Fabrication and characterization of wheat gliadin hydrogels with high strength and toughness

Fabricating a hydrogel with high strength and toughness is still a challenge in many fields. Here, we prepared gliadin-based hydrogels by chemical cross-linking gliadin in acetic acid solution (GS) with glutaraldehyde (GA). Subsequently, the overall properties of the fabricated hydrogels were systematically investigated in terms of their mechanical properties, swelling ratio, weight loss, thermal stability, and the chemical/physical interactions in hydrogels. Results showed that the gliadin-based chemically cross-linked hydrogels exhibited excellent mechanical properties. The optimized hydrogel exhibited the compressive stress of 1.8 MPa at a strain of 70%, and an excellent self-recovery property after 30 cycles of loading-unloading treatments. The strength and toughness of the hydrogels could be tailored by adjusting the ratio of GS/GA. The chemical cross-linking (aldehyde-ammonia reaction) was the main molecular interaction in the hydrogels, including single-/multi-site crosslinking, and the hydrogen bond was the only physical cross-linking in the hydrogels. Moreover, the swelling ratio of the fabricated hydrogels performed a concentration negative-dependency in GA or GS concentration. And a higher GS concentration (40%) with an appropriate GA content (3.0%) could resist the degradation of hydrogels. In addition, the thermodynamic properties of hydrogels also improved by the GA addition. Overall, these findings suggested that gliadin can be applied for fabricating hydrogels with tunable mechanical properties, which will unlock the high-utilization of gliadin as biopolymer and biocompatible materials.     

Mechanical properties of semi-interpenetrating polymer network hydrogels based on poly(2-hydroxyethyl methacrylate) copolymer and chitosan

Semi-interpenetrating polymeric network (semi-IPN) hydrogels based on poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)], and chitosan with different molecular weights were prepared by crosslinking with ethylene glycol dimethacrylate (EGDMA) and poly(ethylene glycol) diacrylate (PEGDA) and their gelation time, water content, mechanical properties, and morphology were investigated. In consideration of the influence of the molecular weight of chitosan, there is no big difference in the water content, while tensile properties and compressive modulus increased as the molecular weight of chitosan increased. The water content increased and tensile properties and compressive modulus decreased with increasing SMA concentration. Considering the effect of the crosslinking agent, PEGDA had higher water content and lower tensile and compressive moduli than EGDMA. It is suggested that PHEMA/chitosan and P(HEMA-co-SMA)/chitosan semi-IPN hydrogels with different structures and physical properties can be prepared depending on the molecular weight of chitosan, the copolymerization with SMA, and the crosslinking agent type.     

Thermal,swelling and stability kinetics of chitosan based semi-interpenetrating network hydrogels

The present study is focused on studying the swelling kinetics, thermal and aqueous stabilities, and determination of various forms of water in the chitosan (CS) and polyacrylonitrile (PAN) blend and semi-interpenetrating polymer network (sIPN). CS/PAN blend hydrogel films were prepared by solution casting technique. The blend film with optimum swelling properties was selected for the synthesis of sIPN. CS in the blend was crosslinked with the vapors of Glutaraldehyde (GTA) to prepare sIPN. The fabricated CS/PAN blend and sIPN hydrogels films were characterized with Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA) and field emission scanning electron microscope (FESEM). The kinetics of swelling, bound and unbound waters and aqueous stability were determined experimentally. FESEM showed good miscibility between CS and PAN, FTIR showed no chemical interaction between CS and PAN; however, it did show a doublet for the sIPN, TGA showed improved thermal stability and swelling kinetic followed second order kinetics. The degree of swelling of the sIPN hydrogels samples at room temperature varied from ~2200 % (with a fair degree of stability (~30 %)) to ~1000 % (with high degree of aqueous stability (43 %)) with increase in the crosslinking time. The calculated unbound water (W_UB) max., for the blend was 52.3 % whereas for the bound (W_B) the max., was 41.9 %. However, for sIPN hydrogel films, the W_UB water decreased (max. 21.0 %) where as the W_B increased (max. 52.0 %). The decrease in W_UB and increase in the W_B is attributed to the formation of a compact structure and increase in the contact area between the water and polymers in sIPN hydrogels due to the induction of new water contacting point in these hydrogel films, respectively.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Improvement of toughness for the hyaluronic acid and adipic acid dihydrazide hydrogel by PEG

