Biocompatible and biodegradable alginate/poly(N‐isopropylacrylamide) hydrogels for sustained theophylline release

Mixed‐interpenetrated polymeric networks based on sodium alginate (ALG) and poly(N‐isopropylacryl amide) (PNIPAAm) covalently cross‐linked with N,N'‐methylenebisacrylamide are studied for their biocompatibility, nontoxicity, and biodegradability aiming their application in drug delivery. The presence of drug‐polymeric matrix interactions and the distribution of the drug in the polymeric network for theophylline‐loaded ALG/PNIPAAm hydrogels are also investigated by spectroscopic and microscopic methods. The quantitative evaluation of theophylline loaded hydrogels performed by NIR‐CI technique shows a better drug entrapment and a higher homogeneity of the samples with increased alginate content. The thermal behavior of the hydrogels is significantly modified by theophylline presence. The application of the ALG/PNIPAAm hydrogels as carriers for sustained drug release formulations was assessed by the theophylline release tests performed both by in vitro and in vivo studies. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40733.     

Design of renewable poly(amidoamine)/hemicellulose hydrogels for heavy metal adsorption

Renewable poly(amidoamine)/hemicellulose hydrogels were prepared from O‐acetylated galactoglucomannan (AcGGM)‐rich biomass and shown to display a significantly high adsorption capacity for Cu²⁺, Cd²⁺, Pb^2+, Zn²⁺, Ni²⁺, Co²⁺, and . Two different acrylamido end‐capped poly(amidoamine) oligomers (PAA) were prepared and covalently immobilized onto an in situ formed polysaccharide network via water‐based free radical graft copolymerization and cross‐linking. The synthetic approach was shown to be viable when using a highly purified AcGGM or a crude spruce hydrolysate, an AcGGM and lignin containing biomass fraction as a reactant. Homogeneous reaction mixtures were obtained in both cases with polysaccharide contents up to 20% by weight. Oscillatory shear measurements indicated a predominantly solid‐like behavior of the hydrogels with an increase in shear storage modulus with increasing cross‐link density. The mechanical integrity of the PAA/hemicellulose hydrogels showed higher water swelling capacity and less fragility than the parent PAA hydrogels and they retained the heavy metal ion absorption ability of the PAA component, even in the presence of the least purified hemicellulose fraction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41695.     

Reinforcing biopolymer hydrogels with ionic‐covalent entanglement hydrogel microspheres

Microscopic hydrogel spheres can be used to improve the mechanical properties of conventional hydrogels. We prepared ionic‐covalent entanglement (ICE) hydrogel microspheres of calcium cross‐linked gellan gum and genipin cross‐linked gelatin using a water‐in‐oil emulsion‐based processing technique. The method was optimized to produce microspheres with number average diameter 4 ± 1 µm. These ICE microspheres were used to reinforce gelatin hydrogels and improve their compressive mechanical properties. The strongest microsphere reinforced hydrogels possessed a compressive mechanical stress at failure of 0.50 ± 0.1 MPa and a compressive secant modulus of 0.18 ± 0.02 MPa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40557.     

A review of the developments of characteristics of PEI derivatives for gene delivery applications

Redox‐active stimuli have gained a great deal of interest as an indicating factor for designing bioresponsive matrices in gene delivery. Hence, a wide range of gene carriers has been designed incorporating the redox‐stimuli characteristics. The most important type of gene carriers is the class of redox responsive polymers. Among them, disulfide incorporated redox‐responsive polyethyleneimine (PEI) and its derivatives, as a result of their outstanding DNA entrapping characteristics and their intrinsic endosomolytic activity, have attracted considerable attention in recent studies. The review presents the main developments of the characteristics of PEI derivatives and their applications in gene delivery. It is found that despite the uniquely stated characteristics, the noncleavable structure of conventional PEI (high molecular weight PEI: 25k), which makes it a nondegradable material, as well as the frequent inclusion of positively charged amino groups, which reduces its blood circulation period, render conventional PEI a very toxic material for gene‐delivery applications. The extremely high cellular toxicity of conventional PEI has restricted its administration for real in‐vivo physiological media. Recent studies have shown that employing low molecular weight PEI cross‐linked by disulfide linkages (SS‐PEI) and assembling low molecular weight disulfide linkages PEI (LMW SS‐PEI) with bio‐detachable anionic groups were two successful approaches for increasing bioavailability of the PEI‐based gene carriers, while keeping outstanding cellular transfection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42096.     

