Activating Adsorption Sites of Waste Crayfish Shells via Chemical Decalcification for Efficient Capturing of Nanoplastics.

The property of being stubborn and degradation resistant makes nanoplastic (NP) pollution a long-standing remaining challenge. Here, we apply a designed top-down strategy to leverage the natural hierarchical structure of waste crayfish shells with exposed functional groups for efficient NP capture. The crayfish shell-based organic skeleton with improved flexibility, strength (14.37 to 60.13 MPa), and toughness (24.61 to 278.98 MJ m-3) was prepared by purposefully removing the inorganic components of crayfish shells through a simple two-step acid-alkali treatment. Due to the activated functional groups (e.g., -NH2, -CONH-, and -OH) and ordered architectures with macropores and nanofibers, this porous crayfish shell exhibited effective removal capability of NPs (72.92 mg g-1) by physical interception and hydrogen bond/electrostatic interactions. Moreover, the sustainability and stability of this porous crayfish shell were demonstrated by the maintained high-capture performance after five cycles. Finally, we provided a postprocessing approach that could convert both porous crayfish shell and NPs into a tough flat sheet. Thus, our feasible top-down engineering strategy combined with promising posttreatment is a powerful contender for a recycling approach with broad application scenarios and clear economic advantages for simultaneously addressing both waste biomass and NP pollutants.

Fabrication of an exosome-loaded thermosensitive chitin-based hydrogel for dental pulp regeneration.

Injective thermosensitive hydrogels are considered promising scaffolds to trigger dental pulp regeneration in devitalized human teeth. In this study, we developed a hydroxypropyl chitin (HPCH)/chitin whisker (CW) thermosensitive hydrogel with enhanced mechanical properties and biological activities. Exosomes can serve as biomimetic tools for tissue engineering, but the rapid clearance of unconjugated exosomes in vivo limits their therapeutic effects. To address this challenge, exosomes were isolated from human pulp stem cells (hDPSCs) and directly embedded into the HPCH/CW pre-gel to form an exosome-loaded hydrogel (HPCH/CW/Exo). The exosome-loaded thermosensitive hydrogel can be easily injected into an irregular endodontic space and gelated in situ. In vitro cell experiments proved that the delivery of exosomes significantly improved the ability of hydrogels to promote odontogenesis and angiogenesis. Meanwhile, in vivo animal experiments revealed the formation of new dental pulp-like tissues in an implanted tooth root model. Therefore, the proposed hydrogel provides a great potential alternative to traditional root canal therapy in dental clinics.

Antifatigue Hydration-Induced Polysaccharide Hydrogel Actuators Inspired by Crab Joint Wrinkles.

Joint wrinkles in animals facilitate frequent bending and contribute to the duration of the joint. Inspired by the morphology and function of joint wrinkles, we developed a bionic hydration-induced polymeric actuator with constructed wrinkles at the selected area. Specifically, we adopt electrical writing to create defined single and double cross-linking regions on chitosan (CS) hydrogel. The covalent cross-linking network was constructed by electrical writing-induced covalent cross-linking between CS chains and epichlorohydrin. Subsequent treatment of sodium dodecyl sulfate allows electrostatic cross-linking at the unwritten area with the simultaneous formation of surface wrinkles. The resulting single and double cross-linking hydrogel demonstrates spontaneous deformation behaviors by the influx and efflux of H2O to the electrostatic cross-linking domain under different ion concentrations. Importantly, the wrinkle structure endows the hydrogel with extraordinary antifatigue bending performance. By regulating the surface morphology and spatial cross-linking, we can design novel biomimetic polysaccharide hydrogel actuators with fascinating functions.

Electrodeposition induced covalent cross-linking of chitosan for electrofabrication of hydrogel contact lenses.

