Synthesis, characterization and thermoreversible behaviours of poly(dimethyl siloxane)/poly(N-isopropyl acrylamide) semi-interpenetrating networks

Simultaneous and sequential poly(N-isopropyl acrylamide) (PNIPAAm)/poly(dimethyl siloxane) (PDMS) semi-interpenetrating polymer networks (IPNs) with different linear PDMS contents were prepared by free radical polymerization method. Their phase morphologies have been characterized by FTIR, DSC and SEM. The simultaneous semi-IPNs exhibited phase transition temperatures (T_pt) shifted higher temperature from glass transition temperatures (T_g) of their respective homopolymers, suggesting a heterophase morphology and only physical entanglement between the PNIPAAm network and linear PDMS with high molecular weight (Mn≈9000 g/mol). For sequential semi-IPNs, the shift of T_pts towards lower temperature suggested that the chemical interaction between the constituents of the IPNs increased with increasing PDMS content in the network. In addition, these semi-IPNs were characterized for their thermo-sensitive behaviour by equilibrium swelling studies. The results showed that incorporation of hydrophobic PDMS polymer into the thermo- and pH-sensitive PNIPAAm and P(NIPAAm-co-IA) (itaconic acid) hydrogels by semi-IPN formation decreased swelling degrees of IPNs without affecting their LCSTs whereas addition of acrylated PDMS (Tegomer V-Si 2250) as crosslinker instead of N,N^′-methylenebisacrylamide (BIS) into the structures of these hydrogels changed their LCSTs along with their swelling degrees.     

Semi‐interpenetrating polymer networks composed of poly(N‐isopropyl acrylamide) and polyacrylamide hydrogels

Three series of semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropyl acrylamide) (PNIPA) and 1 wt % nonionic or ionic (cationic and anionic) linear polyacrylamide (PAAm), were synthesized to improve the mechanical properties of PNIPA gels. The effect of the incorporation of linear polymers into responsive networks on the temperature‐induced transition, swelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with various molar ratios (25:1 to 100:1) of the monomer (N‐isopropyl acrylamide) to the crosslinker (methylenebisacrylamide). The hydrogels were characterized by the determination of the equilibrium degree of swelling at 25 °C, the compression modulus, and the effective crosslinking density, as well as the ultimate hydrogel properties, such as the tensile strength and elongation at break. The introduction of cationic and anionic linear hydrophilic PAAm into PNIPA networks increased the rate of swelling, whereas the presence of nonionic PAAm diminished it. Transition temperatures were significantly affected by both the crosslinking density and the presence of linear PAAm in the hydrogel networks. Although anionic PAAm had the greatest influence on increasing the transition temperature, the presence of nonionic PAAm caused the highest dimensional change. Semi‐interpenetrating polymer networks reinforced with cationic and nonionic PAAm exhibited higher tensile strengths and elongations at break than PNIPA hydrogels, whereas the presence of anionic PAAm caused a reduction in the mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3987–3999, 2004     

Novel Interpenetrating Networks (IPNs) Hydrogels Prepared In Situ by Liquid-Phase Photopolymerization

Novel interpenetrating networks (IPNs) hydrogels responsive to temperature were prepared in situ by liquid-phase photopolymerization. The first network of the IPNs (poly isopropyl acrylamide) were formed with a special kind of hectorite (Laponite XLS) modified by tetrasodium pyrophosphate as cross-linker and 2-oxogultaric acid as photoinitiator. The samples were subsequently immersed in an acrylamide (AAm) aqueous solution for at least one day for preparing IPNs hydrogels, in which acrylamide aqueous solution containing N,N′-Dimetyl acrylamide (MBAA) as cross-linker and 2-oxogultaric acid as photoinitiator. Then the second networks were in situ formed by introducing ultraviolet light irradiated PNIPAAm gels. The swelling/deswelling behaviors of IPNs hydrogels were measured. Compared with the corresponding nanocomposite PNIPAAm hydroges(NC hydrogels), chemically cross-linked PNIPAAm and PAAm IPNs hydrogels, the results indicate that the new IPN hydrogel has a faster deswelling rate above its LCST (≈32 °C). The effect was explained as being an additional contribution of the PAAm chains in IPN hydrogels, which may act as a water-releasing channel when the hydrophobic aggregation of PNIPA takes place.     

