Synthesis and characterization of poly(N-tert-butylacrylamide-<Emphasis Type="Italic">co</Emphasis>-acrylamide) hydrogel with enhanced responsive properties

To synthesize a series of novel temperature sensitive hydrogels, N-tert-butylacrylamide (NtBA) and acrylamide (AAm) were used as the comonomers and polymerized by free-radical crosslinking copolymerizarion. The poly(ethylene glycol) (PEG) with molecular weight of 400, 4000 and 6000 g·mol^-1 was used as the porogen. The equilibrium swelling capacity, swelling/deswelling kinetics and diffusion parameters of obtained hydrogels were systematically evaluated. As revealed by SEM micrographs, the macroporous structure of hydrogels can be modulated by the crosslinking level, PEG molecular weight and dosage. FTIR analysis demonstrated that the porogen PEG was completely leached out of the gel matrix. Compared with the conventional hydrogels, the PEG-modified (PGel) hydrogels exhibited enhanced temperature sensitivity and superior kinetics during the swelling, deswelling and pulsatile swelling processes. Controlled release of salicylic acid also demonstrated the good usability of PGel hydrogel, which rendered it great potential for controlled drug delivery systems.     

Synthesis and physical properties of pH-sensitive semi-IPN hydrogels based on poly(dimethylaminoethyl methacrylate-co-PEG dimethacrylate) and poly(acrylic acid)

Hydrogels of semi-interpenetrating polymer networks (semi-IPNs) were prepared by two step reactions. Dimethylaminoethyl methacrylate (DMAM) and poly(ethylene glycol)-dimethacrylate (PEGDM) were copolymerized to yield hydrogels, and then acrylic acid (AA) monomer were adsorbed in the hydrogels followed by polymerization of AA to produce semi-IPNs. The swelling behavior of semi-IPNs depends largely on pH of medium, showing that the degree of swelling of the semi-IPNs exhibits a minimum at pH 6.0. It is observed that the elastic modulus of semi-IPNs is closely related to its swelling behavior.     

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.     

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.     

Preparation of Photocrosslinked Fish Elastin Polypeptide/Microfibrillated Cellulose Composite Gels with Elastic Properties for Biomaterial Applications

Photocrosslinked hydrogels reinforced by microfibrillated cellulose (MFC) were prepared from a methacrylate-functionalized fish elastin polypeptide and MFC dispersed in dimethylsulfoxide (DMSO). First, a water-soluble elastin peptide with a molecular weight of ca. 500 g/mol from the fish bulbus arteriosus was polymerized by N,N′-dicyclohexylcarbodiimide (DCC), a condensation reagent, and then modified with 2-isocyanatoethyl methacrylate (MOI) to yield a photocrosslinkable fish elastin polypeptide. The product was dissolved in DMSO and irradiated with UV light in the presence of a radical photoinitiator. We obtained hydrogels successfully by substitution of DMSO with water. The composite gel with MFC was prepared by UV irradiation of the photocrosslinkable elastin polypeptide mixed with dispersed MFC in DMSO, followed by substitution of DMSO with water. The tensile test of the composite gels revealed that the addition of MFC improved the tensile properties, and the shape of the stress–strain curve of the composite gel became more similar to the typical shape of an elastic material with an increase of MFC content. The rheology measurement showed that the elastic modulus of the composite gel increased with an increase of MFC content. The cell proliferation test on the composite gel showed no toxicity.     

Preparation and characterization of poly(2-hydroxyethyl methacrylate) grafted bacterial cellulose using atom transfer radical polymerization

The purpose of this study is to synthesize grafted Bacterial Cellulose (BC) nanofibers using Atom Transfer Radical Polymerization (ATRP) reinforced into poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel matrix. Nanofibers grafting polymerizations were conducted in the presence of the catalyst CuCl/CuBr and the initiator 2-bromoisobutyrylbromide (2-BiBr). Degrees of substitution (DS) of BC-macroinitiators were quantified using both elemental analysis and gravimetric method. FTIR results confirmed BC nanofibers’ surface modifications of both initiator and hydroxyethyl methacrylate (HEMA) grafts. X-ray spectroscopy further confirmed the increase in carbonyl content after PHEMA-grafting polymerization. Results of the gravimetric analysis showed an increase in the weight of the grafted BC upon increasing reaction time. Furthermore, the change in the swelling ratio percentages of the reinforced composites product (BC-MI-3-g-PHEMA-1.5) was considerably higher based on reaction time. Slight increase in the swelling ratio of BC-MI-3 nanofibers was observed after 48 hours to reach 31 %. Moreover, results of thermal gravimetric analysis (TGA) demonstrated that decomposition temperature at 50 % weight loss (T₅₀) decreased to 350 °C for BC-MI-3-g-PHEMA-1.5. These characteristics demonstrate potentials for applications in the biomedical fields including drug delivery and wound care.     

