A dynamic and self-crosslinked polysaccharide hydrogel with autonomous self-healing ability.

Natural polymeric hydrogels with self-healing capability that can recover the functionalities and structures of gels after damage are extremely attractive due to their emerging applications in the biomedical field. Here we report a self-healable polymeric hydrogel by self-crosslinking two natural polymers acrylamide-modified chitin (AMC) containing amino groups and oxidized alginate containing dialdehyde groups. The generation of the self-crosslinked hydrogel relies on the dynamic covalent linkage through Schiff base between the polysaccharide chains. The self-healing capability of the crosslinked hydrogel depends on the molar ratio of AMC and oxidized alginate and the surrounding pH. Under certain circumstances, the damaged hydrogel shows a complete recovery and can be stretched to a favorable extent, which is seldom observed for polysaccharide self-healing hydrogel. Notably, we find that the self-healing ability can be "stored" by freeze-drying and "activated" by rehydration. In addition, we demonstrate that the hydrogel can be used as a soft template to guide the repair of inorganic materials like hydroxyapatite. We anticipate that this self-healable hydrogel consisting of biocompatible and biodegradable polysaccharides can be applied to various biomedical fields.

Coding for hydrogel organization through signal guided self-assembly.

Complex structured soft matter may have important applications in the field of tissue engineering and biomedicine. However, the discovery of facile methods to exquisitely manipulate the structure of soft matter remains a challenge. In this report, a multilayer hydrogel is fabricated from the stimuli-responsive aminopolysaccharide chitosan by using spatially localized and temporally controlled sequences of electrical signals. By programming the imposed cathodic input signals, chitosan hydrogels with varying layer number and thickness can be fabricated. The inputs of electrical signals induce the formation of hydrogel layers while short interruptions create interfaces between each layer. The thickness of each layer is controlled by the charge transfer (Q = ∫idt) during the individual deposition step and the number of multilayers is controlled by the number of interruptions. Scanning electron micrographs (SEMs) reveal organized fibrous structures within each layer that are demarcated by compact orthogonal interlayer structures. This work demonstrates for the first time that an imposed sequence of electrical inputs can trigger the self-assembly of multilayered hydrogels and thus suggests the broader potential for creating an electrical "code" to generate complex structures in soft matter.

Chitosan-based hollow nanofiber membranes with polyvinylpyrrolidone and polyvinyl alcohol for efficient removal and filtration of organic dyes and heavy metals.

Due to their large specific surface area and numerous diffusion channels, hollow fibers are widely used in wastewater treatment. In this study, we successfully synthesized a chitosan (CS)/polyvinylpyrrolidone (PVP)/polyvinyl alcohol (PVA) hollow nanofiber membrane (CS/PVP/PVA-HNM) via coaxial electrospinning. This membrane demonstrated remarkable permeability and adsorption separation. Specifically, the CS/PVP/PVA-HNM had a pure water permeability of 4367.02 L·m-2·h-1·bar-1. The hollow electrospun nanofibrous membrane exhibited a continuous interlaced nanofibrous framework structure with the extraordinary advantages of high porosity and high permeability. The rejection ratios of CS/PVP/PVA-HNM for Cu2+, Ni2+, Cd2+, Pb2+, malachite green (MG), methylene blue (MB) and crystal violet (CV) were 96.91 %, 95.29 %, 87.50 %, 85.13 %, 88.21 %, 83.91 % and 71.99 %, and the maximum adsorption capacities were 106.72, 97.46, 88.10, 87.81, 53.45, 41.43, and 30.97 mg·g-1, respectively. This work demonstrates a strategy for the synthesis of hollow nanofibers, which provides a novel concept for the design and fabrication of highly efficient adsorption and separation membranes.

Thermal-controlled active sensor module using enzyme-regulated UiO-66-NH2/MnO2 fluorescence probe for total organophosphorus pesticide determination.

