Synthesis and characterization of temperature‐sensitive block copolymers from poly(N‐isopropylacrylamide) and 4‐methyl‐ε‐caprolactone or 4‐phenyl‐ε‐caprolactone

This study synthesizes thermally sensitive block copolymers poly(N‐isopropylacrylamide)‐b‐poly(4‐methyl‐ε‐caprolactone) (PNIPA‐b‐PMCL) and poly(N‐isopropylacrylamide)‐b‐poly(4‐phenyl‐ε‐caprolactone) (PNIPA‐b‐PBCL) by ring‐opening polymerization of 4‐methyl‐ε‐caprolactone (MCL) or 4‐phenyl‐ε‐caprolactone (BCL) initiated from hydroxy‐terminated poly(N‐isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct₂ as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2‐hydroxyethanethiol (ME) as a chain‐transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), ¹H‐NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (T_g) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases T_g. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA‐b‐PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29–2.74 mg L^?1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of doubly responsive polymer functionalized silica hybrid nanoparticles via a one‐pot thiol‐isocyanate click reaction at room temperature

Well‐defined poly(N‐isopropylacrylamide) and poly(2‐(diethylamino) ethyl methacrylate) were synthesized first by a reversible addition‐fragmentation chain transfer process. These polymers were then reduced to generate an end thiol group to react with isocyanate groups on the surface of silica nanoparticles, which were pretreated with toluene‐2,4‐diisocyanate, by a one‐pot “click” reaction to prepare temperature and pH responsive polymer functionalized hybrid silica nanoparticles. The polymer functionalized silica hybrid nanoparticles were characterized by a range of techniques such as Fourier transform infrared spectroscopy and dynamic light scattering. The doubly responsive polymer functionalized silica hybrid nanoparticles show both temperature and pH responsive behavior and their solution properties were dependent on the ratio of the two polymers on the surface of silica. Covalent functionalization of the silica nanoparticle with well‐defined temperature and pH responsive polymers was accomplished via a one‐pot thiol‐isocyanate click reaction. This reaction was found to be extremely efficient in producing doubly responsive polymer functionalized silica hybrid nanoparticle, even at relatively low reaction temperature and short reaction time. Thermogravimetric analysis indicated that the same ratio of poly(N‐isopropylacrylamide) and poly(2‐(diethylamino)ethyl methacrylate) functionalized silica hybrid nanoparticle consisted of 42.46 wt% polymer. POLYM. COMPOS., 38:1454–1461, 2017. © 2015 Society of Plastics Engineers     

Surface‐initiated atom transfer radical polymerization of regenerated cellulose membranes with thermo‐responsive properties

Using atom transfer radical polymerization (ATRP), thermo‐responsive regenerated cellulose membranes were synthesized. Regenerated cellulose membranes were firstly modified by reacting the hydroxyl groups on the surface with 2‐bromoisobutyryl bromide, followed by grafting with poly(N‐isopropylacrylamide). The membranes had obvious thermally modulated permeability properties. Analysis was carried out by means of X‐ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results showed that N‐isopropylacrylamide had been grafted successfully on the surface of the regenerated cellulose membranes. The thermally modulated permeability properties of the grafted membranes were studied using water flux measurements. It was found that the thermally modulated permeability properties of a cellulose surface can be tailored by the use of the ATRP method. Copyright © 2010 Society of Chemical Industry     

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     

Multiarm star‐like unimolecular micelles with a dendritic core and a dual thermosensitive shell

