can avoid the complexity of drug delivery and improve the efficiency of drug loading. In this work, the oxidation of tunicate cellulose nanocrystals (tCNCs) with NaIO4 was used to prepare di-aldehyde tunicate cellulose nanocrystals (D-tCNCs). Tetracycline (TC) was used as a drug model and pH-responsive drug-loaded aerogels were prepared by the Schiff base reaction between TC and the aldehyde group on D-tCNCs. The chemical structure, crystallinity, morphology, compression properties, porosity, swelling rate and drug loading properties were investigated by FT-IR, XRD, SEM and universal testing machines. The results showed that the porosity and equilibrium swelling ratio of the D-tCNC-TC aerogels were 95.87 % and 17.52 g/g, respectively. The stress of the D-tCNC-TC aerogel at 15 % compression was 0.07 MPa. Moreover, the analysis of drug-loaded aerogels indicated that the drug loading and encapsulation rates of D-tCNC-TC aerogels were 16.86 % and 78.75 %, respectively. In in vitro release experiments, the cumulative release rate of drug-loaded aerogel at pH = 1.2 and pH = 7.4 was 87.5 % and 79.3 %, respectively. These results indicated that D-tCNC-TC aerogels have good drug loading capacity and are pH-responsive in the pH range of 1.2 to 7.4. The prepared D-tCNC-TC aerogels are expected to be applied in drug delivery systems.

Tunicate cellulose nanocrystals reinforced modified calcium sulfate bone cement with enhanced mechanical properties for bone repair

Considering the poor mechanical properties of bone cement, its practical application has always been limited. In this study, we introduced tunicate cellulose nanocrystals (TCNCs) into calcium sulfate bone cement for the first time, and multiple enhanced composite bone cement was prepared by the condensation reflux method. Firstly, high-strength modified calcium sulfate hemihydrate (CSH) bone cement was successfully prepared by using tartaric acid, a crystal modifier with a chiral structure. Secondly, the inclusion of TCNCs not only exhibited significant reinforcement and toughening effects but also stimulated the adhesion, proliferation, and differentiation of related osteoblasts. Furthermore, TCNCs encapsulated the CSH particles, overcoming the limitations of excessive degradation rates in bone cement and enabling sustained release of Ca2+, promoting the healing of bone defects. Overall, this study presents novel ideas and methodologies for designing bone cement with exceptional performance. It also provides a new platform for the development of bone tissue engineering and is expected to become a new type of bone regeneration material. The utilization of oceanic resources in this context holds high-value potential, alleviating environmental burdens and providing clinically applicable bone tissue repair materials with broad application prospects.

Injectable, self-healable and antibacterial multi-responsive tunicate cellulose nanocrystals strengthened supramolecular hydrogels for wound dressings

Wound dressing with an improved structural and functional recapitulation of damaged organs, efficient self-healing and antibacterial properties that can well integrate with tissue are urgently needed in wound management. Supramolecular hydrogels confer control over structural properties in a reversible, dynamic and biomimetic fashion. Herein, a kind of injectable, self-healing and antibacterial supramolecular hydrogel with multi-responses were fabricated by mixing phenylazo-terminated Pluronic F127, quaternized chitosan-graft-cyclodextrin and polydopamine coated tunicate cellulose nanocrystals under physiological conditions. By exploiting the photoisomerization of azobenzene under different wavelengths, a supramolecular hydrogel featuring a changing crosslink density of network was obtained. The corporation of polydopamine coated tunicate cellulose nanocrystals strengthens the hydrogel network with Schiff base bonds and hydrogen bonds, which avoids complete gel-sol transition. The inherent antibacterial property, drug release behavior, self-healing ability, hemostatic performance and biocompatibility were investigated to confirm superiority in wound healing. Moreover, the curcumin loaded hydrogel (Cur-hydrogel) showed multi-responsive release profiles (light, pH, and temperature). A full-thickness skin defect model was built to confirm that Cur-hydrogels significantly accelerated wound healing rate with better granulation tissue thickness and collagen disposition. Overall, the novel photo-responsive hydrogel with coherent antibacterial property has great potential in the healthcare of wound healing.