Swelling Behavior of Semi‐Interpenetrating Polymer Network Hydrogels Based on Chitosan and Poly(acryl amide)

Semi‐interpenetrating polymer networks (semi‐IPNs) composed of chitosan and polyacrylamide (PAAm) hydrogels have been prepared, and the effect of changing pH, temperature, ionic concentration, and applied electric fields on the swelling of the hydrogels was investigated. The swelling kinetics increased rapidly, reaching equilibrium within 60 min. The semi‐IPN hydrogels exhibited a relatively high swelling ratios of 385%–569% at T=25°C. The swelling ratio increased with decreasing pH below pH=7 due to the dissociation of ionic bonds. The swelling ratio of the semi‐IPN hydrogels was pH, ionic concentration, temperature, and electric field dependent. Differential scanning calorimetry (DSC) was used to determine the volume of free water in the semi‐IPN hydrogels, which was found to increase with increasing PAAm content.     

Synthesis and characterization of thermosensitive interpenetrating polymer networks based on N-isopropylacrylamide/N-acryloxysuccinimide, crosslinked with polylysine, grafted onto polypropylene

Interpenetrating polymer networks (IPNs) based on poly (N-isopropylacrylamide), (PNIPAAm) and poly (N-acryloxysuccinimide) (PNAS), grafted onto polypropylene (PP), were synthesized in three consecutive steps using ionizing radiation in the first and second steps and chemical reaction in third one. In the first step a thermosensitive graft copolymer of NIPAAm onto PP film was obtained by gamma radiation with a ⁶⁰Co source. The grafted side chains of PNIPAAm were then crosslinked with gamma radiation to give net-[PP-g-NIPAAm]. The secondary network was obtained in situ by chemical crosslinking between PNAS and polylysine (pLys). The PP-g-IPNs exhibited the lower critical solution temperature (LCST) at around 32 °C. Based on its thermoreversible behavior, this system could be used for immobilization of biomolecules. The phase transition temperature (LCST) and network properties of the IPNs were measured by swelling behavior. Additional characterization by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and infrared (FTIR-ATR) determinations are reported.     

Dual temperature‐ and pH‐sensitive hydrogels from interpenetrating networks and copolymerization of N‐isopropylacrylamide and sodium acrylate

Hydrogels responsive to both temperature and pH have been synthesized in the forms of sequential interpenetrating networks (IPNs) of N‐isopropylacrylamide (NIPAAm) and sodium acrylate (SA) and compared with the crosslinked random copolymers of N‐isopropylacrylamide and SA. Whereas the stimuli‐sensitive behaviors of copolymer hydrogels were strongly dependent on the ionic SA contents, the IPN hydrogels exhibited independent swelling and thermal behaviors of each network component. The sequences and media in the synthesis of IPNs influenced the swelling capacities of the IPNs, but not the temperature or pH ranges at which the swelling changes occurred. In IPNs, a more expanded primary gel network during the synthesis of the secondary network contributed to the better swelling of the final IPNs. Both the swelling and thermal behaviors of the IPNs suggest that poly(N‐isopropylacrylamide) and poly(sodium acrylate) are phase separated regardless of their synthesis conditions. The presence of the poly(sodium acrylate) network did not influence the temperature or the extent of phase transition of the poly(N‐isopropylacrylamide) network in the IPNs, but did improve the thermal stability of the IPNs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3293–3301, 2004     