Stimuli‐responsive unimolecular polymeric micelles have attracted much interest because of their unique structures and properties. In this paper, the double phase transition behavior of unimolecular dendritic three‐layer nanostructures with dual thermoresponsive shells is studied. By using a hydrophobic hyperbranched polyester (Bolton H40)‐based macro reversible addition‐fragmentation transfer (macro‐RAFT) agent, the polymerizations of N‐isopropylacrylamide (NIPAM) and N‐isopropylmethacrylamide (NIPMAM) were conducted via the successive RAFT process. The dendritic core‐shell architecture prepared, i.e. H40‐poly(N‐isopropylacrylamide)‐block‐poly(N‐isopropylmethacrylamide) (H40‐PNIPAM‐b‐PNIPMAM), exists as unimolcular polymeric micelles with hydrophobic dendritic H40 as the core, PNIPAM as the inner shell and PNIPMAM as the corona. Upon continuous heating through the lower critical solution temperatures of PNIPAM and PNIPMAM, dendritic H40‐PNIPAM‐b‐PNIMAM exhibits two‐stage thermoresponsive collapse. Different parts of the shells of H40‐PNIPAM‐b‐PNIMAM were selectively labeled with pyrene (Py) to result in H40‐PNIPAM(Py)‐b‐PNIMAM with inner shell labeling and H40‐PNIPAM‐b‐PNIMAM(Py) with outer corona labeling. Laser light scattering, UV‐visible transmittance, micro‐differential scanning calorimetry and excimer fluorescence measurements were used in combination to probe the conformational changes of chains located at the inner layer and outer corona during the two‐stage collapse upon heating. Results from all four techniques support the double phase transition behavior of this kind of three‐layer dendritic polymer. Copyright © 2010 Society of Chemical Industry     

Preparation of temperature‐ and pH‐sensitive,stimuli‐responsive poly(N‐isopropylacrylamide‐co‐methacrylic acid) nanoparticles

The effects of the monomer ratio, surfactant, and crosslinker contents on the particle size and phase‐transition behavior of the copolymer poly(N‐isopropylacrylamide‐co‐methacrylic acid) (PNIPAAm–MAA) were investigated with Fourier transform infrared, differential scanning calorimetry, and dynamic laser scattering techniques. In addition to the thermoresponsive property of poly(N‐isopropylacrylamide), ionized methacrylic acid groups brought pH sensitivity to the PNIPAAm–MAA copolymer particles. The polymer particle size varied with the amounts of the monomer ratio, surfactant, and crosslinker. As the monomer ratio and crosslinker content increased and the amount of the surfactants decreased, the particle size increased. The influence of the crosslinker content on the particle size was less significant than the effect of the monomer ratio and surfactants. When the temperature increased, the particles tended to shrink and decreased in size to near or below 100 nm. Particle sizes at 20°C decreased to less than 100 nm with increased surfactant content. The control of the particle size within the 100‐nm range makes PNIPAAm–MAA copolymer particles useful for biomedical and heavy‐metal‐ion adsorption applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication of pH‐ or temperature‐responsive single wall carbon nanotubes via a graft from photopolymerization

An ultraviolet light initiated “graft from” polymerization method to fabricate polymer‐functionalized single wall carbon nanotubes (SWNTs) with pendant pH‐ and temperature‐responsive polymer chains is utilized. The attached polymer chains, formed from methacrylic acid and poly(ethylene glycol) methyl ether methacrylate monomers, are well established for its pH‐responsive swelling/deswelling behavior. This special property was utilized here to control the aqueous dispersibility of the carbon nanotubes. Furthermore, poly(N‐isopropylacrylamide), a temperature‐responsive polymer, was utilized in the fabrication of SWNTs whose dispersibility was dependent on solution temperature. The morphology of the polymer‐functionalized carbon nanotubes was characterized by scanning electron microscopy (SEM) before and after functionalization. Environmental SEM was used to further characterize the morphology of the functionalized SWNTs. In addition, covalent bonding of the polymer to the carbon nanotube surface was established using Raman and Fourier transform infrared spectroscopic techniques. The physical and chemical properties of the functionalized nanotubes were further characterized by energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2980–2986, 2012     

Semi‐interpenetrating networks based on poly(N‐isopropyl acrylamide) and poly(N‐vinylpyrrolidone)

Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cephazoline sodium release from poly(N‐isopropyl acrylamide‐co‐N,N‐dimethylacrylamide) hydrogels