Synthesis of polyaminostyrene‐based and polyallylamine‐based sorbents for boron removal

Hydroxyalkyl derivatives of polyaminostyrene (PAS), polyallylamine (PAA), and polyethyleneimine (PEI) containing a 2,3‐dihydroxypropyl moiety with a high degree of modification were synthesized. The chemical structures of the polymer transformation products were characterized with elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and ¹³C‐NMR spectroscopy in the solid state. PAS reacted with glycidol and formed poly[N‐(2,3‐dihydroxypropyl)aminostyrene] with a high degree of functionalization. PAA revealed primarily the graft polymerization of glycidol. In the case of PEI, primary amino groups allowed the formation of an N‐derivative of 3‐aminopropanediol‐1,2. The PAA‐based sorbent showed a high sorption capacity toward boron ions in both acidic and alkaline media. From the sorption isotherm data, the maximum sorption capacity of this sorbent at pH 4 was determined to be 3 mmol/g. The PAS‐based resin maintained a high capacity between pH 9 and 12; the optimum pH was 12. The sorption capacity was 1.7 mmol/g. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43939.     

Highly Flexible,Tough, and Self‐Healable Hydrogels Enabled by Dual Cross‐Linking of Triblock Copolymer Micelles and Ionic Interactions

Development of artificial soft materials that have good mechanical performances and autonomous healing ability is a longstanding pursuit but remains challenging. This work reports a kind of highly flexible, tough, and self‐healable poly(acrylic acid)/Fe(III) (PAA/Fe(III)) hydrogels. The hydrogels are dually cross‐linked by triblock copolymer micelles and ionic interaction between Fe(III) and carboxyl groups. Due to the coexistence of these two cross‐linking points, the resulting PAA/Fe(III) hydrogels are tough and can be flexibly stretched, bent, knotted, and twisted. The hydrogels can withstand a deformation of 600% and an ultimate stress as high as 250 kPa. Moreover, the dynamic ionic interaction also endows the hydrogels self‐healing properties. By varying the ratio of Fe(III)/AA, a compromised healing efficiency of 73% and an ultimate stress of 200 kPa are obtained.

     

Synthesis and characterization of salep sulfate and its utilization in preparation of heavy metal ion adsorbent

A multicomponent polysaccharide obtained from dried tubers of certain natural terrestrial orchids was chemically modified by sulfonation using chlorosulfonic acid–dimethylformamide (HClSO_3–DMF) complex as a reagent. For a structural characterization of salep sulfate ¹H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, and Thermogravimetric analysis (TGA) curves were recorded. The sulfate content of modified salep was determined using elemental analysis. This modified biopolymer was used to prepare a new environment‐friendly heavy metal ion adsorbent, salep sulfate‐graft‐polyacrylic acid hydrogel (SS‐g‐PAA). Swelling rate and equilibrium water absorbency in various pH and saline solutions were investigated to study the effect of salep sulfate on swelling behavior of the hydrogel. In addition, the effect of sulfate content on heavy metal ion adsorption from aqueous solution was investigated. The results show that SS‐g‐PAA can effectively remove heavy metal ions (Co²⁺, Zn²⁺, Cu²⁺) from aqueous solution and swelling behavior of the hydrogels highly dependent on the amount of sulfate group on corresponding modified polysaccharide. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3001–3008, 2013     

High‐Performance Flexible Sensors of Self‐Healing,Reversibly Adhesive,and Stretchable Hydrogels for Monitoring Large and Subtle Strains

Flexible sensors are becoming required in heath monitoring and human–machine interfaces, but it is still a challenge to develop flexible sensors with integrated high performances. Herein, high‐performance flexible sensors are fabricated that are self‐healing, reversibly adhesive, and utilizing stretchable hydrogels, which are composed of a pluronic F127 diacrylate (F127DA) cross‐linked poly(acrylic acid) (PAA) network and polydopamine (PDA), and further cross‐linked by Fe³⁺. The unique structure endows the resulting hydrogels (PAA‐PDA‐Fe³⁺ hydrogels) excellent self‐healing property, reversible adhesion property, mechanical stretchability, and electrical conductivity. On the basis of the excellent properties of PAA‐PDA‐Fe³⁺ hydrogels, flexible sensors with large sensing range (0–575%), high sensitivity (GF = 6.31), low response time (0.25 s), and excellent robustness (>500 cycles) are assembled and further applied in detecting both large and subtle strains induced by human motions and water ripple. Overall, this work not only provides an alternative clue to construct multi‐functional hydrogels, but also offers a new kind of high‐performance materials for flexible electronic devices, especially those for health monitoring and human–machine interface.     