The effects of aspect ratio of cellulose nanocrystals on the properties of all CNC films: Tunicate and wood CNCs

In this study, the physicochemical, mechanical, and thermal properties of films made from cellulose nanocrystals (CNCs) obtained from two sources – wood and tunicate - and their hybrids were investigated. It was found that different morphologies affect the properties of CNC films. Specifically, the surface morphology of tunicate CNC (TCNC) films differed significantly from wood CNC (WCNC) films, and the structure of hybrid CNC (HCNC) films was also different. Compared to wood CNC-containing films, tunicate CNC films exhibited significantly higher BET surface areas, superior thermal properties, greater surface roughness, and very low (≈1 wt.%) dispersibility in water due to their ability to form long-range connectivity. The average BET surface area of TCNC films was measured at 91.9 ± 2.1 m2/g, and this value decreased with the addition of WCNCs to the film structure. The pore diameter also decreased from 11.362 nm for TCNC films to 0.437 nm for WCNC films, indicating the filler effect of WCNCs on the TCNC films. The chiral nematic phase exhibited by WCNC films was confirmed by their iridescent appearance, as observed through cross-sectional SEM images. The TS for TCNC and HCNC3 was measured at 185.2 ± 10.5 MPa and 182.9 ± 13.7 MPa, respectively, which were the highest values among the samples. The lowest TS value of 113.1 ± 9.5 MPa was observed in the WCNC films. A similar decline was observed in the EB values, from 1.76 ± 0.37% for TCNC to 0.9 ± 0.22% for WCNC. This study provides information and knowledge useful for understanding the impact of biomass source on the properties of CNC films for a variety of purposes, including packaging materials, biodegradable coatings, flexible electronics, and membrane applications.

Crosslinked poly (vinyl alcohol) composite reinforced with tunicate, wood, and hybrid cellulose nanocrystals: Comparative physicochemical, thermal, and mechanical properties

The development of sustainable and biodegradable composites has gained increasing attention in recent years. Effective interaction and adhesion between polymers and fillers are crucial. In this study, the effect of different aspect ratios of cellulose nanocrystals (CNCs) and their hybrid within a crosslinked poly (vinyl alcohol) (PVA) nanocomposite has been investigated to develop biodegradable materials. The physicochemical, thermal, and mechanical properties of the specimens have been studied. SEM images indicate that the addition of CNC reduced the porosity of the films. The XPS results confirmed the significant formation of covalent bonds for all composites except those reinforced with wood-CNC, which showed a lower amount of crosslinking and CC formation. EDS maps reveals that the dispersity of the CNCs could be different depending on the aspect ratio of the CNCs. Results from the solubility in water (SW) tests indicated that the use of hybrid-CNC in a crosslinked system decreased the SW significantly. The crosslinking and addition of CNC to the PVA composite led to improved mechanical properties. Elongation at break (EB) decreased significantly for the crosslinked hybrid-CNC nanocomposite. Overall, the results of this study indicate that the aspect ratio of CNCs as fillers in nanocomposites may contribute to their physicochemical, mechanical, and thermal properties for the development of biodegradable materials.

Castor oil-based waterborne polyurethane/tunicate cellulose nanocrystals nanocomposites for wearable strain sensors

In this study, tunicate cellulose nanocrystals (TCNCs) were introduced into castor oil-based waterborne polyurethane (WPU) to prepare bio-based nanocomposites through a simple solution blending method. The effect of TCNCs content on the particle size and stability of the composite dispersions, as well as the thermophysical and mechanical properties of the composite films were studied and discussed. The unique structure and properties of TCNCs, such as high crystallinity, large aspect ratio and high modulus, not only greatly improved the storage stability of WPU, but also showed significant reinforcing/toughening effects and excellent compatibility to WPU. By drip-coating silver nanowires (AgNWs) on the surface of the composite films, the flexible strain sensors were fabricated, which showed excellent sensitivity in monitoring human movement.

