Vinyl triazole carrying metal‐chelated beads for the reversible immobilization of glucoamylase

Poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads with an average diameter of 100–200 μm were obtained by the copolymerization of ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer hydrogel bead composition was determined by elemental analysis and was found to contain 5 EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads were characterized by swelling studies and scanning electron microscopy (SEM). The specific surface area of the poly(EGDMA–VTAZ) beads was found 65.8 m²/g. Cu²⁺ ions were chelated on the poly(EGDMA–VTAZ) beads. The Cu²⁺ loading was 82.6 μmol/g of support. Cu²⁺‐chelated poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used in the immobilization of Aspergillus niger glucoamylase in a batch system. The maximum glucoamylase adsorption capacity of the poly(EGDMA–VTAZ)–Cu²⁺ beads was 104 mg/g at pH 6.5. The adsorption isotherm of the poly(EGDMA–VTAZ)–Cu²⁺ beads fitted well with the Langmuir model. Adsorption kinetics data were tested with pseudo‐first‐ and second‐order models. The kinetic studies showed that the adsorption followed a pseudo‐second‐order reaction model. The Michaelis constant value for the immobilized glucoamylase (1.15 mg/mL) was higher than that for free glucoamylase (1.00 mg/mL). The maximum initial rate of the reaction values were 42.9 U/mg for the free enzyme and 33.3 U/mg for the immobilized enzyme. The optimum temperature for the immobilized preparation of poly(EGDMA–VTAZ)–Cu²⁺–glucoamylase was 65°C; this was 5°C higher than that of the free enzyme at 60°C. The glucoamylase adsorption capacity and adsorbed enzyme activity slightly decreased after 10 batch successive reactions; this demonstrated the usefulness of the enzyme‐loaded beads in biocatalytic applications. The storage stability was found to increase with immobilization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Immobilization of α-chymotrypsin to a temperature-responsive reversibly soluble–insoluble oligomer based on N-isopropylacrylamide

A temperature-responsive N-isopropylacrylamide (NIPAAm) oligomer with an ester functional end group and a molecular weight of 3300 was prepared by chain-transfer polymerization using β-mercaptopropionic acid and subsequently activated by N-hydroxysuccinimide (NHS). This oligomer was coupled to α-chymotrypsin to yield a thermo-sensitive reversibly soluble–insoluble oligomer–enzyme conjugate, which is water-soluble at temperatures below 34°C and that precipitates above 36°C. The conjugated enzyme showed higher activity, and improved thermal stability compared with native enzyme. Kinetic properties and optimum conditions for activity were compared with those of native enzyme. More than 93% enzyme activity of the conjugate was recovered after eight cycles of thermal-induced precipitation. The oligomer–enzyme complex was used for repeated hydrolysis of casein; the biocatalyst was recovered between runs by thermal-induced precipitation and showed good stability. © 1998 Society of Chemical Industry     

Structure and protein separation efficiency of poly(N-isopropylacrylamide) gels: Effect of synthesis conditions

Crosslinked poly(N-isopropylacrylamide) (PNIPA) gels with different crosslink densities in the form of rods and beads were prepared by free-radical crosslinking copolymerization. Solution and inverse suspension polymerization techniques were used for the gel synthesis. The gels were utilized to concentrate dilute aqueous solutions of penicillin G acylase (PGA), bovine serum albumin (BSA), and 6-aminopenicillanic acid (6-APA). The discontinuous volume transition at 34°C observed in the gel swelling was used as the basis of concentrating dilute aqueous protein solutions. PNIPA gels formed below 18°C were homogeneous, whereas those formed at higher temperatures exhibited heterogeneous structures. The water absorption capacity of PNIPA gels in the form of beads was much higher, and their rate of swelling was much faster than the rod-shaped PNIPA gels. It was also found that the polymerization techniques used significantly affect the properties of PNIPA gels. The separation efficiency decreased when the protein molecules PGA or BSA in the external solution were replaced with small-molecular-weight compounds, such as 6-APA. The protein separation efficiency by the gel beads increased to 100% after coating the bead surfaces with BSA. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 805–814, 1998     