Stimuli sensitive polymers for drug delivery systems

Temperature sensitive and electric field sensitive hydrogels were prepared for use in modulated drug release systems. Crosslinked poly(N-isopropyl-acrylamide) and its networks, modified with hydrophobic components by copolymerization or by interpenetrating polymer networks (IPNs) formation, were utilized as temperature sensitive hydrogels. Indomethacin (a model solute)-release from polymer matrix and permeation through polymer membrane demonstrated “on-off” regulation with temperature fluctuation. This was the result of polymer surface properties rather than bulk swelling, as temperature was changed past the swelling transition temperature range of the polymer. The on-off regulation in an electric field was also obtained with a positively charged solute (Edrophonium chloride) release in distilled-deionized water from a matrix of crosslinked poly(2-acrylamido-2-methylpropanesulfonic acid-co-butyl methacrylate). This was attributed to the ion exchange between Edrophonium ion and protons produced at the anode. The swelling changes produced by local pH or ionic strength changes affected non-charged solute release.     

Small angle neutron scattering and dynamic mechanical thermal analysis of dimethacrylate/epoxy IPNs

Dynamic mechanical thermal analysis (DMTA) and small angle neutron scattering (SANS) have been performed on a number of dimethacrylate (or mono-methacrylate)/diepoxy (or mono-epoxy) interpenetrating polymer networks (IPNs) and semi-IPNs to probe their phase structure. The DMTA behaviour ranged from IPNs that produce one tan δ peak, indicative of a single-phase system, to systems that are clearly phase separated, showing two tan δ peaks. These results were correlated with the SANS data - samples that showed two tan δ peaks also showed scattering in the SANS spectrum. Fitting of the scattering data to the Debye-Bueche scattering model for a phase-separated structure gave a scale to this phase separation of about 180Å. DMTA analysis of the rubbery region of the semi-IPNs revealed that they either had a co-continuous morphology or a matrix phase that was crosslinked.     

Quantum-dot-based homogeneous time-resolved fluoroimmunoassay of alpha-fetoprotein

Quantum dots (QDs) with novel photoproperties are not widely used in clinic diagnosis, and homogeneous time-resolved fluorescence assays possess many advantages over current methods for alpha-fetoprotein (AFP) detection. A novel QD-based homogeneous time-resolved fluorescence assay was developed and used for detection of AFP, a primary marker for many cancers and diseases. QD-doped carboxyl-modified polystyrene microparticles (QPs) were prepared by doping oil-soluble QDs possessing a 605 nm emission peak. The antibody conjugates (QPs-E014) were prepared from QPs and an anti-AFP monoclonal antibody, and luminescent terbium chelates (LTCs) were prepared and conjugated to a second anti-AFP monoclonal antibody (LTCs-E010). In a double-antibodies sandwich structure, QPs-E014 and LTCs-E010 were used for detection of AFP, serving as energy acceptor and donor, respectively, with an AFP bridge. The results demonstrated that the luminescence lifetime of these QPs was sufficiently long for use in a time-resolved fluoroassay, with the efficiency of time-resolved Förster resonance transfer (TR-FRET) at 67.3% and the spatial distance of the donor to acceptor calculated to be 66.1 Å. Signals from TR-FRET were found to be proportional to AFP concentrations. The resulting standard curve was log Y = 3.65786 + 0.43863·log X (R = 0.996) with Y the QPs fluorescence intensity and X the AFP concentration; the calculated sensitivity was 0.4 ng mL⁻¹. By assaying test samples against the standard curve, the coefficient of variations was <5%, indicating that QDs were suitable for this homogenous time-resolved fluoroimmunoassay. This work extended the potential applications of QDs in future homogeneous analytical bioassays. In the coming research, hepatitis B surface antigen, another primary marker for hepatocellular carcinoma, will be studied for practical detection using a QD-based homogenous multiplex fluoroimmunoassay.     