An enzyme-regulated UiO-66-NH2/MnO2 fluorescence sensor, fully functionalized with spectrometric capacities, is developed for budget-friendly total organophosphorus pesticides (OPs) determination. The fluorescence probe, UiO-66-NH2/MnO2, is hydrothermally synthesized and morphologically examined. A specialized enzyme-catalyzed reaction, which can be gradually inhibited by OPs, is designed with participations of alkaline phosphatase (ALP) and sodium L-ascorbyl-2-phosphate (AAP). The reaction product of ascorbic acid (AA) decomposes MnO2 and restores UiO-66-NH2 fluorescence, establishing a relationship between OPs level and fluorescence intensity. Interactions among UiO-66-NH2, MnO2, OPs, and AA are clarified. Stepwise optimizations are performed to the UiO-66-NH2/MnO2 probe, ensuring considerable advantages as OPs affinity and fluorescence quenching behavior over rival nanomaterials. Analytical advances are magnified by fabricating an active sensor module, with self-acting thermal regulation for optimal enzyme activity. Under 4 and 20 °C environment, regulation period is less than 40 and 100 s. In total OPs determination for laboratorial and real-vegetable samples, this method exhibits uniform and log-linear responses to common species of OPs in a range as 1.0 × 10-7~10 mg L-1, and limit of detection is established as 8.9 × 10-8 mg L-1. Proposed readouts are validated with certified HPLC and recovery test. Relative errors and recovery rates are found as 2.7-6.4% and 95.8-102.6%, respectively.

Freezing characteristics and relative permittivity of rice flour gel in pulsed electric field assisted freezing.

This study investigated the effect of pulsed electric field assisted freezing treatment on the freezing characteristics of rice flour gel under output voltages varying from 0 to 25 kV. The results indicated that by applying a pulsed electric field, the phase change time decreased. Scanning electron microscopy images indicated that pulsed electric field treatment led to the formation of rounder and smaller ice crystals. For further understanding and quantifying the interaction between rice flour gel and a pulsed electric field, the relative permittivity of rice flour gel with and without the addition of salt was measured between 100 and 3100 kHz and -20 and 20 °C. Relative permittivity increased with decreasing frequency or increasing temperature, and sharp variation was observed during the phase transition period. In addition, salt was proved to be an effective additive for increasing relative permittivity.

Improvements in chitosan-based slurry ice production and its application in precooling and storage of Pampus argenteus.

The effects of microbubbles in chitosan-based slurry ice production were investigated, and the efficiency of chitosan-based slurry ice was evaluated for silver pomfret (Pampus argenteus) precooling and storage at 0 °C. Microbubbles generated though agitation accelerated slurry ice production by promoting ice nucleation and eliminating supercooling. Higher bubble counts improved freezing, but overly large bubbles reduced the performance. The rheological properties of chitosan solutions were also investigaed, and solutions with higher viscosity formed more bubbles. Experiments investigating precooling rates, microbial concentrations, pH, thiobarbituric-acid-reactive substances, and total volatile basic nitrogen all confirmed that chitosan-based slurry ice had higher performance than flake ice or conventional slurry ice. Chitosan-based slurry ice can be used for precooling in the fish industry to reduce energy consumption, accelerate precooling, reduce microbial growth, and improve shelf life.

Recent advances in chitosan-based layer-by-layer biomaterials and their biomedical applications.

In recent years, chitosan-based biomaterials have been continually and extensively researched by using layer-by-layer (LBL) assembly, due to their potentials in biomedicine. Various chitosan-based LBL materials have been newly developed and applied in different areas along with the development of technologies. This work reviews the recent advances of chitosan-based biomaterials produced by LBL assembly. Driving forces of LBL, for example electrostatic interactions, hydrogen bond as well as Schiff base linkage have been discussed. Various forms of chitosan-based LBL materials such as films/coatings, capsules and fibers have been reviewed. The applications of these biomaterials in the field of antimicrobial applications, drug delivery, wound dressings and tissue engineering have been comprehensively reviewed.

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.

Electrodeposition of Polysaccharide and Protein Hydrogels for Biomedical Applications.