Immobilization of β-galactosidase onto magnetic poly(GMA–MMA) beads for hydrolysis of lactose in bed reactor

In the present study, novel magnetic beads were prepared from glycidylmethacrylate and methylmethacrylate via suspension polymerization in the presence of a cross-linker (i.e. ethylenedimethylmethacrylate). The magnetic poly(GMA–MMA) beads were characterized with scanning electron microscope, FT-IR and ESR spectrophotometers. The reactive character of the epoxy groups allowed the attachment of the amino groups. The aminated magnetic beads were used for the covalent immobilization of β-galactosidase via glutaric dialdehyde activation. The maximum amount of immobilized β-galactosidase on the magnetic poly(GMA–MMA) beads was 9.87 mg/g support. The values of Michaelis constants K_m for immobilized β-galactosidase was significant larger, indicating decreased affinity by the enzyme for its substrate, whereas V_max values were smaller for the immobilized β-galactosidase. However, the β-galactosidase immobilized on the magnetic poly(GMA–MMA) beads resulted in an increase in enzyme stability with time. Optimum operational temperature for immobilized enzyme was 5 °C higher than that of the free enzyme and was significantly broader. Finally, a bed reactor with β-galactosidase immobilized was used for hydrolysis of lactose. The enzyme reactor operated continuously at 35 °C for 60 h and the immobilized enzyme lost about 12% of its initial activity after this period.     

Phase behavior of temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) in dilute aqueous solution

Several different composition temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) (P(AA‐g‐NIPAM)) graft copolymers were synthesized by free‐radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA‐g‐NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA‐g‐NIPAM) copolymers have temperature‐ and pH‐sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N‐isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA‐g‐NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ～ 10). In addition, for the P(AA‐g‐NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation of the self‐association behavior of a thermosensitive copolymer with lower critical solubility temperature near human heat by dynamic laser light scattering

The special thermosensitive copolymer with lower critical solubility temperature near human heat of 37°C in aqueous solution has been prepared successfully by copolymerizing N‐isopropylacrylamide (NIPAM) and N‐isopropylmethacrylamide (NIPMAM) randomly at an appropriate monomer ratio. The self‐association behavior of the poly[NIPAM‐ran‐NIPMAM] copolymer has been studied by dynamic laser light scattering (DLLS) at a concentration higher than the critical concentration of the self‐association calculated from viscosity data according to cluster theory. The effect of the concentration and temperature on the self‐association behavior in water has been discussed respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 583–588, 2005     

Thermosensitive properties of amphiphilic N,N‐dimethylacrylamide gel grafted with thermosensitive oligo(N‐isopropylacrylamide)

In this study, thermosensitive oligo(N‐isopropylacrylamide) [oligo(NIPAM)] chains were grafted to amphiphilic N,N‐dimethylacrylamide (DMAA) gel networks to form DMAA‐graft‐oligo(NIPAM) gels. The gels were prepared by copolymerizing oligo(NIPAM) macromonomers with DMAA. On heating, the gel caused structural changes in the gel network without causing a large volume change. The effects of the molecular weights and copolymerization ratios of oligo(NIPAM) on the temperature dependence of the swelling properties of the gel were investigated. Furthermore, to confirm the structural changes in the gel network, the temperature dependence of the diffusivity of rhodamine B through the gel membrane was investigated. Oligo(NIPAM) monomers with different molecular weights (M_n) of 2300, 7000, and 13,000 were prepared. The transition from hydrophilic to hydrophobic for oligo(NIPAM) of M_n 7000 and 13,000 was observed at about 32°C, while that of M_n 2300 was observed between 32 and 45°C. The gels grafted with oligo(NIPAM)s of M_n 7000 and 13,000 shrank above 32°C; in other words, thermosensitivity was clearly observed. On the other hand, the swelling behavior of the gel grafted with oligo(NIPAM) of M_n 2300 was similar to that of the DMAA gel; that is, negligible shrinkage of the gel was observed on heating. The diffusivity of rhodamine B through the gel membrane grafted with oligo(NIPAM) of M_n 2300 increased stepwise between 40 and 45°C. These results suggest that by selecting the molecular weights and copolymerization ratios of oligo(NIPAM), structural changes in the gel network occur without an overall volume change. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Porous dye affinity beads for nickel adsorption from aqueous solutions: A kinetic study