New applications call for many new requirements. In order to improve the toughness of aldehyde hyaluronic acid (A-HA) and adipic acid dihydrazide (ADH) hydrogel, the poly(ethylene glycol) (PEG) was added. PEG content and molecular weight have little effect on the gelation time, and the composite hydrogels can form in situ within 20 seconds at room temperature. The press test showed that the hydrogels containing PEG possessed a better compression resistance, after pressed more than five times, the composite hydrogels could restore. Rheological properties were measured to evaluate the working ability and the effect of PEG on hydrogels. By analyzing the shear viscosity (η _γ=0.01), yield stress (σ ₀) and threshold shear stress (σ _c ), the addition of PEG can make the structure of composite hydrogels get loose and improve the shear resistance. Especially, PEG800 can enhance the antishear ability obviously. The amplitude sweep tests showed a broad linear viscoelastic region, indicating a wide processing range. In the meanwhile, we also found that PEG can improve the optical transmittance of xerogel evidently.     

Hydrophilic and flexible polyurethane foams using sodium alginate as polyol: Effects of PEG molecular weight and cross-linking agent content on water absorbency

Hydrophilic and flexible polyurethane foams were prepared using sodium alginate as a polyol, and characterized by optical microscopy, FT-IR spectroscopy, density measurements, volume swelling, and water absorbency. Optical microscopy revealed that the resulting cells were closed with round and elongated shapes. FT-IR confirmed that the urethane linkages were formed between the isocyanate and sodium-alginate. As an indirect measurement of porosity, the apparent density indicated an initial decrease followed by an increase with increasing glycerin content. The volume-swelling ratio was initially constant, followed by a gradual decrease with glycerin content. The volume swelling ratio increased with PEG molecular weight. The water absorbency initially increased, followed by a decrease with increasing glycerin content. The correlation-ships between water absorbency, density, and volume-swelling ratio indicated that the absorbency was predominantly influenced by density when the PEG molecular weight was low and was greatly affected by the volume-swelling ratio when the PEG molecular weight was relatively high.     

Synthesis and hydrophilicities of Poly(ethylene 2,6-naphthalate)/Poly(ethylene glycol) copolymers

Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using¹H-NMR, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.     

Silk grafting with chitosan and crosslinking agents

Chitosan grafting onto silk was tested with three crosslinking agents: trifunctional epoxy resin Araldite DY-T, PEG400 dimethacrylate, and glutaraldehyde in acetic as well as in tartaric acid solutions. Operating conditions were studied to obtain a significant silk weighting with satisfactory graft yields. With the epoxy crosslinker the weight gain was in the range from 1.8 to 8.8 % with graft yield from 8 to 23 %. In the case of PEG400DMA weight gain was 8–12 % with 22–24 % graft yield. With glutaraldehyde in tartaric acid solution a maximum weight gain of 8.4 % with 27.6 % graft yield was obtained. Results of determination of primary amino groups on the grafted silk showed that with epoxy and glutaraldehyde, unlike PEG400DMA, the amino groups of chitosan were only partially involved in crosslinking. Results of DSC analyses suggested that the modification of fibroin structure in chitosan-grafted silk was stronger with glutaraldehyde than with epoxy or dimethacrylate. FTIR-ATR spectra of grafted fibers were found very similar to that of control silk with an additional weak peak ascribable to chitosan in 1180–1080 cm⁻¹ range. Surface investigation through AFM showed clear morphology differences between chitosan-grafted silk with epoxy or dimethacrylate and that crosslinked with glutaraldehyde; the latter appears uneven and scale-like, the others slightly rougher than the original silk.     

Preparation of porous PVDF nanofiber coated with Ag NPs for photocatalysis application

The porous Polyvinylidene fluoride (PVDF) nanofibers were prepared by leaching method using polyethylene oxide (PEO) as porogen for the first time. The influences of the molecular weight (MW) and concentration of PEO, and the leaching solution on the morphology and the surface area of the porous PVDF nanofiber were systematically investigated. Polyethylene glycol 6000 (PEG6000) showed a better pore-forming effect. Optimized preparation parameters were obtained. With the ratio of PEG6000/PVDF reaching 1:1, the surface area of the resulting porous PVDF nanofiber was about three times higher than that of the pure PVDF nanofiber. Moreover, NaClO solution as leaching solution showed a very limited influence on the surface area of porous PVDF nanofiber. Afterwards, Ag NPs coated PVDF (Ag/PVDF) nanofiber was prepared by physical adsorption of Ag ions and in-situ reduction reaction using sodium borohydride as reductant. The photoactivity of Ag/PVDF nanofiber was evaluated by the photodegradation of methyl orange (MO) under visible light irradiation. Ag/PVDF nanofiber showed a better photoactivity than PVDF-Ag nanofiber prepared by the ex-situ blending method.     

