Evaluation of different crosslinking methods in altering the properties of extrusion-printed chitosan-basedmulti-material hydrogel composites

Three-dimensional printing technologies exhibit tremendous potential in the advancing fields of tissue engineering and regenerative medicine due to the precise spatial control over depositing the biomaterial.Despite their widespread utilization and numerous advantages,the development of suitable novel biomaterials for extrusion-based 3D printing of scaffolds that support cell attachment,proliferation,and vascularization remains a challenge.Multi-material composite hydrogels present incredible potential in this field.Thus,in this work,a multi-material composite hydrogel with a promising formulation of chitosan/gelatin functionalized with egg white was developed,which provides good printability and shape fidelity.In addition,a series of comparative analyses of different crosslinking agents and processes based on tripolyphosphate(TPP),genipin(GP),and glutaraldehyde(GTA)were investigated and compared to select the ideal crosslinking strategy to enhance the physicochemical and biological properties of the fabricated scaffolds.All of the results indicate that the composite hydrogel and the resulting scaffolds utilizing TPP crosslinking have great potential in tissue engineering,especially for supporting neo-vessel growth into the scaffold and promoting angiogenesis within engineered tissues.

Enhanced adsorption of Methylene Blue from aqueous solution by chitosan-g-poly(acrylic acid)/vermiculite hydrogel composites

A series of chitosan-g-poly （acrylic acid）/vermiculite hydrogel composites were synthesized and used as adsorbents for the investigation of the effect of process parameters such as vermiculite content, pH of dye solution, contact time, initial concentration of dye solution, temperature, ionic strength and concentration of surfactant sodium dodecyl sulfate on the removal of Methylene Blue （MB） from aqueous solution. The results showed that the adsorption capacity for dye increased with increasing pH, contact time and initial dye concentration, but decreased with increasing temperature, ionic strength and sodium dodecyl sulfate concentration in the present of the surfactant. The adsorption kinetics of MB onto the hydrogel composite followed pseudo second-order kinetics and the adsorption equilibrium data obeyed Langmuir isotherm. By introducing 10 wt.% vermiculite into chitosan-g-poly （acrylic acid） polymeric network, the obtaining hydrogel composite showed the highest adsorption capacity for MB, and then could be regarded as a potential adsorbent for cationic dye removal in a wastewater treatment process.

Thixotropic composite hydrogels based on agarose and inorganic hybrid gellants

Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.

Engineering Smart Composite Hydrogels for Wearable Health Monitoring

Growing health awareness triggers the public's concern about health problems. People want a timely and comprehensive picture of their condition without frequent trips to the hospital for costly and cumbersome general check-ups. The wearable technique provides a continuous measurement method for health monitoring by tracking a person's physiological data and analyzing it locally or remotely.During the health monitoring process,different kinds of sensors convert physiological signals into electrical or optical signals that can be recorded and transmitted, consequently playing a crucial role in wearable techniques. Wearable application scenarios usually require sensors to possess excellent flexibility and stretchability. Thus, designing flexible and stretchable sensors with reliable performance is the key to wearable technology. Smart composite hydrogels, which have tunable electrical properties, mechanical properties, biocompatibility, and multi-stimulus sensitivity, are one of the best sensitive materials for wearable health monitoring. This review summarizes the common synthetic and performance optimization strategies of smart composite hydrogels and focuses on the current application of smart composite hydrogels in the field of wearable health monitoring.

Preparation and swelling properties of a starch-g-poly（acrylic acid）/organo-mordenite hydrogel composite

A novel hydrogel composite was prepared via inverse suspension polymerization using starch, acrylic acid and organo-mordenite micropowder with the cross- linker, N,N＇-methylenebisacrylamide and the initiator, potassium persulfate. Fourier transform infrared spectro- scopy, X-ray diffraction spectroscopy, scanning electron microscopy, and energy dispersive spectroscopy confirmed that the acrylic acid was grafted onto the backbone of the corn starch, that the organo-mordenite participated in the polymerization, and that the addition of organo-mordenite improved the surface morphology of the hydrogel composite. The swelling capacity of the hydrogel compo- site was evaluated in distilled water, and solutions with different pH values, and various salt solutions. It was found that the incorporation of 10wt-% organo-mordenite enhanced the water absorbency by 144% （from 268 to 655 g-gl） and swelling was extremely sensitive to the pH values, the concentration of the salt solution and cation type. Swelling kinetics and water diffusion mechanism of the hydrogel composite in distilled water were also discussed. Moreover, the hydrogel composite showed excellent reversibility of water absorption even after five repetitive cycles and the hydrogel composite exhibited significant environmental-responsiveness by changing the swelling medium from distilled water to 0.1 mol. L-1 NaC1 solution. In addition, the loading and release of urea by the hydrogel composite were tested and the nutrient-slow- release capability of this material was found to be suitable for many potential applications.