We investigated a new adsorbent system, Reactive Red 120 attached poly(2‐hydroxyethyl methacrylate ethylene dimethacrylate) [poly(HEMA–EDMA)] beads, for the removal of Ni²⁺ ions from aqueous solutions. Poly(HEMA–EDMA) beads were prepared by the modified suspension copolymerization of 2‐hydroxyethyl methacrylate and ethylene dimethacrylate. Reactive Red 120 molecules were covalently attached to the beads. The beads (150–250 μm), having a swelling ratio of 55% and carrying 25.5 μmol of Reactive Red 120/g of polymer, were used in the removal of Ni²⁺ ions. The adsorption rate and capacity of the Reactive Red 120 attached poly(HEMA–EDMA) beads for Ni²⁺ ions was investigated in aqueous media containing different amounts of Ni²⁺ ions (5–35 mg/L) and having different pH values (2.0–7.0). Very high adsorption rates were observed at the beginning, and adsorption equilibria were then gradually achieved in about 60 min. The maximum adsorption of Ni²⁺ ions onto the Reactive Red 120 attached poly(HEMA–EDMA) beads was 2.83 mg/g at pH 6.0. The nonspecific adsorption of Ni²⁺ ions onto poly(HEMA–EDMA) beads was negligible (0.1 mg/g). The desorption of Ni²⁺ ions was studied with 0.1M HNO₃. High desorption ratios (>90%) were achieved. The intraparticle diffusion rate constants at various temperatures were calculated as k_20°C = 0.565 mg/g min^0.5, k_30°C = 0.560 mg/g min^0.5, and k_40°C = 0.385 mg/g min^0.5. Adsorption–desorption cycles showed the feasibility of repeated use of this novel adsorbent system. The equilibrium data fitted very well both Langmuir and Freundlich adsorption models. The pseudo‐first‐order kinetic model was used to describe the kinetic data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:5056–5065, 2006     

Preparation of microspheres with silicone oil cores and poly(N‐isopropylacrylamide) shells by physical coating

Surfactant‐free thermoresponsive microspheres with a silicone oil cores surrounded by poly(N‐isopropylacrylamide) shells have been successfully prepared by physical coating method for the first time. The influences of reaction temperature, N‐isopropylacrylamide (NIPAM) dosage, and stirring rate on the formation, morphology, particle size, and monodispersity of microspheres were experimentally studied. In the preparation of microspheres, when reaction temperature was above the lower critical solution temperature of poly(N‐isopropylacrylamide), products had higher yield of particles and narrower size distribution. With increasing NIPAM dosage, the particle diameter became larger and the shell layer thickened and the monodispersity became better. With increasing stirring rate, the particle diameter and the monodispersity decreased obviously. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5571–5576, 2006     

Preparation of poly(divinylbenzene‐co‐N‐isopropylacrylamide) microspheres and their hydrogen‐bonding assembly behavior for raspberry‐like core‐corona polymer composite

Narrowdisperse poly(divinylbenzene‐co‐N‐isopropylacrylamide) (poly(DVB‐co‐NIPAM)) functional microspheres with the diameter in the range of 630 nm and 2.58 μm were prepared by distillation–precipitation polymerization in neat acetonitrile in the absence of any stabilizer. The effect of N‐isopropylacrylamide (NIPAM) ratio in the comonomer feed on the morphology of the resultant polymer particles was investigated in detail with divinylbenzene (DVB) as crosslinker and 2,2′‐azobisisobutyronitrile (AIBN) as initiator. The monodisperse poly(DVB‐co‐NIPAM) microspheres with NIPAM fraction of 20 wt % were selected for the preparation of raspberry‐like core‐corona polymer composite by the hydrogen‐bonding self‐assembly heterocoagulation with poly(ethyleneglycol dimethacrylate‐co‐acrylic acid) [poly(EGDMA‐co‐AA)] nanospheres. Both of the functional poly(DVB‐co‐NIPAM) microspheres and the core‐corona particles were characterized with scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and elemental analysis (EA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1350–1357, 2007     