To meet the requirement of personalization, there is an urgent need to develop a simple, efficient and versatile manufacturing method for customized contact lens manufabrication. Here, we report a novel electrofabrication methodology (i.e., electrodeposition) for the fabrication of hydrogel contact lenses, which can induce covalent cross-linking between chitosan and epichlorohydrin simultaneously. The transmittance and toughness of hydrogels are improved by electrochemical cross-linking without affecting their oxygen permeability. Furthermore, the geometry of the chitosan based hydrogel contact lenses can be customized simply by the electrode template, and its characteristics can be regulated by electrical signals and electrochemical cross-linking. The electrodeposited hydrogel contact lenses have good optical properties, mechanical properties and biocompatibility, and their anti-adhesion properties to Staphylococcus aureus are close to commercial contact lenses. This work reveals the mechanism of electrochemical cross-linking between chitosan and epichlorohydrin and provides an alternative method for contact lens fabrication.

Highly sensitive formaldehyde sensors based on CuO/ZnO composite nanofibrous mats using porous cellulose acetate fibers as templates.

An innovative formaldehyde sensor based on CuO/ZnO composite nanofibrous mats (C-NFMs) coated quartz crystal microbalance (QCM), which is capable of stable determination of formaldehyde gas at ambient temperatures sensitively and selectively, has been successfully fabricated. Triaxial and highly porous C-NFMs with high surface area (126.53 m2 g-1) were synthesized by electrospinning a sol-gel cellulose acetate (CA)/CuAc2/ZnAc2 complex solution and following by calcination process. Benefiting from the unique heterojunction structure, immense pore interconnectivity and large surface area of C-NFMs, the as-developed QCM sensors exhibited an extremely low limit of detection (LOD) down to 26 ppb and a limit of quantification value equals to 87 ppb. Besides, the C-NFMs coated QCM sensors also demonstrated short response times (80s), the long-term stability during 3 weeks as well as good selectivity to formaldehyde over diverse volatile organic compounds. The sorption equilibrium in the adsorption process of QCM coated sensors was well met with the Freundlich model, which certified the heterogeneous adsorption between formaldehyde gas and C-NFMs.

Determination of darusentan enantiomers in rat plasma by enantioselective liquid chromatography with tandem mass spectrometry using cellulose-based chiral stationary phase.

A sensitive, specific and rapid liquid chromatography-mass spectrometry (LC-MS/MS) method has been developed and validated for enantioselective determination of darusentan enantiomers, orally active potent endothelin-A receptor antagonist, in rat plasma. The plasma samples were pretreated by protein precipitation with methanol and baseline chromatographic separation was performed on a Chiralcel OD-RH column with a mobile phase consisting of acetonitrile/water/formic acid (50:50:0.1, v/v/v) at a flow rate of 0.5 mL/min. The detection was accomplished by multiple-reaction monitoring (MRM) scanning via electrospray ionization (ESI) source operating in the negative ionization mode. The calibration curve was linear over the investigated concentration from 0.500 to 2500 ng/mL (r≥0.995) for each enantiomer using 50 µL of rat plasma. The lower limit of quantitation (LLOQ) for each enantiomer was 0.500 ng/mL. The intra- and inter-day precisions were not more than 10.2% and the accuracy was within the range from -5.4 to 6.3% for darusentan enantiomers. No chiral inversion was observed during the plasma preparation, storage and analysis. The method proved adequate for enantioselective pharmacokinetic studies of darusentan enantiomers after oral administration of three different doses of racemic darusentan.

TiO2/rectorite-trapped cellulose composite nanofibrous mats for multiple heavy metal adsorption.

