Thermo‐responsive injectable hydrogel system based on poly(N‐isopropylacrylamide‐co‐vinylphosphonic acid). I. Biomineralization and protein delivery

To achieve the injectable hydrogel system in order to improve bone regeneration by locally delivering a protein drug including bone morphogenetic proteins, thermo‐responsive injectable hydrogels composed of N‐isopropylacrylamide (NIPAAm) and vinyl phosphonic acid (VPAc) were prepared. The P(NIPAAm‐co‐VPAc) hydrogels were also biomineralized by urea‐mediation method to create functional polymer hydrogels that deliver the protein drug and mimic the bone extracellular matrix. The loosely cross‐linked P(NIPAAm‐co‐VPAc) hydrogels were pliable and fluid‐like at room temperature and could be injected through a small‐diameter aperture. The lower critical solution temperature (LCST) of P(NIPAAm‐co‐VPAc) hydrogel was influenced by the monomer ratio of NIPAAm/VPAc and the hydrogel with a 96/4 molar ratio of NIPAAm/VPAc exhibited an LCST of ～34.5°C. Water content was influenced by temperature, NIPAAm/VPAc monomer ratio, and biomineralization; however, all hydrogels maintained more than about 77% of the water content even at 37°C. In a cytotoxicity study, the P(NIPAAm‐co‐VPAc) and biomineralized P(NIPAAm‐co‐VPAc) hydrogels did not significantly affect cell viability. The loading content of bovine serum albumin in hydrogel, which was used as a model drug, gradually increased with the amount of VPAc in the hydrogel owing to the ionic interaction between VPAc groups and BSA molecules. In addition, the release behavior of BSA from the P(NIPAAm‐co‐VPAc) hydrogels was mainly influenced by the drug loading content, water content, and biomineralization of the hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and swelling behavior of thermosensitive IPN hydrogels based on sodium acrylate and N‐isopropyl acrylamide by a two‐step method

A series of interpenetrating polymer network (IPN) hydrogels having higher swelling ratio (SR) and thermosensitivity were synthesized from sodium acrylate (SA) and N‐isopropyl acrylamide (NIPAAm) by a two‐step method. A series of the porous poly(sodium acrylate ‐co‐1‐vinyl–2‐pyrrolidone) [poly(SA‐co‐VP)], (SV), hydrogels were prepared from acrylic acid having 90% degree of neutralization and VP monomer in the first step. The second step is to immerse the SV dried gels into the NIPAAm solution containing initiator, accelerator, and crosslinker to absorb NIPAAm solution and then polymerized to form the poly(SA‐co‐VP)/poly(NIPAAm) IPN hydrogels (SVN). The effect of the different molar ratios of SA/VP and the content of NIPAAm on the swelling behavior and physical properties of the SVN hydrogels was investigated. Results showed that the SVN hydrogels displayed an obviously thermoreversible behavior when the temperature turns across the critical gel transition temperature (CGTT) of poly(NIPAAm) hydrogel. The pore diameter distributions inside the hydrogel also indicated that the pore sizes inside the SVN hydrogels were smaller than those inside the SV hydrogels. At the same time, the more proportion of SA was added into the hydrogel, the larger pore diameter of the SV hydrogel was formed. The results also showed that the SR decreased with an increase of the VP content in the SV hydrogel and more obviously decreased in the SVN hydrogels. The SVN networks also showed stronger shear moduli than SV hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Dual pH‐ and thermal‐responsive nanocomposite hydrogels for controllable delivery of hydrophobic drug baicalein

Hydrogels have been widely used as mild biomaterials due to their bio‐affinity, high drug loading capability and controllable release profiles. However, hydrogel‐based carriers are greatly limited for the delivery of hydrophobic payloads due to the lack of hydrophobic binding sites. Herein, nano‐liposome micelles were embedded in semi‐interpenetrating poly[(N‐isopropylacrylamide)‐co‐chitosan] (PNIPAAm‐co‐CS) and poly[(N‐isopropylacrylamide)‐co‐(sodium alginate)] (PNIPAAm‐co‐SA) hydrogels which were responsive to both temperature and pH, thereby establishing tunable nanocomposite hydrogel delivery systems. Nano‐micelles formed via the self‐assembly of phospholipid could serve as the link between hydrophobic drug and hydrophilic hydrogel due to their special amphiphilic structure. The results of transmission and scanning electron microscopies and infrared spectroscopy showed that the porous hydrogels were successfully fabricated and the liposomes encapsulated with baicalein could be well contained in the network. In addition, the experimental results of response release in vitro revealed that the smart hydrogels showed different degree of sensitiveness under different pH and temperature stimuli. The results of the study demonstrate that combining PNIPAAm‐co‐SA and PNIPAAm‐co‐CS hydrogels with liposomes encapsulated with hydrophobic drugs is a feasible method for hydrophobic drug delivery and have potential application prospects in the medical field. © 2018 Society of Chemical Industry     