Scalable carbon black deposited fabric/hydrogel composites for affordable solar-driven water purification

Interfacial solar-driven evaporators have presented great potential for water purification owing to their low energy consumption and high steam generation efficiency. However, their further applications are hindered by the high costs and complicated fabrication processes. Here, a scalable bilayer interfacial evaporator was constructed via an affordable technique, in which carbon black deposited nonwoven fabric(CB@NF) was employed as the upper photothermal layer, as well as PVA/starch hybrid hydrogel for selffloating and water transport. Under simulated one sun irradiation, CB@NF layer displayed excellent photothermal conversion performance, whose temperature could increase 30.4 ℃ within 15 min. Moreover,the introduction of starch into PVA endowed the hybrid hydrogels with considerable water-absorption capability on the premise of ensuring mechanical properties. The resultant CB@NF/PVA/starch composites achieved superior interfacial adhesion performance with interfacial toughness at about 200 J m.Combining with good evaporation performance, salt-rejection property and high purification efficiency on pollutants, this evaporation system would become a promising candidate to alleviate water shortage.

Effect of Preparation Methods on Mechanical Properties of PVA/HA Composite Hydrogel

Poly(vinyl alcohol) (PVA)/hydroxyapatite (HA) composite hydrogel specimens were prepared with 15% PVA and 1%,2%, 3%, 4% and 5% HA by repeated freezing-thawing. The tests of static and dynamic mechanical properties were carried out todiscuss the influence of different contents of HA and freezing-thawing cycles on the mechanical properties of PVA/HA compositehydrogel. The results of static mechanical tests showed that the PVA/HA composite hydrogel with 3% HA and ninefreezing-thawing cycles had excellent stress relaxation properties, higher relaxation ratio, lower stress equilibrium value andpresented better properties of creep and recovery. The results of dynamic mechanical test showed that the PVA/HA compositehydrogel with nine freezing-thawing cycles had higher storage modulus and loss modulus, so was the PVA/HA compositehydrogel with 3% HA.

Research on the Long Time Swelling Properties of Poly (vinyl alcohol)/Hydroxylapatite Composite Hydrogel

Poly(vinyl alcohol)/hydroxylapatite(PVA/HA)composite hydrogel was prepared by repeated freezing and thawing.The water loss properties of the resultant hydrogel were investigated by using optical microscope.Long time immersion tests of PVA/HA composite hydrogel were carried out in the diluted calf serum solution to study the change laws of swelling properties with the freezing-thawing cycles and HA content.The micro-morphologies of PVA/HA composite hydrogel after long time immersion were observed by means of the high-accuracy 3D profiler.The results show that the swelling process of PVA/HA composite hydrogel is the converse process of its water loss.Long time swelling ratio curves of PVA/HA composite hydrogel in the calf serum solution are manifested as four stages of quick increase,decrease,slow decrease and stable balance,and its equilibrium swelling ratio decreases with the increase of freezing-thawing cycles and HA content.It is revealed that the network structure of the composite hydrogel immersed for a long period is significantly improved with the increase of HA content. Perfect network structures of PVA/HA composite hydrogel as well as full and equilibrium tissues after swelling equilibrium are obtained when the HA content is 3% and the number of freezing-thawing cycles is 7.

Alginate Composite Hydrogel Bead with Multilayer Flake Structure for Dye Adsorptions

With the rapid development of textile industry,a large amount of dye-contaminated effluents was produced and caused serious environmental problem.To remove the dye from effluents,adsorption materials have been applied because of their relatively cheap,high efficiency,and easy handling.In this study,a novel composite hydrogel bead with unique multilayer flake structure was fabricated by alginate,acrylamide and attapulgite for dye adsorption.Acrylamide was grafted polymerization onto alginate to obtain alginate-g-poly(acrylamide).Then alginate-g-poly(acrylamide)was cross-linked by Ca2+ions in present of attapulgite to form composite hydrogel bead.Scanning electron microscopy(SEM)results show that the freeze dried composite hydrogel bead has multilayer flake structure incorporating attapulgite.Fourier transform infrared spectroscopy(FTIR)and Thermo-gravimetric analysis(TGA)results indicate that acrylamide has been successfully grafted polymerization on sodium alginate.Grafting polymerization of acrylamide onto sodium alginate obviously enhances the swelling of hydrogel bead.Incorporating of attapulgite into hydrogel bead effectively enhances the adsorption capacity to methylene blue and the maximum adsorption capacity is 155.7 mg g-1.Multilayer flake structure increases the adsorption area for methylene blue,but hinders the diffusion of methylene blue into the inner of composite hydrogel bead.High pH solution is beneficial to the adsorption.Pseudo-second order model and Fraundlinch model best describe the adsorption kinetic and isotherm,respectively.These results indicate that composite hydrogel bead is a promising adsorption material for dye-contaminated water treatment.