Preparation and thermal response behavior of poly(N‐isopropylacrylamide‐co‐a crylic acid) microgels via soap‐free emulsion polymerization based on AIBN initiator

Poly(N‐isopropylacrylamide‐co‐acrylic acid) (poly(NIPAM‐co‐AA)) microgels with different copolymer compositions were prepared through soap‐free emulsion polymerization at 80°C, and 2, 2′‐azobisisobutyronitrile (AIBN) was used as initiator. Scanning electron microscope (SEM) characterization shows that the prepared microgels are regular and smooth and not easy to distort. Result of ¹H‐NMR characterization shows that with increasing of the initial concentration of AA (AA in feed), the AA content in polymer chains increases. The thermal response of microgels latex was investigated by UV‐3010 spectrophometer through detecting the transmittance of the latex at different temperature in the range of 190–900 nm. The thermal response of the poly(NIPAM‐co‐AA) microgels was tested by dynamic light scattering (DLS). The results show that with the increase of AA content in polymer chains, the low critical solution temperature (LCST) of microgels latex first decreases and then increases. Still, with increasing of AA in poly(NIPAM‐co‐AA) microgels, the LCST of microgels first increases and then decreases. The basic reasons causing the changes of LCST of microgels latex and microgels are interpreted clearly in this article from the perspective of hydrogen bonding interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enzyme flow microcalorimetry—a useful tool for screening of immobilized penicillin G acylase

Screening of a representative series of immobilized penicillin G acylase biocatalysts (enzyme, cells) using enzyme flow microcalorimetry is described. Immobilized penicillin G acylase biocatalysts were either prepared in the laboratory by various techniques or obtained from four commercial manufacturers. An industrial strain of Escherichia coli was entrapped in (poly)acrylamide gel or hardened calcium pectate gel. Semi-purified enzyme was immobilized in various ways—either by covalent binding to oxirane-acrylic beads or chlorotriazine bead cellulose or by entrapment in (poly)acrylamide gel. The validity of the enzyme flow microcalorimetry results was corroborated by a pH-stat method, showing enzyme flow microcalorimetry to be a suitable method for rapid screening of immobilized biocatalysts regardless of the immobilization technique, carrier type or the biocatalyst source. © 1998 Society of Chemical Industry     

Swelling–deswelling kinetics of poly(N‐isopropylacrylamide) hydrogels formed in PEG solutions

A series of poly(N‐isopropylacrylamide) (PNIPA) hydrogels was prepared by free‐radical crosslinking copolymerization of N‐isopropylacrylamide (NIPA) and N,N′‐methylenebisacrylamide (BAAm) in aqueous solutions of poly(ethylene glycol) of molecular weight 300 g/mol (PEG). The amount of PEG in the polymerization solvent, the crosslinker (BAAm) content, and the gel preparation temperature (T_prep) were varied in the gelation experiments. The hydrogels were characterized by the equilibrium swelling and elasticity tests as well as by the measurements of the deswelling–reswelling kinetics of the hydrogels in response to a temperature change between 25 and 48°C. The rate of deswelling of the swollen gel increases while the rate of reswelling of the collapsed gel decreases as the amount of PEG in the polymerization solvent is increased or as the crosslinker content is decreased. The T_prep effect on the swelling kinetics of the hydrogels was only observed if the PEG content of the polymerization solvent is less than 20%, which is explained with the screening of H‐bonding interactions in concentrated PEG solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 37–44, 2006     

Immobilization of polyphenol oxidase on carboxymethylcellulose hydrogel beads: preparation and characterization