Ethylene‐co‐vinyl acetate copolymer crosslinking through ester–alkoxysilane exchange reaction catalyzed by dibutyltin oxide: mechanistic aspects investigated through model compounds by multinuclear NMR spectroscopy

It was shown that the crosslinking of ethylene‐co‐vinyl acetate (EVA) copolymer by a tetraalkoxysilane in molten state, in the temperature range 100–250 °C, was obtained only in the presence of dibutyltin oxide. At this temperature EVA pendant ester groups readily react with dibutyltin oxide to give a dimeric 1‐alkoxy‐3‐acetoxytetrabutyldistannoxane distributed along the polymer chains. The exact role of this tin compound in the ester–alkoxysilane reaction was elucidated through reactions of the tetraalkoxysilane with parent tin compounds: tributylethoxytin, dimeric diacyloxydistannoxane and finally a dimeric 1‐alkoxy‐3‐acyloxydistannoxane, obtained by reaction of the dibutyltin oxide with a model ester instead of the EVA‐ester pendant group. Ligand exchanges on tin atoms characterized by multinuclear NMR spectroscopy (¹H, ¹³C and ¹¹⁹Sn) showed that substitutions were selective and concern only the exo‐cyclic tin ligand (OR or OCOR′) without alteration of the dimeric distannoxane structure. Furthermore, these ligand exchanges occurred at room temperature. This approach with model compounds gave evidence that the crosslinking occurred via an alkoxy‐Sn/alkoxy‐Si exchange on the exo‐cyclic sites of the distannoxane structure formed in situ. This distannoxane was shown to be an efficient catalyst of this transesterification. The temperature of formation of this catalytic species governed the temperature of the beginning of the crosslinking reaction. Copyright © 2004 Society of Chemical Industry     

Environmentally sensitive hydrogels: N‐isopropyl acrylamide/Acrylamide/ Mono‐, Di‐, Tricarboxylic acid crosslinked polymers

Environmentally sensitive hydrogels responsive to various stimuli such as temperature, pH, ionic strength of the medium and the solvent were prepared by using N‐isopropyl acrylamide (NIPAM), acrylamide (AAm) and monomers that have various number of carboxylic acid (XA) functionality using N,N′‐methylene bisacrylamide (Bis) as crosslinker. Hydrogels were prepared via free radical polymerization reaction in aqueous solution. P(NIPAAm‐co‐AAm) and p(NIPAAm‐co‐AAm)/XA hydrogels that contain monoprotic crotonic acid (CA) exhibit a lover critical solution temperature (LCST) at 28°C, whereas p(NIPAAm‐co‐AAm)/IA (IA:itaconic acid), and P(NIPAAm‐co‐AAm)/ACA (ACA:acotonic acid) hydrogels exhibit a lover critical solution temperature at 30.7°C and 34.4°C, respectively. Spectroscopic and thermal analyses were performed for the structural and thermal characterizations of the prepared hydrogel. The swelling experiments as equilibrium swelling percentages by gravimetrically were carried out in different solvents, at different solutions temperature, pH, and ionic strengths to determine their effects on swelling characteristic of hydrogels. POLYM. ENG. SCI., 55:843–851, 2015. © 2014 Society of Plastics Engineers     

Stabilized electrospinning of heat stimuli/in situ crosslinkable nanofibers and their self‐same nanocomposites