In the last few decades, polysaccharide and protein hydrogels have attracted significant attentions and been applied in various engineering fields. Polysaccharide and protein hydrogels with appealing physical and biological features have been produced to meet different biomedical applications for their excellent properties related to biodegradability, biocompatibility, nontoxicity, and stimuli responsiveness. Numerous methods, such as chemical crosslinking, photo crosslinking, graft polymerization, hydrophobic interaction, polyelectrolyte complexation and electrodeposition have been employed to prepare polysaccharide and protein hydrogels. Electrodeposition is a facile way to produce different polysaccharide and protein hydrogels with the advantages of temporal and spatial controllability. This paper reviews the recent progress in the electrodeposition of different polysaccharide and protein hydrogels. The strategies of pH induced assembly, Ca2+ crosslinking, metal ions induced assembly, oxidation induced assembly derived from electrochemical methods were discussed. Pure, binary blend and ternary blend polysaccharide and protein hydrogels with multiple functionalities prepared by electrodeposition were summarized. In addition, we have reviewed the applications of these hydrogels in drug delivery, tissue engineering and wound dressing.

Effect of Sodium Trimetaphosphate on Chitosan-Methylcellulose Composite Films: Physicochemical Properties and Food Packaging Application.

Environmentally friendly food packaging currently attracts much interest. Sodium trimetaphosphate (STMP) finds specialized applications in food, but it is rarely used as a crosslinking agent. In this study, STMP was used as a crosslinking agent to prepare chitosan/methylcellulose composite films. Both antibacterial and physicochemical properties of the composite film were improved by crosslinking with STMP. The crosslinked films, with good antibacterial activity (~99%), had increased tensile strength, a higher elongation at break, a lower swelling ratio and solubility, and a lower enzymatic degradation than the non-crosslinked films. Furthermore, the crosslinked films showed an excellent preservative effect on fresh-cut wax gourd after three days at room temperature. The obtained films crosslinked by STMP can be potentially applied to the food industry, such as food functional packaging, providing a novel alternative to traditional plastic packages.

Emerging Chitosan-Based Films for Food Packaging Applications.

Recent years have witnessed great developments in biobased polymer packaging films for the serious environmental problems caused by the petroleum-based nonbiodegradable packaging materials. Chitosan is one of the most abundant biopolymers after cellulose. Chitosan-based materials have been widely applied in various fields for their biological and physical properties of biocompatibility, biodegradability, antimicrobial ability, and easy film forming ability. Different chitosan-based films have been fabricated and applied in the field of food packaging. Most of the review papers related to chitosan-based films are focusing on antibacterial food packaging films. Along with the advances in the nanotechnology and polymer science, numerous strategies, for instance direct casting, coating, dipping, layer-by-layer assembly, and extrusion, have been employed to prepare chitosan-based films with multiple functionalities. The emerging food packaging applications of chitosan-based films as antibacterial films, barrier films, and sensing films have achieved great developments. This article comprehensively reviews recent advances in the preparation and application of engineered chitosan-based films in food packaging fields.

Electrochemical writing on edible polysaccharide films for intelligent food packaging.

Polysaccharide films used as intelligent food packaging possess the advantages of renewability, safety and biodegradability. Printing on the polysaccharidic food packaging is challenging due to the high demand for edible-ink and the need for a suitable printing technique. In this work, we propose an electrochemical method for writing on polysaccharide film. Unlike conventional printing, this electrochemical writing process relies on the pH responsive color change of anthocyanin embedded in the chitosan/agarose hydrogel. By biasing a negative potential to a stainless wire (used as a pen) contacting the surface of the chitosan/agarose/ATH hydrogel, the locally generated pH change induced the color change of ATH and wrote programmed information on the hydrogel. We demonstrate the writing can be temporary in the hydrogel but stable when the hydrogel is dried. We further demonstrate that the written film is applicable for the detection of the spoilage of crucian fish. The reported electrochemical writing process provides a novel method for printing information on polysaccharide film and great potential for intelligent food packaging.

VO2(B)/Graphene Composite-Based Symmetrical Supercapacitor Electrode via Screen Printing for Intelligent Packaging.