The anthropogenic release of highly toxic heavy metals into the environment presents a huge challenge for ecosystems and human society. Recoverable and efficient adsorption materials could be obtained by trapping inorganic adsorbents (e.g., TiO2 nanoparticles and rectorite (REC)), in a natural polymer matrix. In this study, a series of cellulose-TiO2/REC composite nanofibrous mats were fabricated via electrospinning. The interactions between inorganic adsorbents and cellulose molecules improved the thermal stability, surface area, tensile strength and adsorption capacity of the mats. We focused on the adsorption of Pb2+, Cu2+ and Cd2+ from acidic solutions onto cellulose-TiO2/REC composite nanofibrous mats in multiple systems because the magnitudes of heavy metal concentrations in wastewater typically varied. The maximum total adsorption capacity of 69.81 mg/g was obtained by Cellulose-TiO2/REC2:1 nanofibrous mats. The composite nanofibrous mats successfully trapped TiO2 nanoparticles, and the obtained cellulose-TiO2/REC nanofibrous mats could be used to remove heavy metals from acidic wastewater.

Hollow cellulose-carbon nanotubes composite beads with aligned porous structure for fast methylene blue adsorption.

Polysaccharide based beads with unique porous structure have gained considerable interests due to their specific adsorption behaviors and biodegradability. The purpose of this paper was to develop hollow cellulose/carbon nanotubes composite beads with aligned porous structure which have potential applications in fast adsorption field. The composite beads were fabricated by ice template and freeze-drying technology. Different characterizations have proved that the carbon nanotubes and magnetic nanoparticles have been incorporated into the cellulose beads. Higher concentration of carbon nanotubes and cellulose would result in a larger diameter of the composite beads. The composite beads can effectively adsorb the methylene blue (MB). The pseudo-second-order model and Langmuir isotherm were best fitted to the adsorption. The composite beads showed a fast adsorption behavior towards MB with a t1/2 of 1.07 min obtained from pseudo-second-order model. The maximum adsorption capacity was 285.71 mg g-1 at pH 7.0. The composite beads also showed good reusability and biodegradability. We anticipate that different polysaccharides based composite beads with aligned porous structure can be obtained through the similar methods and applied in adsorption fields.

Electrofabrication of flexible and mechanically strong tubular chitosan implants for peripheral nerve regeneration.

The development of peripheral nerve tissue engineering requires a safe and reliable methodology to construct biodegradable conduits. Herein, a new type of chitosan-based nerve-guide hydrogel conduit (CNHC) with enhanced mechanical flexibility in the wet state was fabricated using a one-step electrofabrication technology. The formation of the chitosan conduit is a physical process which can be conducted in a mild water phase without toxic crosslinks. The current density during electrofabrication has a profound effect on the physical and structural properties of the conduits. Cytocompatibility results indicate that the CNHC can promote cell proliferation and adhesion. Functional and histological tests indicate that the CNHC has the ability to guide the growth of axons through the conduit to reach a distal stump, which is closely similar to the autograft group. Overall, the results of this study demonstrate that the CNHCs from electrofabrication have a great potential in peripheral nerve regeneration.

One-step electrochemically induced counterion exchange to construct free-standing carboxylated cellulose nanofiber/metal composite hydrogels.

The fabrication of polymeric composite hydrogel with hierarchical structure in a simple, controllable, and straightforward process poses great importance for manufacturing nanomaterials and subsequent applications. Herein, we report a one-step and template-free counterion exchange method to construct free-standing carboxylated cellulose nanofiber composite hydrogels. Metal ions were electrochemically and locally released from the electrode and chelated with carboxylated cellulose nanofibers, leading to the in-situ formation of composite hydrogels. The properties of composite hydrogels can be easily programmed by the type of electrode, current density, and electrodeposited suspension. Significantly, the composited hydrogels exhibited interconnected nanoporous structure, enhanced thermal degradation, improved mechanical strength and antibacterial activity. The results suggest great potential of anodic electrodeposition to fabricate nanofiber/metal composite hydrogels.

Applications of chitin and chitosan nanofibers in bone regenerative engineering.