We present a strategy for stabilizing the morphological integrity of electrospun polymeric nanofibers by heat stimuli in situ crosslinking. Amorphous polymer nanofibers, such as polystyrene (PS) and its co‐polymers tend to lose their fiber morphology during processing at temperatures above their glass transition temperature (T_g) typically bound to happen in nanocomposite/structural composite applications. As an answer to this problem, incorporation of the crosslinking agents, phthalic anhydride (PA) and tributylamine (TBA), into the electrospinning polymer solution functionalized by glycidylmethacrylate (GMA) copolymerization, namely P(St‐co‐GMA), is demonstrated. Despite the presence of the crosslinker molecules, the electrospinning polymer solution is stable and its viscosity remains unaffected below 60 °C. Crosslinking reaction stands‐by and can be thermally stimulated during post‐processing of the electrospun P(St‐co‐GMA)/PA‐TBA fiber mat at intermediate temperatures (below the T_g). This strategy enables the preservation of the nanofiber morphology during subsequent high temperature processing. The crosslinking event leads to an increase in T_g of the base polymer by 30 °C depending on degree of crosslinking. Crosslinked nanofibers are able to maintain their nanofibrous morphology above the T_g and upon exposure to organic solvents. In situ crosslinking in epoxy matrix is also reported as an example of high temperature demanding application/processing. Finally, a self‐same fibrous nanocomposite is demonstrated by dual electrospinning of P(St‐co‐GMA) and stabilized P(St‐co‐GMA)/PA‐TBA, forming an intermingled nanofibrous mat, followed by a heating cycle. The product is a composite of crosslinked P(St‐co‐GMA)/PA‐TBA fibers fused by P(St‐co‐GMA) matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44090.     

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

A pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40737.     

Poly(acrylonitrile‐co‐vinyl acetate)/Ag composite microspheres: One‐pot fabrication and application as catalyst

Waxberry‐like poly(acrylonitrile‐co‐vinyl acetate)/Ag composite microspheres have been prepared simply and directly via a one‐step self‐assembly approach. The morphology, formation, and catalytic activity of the as‐prepared composite microspheres are further investigated. The difference in the solubility among different segments of poly(acrylonitrile‐co‐vinyl acetate) is the basis of the formation of poly(acrylonitrile‐co‐vinyl acetate) microspheres, while the ? CN groups on the surface of poly(acrylonitrile‐co‐vinyl acetate) microspheres play an important role in the growth process from poly(acrylonitrile‐co‐vinyl acetate) microsphere to poly(acrylonitrile‐co‐vinyl acetate)/Ag composite microsphere. It is found that bulk quantities of composite microspheres with high density of Ag nanoparticles on the surface can be obtained readily by controlling the concentration of AgNO₃. The as‐prepared composite microsphere exhibits excellent catalytic activity on reduction of p‐nitrophenol. This study may shed some light on the self‐assembly of other metal/polymer composite microspheres. POLYM. ENG. SCI., 50:1767–1772, 2010. © 2010 Society of Plastics Engineers     

Photopatterning and degradation study of dextran‐glycidyl methacrylate hydrogels

An approach to synthesizing photopatternable enzymatic degradable dextran hydrogel is presented. The glycidyl methacrylate derivatized dextran (Dex‐GMA) was first prepared by reacting dextran with glycidyl methacrylate at 45°C with grafting efficiency of 10%. The degree of substitution (DS) was confirmed by ¹H‐NMR. Next, Dex‐GMA hydrogels were prepared by crosslinking in the presence of a crosslinker: N,N′‐ methylene‐bisacrylamide (NMBA), and a photoinitiator: 2,2′‐dimethoxy‐2‐phenyl acetophenone (DMPA) in dimethyl sulfoxide (DMSO) solution. Further, the Dex‐GMA hydrogels were photopatterned using liquid‐phase photopolymerization (LP³) technique. The structure size ranged from 5 mm to 300 μm and three different shapes of structures‐ ‐ —round, square, and star‐ ‐ —were demonstrated. The patterned Dex‐GMA hydrogel structures not only exhibited mechanical robustness but also biodegradability. The dextranase‐catalyzed degradation of Dex‐GMA hydrogels with different DS was investigated at 37°C. The morphology of the degraded Dex‐GMA hydrogels determined by SEM revealed the degree of enzymatic degradation due to dextranase. The Dex‐GMA hydrogel was fully degraded by dextranase with concentration of 2 U/ml in 5 days. The Dex‐GMA hydrogel also showed the ability to be readily integrated with microfluidics. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis and characterization of a porous poly(hydroxyethylmethacrylate‐co‐ethylene glycol dimethacrylate)‐based hydrogel device for the implantable delivery of insulin