Micropatterned Hydrogels with Highly Ordered Cellulose Nanocrystals for Visually Monitoring Cardiomyocytes (Small 45/2022)

Cardiomyocyte Monitoring In article number 2202235, Chunyu Chang, Donghui Zhang, and co-workers develop micropatterned hydrogels with anisotropic structural colors by locking shear-oriented tunicate cellulose nanocrystals (TCNCs) in hydrogel networks through in situ polymerization. The autonomous beating of cardiomyocytes drives synchronous deformations of the micropatterned hydrogels, causing periodic changes in transmittance colors. This system has potential as a high-throughput assay to visually monitor cardiomyocyte function.

Triple physically cross-linked hydrogel artificial muscles with high-stroke and high-work capacity

Owing to the high-water content and excellent biocompatibility, polymeric hydrogels are good candidates to mimic natural muscles in biomedical and bioengineering fields, but the low stroke and low work capacity limited them to be used as artificial muscles. Herein, inspired by the ordered structure of skeletal muscles, high performance anisotropic hydrogels comprising of triple physically cross-linked networks are developed by the electrostatic interactions between positively charged tunicate cellulose nanocrystals (TCNC) and –COO− of polymers, hydrophobic association of stearyl methacrylate (SMA) moiety in sodium dodecyl sulfate (SDS) micelles, and –COO−/Fe3+ ionic coordination. The elastic potential energy can be stored in polymeric networks by locking the pre-stretched hydrogel via ionic coordination, which can be released by dissociating the ionic coordination under acidic condition. Based on their excellent mechanical property reinforced by TCNCs, the developed hydrogel artificial muscles exhibit high actuation stroke (75 %) and high-work capacity (210 J kg−1), which are higher than those of skeletal muscles. These hydrogel muscles demonstrated potential for wide applications in being designed as biceps to lift skeleton’s arm and as micromotors to drive boat model under acidic condition because of their high-stroke, high-work capacity and comparable output efficiency with natural muscles.

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.

Ionic coordination strengthening of temperature-driven gradient hydrogel actuators with rapid responsiveness

Emerging applications of stimuli-responsive hydrogels as soft actuators and robotics have attracted great attention, but they face challenges in practical applications due to their poor mechanical properties, low driving force, and low actuation speed. Herein, we presented tough hydrogel actuators composed of a copolymer of N-isopropylacrylamide (NIPAM) and 3-sulfopropyl methacrylate potassium salt (SPA) monomers, and tunicate cellulose nanocrystals (TCNCs). The negatively charged TCNCs as nanofillers were gradient arranged by a direct current electric field (DC-EF) via electrophoresis. After in situ polymerization, TCNCs gradient distributed across the thickness of hydrogel, resulting in the formation of gradient crosslinking density of networks. Hydrogel actuators with high strength were obtained via Zr4+/−SO3- ionic coordination, whose tensile strength was about 200 times of hydrogel without ionic coordination. These hydrogel actuators exhibited rapid bending velocity, excellent stability, and good cycling performance in response to temperature. Importantly, these hydrogel actuators could be designed as soft robots to lift and transport objects by changing environment temperature. This work provided a facile yet efficient strategy to fabricate soft actuators with high strength and rapid responsiveness.