Physico-mechanical, thermal and morphological behaviour of polyurethane/poly(methyl methacrylate) semi-interpenetrating polymer networks

Semi-interpenetrating polymer networks (SIPNs) of polyurethane (PU) and poly(methyl methacrylate) (PMMA) in different weight ratios viz., 90/10, 70/30, 60/40 and 50/50 were prepared. The SIPNs were characterized for physico-mechanical properties like density, tensile strength and elongation at break. Thermal stability of IPNs was measured using thermogravimetric analysis (TGA). From the TGA thermograms it was noticed that all IPNs are stable up to 325 °C and undergo three-step thermal degradation in the temperature ranges 251-400, 378-508 and 445-645 °C for first, second and third steps, respectively. Thermal degradation kinetic parameters like activation energy (E_a) were calculated using Broido, Coats-Redfern and Horowitz-Metzger models. The values obtained by Broido and Horowitz-Metzger methods showed concurrency, whereas Coats-Redfern method showed relatively lower values. Surface morphology measured using scanning electron microscope (SEM) showed two-phase morphology for all the IPNs.     

Investigation of swelling,drug release and diffusion behaviors of poly(N‐isopropylacrylamide)/poly (N‐vinylpyrrolidone) full‐IPN hydrogels

The synthesis of sequential full interpenetrating polymer networks (IPNs) based on poly (N‐isopropylacrylamide) (PNIPAAm) and negatively charged poly(N‐vinyl‐2‐pyrrolidone) (PNVP) was described and their swelling, drug release, and diffusion studies were investigated. PNIPAAm was used as a host network. According to swelling experiments, IPNs gave relatively lower swelling ratios compared to PNIPAAm hydrogel due to the higher cross‐linking density. Lidocaine (LD) was used as a model drug for the investigation of drug release behavior of IPNs. LD uptake of the IPNs were found to increase from 24 to 166 (mg LD / g dry gel) with increasing amount of PNIPAAm and AMPS contents in the IPN structure. It was observed that the specific interaction between drug and AMPS co‐monomer influenced the drug release profile. In the diffusion transport mechanism study in water, the results indicated that the swelling exponents n for all IPNs are in the range from 0.50 to 0.72. This implies that the swelling transport mechanism was transferred from Fickian to non‐Fickian transport, with increasing AMPS content and NIPAAm character in the IPN structure. In addition, diffusion of LD within the IPNs showed similar trend. The incorporation of AMPS leads to an increase in electrostatic interaction between charge sites on carboxylate ions and cationic LD molecules. Therefore, the highest diffusion coefficient (D) of drug was found for IPN2 sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Interpenetrating polymer networks based on polyurethane and polysiloxane

A series of interpenetrating polymer networks (IPNs), based on a polyurethane (PU) and polydimethylsiloxane, has been synthesized and characterized by means of DSC, TEM, TGA, 1H-NMR and IR spectroscopies, and other techniques. The homo-networks have been characterized by swelling in n-hexane and chloroform. The IPNs are obtained by combination of a PU based of the castor oil and 2,4-toluene diisocyanate (TDI) with different amounts of polydimethylsiloxane-α,ω-diol (PDMS). These materials have interesting individual physical properties, but some IPNs exhibited superior properties than either of the separate networks. For interesting results, it was used as compatibilizer the polydimethylsiloxane graft polyalkylene oxide. All the IPNs exhibited phase separation and maximum extent at the point of phase inversion.     

Investigation of the chromatographic behaviour of some selenium species—Comparison with their octanol-water partitioning

The retention behaviour of selenites (Se(IV)), selenates (Se(VI)), seleno-dl-methionine (Se-Met), selenocystine (Se-Cyst), selenocystamine (Se-CM) and selenourea (Se-U) was investigated using a Discovery end-capped reversed-phase column as stationary phase and different mobile phase conditions. Extrapolated to 100% aqueous mobile phase retention factors (log k_w) of the investigated Se species, determined using different methanol fractions (φ) as organic modifier, were compared with the corresponding actual values. The proper operation of this column even at 100% aqueous phase proved to be valuable for the accurate determination of log k_w values of Se-CM and Se-Cyst, presenting a convex curvature log k = f(φ) at low MeOH fractions, often neglected in the extrapolation procedure. The effect of the presence of n-decylamine as well as saturation of the mobile phase with n-octanol was also studied. For ampholytic Se-Met and Se-Cyst the effect of n-decylamine in retention reflected the predominance of zwitterionic nature in the case of Se-Met in contrary to the non-zwitterionic species found in the case of Se-Cyst, in accordance with our previous findings concerning partitioning experiments in the n-octanol/water system. Finally, an attempt was made to correlate log k_w values with the logarithm of n-octanol/water distribution coefficient, log D, of the investigated Se species and an indicative log D value of Se-U was derived.     