Poly(hydroxyethylmethacrylate‐co‐ethylene glycol dimethacrylate) [poly(HEMA‐co‐EGDMA)]‐based hydrogel devices were synthesized by a free‐radical polymerization reaction with 2‐hydroxyethylmethacrylate as the monomer, different concentrations of ethylene glycol dimethacrylate (EGDMA) as the crosslinking agent, and ammonium persulfate/N,N,N′,N′‐tetra‐methyl ethylenediamine as the free‐radical initiator. The porosity of the poly(HEMA‐co‐EGDMA) hydrogels was controlled with water as the porogen. The Fourier transform infrared spectrum of poly(HEMA‐co‐EGDMA) showed absorption bands associated with ? C?O stretching at 1714 cm^?1, C? O? C stretching vibrations at 1152 cm^?1, and a broad band at 3500–3800 cm^?1 corresponding to ? OH stretching. Atomic force microscopy studies showed that the hydrogel containing 67% water had pores in the range of 3500–9000 nm, whereas the hydrogel containing 7% water did not show measurable pores. The hydrogel synthesized with 1% EGDMA showed 50% thallium‐201 release within the first 30 min and about 80% release within 60 min. In vitro insulin‐release studies suggested that the hydrogel with 27% water showed sustained release up to 120 min, whereas the hydrogels with 47 and 67% water showed that nearly all of the insulin was released within 60 min. Hydrogel devices synthesized with 27% water and filled with insulin particles showed sustained release for up to 8 days, whereas the hydrogels synthesized with 47 and 67% water released insulin completely within 3 days of administration. Animal studies suggested that the hydrogel devices synthesized with 27% water and filled with insulin‐loaded particles (120 IU) were able to control blood glucose levels for up to 5 days after implantation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Different dispersion polymerization strategies influence the quality of fluorescent poly (St‐co‐GMA) microspheres

The polymerization strategy plays a vital role in the preparation of functional microspheres. In this work, fluorescent poly (styrene‐co‐glycidyl methacrylate) (PSt‐GMA) microspheres were synthesized via one‐stage and two‐stage dispersion polymerization with 4‐Bis(5‐phenyl‐1,3‐oxazol‐2‐yl)benzene (POPOP) as fluorescence agent. SEM and DLS were adopted to characterize the properties of prepared microspheres. The UV‐vis and fluorescence spectroscopy were used to analyze the mechanisms of two‐stage dispersion polymerization. The experimental results showed that the size distribution and fluorescence intensity of prepared microspheres could be improved by two‐stage dispersion polymerization compared to one‐stage dispersion polymerization. In addition, according to UV‐vis, the interactions between POPOP and Poly (N‐vinyl pyrrolidone) (PVP) as well as POPOP and Glycidyl methacrylate (GMA) could affect the particle size and its distribution. UV‐vis and fluorescence spectra implied that the POPOP existed outside of the particle's core via two‐stage strategy. The monomer conversion of styrene was similar at the beginning of reaction; however, the monomer conversion of styrene by two‐stage strategy was higher than that of by one‐stage strategy. In a word, two‐stage dispersion polymerization could prepare fluorescent microspheres with the monodispersion micrometer‐size and high quality. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41927.     

Synthesis and characterization of a novel stimuli‐responsive magnetite nanohydrogel based on poly(ethylene glycol) and poly(N‐isopropylacrylamide) as drug carrier

A novel stimuli‐responsive magnetite nanohydrogel (MNHG), namely [poly(ethylene glycol)‐block‐poly(N‐isopropylacrylamide‐co‐maleic anhydride)₂]‐graft‐poly(ethylene glycol)/Fe₃O₄ [PEG‐b‐(PNIPAAm‐co‐PMA)₂]‐g‐PEG/Fe₃O₄, was successfully developed. For this purpose, NIPAAm and MA monomers were block copolymerized onto PEG‐based macroinitiator through atom transfer radical polymerization technique to produce PEG‐b‐(PNIPAAm‐co‐PMA)₂. The synthesized Y‐shaped terpolymer was crosslinked through the esterification of maleic anhydride units using PEG chains to afford a hydrogel. Afterward, magnetite nanoparticles were incorporated into the synthesized hydrogel through the physical interactions. The chemical structures of all synthesized samples were characterized using Fourier transform infrared and proton nuclear magnetic resonance spectroscopies. Morphology, thermal stability, size, and magnetic properties of the synthesized MNHG were investigated. In addition, the doxorubicin hydrochloride loading and encapsulation efficiencies as well as stimuli‐responsive drug release ability of the synthesized MNHG were also evaluated. The drug‐loaded MNHG at physiological condition exhibited negligible drug release values. In contrast, at acidic (pH 5.3) condition and a little bit higher temperature (41 °C) the developed MNHG showed higher drug release values, which qualified it for cancer chemotherapy due to especial physiology of cancerous tissue in comparison with the surrounding normal tissue. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46657.     