Promoting bone regeneration and repairing defects are urgent and critical challenges in orthopedic clinical practice. Research on bone substitute biomaterials is essential for improving the treatment strategies for bone regeneration. Chitin and its derivative, chitosan, are among the most abundant natural biomaterials and widely found in the shells of crustaceans. Chitin and chitosan are non-toxic, antibacterial, biocompatible, degradable, and have attracted significant attention in bone substitute biomaterials. Chitin/chitosan nanofibers and nanostructured scaffolds have large surface area to volume ratios and high porosities. These scaffolds can be fabricated by electrospinning, thermally induced phase separation and self-assembly, and are widely used in biomedical applications such as biological scaffolds, drug delivery, bacterial inhibition, and wound dressing. Recently, some chitin/chitosan-based nanofibrous scaffolds have been found structurally similar to bone's extracellular matrix and can assist in bone regeneration. This review outlines the biomedical applications and biological properties of chitin/chitosan-based nanofibrous scaffolds in bone tissue engineering.

Incorporating chitin derived glucosamine sulfate into nanofibers via coaxial electrospinning for cartilage regeneration.

Chitin is the second abundant natural polysaccharide, and the development of chitin and its derivatives have received more and more attention. Glucosamine sulfate (GAS) obtained by the hydrolysis of chitin can promote the growth of chondrocytes. The coaxial electrospinning technology had been utilized to encapsulated GAS into the core of polycaprolactone (PCL) nanofibers. It could protect the GAS from the environment and allow it to release sustainably over time. From the results of scanning electron microscopy (SEM), PCL/GAS nanofibers performed a typical fiber scaffold surface. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) results confirmed the feasibility to use coaxial electrospinning to load GAS. Tensile tests exhibited that PCL/GAS mats could be stretched more than twice its own length. Besides, the cell experiments illustrated that PCL/GAS had a significant effect on the proliferation and growth of rat articular chondrocytes, attesting its prospect for cartilage regeneration.

Chitosan/tannic acid bilayers layer-by-layer deposited cellulose nanofibrous mats for antibacterial application.

The research and development of environmentally friendly and nontoxic biomass products has become an important topic of worldwide concern. In this study, natural materials were used for producing a kind of antibacterial mats. Cellulose acetate (CA) mats prepared by electrospinning technology were converted to cellulose mats via alkali hydrolysis. Chitosan (CS) and tannic acid (TA) were used to fabricate the composite mats by using layer-by-layer (LBL) self-assembly technology. The cellulose mats exhibited good fibrous structure, three-dimensional network and small average fiber diameter ranging from 300 to 400 nm. Besides, the results of mechanical properties testing and water contact angle measurements of these LBL-structured mats demonstrated that the LBL technology was able to improve their surface characteristics, hydrophilicity and mechanical properties. The analysis of antibacterial activity of the mats revealed over 86% antibacterial activity against Escherichia coli and up to 99% antibacterial activity against Staphylococcus aureus. Hence, the LBL-structured cellulose mats have excellent antibacterial activity and mechanical properties. Therefore, these nano-cellulose mats can be expected to have considerable development prospects for food packaging or wound dressing.

Emerging chitin nanogels/rectorite nanocomposites for safe and effective hemorrhage control.

Excessive bleeding due to trauma, surgery and diseases may cause severe mortalities. Here, an emerging chitin nanogel/rectorite nanocomposite is developed for effective hemorrhage control. Chitin chains are intercalated into rectorite and subsequent mechanical high speed stirring generates chitin nanogels, which assemble on the surface of the rectorite nanoplates through electrostatic interactions to form a sandwich structure. The in vitro experiments reveal that the nanocomposite exhibits favorable biocompatibility and negligible hemolysis (<3.5%) as compared to rectorite (40%). The nanocomposite stops bleeding in 121 s in rat tail incision and exhibits higher hemostatic activity in the rabbit artery injury model as compared to a commercialized chitosan hemostat, Celox. The efficient blood clotting activity is attributed to the induction of a coagulation cascade by rectorite and the quick adsorption and aggregation of platelets and red blood cells by chitin. The enhanced biocompatibility and hemostatic activity of the chitin/rectorite nanocomposite make it a safe and cost effective hemostat to control bleeding.