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.     

Surface modification of microporous polypropylene membrane by UV-initiated grafting with poly(ethylene glycol) diacrylate

Poly(ethylene glycol) diacrylate (PEGDA) was grafted, through UV-initiated grafting, onto a microporous polypropylene (PP) membrane in order to develop a moisture-sensitive porous structure. Based on the concentration of the PEGDA grafting solution, as well as other variables, the pores of the membrane were filled to varying degrees with cross-linked PEGDA hydrogel, decreasing the pore sizes. This decrease in pore size was highly dependent on the grafting degree (weight add-on of the grafted polymer) that was dependent upon grafting conditions. Grafting with PEGDA resulted in a microporous polypropylene membrane with increased hydrophilicity and moisture-responsive pores. The functional membrane can be used in biological protective materials to limit the transport of liquid-borne pathogens while maintaining moisture transport properties.     

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.     

Improvement in mechanical properties of aluminum polypropylene composite fiber

Aluminum particles (Al) were added to polypropylene (PP) in the presence of poly ethylene glycol (PEG) and polypropylene-graft-maleic anhydride to produce composites. The composites were then melt-spun into a mono filament and tested for tensile properties, diameter evenness and morphology. Melt rheological properties of Al/PP composites were studied in linear viscoelastic response regions. It was observed that level of dispersion of aluminum particles within a polypropylene composite fiber could be improved by incorporating polyethylene glycol. The improvement of dispersion led to an improvement in the fibers mechanical properties through a reduction of the coefficient of variation of fiber diameter.     

Characterization of the polyurethane foam using alginic acid as a polyol

In this study, polyurethane foams (PUF) were prepared using alginic acid, glycerin, and poly(ethylene glycol) (PEG) as polyols, 1,6-hexamethylene diisocyanate (HDI) as a diisocyanate, and water as a foaming agent by one-shot process. Their structura, mechanical, and water-absorbing properties were investigated. The amount of alginic acid was varied up to 30 wt%. Fourier transform infrared (FT-IR) analysis showed that urethane linkage was formed by the reactions between −NCO groups of diisocyanate and −OH groups of all polyols used. Also urea linkage was formed by the reactions between −NCO groups of HDI and water or −COO⁻ groups of alginic acid. The reaction times for cream forming increased with increasing alginic acid but foam structures were not formed when alginic acid content in polyols was above 30 wt%. The optical micrographs showed that the average cell size of PUF slightly increased with increasing alginic acid. However, the density of PUF decreased with alginic acid content. The compressive modulus of PUF decreased with increasing alginic acid content. In the mean time, the water absorbency of PUF increased with increasing alginic acid content.     

锰离子对天然橡胶老化性能的影响

研究锰离子含量对天然橡胶(NR)热氧老化、紫外老化和臭氧老化前后性能的影响,并采用核磁交联密度分析仪、DSC分析仪和傅里叶红外分析仪探究老化前后分子链结构的变化。结果表明,在老化之前,含有不同量的锰离子的天然橡胶的物理机械性能基本一致。经3种方式老化后的胶样性能均有不同程度的下降,当锰离子质量分数为0.000 30%时,天然橡胶老化后的拉伸强度、300%定伸应力、700%定伸应力下降程度最小。核磁交联密度测试表明,总交联密度(XLD)与网链分子量(Mc)有很好的对应关系,XLD随着锰离子质量分数的增加而先增大后减小,表明天然橡胶老化过程中交联反应和断裂反应存在竞争关系。示差扫描量热(DSC)测试发现,随着锰离子质量分数的增加,天然橡胶的玻璃化转变温度(Tg)先升高后降低,与核磁交联密度测试结果一致。红外分析(FTIR)发现,天然橡胶老化过程中发生了交联和断裂反应。     

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.     

Preparation of PHEMA/nHAP nanocomposites via <Emphasis Type="Italic">in situ</Emphasis> polymerization in supercritical carbon dioxide for biomedical applications

Poly(2-hydroxyethylmethacrylate) (PHEMA)/hydroxyapatite (HAP) nanocomposites were synthesized through a new route involving nano-sized HAP (nHAP) particles or modified nHAP mixed with monomer 2-hydroxyethylmethacrylate via in situ polymerization in supercritical carbon dioxide (scCO₂). Fourier-transform infrared spectroscopy showed phosphate peak increased with nHAP content in composite. X-ray diffraction patterns of PHEMA/nHAP revealed the presence of crystallized nHAP. Thermogravimetric analysis showed that the ultimate nHAP content in PHEMA/nHAP composites is consistent with its initial amount. Scanning electron microscopy revealed that nanocomposite particles are much smaller than PHEMA particles. PHEMA/nHAP composites with average diameter of approximately 600 nm were obtained in scCO₂ with 94 % yield. Mechanical properties of PHEMA/nHAP nanocomposites were better than those of PHEMA, and compressive modulus and strength of composites with 30 wt.% nHAP were 193 and 29 MPa, respectively. Nanocomposite adsorption toward bovine serum albumin was evaluated, and results indicated that analyte adsorption amount can reach up to 282 mg/g.     