Gloss reduction and morphological properties of polycarbonate and poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) blends with SAN‐co‐GMA as a reactive compatibilizer

The gloss properties of the polycarbonate (PC)/poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) (MABS) blend with styrene‐acrylonitrile‐co‐glycidyl methacrylate (SAN‐co‐GMA) as a compatibilizing agent were investigated. For the PC/poly(MABS)/SAN‐co‐GMA (65/15/20, wt %) blend surface, the reduction of gloss level was observed most significantly when the GMA content was 0.1 wt %, compared with the blends with 0.05 wt % GMA or without GMA content. The gloss level of the PC/poly(MABS)/SAN‐co‐GMA (0.1 wt % GMA) blend surface was observed to be 35, which showed 65% lower than the PC/poly(MABS)/SAN‐co‐GMA blend without GMA content. The gloss reduction was most probably caused by the insoluble fractions of the PC/poly(MABS)/SAN‐co‐GMA blend that were formed by the reaction between the carboxylic acid group in poly(MABS) and epoxy group in SAN‐co‐GMA. The results of optical and transmission electron microscope analysis, spectroscopy study, and rheological properties supported the formation of insoluble structure of the PC/poly(MABS)/SAN‐co‐GMA blend when the GMA content was 0.1 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46450.     

Functionalization of poly(ester‐urethane) surface by radiation‐induced grafting of N‐isopropylacrylamide using conventional and reversible addition–fragmentation chain transfer‐mediated methods

The functionalization of poly(ester‐urethane) (PUR) surface was conducted using radiation‐induced grafting. A thermosensitive layer constructed from N‐isopropylacrylamide (NIPAAm) was introduced onto a polyurethane film and characterized using attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopies and contact angle measurements. Size exclusion chromatography was used to analyse the PUR‐graft‐PNIPAAm copolymers and homopolymers formed in solution. Additionally, reversible addition–fragmentation chain transfer (RAFT) polymerization was performed in order to obtain PNIPAAm‐grafted surfaces with well‐defined properties. Atomic force microscopy was used to evaluate the surfaces synthesized via conventional and RAFT‐mediated grafting methods. The results of various techniques confirmed the successful grafting of NIPAAm from PUR film. © 2015 Society of Chemical Industry     

Immobilization of lipase on poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) hydrogel

Lipase from Candida rugosa was immobilized by entrapment while polymerizing a poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) [poly(VP‐co‐ST)] hydrogel using ethylene dimethacrylate (EDMA) as the crosslinking agent. The immobilized enzymes were used in the esterification reaction of oleic acid and butanol in hexane. The activities of the immobilized enzymes and the leaching ability of the enzyme from the support with respect to the different compositions of the hydrogels were investigated. The thermal, solvent, and storage stability of the immobilized lipases were also determined. The activities were relatively higher when the percent compositions of VP(%):ST(%) were 50:50 and 30:70. The lipase immobilized on VP(%):ST(%) 50:50 showed the highest thermal stability, while lipase immobilized on VP(%):ST(%) 30:70 exhibited the highest solvent stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1404–1409, 2001     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Temperature/pH‐sensitive comb‐type graft hydrogels composed of chitosan and poly(N‐isopropylacrylamide)