Synthesis and characterization of pH‐sensitive PAMPS/PVP nanogels in aqueous media

A novel method for preparing poly (2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS) and poly (vinylpyrrolidone) (PVP) complex nanogels in PVP aqueous solution is discussed in this paper. The PAMPS/PVP complex nanogels were prepared via polymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) monomer in the presence of PVP nanoparticles which formed in water/acetone cosolvent in presence of N, N′‐methylenebisacrylamide (MBA) as a crosslinker, N, N, N′, N′‐tetramethylethylenediamine (TEMED) and potassium peroxydisulfate (KPS) as redox initiator system. The results of FTIR and ¹H NMR spectra indicated that the compositions of PAMPS/PVP are consistent with the designed structure. TEM micrographs proved that PAMPS/PVP nanogels possess the spherical morphology before and after swelling. These PAMPS/PVP nanogels exhibited pH‐induced phase transition due to protonation of PAMPS chains. The properties of PAMPS/PVP nanogels indicate that PAMPS/PVP nanogels can be developed into a pH‐controlled drug delivery system. Copyright © 2009 John Wiley & Sons, Ltd.     

Substituent effects in the ring-chain tautomerism of 1,3-diaryl-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazines

Condensation of Betti base analogue amino naphthols with substituted benzaldehydes led to 1,3-diaryl-2,3-dihydro-1H-naphth[1,2-e][1,3]oxazines (3-9) which proved to be three-component (r¹-o-r²) tautomeric mixtures in CDCl₃ at 300 K. The electronic effects of the 3-aryl groups on the ratios of the ring-chain tautomeric forms at equilibrium could be described by the equation log K_X=ρσ⁺+log K_X=H. The value of the intercept was found to be strongly influenced by the steric arrangement of the 1,3-diaryl substituents.     

Interpenetrating Polymer Networks of Uralkyd Resin Based on Hydrogenated Castor Oil and Poly(Butyl Acrylate)

Abstract

Semi‐ and full‐interpenetrating polymer networks (IPNs) of uralkyd (UA) resin based on hydrogenated castor oil and poly(butyl acrylate) (PBA) were prepared by the sequential mode of synthesis. These IPNs were characterized for their resistance to thermal behavior, swelling (%), and mechanical properties. The morphology of the IPNs was studied by scanning electron microscopy (SEM). The effect of the variations of the blend ratios on the above‐mentioned properties was examined. The mechanical properties significantly enhanced by increasing UA component in the blend. Full‐IPNs exhibited higher apparent densities, mechanical properties, and thermal stability than the corresponding semi‐IPNs.     

Temperature-induced phase transition in hydrogels of interpenetrating networks poly(N-isopropylmethacrylamide)/poly(N-isopropylacrylamide)

The combination of ¹H NMR spectroscopy, DSC, dynamic mechanical spectroscopy, and optical microscopy was used to investigate temperature-induced volume phase transition in hydrogels of interpenetrating networks (IPNs) poly(N-isopropylmethacrylamide)/poly(N-isopropylacrylamide) (PNIPMAm/PNIPAm) with various PNIPMAm content. In these IPNs, both networks are thermosensitive; such systems were not examined so far. All methods showed phase transition starting at 307 K, which is the volume phase transition temperature of PNIPAm, the major network component. Only the sample with the lowest content of PNIPAm (~54 %) shows two-step collapse transition, other samples with higher PNIPAm content show a single transition in NMR and DSC which indicates enhanced mutual entanglement of both components. In all samples, the phase transition results in substantial increase of both components of the shear modulus. Although the properties of all samples change with temperature in similar way, differences in dependence on the PNIPMAm content and the shape of the sample can be seen.     