Construction of cellulose nanofibers/quaternized chitin/organic rectorite composites and their application as wound dressing materials.

Traumatic injury is a major cause of mortality, and poor wound healing affects millions of people. Thus, the development of effective wound dressings is essential for speeding up wound healing and decreasing mortality. In this study, a suspension of carboxylated brown algae cellulose nanofibers (BACNFs) with a high aspect ratio was freeze dried to prepare a sponge. The sponge showed high porosity and water absorption capacity; thus, it can absorb wound exudates when used as a wound dressing. In addition, quaternized ß-chitin (QC) with antibacterial properties was intercalated into the interlayer space of the organic rectorite (OREC) via electrostatic interactions to obtain composite suspensions (QCRs) with improved antimicrobial activity compared to that of QC alone. Subsequently, the BACNF sponge was soaked in the QCR suspension to absorb QCRs via electrostatic interactions and hydrogen bonding from which cellulose nanofiber/quaternized chitin/organic rectorite composite (BACNF/QCR) sponges were constructed via freeze-drying. The in vivo animal tests demonstrated that the BACNF/QCR sponges rapidly induced hemostasis in a rat tail amputation test, making them superior to the traditional hemostatic materials. Furthermore, BACNFs/QCRs could substantially promote collagen synthesis and neovascularization, thereby accelerating wound healing 3 days earlier than gauze. This multi-functional biomedical material, fabricated using natural substances, shows great potential to be used for wound healing.

Egg source natural proteins LBL modified cellulose nanofibrous mats and their cellular compatibility.

Natural-based nanocomposites are competitive and promising materials for biomedical applications due to their biocompatibility. Herein, a novel natural-based composite was fabricated by alternately depositing lysozyme (LY) and albumin egg (AE) on electrospun cellulose nanofibrous mats via layer-by-layer self-assembly (LBL) technology. To indicate the successful deposition process and investigate the variations of the mats during LBL process, the surface morphology, physical property, chemical composition, wetting behavior and thermal stability were systematically studied. The results showed that the surface morphology and composition of the mats were significantly influenced by LBL process, which further resulted in the variation of wetting behavior. Besides, the mechanical properties were enhanced after LBL modification. In addition, the LBL structured nanofibrous mats exhibited antibacterial activity and excellent biocompatibility with L929 fibroblasts. In brief, LY and AE coated LBL structured cellulose nanofibrous mats, especially the 15 bilayers coated mats, have considerably potential applications in the biomedical field.

Stretchable, tough, self-recoverable, and cytocompatible chitosan/cellulose nanocrystals/polyacrylamide hybrid hydrogels.

As medical practitioners' interest in hydrogels continues to grow, their new expectations in terms of mechanical properties, biocompatibility and durability are changed. Here, we demonstrated a new strategy to improve both mechanical properties and self-recovery of double network (DN) hydrogels by introducing a self-healing network, consisting of carboxymethyl chitosan (CMC) and dialdehyde cellulose nanocrystals (DACNC). Notably, the hydrogel could be repeatedly stretched to 4 times its initial length and has tensile strength of 244 kPa, and completely recovered its shape when compressed by 90% and had the compressive strength up to 8 MPa. In addition, the deformed hydrogel recovered 81.3% of its dissipated energy at room temperature without any external stimuli. The hydrogel also exhibited good biocompatibility. We have developed a new method to fabricate stretchable and tough hydrogels that could spontaneously self-repair following mechanical deformation. They are promising for controlled drug release and dye adsorption.

Preparation, characterization, and antimicrobial activity of quaternized chitosan/organic montmorillonite nanocomposites.