Hydrogels are hydrophilic polymers that swell to an equilibrium volume in the presence of water, preserving their shape. The dynamic swelling behavior of poly(N‐isopropylacrylamide‐co‐N,N‐dimethylacrylamide) [poly(NIPA‐co‐DMA)] copolymers at 37°C was investigated. It was observed that the swelling degree in the copolymers decreases with the N‐isopropylacrylamide content. In addition, the liberation mechanism was found to be Fickian. Diffusion coefficients according to Fick′s law as a function of the N‐isopropylacrylamide concentration and results of the release process are reported. The kinetics of cephazoline sodium release from poly(NIPA‐co‐DMA) hydrogels with different compositions was studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3433–3437, 2004     

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

Titania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO₂ microparticles via a straightforward controlled surface‐initiated polymerization method.     

Hollow poly(N‐isopropylacrylamide)‐co‐poly(acrylic acid) microgels with high loading capacity for drugs

A convenient approach has been developed for the preparation of microsize hydrogels composed of crosslinked poly(acrylic acid) (PAA) and poly(N‐isopropylacrylamide) (PNIPAm). First, semi‐interpenetration polymer networks of hydropropylcellulose (HPC) and PNIPAm‐co‐PAA copolymer are formed through the copolymerization and crosslinking of monomer acrylic acid and N‐isopropylacrylamide in HPC aqueous solution. After the selective removal of HPC from networks due to ionization of PAA units and disruption of hydrogen bonding with increasing pH, PNIPAm‐co‐PAA microgels are obtained, whose volume is confirmed to be responsive to both temperature and pH. Doxorubicin hydrochloride (Dox) can be encapsulated in PNIPAm‐co‐PAA microgels with high drug loading driven by the electrostatic interaction, and a sustained‐release characteristic of Dox from the microgels is observed under physiological pH value and temperature. In vitro cell experiments, the drug‐loaded microgels can be taken up by LoVo cells and release their payload in cell cytoplasm without loss of drug efficacy. This indicates that PNIPAm‐co‐PAA microgels might be a potential drug delivery carriers especially for water‐soluble or polypeptide drugs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on pH‐sensitive and thermosensitive polymer networks containing polyacetal segments

A series of pH‐sensitive and thermosensitive polymer networks were first obtained by copolymerization of telechelic poly(1,3‐dioxolane) (PDXL) with acrylic acid (AA), acrylamide (AM), and N‐isopropylacrylamide (NIPAM), respectively. The copolymerization of PDXL diacrylate (PDXLDA) with AA, AM, or NIPAM is expected to lead to polymer networks in which homopolymeric segments of the monomer are connected by polyacetal segments. As a combination of these two parts, these polymer networks can have some interesting physical properties. For example, the copolymer networks of poly(AA‐b‐DXL) showed pH sensitivity, and both the copolymer networks of poly(AM‐b‐DXL) and poly(NIPAM‐b‐DXL) showed temperature sensitivity. Moreover, because of the low ceiling temperature of polyDXL, the networks containing polyacetal segments (PDXL) can degrade by treatment with a trace of appropriate cationic initiator. The polymer networks prepared were characterized by Fourier transform infrared, differential scanning calorimetry, and swelling data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3002–3006, 2002; DOI 10.1002/app.2329     

Thermosensitive nanoparticles prepared from poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) and its blend with poly(lactide‐co‐glycolide) for efficient drug delivery system

Temperature‐responsive polymers have become increasingly attractive as carrier for the injectable drug delivery systems. In the present work, we have studied the preparation of poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) (NIPAAm‐AAm‐VP terpolymer) nanoparticulated terpolymer and its blend with poly(lactide‐co‐glycolide, PLGA; molar ratio of lactide/glycolid 1/3). Thermosensitive terpolymer, poly(NIPAAm‐AAm‐VP) was prepared by free‐radical polymerization in aqueous solution. The nanoparticles of poly(NIPAAm‐AAm‐VP) and its blend with PLGA containing naltrexone were prepared using the evaporation and w/o emulsion‐solvent evaporation methods, respectively. Nanoparticles prepared from terpolymer‐PLGA blend at low polymer concentration (5%) shows larger particle size (>300 nm) and higher drug content%. Various types of nanoparticles showed a burst release of less than 10% after 24 h . The results suggest that by regulating different variables, desired release profiles of naltrexone can be achieved using a blend of PLGA‐poly(NIPAAm‐AAm‐VP) nanoparticulate system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Lower critical solution temperatures of thermo‐responsive poly(N‐isopropylacrylamide) copolymers with racemate or single enantiomer groups