Syntheses and characterization of physically crosslinked hydrogels from dithiocarbamate‐derived polyurethane macroiniferter

A dithiocarbamate (DC)‐based polyurethane macroiniferter (PUMI) was synthesized and used to prepare physically crosslinked polyurethane‐block‐poly (acrylamide) (PU‐b‐PAAm) and polyurethane‐block‐poly(vinyl pyrrolidone) (PU‐b‐PVP) hydrogels. The success of the reactions has been confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR Spectroscopy analyses. The number average molecular weight of the block copolymers increased linearly with conversion and copolymerization time and thus followed a “living” radical mechanism. The water transport behavior of these polyurethane‐based hydrogels such as water uptake rate, equilibrium water content (EWC), transport number (n), characteristic diffusion rate constant (K), diffusion coefficient (D), and pH effect on EWC has been investigated. The results revealed that PU‐b‐PAAm hydrogels followed Fickian diffusion suggesting diffusion controlled swelling kinetics, whereas the PU‐b‐PVP hydrogels followed non‐Fickian diffusion indicating that both diffusion and structural relaxation controlled the water transport. The PU‐b‐PAAm hydrogels showed higher swelling at both low and high pH than at a neutral pH. This is attributed to protonation of the tertiary amines of N,N′‐diethyl‐N,N′‐bis(2‐hydroxyethyl) thiuram disulfide (DHTD) at low pH and base hydrolysis of amide segments at high pH. In the thermogravimetric analysis; PUMI, PU‐b‐PVP and PU‐b‐PAAm have degraded in three distinct stages related to CS₂ evolution, hard segment degradation, and soft segment degradation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6272–6284, 2008     

Radiation synthesis of n-vinyl 2-pyrrolidone/acrylonitrile interpenetrating polymer networks and their use in uranium recovery from aqueous systems

Interpenetrating Polymer Networks (IPNs) based on Poly n-vinyl 2-pyrrolidone (PVP) and Acrylonitrile (AN) were prepared by irradiating PVP solutions prepared in AN. PVP/AN mixtures were irradiated by ⁶⁰Co-γ rays at room temperature at a dose rate of 0.5 kGy/hour. IPNs were characterized by using FT-IR and Thermal Analysis techniques. The chelating adsorbents containing amidoxime groups were prepared by the reaction of these IPNs with hydroxylamine in aqueous NaOH solution at 50°C. These amidoxime containing adsorbents were used in adsorption studies for the recovery of uranium from aqueous systems. The adsorption capacity of an IPN with equivolume fraction of PVP and amidoximated PAN was found to be 750mg UO₂²⁺/g dry amidoximated IPN.     

Swelling behavior of strong polyelectrolyte poly(N-t-butylacrylamide-co-acrylamide) hydrogels

Temperature-sensitive ionic hydrogels based on N-t-butylacrylamide (TBA), acrylamide (AAm), 2-acrylamido-2-methylpropane sulfonic acid sodium salt (AMPS) and N,N^′-methylenebis(acrylamide) (BAAm) monomers were prepared. The molar ratio of TBA to the monomers AAm and AMPS was fixed at 60/40, while the AMPS content of the hydrogels was varied. The elastic modulus of the hydrogels was in the range of 347-447 Pa, much lower than the modulus of PAAm or poly(N-isopropylacrylamide) hydrogels due to the reduced crosslinking efficiency of BAAm in TBA/AAm copolymerization. The hydrogels exhibited swelling-deswelling transition in water depending on the temperature. Increasing ionic group (AMPS) content resulted in shifting of the transition temperature interval in which the deswelling takes place. The higher the ionic group content, the broader the temperature interval at the phase transition. Ionic hydrogels exhibited first-order reentrant conformational transitions in ethanol-water and in dimethylsulfoxide (DMSO)-water mixtures. The higher the ionic group content of the hydrogels the narrower the ethanol (or DMSO) range in which the reentrant phenomena occur. By taking into account the difference of the solvent mixture composition inside and outside the gel, the equilibrium swelling theory provided a satisfactory agreement to the experimental swelling data of the hydrogels immersed in the solvent mixtures.