Synthesis and characterization of sodium acrylate and 2-acrylamido-2-methylpropane sulphonate (AMPS) copolymer gels

A series of superabsorbents based on acrylic acid (AA), sodium acrylate, 2-acrylamido-2-methylpropane sulphonic acid, N,N′-methylene bis-acrylamide (MBA) were prepared by inverse suspension polymerization. These hydrogels were further crosslinked on the surface with polyethylene glycol-600 (PEG-600). The water absorbency or swelling behaviors for these xerogels in water and 0.9% saline solutions, both under free condition and under load were investigated. Absorption characteristics of these hydrogels were found to depend on nature and concentration of crosslinker in the system. It was also found that the saline absorption was significantly improved as the incorporation of AMPS in the polymer was increased. The surface crosslinking introduced in the polymers was found to improve the absorption under load characteristics without lowering the free water absorption capacities of the polymer to a considerable extent.     

Preparation of poly(vinyl alcohol)/silver-zeolite composite hydrogels by UV-irradiation

Poly(vinyl alcohol) (PVA)/Ag-zeolite nanocomposite hydrogels were prepared by UV irradiation using PVA solution mixed with Ag-zeolite nanoparticles. Physical properties and changes in morphology of the PVA/Ag-zeolite hydrogels were investigated. The PVA/Ag-zeolite hydrogels were prepared at a PVA concentration of 9 wt% with a UV irradiation distance of 15 cm, where gel fraction and swelling ratio were optimized. Hardness of the PVA/Ag-zeolite hydrogels decreased with increasing amounts of Ag-zeolite, reaching that of soft elastomer when the amount of Ag-zeolite was 5 % by weight. The PVA/Ag-zeolite hydrogels showed strong antimicrobial activities against Staphylococcus aureus and Klebsiella pneumoniae, inducing a reduction of bacteria of over 99.9 % at a Ag-zeolite content of 3 wt%.     

Thermal and structure properties of biobased cellulose nanowhiskers/poly (lactic acid) nanocomposites

Cellulose nanowhiskers were used to improve the performance of poly (lactic acid) (PLA). The nanocomposites mixed with three different molecular weight of poly (ethylene glycol) (PEG) were characterized by mechanical testing, thermal gravimetry and differential scanning calorimetry. The tensile test showed an increase in tensile strength and elongation at break with the addition of PEG to PLA/CNW nanocomposites, the thermal analysis results showed an increase of crystallization temperature (T _c) and crystallization compatibility (larger crystallization and melting areas), which indicated that the cellulose nanowhiskers (CNW) and PEG or CNW alone should not be considered as nucleating agents for the PLA matrix; The CNW was homo-dispersed which contributed to decreasing mobility of polymer chain segments. The compatibility between hydrophobic PLA matrix and the hydrophilic CNW was improved by the addition of different molecular weight polymeric-PEG. The thermo gravimetric analysis indicated that the thermal stability of the different composites were reflected well in the region between 25 °C and 245 oC. The structure of the PLA/CNW/PEG composites was characterized by AFM, which showed that the CNW dispersed in the PLA matrix evenly.     

Formaldehyde free cross-linking agents based on maleic anhydride copolymers

Low molecular weight copolymers of maleic anhydride and vinyl acetate were prepared to develop formaldehyde free cross-linking agents. Since lower molecular weight is favorable for efficient penetration of the finishing agent into the cotton fibers in the padding process, the concentration of the initiator, chain transfer agent and the monomer ratios were varied to obtain copolymers of low molecular weights. The prepared polymers were characterized by GPC,¹H-NMR, FTIR, DSC and TGA. Copolymers of molecular weights of 2 000 to 10 000 were obtained and it was found that the most efficient method of controlling the molecular weight was by varying the monomer ratios. Poly(maleic anhydride-co-vinyl acetate) did not dissolve in water, but the maleic anhydride residue hydrolyzed within a few minutes to form poly(maleic acid-co-vinyl acetate) and dissolved in water. However, the maleic acid units undergo dehydration to form anhydride groups on heating above 160 °C to some extent even in the absence of catalysts. The possibility of using the copolymers as durable press finishing agent for cotton fabric was investigated. Lower molecular weight poly(maleic anhydride-co-vinyl acetate) copolymers were more efficient in introducing crease resistance, which appears to be due to the more efficient penetration of the crosslinking agent into cotton fabrics. The wrinkle recovery angles of cotton fabrics treated with poly(maleic anhydride-co-vinyl acetate) copolymers were slightly lower than those treated with DMDHEU and were higher when higher curing temperatures or higher concentrations of copolymer were used, and when catalyst, NaH₂PO₂, was added. The strength retention of the poly(maleic anhydride-co-vinyl acetate) treated cotton fabrics was excellent.     