Influence of cellulose nanocrystal aspect ratio on shear force aligned films: Physical and mechanical properties

The present study investigates the effect of cellulose nanocrystals (CNCs) aspect ratio on the shear force alignment. A molecular CNC exhibits anisotropic behavior because of its different chemical bonds in different directions, especially its different mechanical properties parallel and perpendicular to its axial direction. We used these shear-force aligned films to develop biodegradable and sustainable films in a sandwiched starch/chitosan system. According to the results from 2D-XRD on the CNC films, at lower initial CNC suspension (≈1%), the calculated Hermans order parameters was much higher for the high AR (≈ 63) tunicate CNC (TCNC) as compared to the low AR (≈ 12) wood CNC (WCNC). Compared to the TCNC's Hermans order parameter, the hybrid CNC films (HCNC) (1:1 ratio of WCNC:TCNC) showed approximately similar order parameters. WCNC shear force aligned films were chiral nematically organized and did not show any alignment. Accordingly, alignment significantly affected the TCNC and HCNC's physical and mechanical properties, such as water vapor permeability, elastic modulus, and tensile strength. This paper reports the study results on the alignment of CNCs with different ARs and the hybrid configuration under shear force and its effect on the physical and mechanical properties of the polymeric nanocomposites.

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.

Study on the effect of tunicate cellulose nanocrystals in the preparation of sodium alginate-based enteric capsule

In this work, tunicate cellulose nanocrystals (tCNCs) were extracted from the tunicate by bleaching and acid hydrolysis. They were used as filler in the preparation of sodium alginate-based enteric capsules. The addition of tCNCs with a high aspect ratio (65) rendered the enteric capsule excellent physical properties. Compared with the control sample, when the addition of tCNCs were 10% (wt), the water contact angle of the capsule was enhanced by 46.0%, the opacity was increased by 356.8%, the maximum tensile stress was increased by 142.6%, the modulus of elasticity was increased by 240.3%, and the elongation at break was increased by 133.8%. In the in vitro degradation experiments, the capsule hardly degraded in the gastric environment (pH 1.2), while in the intestinal environment (pH 6.8), the degradation became slower with the increase of tCNC content, which was consistent with the properties of the enteric capsule. This research developed a new direction for the application of tCNCs in the pharmaceutical material productions.Graphical abstract

Preparation and characterization of super hydrophobic aerogels derived from tunicate cellulose nanocrystals

First time aerogels composite with super hydrophobic properties were developed by using tunicate cellulose nanocrystals (TCNC), which expanded the application scope of animal cellulose resources. In this study, the TCNC was firstly cross-linked with silica and methyltrimethylsilane (MTMS), further coated with fluorodopa to form an aerogel with super hydrophobic properties. The aerogel was characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), and X-ray photoelectron spectroscopy (XPS). Results indicated that the contact angle of aerogel was 158.7°, which showed good hydrophobicity. The composite aerogel has superior stability in wide pH range, after 72 h immersion in pH = 0 and 12 solutions, the contact angle was still greater than 150°. The aerogel shows excellent oil-water separation ability and it can be repeatedly used more than 10 times. The separation efficiency can all reach more than 90% for different water-oil mixtures. This synthesized super hydrophobic aerogels derived from tunicate cellulose has greatly extended the application of marine animal celluloses.

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.

Superabsorbent hydrogels enhanced by quaternized tunicate cellulose nanocrystals with adjustable strength and swelling ratio

Superabsorbent hydrogels were prepared from biodegradable material, where the matrix was cross-linked cellulose and carboxymethyl cellulose and reinforced by quaternized tunicate cellulose nanocrystals (Q-TCNCs). Due to the large amount of hydrophilic groups on cellulose, carboxymethyl cellulose, and Q-TCNCs, the hydrogels had excellent water absorption capacity. The equilibrium swelling ratio of superabsorbent hydrogels exceeded 500 g/g in deionized water and exceeded 120 g/g even in synthetic urine, which was higher than those of commercial absorbent materials composed of copolymers of acrylic acid and acrylamide. The water absorption performances and mechanical properties of the hydrogels could be adjusted by changing the content of Q-TCNCs. The resultant materials were expected to replace those polyolefin-based materials, thereby reducing environmental pollution.