More multipurpose and convenient demand driven by Radio Frequency Identification (RFID) and intelligent packaging require flexible power sources. A VO2(B)/graphene (VO2(B)/GN) core-shell composite was successfully synthesized by the hydrothermal treatment with V2O5 and graphite. The as-obtained sample was characterized by XRD, FT-IR, SEM, TEM, and XPS measurements. In addition, the electrochemical properties of VO2(B)/GN were tested. Due to its great electrochemical performance and mechanical properties, graphene could increase the electrochemical performance and strengthen the structural stability of the material at the same time. With increasing loading amount of GN, the specific capacitance of VO2(B)/GN increased correspondingly. With 20% GN loading, the initial discharge specific capacity could reach 197 F g-1 at 0.5 A g-1, and 160 F g-1 at 1 A g-1 in 0.5 M Na2SO4 electrolyte, which is better than that of pure rod-like VO2(B). The capacitance of the VO2(B)/GN (20%) composite electrode retains 95.49% after 1000 cycles, which is higher than that of a pure VO2(B) electrode (85.43%), indicating that the VO2(B)/GN composite possesses better cycling stability. Moreover, a symmetrical solid-state supercapacitor (SCs) using VO2(B)/GN(20%) as the anode was assembled. Four printed SCs were connected in series to light up a 1.5 V red LED. This demonstrates its potential application in intelligent packaging to trace food safety.

A facile synthesis of 1,3,6,8-pyrenesulfonic acid tetrasodium salt as a hydrosoluble fluorescent ink for anti-counterfeiting applications.

In this work, 1,3,6,8-pyrenesulfonic acid sodium salt (PTSA) was successfully synthesized via a one-step sulfonating reaction. This method is more convenient, effective and eco-friendly than the traditional one. The as-prepared PTSA exhibits pure blue fluorescence under UV light. Due to its excellent fluorescent properties and water solubility, PTSA was used to prepare water-soluble invisible inks based on hydroxyethyl cellulose (HEC) aqueous solution. Notably, the resulting inks possessed acceptable stability after being stored for 30 days. Besides, the red/green/blue fluorescent inks were obtained by adding extra pigments, all of which exhibited excellent rheology and thixotropy properties. Subsequently, various patterns, including a QR code, the logo of Wuhan University, Chinese characters and so on, were printed on non-background paper through ink-jet and screen printing, and the as-prepared materials exhibited good water solubility and outstanding fluorescence performances, indicating that the fluorescent PTSA material is a promising candidate for anti-counterfeiting applications.

Recent advances in engineered chitosan-based nanogels for biomedical applications.

In the last few decades, chitosan-based nanostructured materials have attracted significant attention and have been applied in different biomedical fields. Chitosan-based nanogels with appealing physical and biological characteristics have been developed for various biomedical applications due to their excellent properties related to biocompatibility, biodegradability, antibacterial activity, low immunogenicity, large surface area, and stimuli responsiveness. Numerous approaches, such as physical gelation, self-assembly, polymerization, ionic gelation and microemulsion, have been employed to fabricate chitosan-based nanogels with multiple functionalities. These nanogels are promising as effective vehicles for drug delivery, cell culture, bioimaging and therapy. This paper reviews recent progress in the preparation and application of engineered chitosan-based nanogels in biomedical fields.

Facile synthesis of optical microcavities by a rationally designed anodization approach: tailoring photonic signals by nanopore structure.

Structural engineering of porous anodic aluminum oxide (AAO) nanostructures by anodization has been extensively studied in the past two decades. However, the transition of this technique into the fabrication of AAO-based one-dimensional photonic crystal is still challenging. Herein, we report for the first time on the fabrication of AAO optical microcavities by a rationally designed anodization approach. In our study, two feasible methods are used to fabricate microcavities with tunable resonance peak across the visible and near-infrared spectra. Distributed Bragg reflector (DBR) nanostructures are first fabricated by pulse anodization approach, in which the anodization voltage was periodically manipulated to achieve pseudosinusoidal modulation of the effective refractive index gradient along the depth of the AAO nanostructures. Microcavities were created by creating a nanoporous layer of constant porosity between two AAO-DBR nanostructures, and by introducing a shift of the phase of the porosity gradient along the depth of AAO. The position of the resonance peak in these microcavities can be linearly tuned by means of the duration of the high voltage anodization. These optical nanostructures are sensitive to alterations of the effective media inside the nanopores. The AAO microcavity shows a central wavelength shift of 2.58 ± 0.37 nm when exposed to water vapor. Our research highlights the feasibility of anodization technique to fabricate AAO-based photonic nanostructures for advanced sensing applications.