Carboxymethylcellulose (CMC) beads were prepared by a liquid curing method in the presence of trivalent ferric ions, and epicholorohydrin was covalently attached to the CMC beads. Polyphenol oxidase (PPO) was then covalently immobilized onto CMC beads. The enzyme loading was 603 µg g⁻¹ bead and the retained activity of the immobilized enzyme was found to be 44%. The K_m values were 0.65 and 0.87 mM for the free and the immobilized enzyme, and the V_max values were found to be 1890 and 760 U mg⁻¹ for the free and the immobilized enzyme, respectively. The optimum pH was 6.5 for the free and 7.0 for the immobilized enzyme. The optimum reaction temperature for the free enzyme was 40 °C and for the immobilized enzyme was 45 °C. Immobilization onto CMC hydrogel beads made PPO more stable to heat and storage, implying that the covalent immobilization imparted higher conformational stability to the enzyme. © 2000 Society of Chemical Industry     

The effect of external stimuli on the invertase adsorption capacity of poly(N-vinyl-2-pyrrolidone-co-itaconic acid) hydrogels

Polyelectrolyte Poly(N-vinyl-2-pyrrolidone-co-itaconic acid) hydrogels (P(VP/IA)) with varying compositions were prepared from ternary VP/IA/water mixtures. The effect of external stimuli such as pH of the solution, temperature, substrate concentration of solution, and storage stability on the invertase adsorption capacity of P(VP/IA) hydrogels was investigated. The adsorption capacity of the hydrogels was found to increase from 4.4 to 18.4 mg invertase/g dry gel with increasing amount of IA in the gel system, while P(VP) gel adsorbed only 3.1 mg invertase/g dry gel. Kinetic parameters were calculated as Michaelis-Menten constant K_m = 20.6 mmol L^–1 and maximum velocity V_max = 6.44×10^–5 mol dm^–3 min^–1 for free enzyme and in the range of K_m = 26.4–41.1 mmol L^–1 and V_max = 6.35·10^–5–6.66·10^–5 mol dm^–3 min^–1, depending on the amount of IA in the hydrogel. Enzyme activities were found to increase from 59.0% to 72.0% with increasing amount of IA in the gel system and retained their activities for one month storage. The enzyme activities, after storage for one month at 4°C, were found to be 21.0% and 59.0–74.0% of the initial activity values for free and adsorbed enzyme, respectively. The optimal pH values for free and adsorbed enzymes were determined as 4.56 and 5.00, respectively. The optimum temperature for free and adsorbed enzymes was 55°C. Adsorption studies have shown that not only the gel composition but also the stimuli, temperature and pH of the solution play an important role on the invertase adsorption capacity of poly(VP/IA) hydrogels.     

Immobilization of catalase in poly(isopropylacrylamide-co-hydroxyethylmethacrylate) thermally reversible hydrogels

Catalase was entrapped in thermally reversible poly(isopropylacrylamide-co-hydroxyethylmethacrylate) (pNIPAM/HEMA) copolymer hydrogels. The thermoresponsive hydrogels, in cylindrical geometry, were prepared in an aqueous buffer by redox polymerization. It was observed that upon entrapment, the activity retention of catalase was decreased between 47 and 14%, and that increasing the catalase loading of hydrogel adversely affected the activity. The kinetic behaviour of the entrapped enzyme was investigated in a batch reactor. The apparent kinetic constant of the entrapped enzyme was determined by the application of Michaelis–Menten model and indicated that the overall reaction rate was controlled by the substrate diffusion rate through the hydrogel matrix. Due to the thermoresponsive character of the hydrogel matrix, the maximum activity was achieved at 25 °C with the immobilized enzyme. The K_m value for immobilized catalase (28.6 mM) was higher than that of free enzyme (16.5 mM). Optimum pH was the same for both free and immobilized enzyme. Operational, thermal and storage stabilities of the enzyme were found to increase with immobilization. © 1999 Society of Chemical Industry     

Thermotropic color changing nanoparticles prepared by encapsulating blue polystyrene particles with a poly‐N‐isopropylacrylamide gel