Preparation and Properties of Nanocellulose/Sodium Alginate Composite Hydrogel

Cellulose nanofiber(CNF)was isolated from Okara using deep eutectic solvent(DES)with high-speed stirring.The composite hydrogels obtained by using different proportions of CNF and sodium alginate(SA)had different properties.The CNF/SA composite hydrogels were analyzed using Fourier transform infrared spectroscopy and scanning electron microscopy and tested for compression properties,rheological properties,water content,and swelling degree.Physical crosslinking between SA and Ca^(2+),and different degrees of hydrogen bond formation between SA and CNF were observed.The CNF/SA composite hydrogel have great potential as reinforcements in eco-friendly composite hydrogels for diverse applications.

Droplet-based bioprinting enables the fabrication of cell–hydrogel–microfibre composite tissue precursors

Composites offer the option of coupling the individual benefits of their constituents to achieve unique material properties,which can be of extra value in many tissue engineering applications.Strategies combining hydrogelswith fibre-based scaffolds can create tissue constructs with enhanced biological and structural functionality.However,developing efficient and scalable approaches to manufacture such composites is challenging.Here,we use a droplet-based bioprinting system called reactive jet impingement(ReJI)to integrate a cell-laden hydrogel with a microfibrous mesh.This system uses microvalves connected to different bioink reservoirs and directed to continuously jet bioink droplets at one another in mid-air,where the droplets react and form a hydrogel that lands on a microfibrous mesh.Cell–hydrogel–fibre composites are produced by embedding human dermal fibroblasts at two different concentrations(5×10^(6) and 30×10^(6) cells/mL)in a collagen–alginate–fibrin hydrogel matrix and bioprinted onto a fibre-based substrate.Our results show that both types of cell–hydrogel–microfibre composite maintain high cell viability and promote cell–cell and cell–biomaterial interactions.The lower fibroblast density triggers cell proliferation,whereas the higher fibroblast density facilitates faster cellular organisation and infiltration into the microfibres.Additionally,the fibrous component of the composite is characterised by high swelling properties and the quick release of calcium ions.The data indicate that the created composite constructs offer an efficient way to create highly functional tissue precursors for laminar tissue engineering,particularly for wound healing and skin tissue engineering applications.

Preparation and Properties of Guiqi Polysaccharides/Chitosan/Alginate Composite Hydrogel Microspheres

A series of the Guiqi polysaccharides/chitosan/alginate composite hydrogel microspheres(GPcM)with different particle sizes were prepared with Guiqi polysaccharides(GP),chitosan(CS)and sodium alginate(Alg).The optimum preparation process was also determined by single factor and orthogonal experiment analysis.The GPcM were characterized by fourier transform infrared spectroscopy(FT-IR),scanning electron microscope(SEM),drug loading efficiency test(LE),encapsulation efficiency test(EE)and in vitro release study.The results showed that the Guiqi polysaccharides chitosan hydrogel(GPCH)and sodium alginate hydrogel(SAH)formed a crossover system in GPcM.The GPcM have a uniform particle size ranging from 395.1μm to 841.5μm.The drug loading efficiency and encapsulation efficiency of the GPcM were 56.3%and 72.6%,respectively.The bovine serum albumin(BSA)loaded in the GPcM released slowly within 180 h.The results suggested that the GPcM may have potential application value in drug sustained and controlled release system.