Emerging chitin and chitosan nanofibrous materials for biomedical applications.

Over the past several decades, we have witnessed significant progress in chitosan and chitin based nanostructured materials. The nanofibers from chitin and chitosan with appealing physical and biological features have attracted intense attention due to their excellent biological properties related to biodegradability, biocompatibility, antibacterial activity, low immunogenicity and wound healing capacity. Various methods, such as electrospinning, self-assembly, phase separation, mechanical treatment, printing, ultrasonication and chemical treatment were employed to prepare chitin and chitosan nanofibers. These nanofibrous materials have tremendous potential to be used as drug delivery systems, tissue engineering scaffolds, wound dressing materials, antimicrobial agents, and biosensors. This review article discusses the most recent progress in the preparation and application of chitin and chitosan based nanofibrous materials in biomedical fields.

Tunable thermosensitive behavior of multiple responsive chitin.

Chitin can be dissolved and homogeneously functionalized in NaOH/urea aqueous solvent. Previously, we reported that chitin modified with acrylamide (AMC) possesses high water solubility and can undergo a sol-gel transition responding to pH and cationic ions. In this report, we further explored the thermosensitive behavior of this multiple responsive chitin. We showed that the sol-gel transition temperature of AMC can be facilely adjusted by the degree of substitution (DS), pH, polymer concentration and the presence of anions or cations. Importantly, AMC can form a hydrogel at 37 °C and return to solution at 4 °C by adjusting experimental parameters. We anticipate this multiple responsive chitin may have potential applications in injectable materials and smart drug delivery.

Chitin-based fast responsive pH sensitive microspheres for controlled drug release.

Ionically crosslinked chitin microspheres were prepared by using electrostatic droplet method and the drug release from the microspheres was controlled by adjusting external pH. Specifically, chitin was dissolved in NaOH/urea solution at low temperature and functionalized with acrylamide moieties. Acrylamide-modified chitin microspheres with a diameter of 400-500 µm can be obtained at the voltage of 6 kV and the pump speed of 5 mL h(-1). The formed microspheres were ionically crosslinked with Fe(3+) and then complexed with polycationic polysaccharide chitosan. The structure of the microspheres was characterized by FT IR, SEM, and EDS analyses. Besides, the drug release behavior of the microspheres exhibited a fast responsive and pH sensitive release of vancomycin. It took 30 h for complete release of vancomycin in pH 4.0 buffer and pH 1.2 HCl solution while a fast release (10 min) occurred in pH 7.4 buffer. The results showed that the microspheres could be used in drug delivery.

Controllable antioxidative xylan-chitosan Maillard reaction products used for lipid food storage.

Controllable antioxidative xylan-chitosan Maillard reaction products (MRPs) were prepared by co-heating xylan and chitosan at different time periods and used for lipid food storage in lecithin model system and refrigerated pork meat. The results of antioxidant protective effect on lecithin liposome peroxidation induced by 2,2'-azobis(2-methylpropionamidine) dihydrochloride revealed that the MRPs heated for 120 min and 180 min showed much higher inhibitory activity than chitosan or MRP heated for 60 min. In the experiment of fresh pork protection, the MRPs heated for 60 and 120 min retarded the growth of spoilage organisms more effectively. Lipid oxidation potential of the meat, determined by thiobarbituric acid reactive substances, also showed that the samples treated by the MRPs heated for 60 and 120 min had higher acceptance than others. These results demonstrate that the MRPs of xylan and chitosan are promising controllable antioxidative preservatives for lipid food formulations, and the antioxidant behavior depends not only on the antioxidant substances, but also on the interaction of the food systems.