Trifunctional cross‐linker trimethylol melamine enhancing adhesive force of PVA hydrogels

Adhesive force is a critical feature in vitro for soft hydrogels as wound dressing. Here we employ trimethylol melamine as a tri‐functional cross‐linker to enhance the adhesive force of poly(vinyl alcohol) (PVA) hydrogels. First, trimethylol melamine was prepared using melamine and formaldehyde by a condensation reaction. Then PVA was cross‐linked in an aqueous medium to form hydrogels by using trimethylol melamine as a cross‐linker. It was found that trimethylol melamine cross‐linked PVA hydrogels (TMCPVA) exhibited a good adhesion property with a low degree of cross‐linking and no residue after the TMCPVA peeled from skins, indicating the TMCPVA were suitable for adhesive wound dressing. Moreover, their structures, morphology and adhesive forces were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and texture analyzer (TA). The results indicated that TMCPVA would be promising wound dressing materials with biocompatible and well‐adhesive properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43774.     

Improvement in impact strength of modified cardanol‐bonded cellulose thermoplastic resin by adding modified silicones

The impact strength of cellulose diacetate (CDA) bonded with a modified cardanol (3‐pentadecylphenoxy acetic acid: PAA) was greatly improved up to 9 kJ/m² by adding a relatively small amount of modified silicones while suppressing a decrease in bending strength. In our recent research, this thermoplastic resin (PAA‐bonded CDA) exhibited high rigidity, glass transition temperature, and water resistance. However, its impact strength was insufficient for use in durable products. Therefore, silicones modified with polyether, amino, and epoxy groups were investigated as possible ways to improve the impact strength. The results show that adding polyether‐modified silicone (polyether silicone) with moderate polarity relative to PAA‐bonded CDA resulted in shearing deformation greatly enhances its impact strength while maintaining other properties, including glass transition temperature (T_g), water resistance, and thermoplasticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40366.     

Self-crosslinked poly-L-ornithine and poly-L-arginine networks: Synthesis,characterization, pH-responsibility,biocompatibility, and AIE-functionality

A pH-responsive hydrogel consists of polypeptides only is a promising biomaterial with the advantages of good biocompatibility and non-toxicity. This work reports the synthesis of poly-L-ornithine(poc) (polyLOpoc) serving as the precursor for hydrogels of poly-L-ornithine (polyOrn) and poly(L-arginine-r-L-ornithine) (poly(Arg-r-Orn)). Their controllable degree of crosslinking, good mechanical properties, good biocompatibility, and pH-responsibility are detailedly investigated. The swelling ratio of polyOrn hydrogel in acidic aqueous solution is 5.7 times higher than that in a basic environment. In the deprotection of phenoxycarbonyl group, polyLOpoc releases amino pendant groups, which attack the remaining poc-protected amino groups to fulfill self-crosslinking without any crosslinking agent. In addition, the pH-responsive behavior of hydrogels is visualized by aggregation-induced emission phenomena with polyOrn and poly(Arg-r-Orn) containing tetrakis(4-aminophenyl)ethene moisture.     

Preparation and characterization of hyaluronan/chitosan scaffold cross‐ linked by 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide

A novel biocompatible scaffold was prepared by cross‐linking hyaluronan (HA) and chitosan (CS). The carboxyl groups of HA were activated by 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide (EDC) and then cross‐linked with amino groups of CS by forming amide bonds. The HA/CS scaffold thus prepared was characterized using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and differential scanning calorimetry. FTIR spectra showed that the absorbance of the amide (1550 cm^?1) and carbonyl (1633 cm^?1) bond in the cross‐linked scaffold was stronger than that in HA or CS. SEM micrographs showed that the cross‐linked scaffold produced at low EDC concentration had an intertwisted ribbon‐like microstructure, while the product prepared at higher EDC concentration had a porous structure. The concentration of EDC in the reaction system greatly affected the structure and properties of the HA/CS scaffold. The prepared scaffold could strongly resist degradation by hyaluronidase, free radicals in vitro and stress. Copyright © 2007 Society of Chemical Industry     