Comb‐type graft hydrogels, composed of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm), were prepared to manifest rapid temperature and pH sensitivity. Instead of directly grafting the NIPAAm monomer onto the chitosan chain, semitelechelic PNIPAAm with carboxyl end group was synthesized by radical polymerization using 3‐mercaptopropionic acid as the chain‐transfer agent, and was grafted onto chitosan having amino groups. The comb‐type hydrogels were prepared with two different graft yields and grafting regions, such as surface‐ and bulk‐grafting, and then compared with a chitosan hydrogel. The synthesis of telechelic PNIPAAm and the formation of amide group were confirmed by using FTIR spectroscopy and gel permeation chromatography. Results from the water state and thermal stability revealed that the introduction of the PNIPAAm side chain disturbed the ordered arrangement of the chitosan molecule, resulting in an increase in the equilibrium water content. Comb‐type graft hydrogels showed rapid temperature and pH sensitivity because of the free‐ended PNIPAAm attached to the chitosan main chain and the chitosan amino group itself, respectively. In particular, the surface graft hydrogel maintained its dimension at low pH, although the chitosan main chain was not crosslinked, whereas chitosan and bulk graft hydrogel were dissolved as a result of the coating effect of pH‐independent PNIPAAm. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2612–2620, 2004     

Fourier transform near‐infrared and electron spin resonance studies on the crosslinking reaction of liquid carboxylated poly(acrylonitrile‐co‐butadiene) rubber with dicumyl peroxide in dioxane

The crosslinking reaction of liquid carboxylated poly(acrylonitrile‐co‐butadiene) [or nitrile rubber (NBR); acrylonitrile = 10 wt %] with dicumyl peroxide (DCPO) was studied in dioxane by means of Fourier transform near‐infrared spectroscopy (FT‐NIR) and electron spin resonance spectroscopy (ESR). Among the three butadiene units (1,2, cis‐1,4, and trans‐1,4 units) of NBR, only the pendant vinyl group of the 1,2 unit showed an absorption at 6110 cm^?1 from the FT‐NIR examination of dioxane solutions of NBR, 1‐octene, 3,3‐dimethyl‐1‐butene, trans‐2‐octene, cis‐5‐octen‐1‐ol, poly‐cis‐1,4‐butadiene, and poly‐1,2‐butadiene. The crosslinking reaction was followed in situ in dioxane by the monitoring of the disappearance of the pendant vinyl double bond with FT‐NIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.9[NBR]^?0.2 (120°C). The overall activation energy of the reaction was calculated to be 20.7 kcal/mol. This unusual rate equation suggests unimolecular termination due to degradative chain transfer and depressed reactivity of the vinyl group caused by crosslinking. ESR study of the reaction mixture revealed that an allyl‐type polymer radical was formed in the reaction, and its concentration increased with time and was then saturated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2095–2101, 2003     

Poly(glycidyl methacrylate‐co‐3‐thienyl‐methylmethacrylate) based working electrodes for hydrogen peroxide biosensing

BACKGROUND: Hydrogen peroxide biosensors based on Poly(glycidyl methacrylate‐co‐3‐thienylmethylmethacrylate)/ Polypyrrole [Poly(GMA‐co‐MTM)/PPy] composite film were reported. Poly(GMA‐co‐MTM) including various amounts of GMA and MTM monomers was synthesized via the radical polymerization. Enzyme horseradish peroxidase (HRP) was trapped in Poly(GMA‐co‐MTM)/PPy composites during the electropolymerization reaction between pyrrole and thiophene groups of MTM monomer, and chemically bonded via the epoxy groups of GMA. Analytical parameters of the fabricated electrodes were calculated and are discussed in terms of film electroactivity and mass transfer conditions of the composite films. RESULTS: The amount of electroactive HRP was found to be 1.25, 0.34 and 0.213 µg for the working electrodes of Poly(GMA_30%‐ co‐MTM_70%)/PPy/HRP, Poly(GMA_85%‐co‐MTM_15%)/PPy/HRP and Poly(GMA_90%‐co‐MTM_10%)/PPy/HRP, respectively. Optimal response of the fabricated electrodes was obtained at pH 7 and an operational potential of ? 0.35 V. It was observed that effective enzyme immobilization and electroactivity of the composite films could be changed by changing the ratios of GMA and MTM fractions of Poly(GMA‐co‐MTM) based working electrodes. CONCLUSION: The amount of electroactive enzyme increases with increasing MTM content of the final copolymer. High operational stabilities of the biosensors can be attributed to the strong covalent enzyme linkage via the epoxy groups of GMA due to preventing enzyme deterioration and loss. A more convenient microenvironment for mass transfer was provided for the electrodes by higher GMA ratios. It is observed that mass transfer is dominated by the mechanism of electron transfer to obtain effective sensitivity values. This work contributes to discussions clarifying the problems regarding the design parameters of biosensors. Copyright © 2011 Society of Chemical Industry