BACKGROUND: Thermo‐responsive copolymers with racemate or single enantiomer groups are attracting increasing attention due to their fascinating functional properties and potential applications. However, there is a lack of systematic information about the lower critical solution temperature (LCST) of poly(N‐isopropylacrylamide)‐based thermo‐responsive chiral recognition systems. In this study, a series of thermo‐responsive chiral recognition copolymers, poly[(N‐isopropylacrylamide)‐co‐(N‐(S)‐sec‐butylacrylamide)] (PN‐S‐B) and poly[(N‐isopropylacrylamide)‐co‐(N‐(R,S)‐sec‐butylacrylamide)] (PN‐R,S‐B), with different molar compositions, were prepared. The effects of heating and cooling processes, optical activity and amount of chiral recognition groups in the copolymers on the LCSTs of the prepared copolymers were systematically studied. RESULTS: LCST hysteresis phenomena are found in the phase transition processes of PN‐S‐B and PN‐R,S‐B copolymers in a heating and cooling cycle. The LCSTs of PN‐S‐B and PN‐R,S‐B during the heating process are higher than those during the cooling process. With similar molar ratios of N‐isopropylacrylamide groups in the copolymers, the LCST of the copolymer containing a single enantiomer (PN‐S‐B) is lower than that of the copolymer containing racemate (PN‐R,S‐B) due to the steric structural difference. The LCSTs of PN‐R,S‐B copolymers are in inverse proportion to the molar contents of the hydrophobic R,S‐B moieties in these copolymers. CONCLUSION: The results provide valuable guidance for designing and fabricating thermo‐responsive chiral recognition systems with desired LCSTs. Copyright © 2008 Society of Chemical Industry     

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     

Fast responsive and strong swelling hydrogels based on N‐isopropylacrylamide with sodium acrylate

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels with N,N‐methylene bisacrylamde (BIS) as crosslinker were prepared by free radical polymerization method at the temperature of 35°C, which was just around the lower critical solution temperature (LSCT) of the hydrogels. The gels synthesized at 35°C demonstrated strong swellability and fast responseability when compared with the gels synthesized at the temperature of 0 and 18°C (below the LCST) and 50 and 80°C (above the LSCT). The response rate and swelling behavior of poly(N‐isopropylacrylamide‐co‐sodium acrylate) gels was investigated and characterized by the temperature‐dependent swelling ratio and swelling and deswelling kinetics. The swelling behavior of the gels indicated that the synthesis temperature was the main factor when the swellability concerned and also had effect on the responseability of the resulting hydrogels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of amphiphilic temperature‐sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers and micellar characterization

Amphiphilic thermally sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers were synthesized by ring‐opening polymerization of tetramethylene carbonate with hydroxyl‐terminated poly(N‐isopropylacrylamide) (PNiPAAm) as macro‐initiator in the presence of stannous octoate as catalyst. The synthesis involved PNiPAAm bearing a single terminal hydroxyl group prepared by telomerization using 2‐hydroxyethanethiol as a chain‐transfer agent. The copolymers were characterized using ¹H NMR and Fourier transform infrared spectroscopy and gel permeation chromatography. Their solutions show reversible changes in optical properties: transparent below the lower critical solution temperature (LCST) and opaque above the LCST. The LCST depends on the polymer composition and the media. Owing to their amphiphilic characteristics, the block copolymers form micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range 1.11–22.9 mg L^?1. Increasing the hydrophobic segment length or decreasing the hydrophilic segment length in the amphiphilic diblock copolymers produces lower CMCs. A core‐shell structure of the micelles is evident from ¹H NMR analyses of the micelles in D₂O. Transmission electron microscopic analyses of micelle morphology show a spherical structure of both blank and drug‐loaded micelles. The blank and drug‐loaded micelles have an average size of less than 130 nm. Observations show high drug‐entrapment efficiency and drug‐loading content for the drug‐loaded micelles. Copyright © 2010 Society of Chemical Industry     