Study on a new polymer/graphene oxide/clay double network hydrogel with improved response rate and mechanical properties

pH‐ and temperature‐responsive double network hydrogels (DN hydrogels) were prepared by using poly (N‐isopropylacrylamide) (PNIPAM) as a tightly crosslinked network (1st network), polyacrylic acid (PAA) as a loosely crosslinked network (2nd network), with clay and graphene oxide as effective crosslinkers and reinforcing fillers. The structure and morphology of the hydrogels were characterized by SEM, FTIR, DSC, and TGA. The synergetic effects of clay, GO and DN structure on various physical properties were investigated. With the increasing of crosslinking densities, the swelling ratios of DN hydrogels gradually decreased by increasing the contents of graphene oxide and PAA. While the DN hydrogels had much better mechanical properties than that of the conventional chemically cross‐linked PNIPAM hydrogels. POLYM. ENG. SCI., 55:1361–1366, 2015. © 2015 Society of Plastics Engineers     

pH/temperature‐responsive semi‐IPN hydrogels composed of alginate and poly(N‐isopropylacrylamide)

Amino semitelechelic poly(N‐isopropylacrylamide) (PNIPAAm) was prepared by radical polymerization with aminoethanethiol hydrochloride as a chain‐transfer agent. Semi‐interpenetrating polymer network (semi‐IPN) hydrogels, composed of alginate and amine‐terminated PNIPAAm, were prepared by crosslinking with calcium chloride. From the swelling behaviors of semi‐IPNs at various pH's and Fourier transform infrared spectra at high temperatures, the formation of a polyelectrolyte complex was confirmed from the reaction between carboxyl groups in alginate and amino groups in modified PNIPAAm. Semi‐IPN hydrogels reached an equilibrium swelling state within 24 h. The water state in hydrogels, investigated by differential scanning calorimetry, showed that sample CAN55 [alginate/PNIPAAm (w/w) = 50/50] exhibited the lowest equilibrium water content and free water content among the hydrogels tested, which was attributed to its more compact structure compared to other samples and the high content of interchain bonding within the hydrogels. Alginate/PNIPAAm semi‐IPN hydrogels exhibited a reasonable sensitivity to the temperature, pH, and ionic strength of swelling medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1128–1139, 2002     

Effect of chemical composition on the response of zwitterionic glucose sensitive hydrogels studied by design of experiments

A stimuli‐responsive hydrogel that contains the anionic monomer 3‐acrylamidophenylboronic acid and the cationic monomer N‐[3‐(dimethylamino)propyl]acrylamide binds with cis‐diol groups of glucose molecules selectively and reversibly. Even though such hydrogels have good selectivity for glucose, there are still remaining thresholds that should be overcome to enhance the sensitivity (swelling pressure response magnitude) and to reduce the response time (inverse of 1st order rate constant). In this study, the sensitivity and response time of zwitterionic glucose sensitive hydrogels (GSHs) were studied with three factor DOE analysis. The DOE results show that the molar ratio of 3‐acrylamidophenylboronic acid/N‐[3‐(dimethylamino)propyl]acrylamide and the wt % of monomer in the pregel solution are the most important factors for enhancing the hydrogel sensitivity. In addition, fast response times can best be achieved by decreasing the molar ratio of cross‐linker. The results of this study will be useful as guidelines for the optimal synthesis of glucose sensitive hydrogels. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40667.     

Synthesis of a photo‐patternable cross‐linked epoxy system containing photodegradable carbonate units for deep UV lithography

Bis(2‐(oxiran‐2‐ylmethyl)‐1,3‐dioxoisoindolin‐5‐yl) carbonate and polymers containing 9‐anthracenylmethylmethacrylate (AMMA), p‐tert‐butoxy styrene (PTBS), and methacrylic acid (MAA) monomeric units were synthesized with the aim of developing a novel photo‐patternable cross‐linked epoxy system. The oxirane groups in bis(2‐(oxiran‐2‐ylmethyl)‐1,3‐dioxoisoindolin‐5‐yl) carbonate were reacted with the carboxylic acid in the polymer to generate a cross‐linked epoxy film, and the photo degradation of the cross‐linked film was achieved through decomposition of the carbonate groups in the cross‐linked film by deep UV irradiation. Because the copolymer containing anthracene groups has relatively high reflective index and absorption at 248 nm, this cross‐linked system can be applied to patternable bottom antireflective coating materials for deep UV lithography applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrospun poly(acrylic acid)/lysine fibers and the interactive effects of moisture,heat, and cross‐link density on their behavior