Fabrication and Characterization of Chitosan Based Injectable Thermosensitive Hydrogels Containing Silica/Calcium Phosphate Nanocomposite Particles

In this study, the effect of silica/calcium phosphate (SiCaP) nanocomposite particles on the properties of a novel chitosan-based thermosensitive hydrogel system was examined. SiCaP nanocomposite powder was fabricated using a sol-gel method and then used to fabricate nanocomposite hydrogels (Ch- β/7.5SiCaP and Ch-β/15SiCaP) including chitosan and β-glycerophosphate (Ch-β) as a matrix. Results revealed that compared to the Ch-β hydrogel without SiCaP, the presence of SiCaP particles in nanocomposite hydrogels maintained pH stability during the sol-gel transition, accelerated the gelation and improved the stiffness of nanocomposite hydrogels. Gelation time at 37℃ was reduced approximately 75% and stiffness was increased approximately 115%. Both of these changes are attributed to chemical and physical interactions of the SiCaP bioactive particles with chitosan. Furthermore, compared to the Ch-β hydrogel, the presence of SiCaP in the Ch-β/7.5SiCaP nanocomposite hydrogel did not affect biocompatibility negatively, but improved osteoblastic cell differentiation. Our studies suggest that these nanocomposite hydrogels may offer an innovative approach to bone regeneration strategies.

Production of a novel non-toxicγ-PGA/casein composite hydrogel using MTG and optimization by response surface methodology

Theγ-PGA-based food hydrogel exhibits good biodegradability and biocompatibility,and is non-toxic to humans.In this study,a novel hydrogel(γ-PGA/casein composite hydrogel)was prepared by combining casein with y-PGA separated from natto using microbial transglutaminase(MTG)as the crosslinker.The effects of the MTG mass concentration,gelation time,crosslinking temperature,pH,and the mass ratio of y-PGA to casein on the crosslinking ratio of y-PGA and swelling ratio of theγ-PGA/casein hydrogel were investigated.Furthermore,the synthesis conditions were optimized by response surface methodology to optimize three important factors,i.e.crosslinking temperature,pH and the mass ratio of y-PGA to casein.The results of single factor experiments showed that the MTG mass concentration and crosslinking time had little impacts on the crosslinking ratio of y-PGA and the swelling ratio;the preferred MTG mass concentration,crosslinking time,temperature and pH were selected as 0.3%,7 h,40℃and 7.5;and the preferred mass ratio ofγ-PGA to casein was 0.1 for the crosslinking ratio ofγ-PGA and 0.2 for the swelling ratio.The response surface experiment results showed that the optimum crosslinking temperature,pH and the mass ratio of y-PGA to casein ratio were 42.4℃,7.33,and 0.18,respectively.Under these optimum conditions,the predicted crosslinking ratio of y-PGA and swelling ratio reached 90.35%and 112.07%,which were highly consistent with the experimental values(88.00%and 115.87%).Theγ-PGA/casein composite hydrogel developed in this study shows promising application potential in food industry,biomedical field,and cosmetic industry.

Nanocellulose/nitrogen and fluorine co-doped graphene composite hydrogels for high-performance supercapacitors

Three-dimensional graphene materials have been studied as typical supercapacitors electrode materials by virtue of their ultrahigh specific surface area and good ion transport capacity.However,improvement of the poor volumetric electrochemical performance of these graphene materials has been required although they have high gravimetric energy density.In this work,nanocellulose/nitrogen and fluorine co-doped graphene composite hydrogels(NC-NFGHs)were prepared through a convenient hydrothermal approach utilizing ammonium fluoride as the heteroatom source.Nanocellulose(NC)and high concentration of graphene oxide(GO)were utilized to adjust the structure of NC-NFGHs and increase their packing density.Subsequently,the aqueous symmetric supercapacitor based on NC-NFGH-80 exhibits remarkable gravimetric(286.6 F·g^(-1))and volumetric(421.3 F·cm^(-3))specific capacitance at 0.3 A·g^(-1),good rate performance,and remarkable cycle stability up to 10,000 cycles.Besides,the all-solid-state flexible symmetric supercapacitors(ASSC)fabricated by NC-NFGH-80 also delivered a large specific capacitance of 117.1 F·g^(-1)at 0.3 A·g^(-1)and long service life over 10,000 cycles at 10 A·g^(-1).This compact porous structure and heteroatom co-doped graphene material supply a favorable strategy for high-performance supercapacitors.