Highly efficient adsorbent for organic dyes based on a temperature‐ and pH‐responsive multiblock polymer

The self‐assembly behavior of amphiphilic block copolymers in selective solutions has many applications in environmentally responsive polymer materials. In this article, we report on a new amphiphilic, temperature and pH dual‐responsive poly[2‐dimethylaminoethyl methacrylate‐co‐(methyl methacrylate)]‐b‐poly[poly(ethylene glycol) methacrylate] [P(DMAEMA‐co‐MMA)‐b‐PPEGMA], which was synthesized via reversible addition–fragmentation chain‐transfer polymerization. The structure, self‐assembly behaviors, and process of organic dye adsorption were characterized by ¹H‐NMR, ultraviolet–visible absorbance spectroscopy, and DLS measurements. P(DMAEMA‐co‐MMA)‐b‐PPEGMA was proven to be an outstanding adsorbent with excellent reversibility. Methyl red was released from the micelles as the pH value of the solution was adjusted to 4, and it could also be encapsulated again when the pH value was adjusted to 7.4 because of the sensitive pH‐responsive ability. It is promising that the triblock polymer had a positive effect on dye adsorption for environmental protection. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46626.     

Swelling and hydrolytic degradation behaviour of pH‐responsive hydrogels of poly[(N‐isopropylacrylamide)‐co‐(methacrylic acid)] crosslinked by biodegradable polycaprolactone chains

BACKGROUND: Stimuli‐responsive hydrogels are typically obtained from non‐biodegradable monomers. The use of biodegradable crosslinkers can overcome this limitation. In this context, the main aim of this work was to use modified polycaprolactone as a crosslinker in the preparation of pH‐responsive hydrogels based on N‐isopropylacrylamide and methacrylic acid to give poly[(N‐isopropylacrylamide)‐co‐(methacrylic acid)] (P(N‐iPAAm‐co‐MAA)). RESULTS: Poly(caprolactone) dimethacrylate macromonomer was synthesized and successfully employed as crosslinker with various ratios in the synthesis of well‐known pH‐responsive hydrogels of P(N‐iPAAm‐co‐MAA). The swelling properties of these degradable hydrogels were investigated. They practically do not swell at pH = 2, but exhibit a very high swelling capacity in distilled water and in solutions of pH = 7. In addition, degradation studies at pH = 12 showed that the hydrolysis of the ester groups in the polycaprolactone chains produces, after a relatively short time, the total solubilization of the polymer chains. CONCLUSION: The hydrogels under study have certain characteristics that could make them good candidates for use as matrices in controlled drug delivery. On the one hand, they do not swell in acid pH solution (stomach conditions) but they swell extensively at neutral pH. On the other hand, they became rapidly water soluble following degradation. Copyright © 2009 Society of Chemical Industry     

A new route for the preparation of cyano‐containing poly(N‐isopropylacrylamide) microgel latex for specific immobilization of antibodies

A prepolymerization process was used to prepare functionalized poly(N‐isopropylacrylamide) latexes with surface cyano groups. The functionalized latexes prepared were characterized by FTIR, ¹H NMR, scanning electron microscopy and quasi‐elastic light scattering. In addition, the polymerization conversion and the water‐soluble polymer amounts were quantified. The polymerization conversions were found to be above 80% with 5–14 wt% of water soluble polymer formation. The immobilization of antibody (immunoglobulin) onto such cyano‐containing thermally sensitive particles, suggests the feasibility of specific dipole–dipole interactions between the cyano and hydroxyl functional groups from particle and antibody, respectively. Copyright © 2004 Society of Chemical Industry