High water content silk protein-based hydrogels with tunable elasticity fabricated via a Ru(II) mediated photochemical cross-linking method

Silk is very promising in the field of biomaterials as a natural biomacromolecule. Silk protein can be made into various forms of materials, including hydrogels. However, silk protein-based hydrogels have not attracted much attention due to its weak mechanical properties. Here, we report high water content silk protein-based hydrogels with tunable elasticity which were fabricated through Ru(II) mediated photochemically cross-linking tyrosine residues in regenerated silk protein. The regenerated silk protein was characterized by Fourier transform infrared spectroscopy (FTIR). The gelation kinetics of the silk protein was studied by rheology measurements. The compressive mechanical properties of the silk protein-based hydrogels was investigated using compressive tests and dynamic mechanical analysis (DMA). Compressive modulus of the hydrogels reached 349±64 MPa at 15 % strain. The fabricated silk protein-based hydrogels were also characterized by Scanning electron microscopy (SEM), revealing an interconnected porous network structure, typical of hydrogels, with an average pore size of approximately 130 μm. Finally, biocompatibility of the silk protein-based hydrogels was demonstrated through cell culture studies using a human fibroblast cell line, HFL1. The reported silk protein-based hydrogels represent a promising candidate for biomaterial applications.     

天然橡胶贮存过程中分子交联网络分析

天然橡胶(NR)在贮存过程中发生轻微的分子交联,塑性初值、门尼粘度和凝胶含量增加,致使其加工性能降低,后续加工能耗增加。采用高速冷冻离心、蛋白酶及脂肪酶处理天然胶乳制备离心天然橡胶(CNR)、脱蛋白天然橡胶(DPNR)、脱脂肪-脱蛋白天然橡胶(P-DPNR),并分析其贮存过程中的交联密度、交联点数量、凝胶含量、分子量和塑性初值(P0)的变化。结果表明:在贮存过程中,随贮存时间的延长,NR、CNR、DPNR的交联密度、交联点数量、凝胶含量、分子量和塑性初值(P0)均呈现显著的增大趋势。而P-DPNR的交联密度、交联点数量、凝胶含量、分子量和塑性初值(P0)在加速贮存0~12 h时,略有增加,加速贮存12~48 h时,变化比较平缓。红外谱图分析表明NR、CNR、DPNR的1 740 cm-1长链脂肪酸特征峰随贮存时间的延长而略微减小,P-DPNR的长链脂肪酸特征峰减弱。综合分析表明天然橡胶贮存过程中,醛基和环氧基等官能基团、表面蛋白、结合蛋白及脂质均影响分子交联网络的形成,其中脂质对交联网络的形成影响较大。     

Study on oil adsorption/desorption kinetics and polymer network parameters of poly(lauryl methacrylate-<Emphasis Type="Italic">co</Emphasis>-hydroxyethyl methacrylate)

In the present work, oil adsorption, desorption, and resorption of poly(lauryl methacrylate-co-hydroxyethyl methacrylate) P(LMA-co-HEMA) were evaluated with different oils by a gravimetric method. Adsorption kinetics were modeled using pseudo-first-order and pseudo-second-order equations. Polymer network parameters of P(LMA-co-HEMA) regarding average molecular weight (Mc) between two crosslink piontss can be calculated by oil absorbency at equilibrium (Q _e ), the solubility parameter (δ) and polymer-solvent interaction parameter (χ) with Flory-Huggins relation. The results showed pseudo-second-order model has a better fit to the oil adsorption kinetic data The desorption can be analyzed by fitting a prediction of exponential-like decay to the deswelling curves. A typical oil desorption exhibited two stages: a burst release driven by concentration gradient, and a slow release controlled by diffusion and the elastic recovery of polymer networks. For reusability, the resorption behavior of P(LMA-co-HEMA) was also investigated. It was worth noting that oil resorption was faster than the first adsorption due to potential passages. Moreover, the adsorption capacity was not significantly changed after regeneration.     