Synthesis and Characterization of PVA-HA-Silk Composite Hydrogel by Orthogonal Experiment

PVA-HA-Silk composite hydrogel was synthesized with polyvinyl alcohol （PVA）, nano-hydroxyapatite （HA） and natural silk by using the method of repeated freezing and thawing. A series of tests were performed to study water content, stress relaxation behavior, elastic modulus, and creep characteristics of PVA-HA-Silk composite hydrogel. Orthogonal experimental design method was used to analyze the influence degree of PVA, HA and silk （three kinds of raw materials） on mechanical properties and water content of the PVA-HA-Silk composite hydrogel to select the best material ratio according to their overall performance. The results demonstrate that the mass percentage of PVA has the greatest impact on the water content, followed by HA and silk. Compression stress-strain variation of PVA-HA-Silk composite hydrogel presents a nonlinear relationship, which proves that it is a typical viscoelastic material. Comparing the mechanical properties of 16 formulas, the formula of PVA-HA-silk composite hydrogel with mass percentage of PVA 15%, HA 2.0% and silk 1.0% is the best.

Research on the Interstitial Fluid Load Support Characteristics and Start-Up Friction Mechanisms of PVA-HA-Silk Composite Hydrogel

Hydrogel has been extensively studied as an articular cartilage repair and replacement material. PVA-HA-Silk composite hydrogel was prepared by freezing-thawing method in this paper. Mechanical properties were determined by experiments and the friction coefficient of PVA-HA-Silk composite hydrogel against steel ball was verified using micro-tribometer. Finite Element Method （FEM） was used to study the lubrication mechanism of PVA-HA-Silk composite hydrogel and the relation between the interstitial fluid load support and the start-up friction resistance. The results show that the elastic modulus and the permeability are 2.07 MPa and 10^-15m^4N^-1s^-1, respectively, and the start-up friction coefficients of PVA-HA-Silk composite hydrogel are in the range of 0.154）.2 at different contact loads, contact time and sliding speeds. The start-up friction resistance of PVA-HA-Silk composite hydrogel increases with the contact load and contact time. With the increase in sliding speed, the start-up friction resistance of PVA-HA-Silk composite hydrogel decreases. There is an inverse relation between the start-up friction resistance and the interstitial fluid load support. The change of fluid flow with the increase in sliding displacement has an important effect on the interstitial fluid load support and friction resistance. The interstitial fluid load support decreases with the increase in contact load and contact time, while the interstitial fluid load support reinforces with the increase in sliding speed. Moreover, PVA-HA-Silk composite hydrogel has mechanical properties of recovery and self-lubricating.

Three-dimensional boron nitride network/polyvinyl alcohol composite hydrogel with solid-liquid interpenetrating heat conduction network for thermal management

Polyvinyl alcohol hydrogels have been used in wearable devices due to their good flexibility and biocompatibility.However,due to the low thermal conductivity(κ)of pure hydrogel,its further application in high power devices is limited.To solve this problem,melamine sponge(MS)was used as the skeleton to wrap boron nitride nanosheets(BNNS)through repeated layering assembly,successfully preparing a three-dimensional(3D)boron nitride network(BNNS@MS),and PVA hydrogels were formed in the pores of the network.Due to the existence of the continuous phonon conduction network,the BNNS@MS/PVA exhibited an improvedκ.When the content of BNNS is about 6 wt.%,κof the hydrogel was increased to 1.12 W m^(-1)K^(-1),about two times higher than that of pure hydrogel.The solid heat conduction network and liquid convection network cooperate to achieve good thermal management ability.Combined with its high specific heat capacity,the composites have an important application prospect in the field of wearable flexible electronic thermal management.

Decoding the annulus fibrosus cell atlas by scRNA-seq to develop an inducible composite hydrogel:A novel strategy for disc reconstruction

Low back pain is one of the most serious public health problems worldwide and the major clinical manifestation of intervertebral disc degeneration(IVDD).The key pathological change during IVDD is dysfunction of the annulus fibrosus(AF).However,due to the lack of an in-depth understanding of AF biology,the methods to reconstruct the AF are very limited.In this study,the mice AF cell atlas were decoded by single-cell RNA sequencing to provide a guide for AF reconstruction.The results first identify a new population of AF cells,fibrochondrocyte-like AF cells,which synthesize both collagen Ⅰ and collagen Ⅱ and are potential functional cells for AF reconstruction.According to the dual features of the AF extracellular matrix,a composite hydrogel based on the acylation of methacrylated silk fibroin with methacrylated hyaluronic acid was produced.To obtain the ability to stimulate differentiation,the composite hydrogels were combined with a fibrochondrocyte-inducing supplement.Finally,reconstruction of the AF defects,by the novel AF stem cell-loaded composite hydrogel,could be observed,its amount of chondroid matrices recovered to 31.7% of AF aera which is significantly higher than that in other control groups.In summary,this study decodes the AF cell atlas,based on which a novel strategy for AF reconstruction is proposed.