Quaternized chitosan/layered silicate nanocomposite was prepared by simple solution-mixing in aqueous media. Montmorillonite (MMT) modified with cetyltrimethyl ammonium bromide was used as an organically modified layered silicate. XRD and TEM analyses respectively confirmed that silicate layers of MMT were intercalated and nicely distributed in quaternized chitosan matrix in despite of the high content of MMT (25-50 wt %). The interactions between the quaternized chitosan macromolecules and MMT in aqueous media were analyzed using FTIR, XRD, and zeta-potential measurements. Antimicrobial studies showed that the nanocomposites could strongly inhibit the growth of a wide variety of microorganisms, including Gram-positive bacteria, Gram-negative bacteria, and fungi; more importantly, they exhibited good antimicrobial capacity in whichever medium, in weak acid, water, or weak base. As the amount of MMT increased, the nanocomposites had better inhibitory effect on microorganisms, especially Gram-positive bacteria. The lowest minimum inhibition concentration (MIC) value of the nanocomposites against Staphylococcus aureus and Bacillus subtilis were less than 0.00313% (w/v) under all the conditions. The adsorption action of MMT on bacteria was simply discussed via SEM images. The results revealed that the strong antimicrobial of the nanocomposites may be attributed to the fine dispersion and the interaction between quaternized chitosan and MMT.

A versatile and injectable poly(methyl methacrylate) cement functionalized with quaternized chitosan-glycerophosphate/nanosized hydroxyapatite hydrogels.

Injectable polymethylmethacrylate (PMMA) bone cement is alluring because it allows a minimally invasive surgical approach, reducing both the cost of treatment and patient discomfort. However, several documented drawbacks have necessitated the design of a more versatile version with adorable properties for future application. In this study, to amend the bulk behavior of PMMA cement, we synthesized a modified version by combining PMMA with quaternized chitosan (N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride, HTCC)-based hydrogels loaded with nanosized hydroxyapatite (Nano-HA). Then, the physicochemical properties, antimicrobial properties, remineralization capacity and mechanical performance changes under imitated physiological conditions were tested for these cements using a type K thermocouple, scanning electron microscope (SEM), microcomputed tomography (µ-CT), calcium ion test kit and mechanical compression tests. The results demonstrated that the HTCC-GP thermosensitive hydrogel generated interconnected pores, lower the Tmax value, lengthened the working time, developed appropriate mechanical properties and imparted excellent antibacterial activity to the cement. The Nano-HA particles engendered improved biomineralization ability of the cements without adversely influencing the mechanical performance. Hence, these results indicated that the injectable and multifunctional cement resulting from the p-PMMA/HTCC-GP/Nano-HA combination grips rosy prospect for future applications in bone reconstruction.

Alginate/polyethylene glycol blend fibers and their properties for drug controlled release.

Fibers of alginate and polyethylene glycol (PEG), with salicylic acid (SA) as model drug incorporated in different concentrations, were obtained by spinning their solution through a viscose-type spinneret into a coagulating bath containing aqueous CaCl(2) and ethanol. Chemical, morphological, and mechanical properties characterization were carried out, as well as the studies of the factors that influence the drug releasing from alginate/PEG fibers. These factors included the component ratio of alginate and PEG, the loaded amount of SA, the pH, and the ionic strength of the release solution and others. The best values of the tensile strength at 13.41 cN/tex and breaking elongation at 23.13% of blend fibers were obtained when the PEG content was 5 wt %; the water swelling ratio (WSR) of blend fibers increased as the composition of PEG was raised. The results of controlled release tests showed that the amount of SA released increased with an increase in the proportion of PEG present in the fiber. Moreover, the release rate of drug decreased as the amount of drug loaded in the fiber increased, but the cumulative release amount is increasing. The alginate/PEG fibers were also sensitive to pH and ionic strength. For pH 7.4 the drug release was faster compared to pH 1.0, being simultaneously accelerated by a higher ionic strength. All the results indicated that the alginate/PEG fiber was potentially useful in drug delivery systems.