Electrospun curcumin loaded poly(lactic acid) nanofiber mat on the flexible crosslinked PVA/PEG membrane film: Characterization and <Emphasis Type="Italic">in vitro</Emphasis> release kinetic study

Herein, a biodegradable and biocompatible composite comprising of support membrane based on crosslinked PVA/PEG film and curcumin loaded electrospun poly(lactic acid) (PLA) nanofiber mat is introduced. The membrane film was prepared from PVA/PEG blend followed by crosslinking with an optimum amount of citric acid, 15 wt.%. After then, PLA solutions with different curcumin content, 0-11 wt.%, were electrospinned on the prepared membrane substrate. The prepared film showed high water absorption, water vapor transmission rate and superior mechanical properties with improved elastic modulus, tensile strength and with an elongation of around 320 % with respect to the non-crosslinked one. Also, the scanning electron microscopy was revealed uniformly dispersed pores throughout the membrane film with a nearly narrow in size distribution centered at 36 μm. As well, a nanostructure porous morphology was found for the electrospun fibrous curcumin loaded PLA from the scanning electron microscopy micrographs and the average fiber diameter was decreased with curcumin content. In vitro drug release from the prepared flexible composite into the vertical diffusion cell was recorded by the measuring curcuminoids content using high performance liquid chromatography and drug release kinetic evaluations were revealed that the release pattern of all prepared samples, containing different content of curcumin, well fitted to the Higuchi’s model signifying diffusion-controlled release mechanism. As well, the determined release rate at the second release stages, i.e. steady state flux (J), was varied from 0.31 to 43.53 μg·cm^-2·h^-1 with increasing drug content from 1 to 11 wt.%. Regarding this results, this flexible composite by providing the moist environment along with miraculous healing properties of curcumin, can be potential candidate for transdermal drug delivery.     

Mechanical,Thermal, and Swelling Properties of Cross-linked Hydrogels Based on Oxidized Cellulose Nanowhiskers and Chitosan/poly(vinyl alcohol) Blends

Cross-linked hydrogels of chitosan/poly(vinyl alcohol) (PVA)/oxidized cellulose nanowhiskers (CNWs) were prepared by using oxidized CNWs as a cross-linker. The effects of the oxidation level of CNWs on the swelling behavior, thermal stability, viscoelastic properties and compressive strength of the hydrogels were studied. Chemical cross-links, hydrogen bonds, as well as nanofiller reinforcement between the three materials played a major role in determining the properties of the hydrogels. Swelling test results showed that the incorporation of oxidized CNWs decreased the water absorbability of the hydrogels due to the increase in cross-linking degree. Viscoelastic properties of the hydrogels with oxidized CNWs was increased by 537 % in storage modulus, from 4.65 kPa to 29.6 kPa. Compressive strength of 181.5 kPa at 50 % strain was observed from the cross-linked hydrogels, compared with 21.2 kPa of the non-cross-linked hydrogels. The thermal experiments showed that the chemical cross-linking slightly increase the resistance toward thermal degradation of the hydrogels.     

Effect of aldehydes crosslinkers on properties of bacterial cellulose-poly(vinyl alcohol) (BC/PVA) nanocomposite hydrogels

The effects of the aldehydes crosslinkers on properties of the BC/PVA nanocomposite hydrogels were investigated. BC as the reinforcement and PVA as the matrix materials of the BC/PVA nanocomposite hydrogels, the hydrogels were prepared in coagulating bath of sodium sulfate and cross-linked with kinds of aldehydes. The hydrogels were characterized by Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), Equilibrium swelling ratio (ESR) tests, mechanical properties tests, thermo-gravimetric analysis (TGA) and X-ray diffraction (XRD) analysis. It was found that the dialdehyde (glyoxal, glutaraldehyde) crosslinkers were more efficient than monoaldehyde (formaldehyde, acetaldehyde) crosslinkers. The ESR, mechanical properties of the BC/PVA nanocomposite hydrogels were obviously influenced by aldehydes crosslinkers. However, their thermo stability and crystallinity were scarcely influenced. The nanocomposite hydrogels described in this study provides information for further development and optimization of a variety of nanofiber-polymer matrix composite hydrogels.     

Laccase-mediated enhancement of the properties of regenerated fibers from wheat gliadin

In this study, laccase-mediated crosslinking was used to develop regenerated protein fibers from wheat gliadin with good mechanical properties and water stability. The oxygen consumption during laccase catalyzed oxidation of gliadin, molecular weight of gliadin, mechanical properties, water stability, thermal properties and morphology of gliadin fibers were tested to prove the effect of laccase as the crosslinker of gliadin. The rapid decrease of dissolved oxygen in gliadin solution indicated laccase was active in oxidizing gliadin. The results of SDS-PAGE and SEC demonstrated that laccase-mediated crosslinking reaction effectively occurred. The mechanical properties and water stability of the gliadin fibers with laccase treatment significantly were improved. The fibers from gliadin with laccase treatment exhibited a much smoother and more uniform surface was observed by SEM for the laccase-mediated modified gliadin fibers.