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.     

Synthesis and flame-retardancy of UV-curable methacryloyloxy ethyl phosphates

Tris[2-methacryloyloxy ethyl] phosphate (TMEP), bis(2-methacryloyloxy) ethyl phosphate (DMEP), and 2-(methacryloyloxy ethyl) phosphate (MMEP) were synthesized from phosphorous oxychloride and 2-hydroxyethyl methacrylate, which can be used as flame retardant monomers for UV-curable coating systems. The characterization of the synthesized monomers was carried out by ¹H-NMR, FT-IR, thermo-gravimetric analysis, and the limited oxygen index (LOI) test. The thermal behavior of the cured films depended on phosphorous content and the methacrylate groups in the monomer. The UVcured films from TMEP, DMEP, and MMEP monomers showed LOIS of 28.5, 30.3, and 35.1 respectively. Also, LOI up to 25.4 was obtained for the UV-coated cotton fabrics, which presumably occur through a condensed phase mechanism as verified in the increased residue number. The higher performance of UV-coated cotton fabrics compared to PET was attributed to the facile dehydration and crosslinking of the cellulosic materials.     

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.     

2-巯基苯并噻唑制备的恒粘天然橡胶加工性能的研究

采用2-巯基苯并噻唑制备恒粘天然橡胶（MBT-CVNR）,并与盐酸羟胺制备的恒粘天然橡胶（HH-CVNR）进行对比,采用橡胶加工分析仪并结合交联密度、硫化特性、分子量、门尼粘度和凝胶含量研究加速贮存前后恒粘剂对天然橡胶(NR)加工性能的影响,同时探究交联密度、硫化特性、分子量、门尼粘度和凝胶含量与加工性能之间的关系。结果表明：加速贮存前,加入恒粘剂后,NR的交联密度、分子量、门尼粘度、凝胶含量和弹性模量都减小,损耗因子增大;加速贮存后,NR和HH-CVNR的交联密度、分子量、门尼粘度和凝胶含量都出现增大趋势,NR增大最多,流动性明显变差,加工性能最差,而MBT-CVNR几乎没有变化,加工性能受影响不大。     

Effects of Chemical Functionalization of MWCNTs on the Structural and Physical Properties of Elastomeric Copolyetherester-based Composite Fibers

Elastomeric copolyetherester (CPEE)-based composite fibers incorporating various neat and functionalized multiwalled carbon nanotubes (MWCNTs) were prepared through a conventional wet-spinning and coagulation process. The influence of functionalized MWCNTs on the morphological features, and the thermal, mechanical properties and electrical conductivity of CPEE/MWCNT (80/20, w/w) composite fibers were investigated. FE-SEM images show that a composite fiber containing poly(ethylene glycol)-functionalized MWCNTs (MWCNT-PEG) has a relatively smooth surface owing to the good dispersion of MWCNT-PEGs within the fiber, whereas composite fibers including pristine MWCNTs (p-MWCNT), acid-functionalized MWCNTs (a-MWCNT), and ethylene glycol-modified MWCNTs (MWCNT-EG) have quite a rough surface morphology owing to the presence of MWCNT aggregates. As a result, the CPEE/MWCNT-PEG composite fiber exhibits noticeably increased thermal and tensile mechanical properties as well as a faster crystallization behavior, which stems from an enhanced interfacial interaction between the CPEE matrix and MWCNT-PEGs.     

Enzyme-modified casein fibers and their potential application in drug delivery

Enzymatic crosslinking of casein fibers was done using Transglutaminase (TGase) to improve the mechanical properties, particularly the stability in aqueous conditions and make them suitable for controlled drug release application. Crosslinking casein with 5 U/g of TGase in the spinning dope for 60 min at 25 °C increased the tenacity and tensile strain of the fibers from 0.40 g/den and 4.2 % to 0.70 g/den and 23.1 %, respectively. The stability of the fibers in water at different pH levels was considerably improved after the enzymatic crosslinking. The SDS-PAGE electrophoresis confirmed that higher molecular weight proteins were formed in TGase-crosslinked fibers. Thermogravimetric analysis (TGA) showed that TGase treated fibers also had a higher thermal degradation temperature than the non-crosslinked fibers. Crosslinked fibers exhibited delayed and lower rate of drug release from the fibers suggesting their suitability for controlled drug release.