Water‐dispersed thermotropic nanoparticles with core‐shell structures were synthesized by the in situ polymerization of a lightly crosslinked shell of poly(N‐ isopropylacrylamide) [poly(NIPAM)] onto blue polystyrene cores. At room temperature, the thermal responsive outer shell is hydrophilic and is in a fully swollen gel state; but as the temperature is raised above 31°C, it becomes increasingly hydrophobic and eventually collapses as the temperature reaches the lower critical solution temperature (LCST) of the poly(NIPAM). Passing through the LCST has a drastic effect on the color of the latex solution, which exhibited an intense blue color at room temperature and gradually pales or lightens as the temperature is raised above 31°C. Analysis using spectroscopic and dynamic light scattering techniques showed that it is a reversible process. Microscopy evaluation of samples dried by the evaporation of water at temperatures above and below the LCST revealed that the swollen/collapse state of the polymer shell influenced the morphology of the dry state. Drying at room temperature resulted in thin films in which only particles of sizes corresponding to the polystyrene core are clearly seen in the microscopy images; but for samples prepared above the LCST, the images revealed a morphology made of much larger particles with diameters of 400–500 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

One-step preparation of poly(NIPAM-pyrrole) electroconductive composite hydrogel and its dielectric properties

Conductive polymers and hydrogels are two of the hot prospect polymer types that are used for new stimuli responsive materials. In this study, one-step preparation of electroconductive composite hydrogels containing polypyrrole (PPy) and N-isopropylacrylamide (NIPAM) using free radical polymerization technique was achieved with N,N-methylenebisacrylamide as a crosslinker and ammonium peroxy disulphate (APS) as initiator, in mixture of water/isopropyl alcohol. The equilibrium swelling degree of the poly(NIPAM)-pyrrole) electroconductive composite hydrogel was 9.88 g of H₂O/g dry polymer. According to TGA results, the thermal stability of the prepared composite poly(NIPAM-PPy) conductive hydrogel (700°C) hydrogel is higher than that of pure poly(NIPAM) hydrogel (600°C). Furthermore, prepared samples were characterized by FTIR, and SEM analyzes. Later, the samples were pressured into pellets so that electrical impedance spectroscopy (EIS) measurements were taken between 10 and 10 MHz at room temperature. The dielectric constant value of composite poly(NIPAM-PPy) hydrogel at 10 Hz is almost 10 times higher than that of poly(NIPAM) hydrogel. Both samples' real and imaginary parts of dielectric constant decreased with increased frequency. Samples exhibited non-Debye relaxation since experimental data fit into dielectric model of Havriliak-Negami. Moreover, low frequency data yielded d.c. conductivity of the pure and composite samples as 3.74 × 10⁻¹¹ and 1.02 × 10⁻⁸ S/cm, respectively. Real part of impedance at low frequencies also points out ~10³ times lower resistance values at 10 Hz for composite poly(NIPAM-PPy) hydrogel. Therefore, EIS results support that electroconductive composite hydrogel fabrication was achieved using free radical polymerization technique.     

Release behavior of freeze‐dried alginate beads containing poly(N‐isopropylacrylamide) copolymers

Beads composed of alginate, poly(N‐isopropylacrylamide) (PNIPAM), the copolymers of N‐isopropylacrylamide and methacrylic acid (P(NIPAM‐co‐MAA)), and the copolymers of N‐isopropylacrylamide, methacrylic acid, and octadecyl acrylate (P(NIPAM‐co‐MAA‐co‐ODA)), were prepared by dropping the polymer solutions into CaCl₂ solution. The beads were freeze‐dried and the release of blue dextran entrapped in the beads was observed in distilled water with time and pH. The degree of release was in the order of alginate bead < alginate/PNIPAM bead ≈ alginate/P(NIPAM‐co‐MAA) bead < alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead. On the other hand, swelling ratios reached steady state within 20 min, and the values were 200–800 depending on the bead composition. The degree of swelling showed the same order as that of release. Among the beads, only alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead exhibited pH‐dependent release. At acidic condition, inter‐ and intraelectrostatic repulsion is weak and P(NIPAM‐co‐MAA‐co‐ODA) could readily be assembled into an aggregate due to the prevailing hydrophobic interaction of ODA. Thus, it could block the pore of bead matrix, leading to a suppressed release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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