Poly(acrylic acid) (PAA) is an important polymer frequently used as a superabsorbent in health and hygiene products. As a polyelectrolyte that swells with absorption of water it has potential application in other fields including drug delivery, tissue scaffolds, actuators, and desiccation and humidity control. To be useful in such applications the membrane's mechanical integrity must be maintained while optimizing its moisture absorption properties. In this work PAA membranes are electrospun with lysine as cross‐linking agent. The effects of varying the concentration of the lysine on the cross‐link density and consequently on the thermo‐ and hygro‐mechanical properties of the membranes are studied through electron microscopy, FTIR spectroscopy, and dynamic mechanical thermal analysis (DMTA). Isothermal glass transitions are shown to occur with varying moisture content. The moisture content (or relative humidity) at which the transition occurs is reduced by increasing temperature and can be controlled by varying the cross‐link density. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41252.     

Fluconazole release through semi‐interpenetrating polymer network hydrogels based on chitosan,acrylic acid,and citraconic acid

Semi‐interpenetrating polymer network hydrogels with different compositions of chitosan (Cs), acrylic acid, and citraconic acid were synthesized via free‐radical polymerization with ethylene glycol dimethacrylate as a crosslinker. The variations of the swelling percentages of the hydrogels with time, temperature, and pH were determined, and Cs–poly(acrylic acid) (PAA) hydrogels were found to be most swollen at pH 7.4 and 37°C. Scanning electron micrographs of Cs–PAA and Cs–P(AA‐co‐CA)‐1 (Cs‐poly(acrylicacid‐co‐citraconir acid)^?1) were taken to observe the morphological differences in the hydrogels. Although the less swollen hydrogel, Cs–P(AA‐co‐CA)‐1, had a sponge‐type structure, the most swollen hydrogel, Cs–PAA, displayed a uniform porous appearance. Fluconazole was entrapped in Cs–P(AA‐co‐CA)‐1 and Cs–PAA hydrogels, and the release was investigated at pH 4.0 and 37°C. The kinetic release parameters of the hydrogels (the gel characteristic constant and the swelling exponent) were calculated, and non‐Fickian diffusion was established for Cs–PAA, which released fluconazole much more slowly than the Cs–P(AA‐co‐CA)‐1 hydrogel. A therapeutic range was reached at close to 1 h for both hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A thiol‐ene clickable hyperbranched polyester via a simple single‐step melt trans‐esterification process

Self‐condensation of AB₂ type monomers (containing one A‐type and two B‐type functional groups) generates hyperbranched (HB) polymers that carry numerous B ‐type end‐groups at their molecular periphery; thus, development of synthetic methods that directly provide quantitatively transformable peripheral B groups would be of immense value as this would provide easy access to multiply functionalized HB systems. A readily accessible AB₂ monomer, namely diallyl, 5‐(4‐hydroxybutoxy)isophthalate was synthesized, which on polymerization under standard melt‐transesterfication conditions yielded a peripherally clickable HB polyester in a single step; the allyl groups were quantitatively reacted with a variety of thiols using the facile photoinitiated “thiol‐ene” reaction to generate a wide range of derivatives, with varying solubility and thermal properties. Furthermore, it is shown that the peripheral allyl double bonds can also be readily epoxidized using meta‐chloroperoxybenzoic acid to yield interesting HB systems, which could potentially serve as a multifunctional cross‐linking agent in epoxy formulations. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40248.     

In situ injectable poly(γ‐glutamic acid) based biohydrogel formed by enzymatic crosslinking

Enzymatic crosslinking was developed to prepare in situ forming poly(γ‐glutamic acid) (γ‐PGA) based hydrogel in this study. First, the precursor of poly(γ‐glutamic acid)–tyramine (γ‐PGA–Ty) was synthesized through the reaction of carboxyl groups from a γ‐PGA backbone with tyramine. The structure of the grafted precursor was confirmed by ¹H‐NMR and Fourier transform infrared spectroscopy. After that, the crosslinking of the phenol‐containing γ‐PGA–Ty precursor was triggered by horseradish peroxidase in the presence of H₂O₂; this resulted in the formation of the γ‐PGA–Ty hydrogels. The equilibrium water content, morphology, enzymatic degradation rate, and mechanical properties of the hydrogels were characterized in detail. The data revealed that the well‐interconnected hydrogels had tunable water contents, mechanical properties, and degradability through adjustments of the composition. Furthermore, cell experiments proved the biocompatibility of the hydrogels by 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay. These characteristics provide an opportunity for the in situ formation of injectable biohydrogels as potential candidates in cell encapsulation and drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42301.