Preparation of poly(N-normalpropyl- acrylamide) gel beads

 The gel beads of N-normal-propylacrylamide are prepared by the radical copolymerization of N-normalpropylacrylamide and N,N′-methylene-bis-acrylamide in water. The optimum reaction conditions to obtain the gel beads are revealed from the phase diagram of the reaction system together with the scanning electron microscopy of the reaction products. The scanning electron microscopy of the reaction products also indicates the formation of the spherical gel beads of sub-micron size ranging from 250 to 500 nm in diameter. The viscosity measurements of the suspension of the gel beads indicate that the concentration dependence of the viscosity of the suspension is well described by Einstein’s theory of the viscosity of colloidal particles. The intrinsic viscosity of the suspension of gel beads is then determined. The density of the gel beads, which was obtained from the intrinsic viscosity of the suspension, indicates that the gel beads are in the swollen state at a temperature of 20 ^°C. Received: 12 September 1997 Accepted: 17 December 1997     

Fluorescence studies on volume phase transition in poly(acrylamide) and poly(N-isopropylacrylamide) gels

The changes in microenvironments during the volume phase transition of poly(acrylamide) and poly(N-isopropylacrylamide) gels induced by pH change or the change in solvent composition were studied by using dansyl or pyrenyl fluorescent probes.     

Fluorescence and viscometry study of complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide)

Interpolymer complexation of poly(acrylic acid) with poly(acrylamide) and hydrolysed poly(acrylamide) was studied by fluorescence spectroscopy and viscometry in dilute aqueous solutions. Changes in chain conformation and flexibility due to the interpolymer association are reflected in the intramolecular excimer fluorescence of pyrene groups covalently attached to the polymer chain. Both poly(acrylamide) and hydrolysed poly(acrylamide) form stable complexes with poly(acrylic acid) at low pH. The molecular weight of poly(acrylic acid) and solution properties such as pH and ionic strength were found to influence the stability and the structure of the complexes. In addition, the polymer solutions mixing time showed an effect on the mean stoichiometry of the complex. The intrinsic viscosity of the solutions of mixed polymers at low pH suggested a compact polymer structure for the complex.     

Swelling of hydrophobically modified poly(acrylamide) and poly(acrylamide)-co-(acrylic acid) gels in surfactant solutions

A series of hydrophobically modified polyacrylamide and polyacrylamide-co-poly(acrylic acid) gels with systematically varying hydrophobicity were prepared by free-radical polymerization of acrylamide, n-alkylacrylamides (n = 10, 12, and 14), and acrylic acid. The swelling of these gels was examined in water and in both anionic and cationic surfactant solutions. It was found that the gels which incorporated acrylic acid showed extremely high swelling in water. Maximum swelling was observed in gels which incorporated 10 mol% acrylic acid. The swelling of these gels was much less in solutions of both anionic and cationic surfactants than in water. The gels which did not incorporate acrylic acid demonstrated little swelling in water, but showed increased swelling in both anionic and cationic surfactant solutions with increased hydrophobicity of the gel. Received: 1 February 1999 Accepted in revised form: 5 March 1999     

Positron annihilation studies of poly(N‐isopropyl acrylamide) gel in mixed solvents

Positron annihilation lifetime spectroscopy was used to characterize the reentrant volume‐phase‐transition behavior of poly(N‐isopropyl acrylamide) hydrogel in an ethanol/water mixed solvent. The polymer gel was synthesized with γ irradiation. The ortho‐positronium lifetime (τ₃) in the gel slowly increased with an increase in the ethanol content in the mixed solvent. τ₃ was not influenced by the volume phase transition. The ortho‐positronium intensity decreased with the collapse of the gel in an approximately 10% ethanol/water mixture. When swelled in pure ethanol, τ₃ initially increased with the solvent amount in the gel, showing the destruction of intramolecular hydrogen bonding and the relaxation of polymer chains. The lower critical solution temperature of the gel in the 10% ethanol/water mixture was lower than that in pure water, and τ₃ for various solvent contents showed behavior similar to that seen in pure solvent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1028–1036, 2002     

The synthesis of poly(hydroxamic acid) from poly(acrylamide)

Poly(hydroxamic acid) in gel or water soluble from was prepared from the reaction of poly(acrylamide) and hydroxylamine in basic aqueous solution (pH > 12) at room temperature. The polymers were composed of 70% hydroxamic acid groups, less than 5% carboxylic acid groups, and 25% unreacted amide groups. The polymers exhibited high affinity to iron(III) and copper(II) in the pH range of 1 to 5 with a high binding rate. A binding of 3 mmol/g for both metals was achieved. Preliminary tests demonstrated the urease inhibitory activity of both linear and crosslinked poly(hydroxamic acids).     

Thermoresponsive poly(N-isopropylacrylamide) nanogels/poly(acrylamide) nanostructured hydrogels

Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (T_VPT). Their swelling kinetics, T_VPT's and mechanical properties at the equilibrium-swollen state (H_eq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher H_eq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The T_VPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, T_VPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization.     

Transition between collapsed state phases and the critical swelling of a hydrogen bonding gel: poly(methacrylic acid-co-dimethyl acrylamide)

Transition between collapsed state phases and discontinuous volume phase transition for a hydrogen bonding gel, poly(methacrylic acid-co-dimethyl acrylamide), were observed by using both the volume measurements and fluorescence intensity of the pyranine fluoroprobe (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt) bonded to the gel by means of electrostatic interactions. In the collapsed state, while there is no appreciable change in the volume of the gel, a considerable variation in the fluorescence intensity occurred around 30 degrees C signaling a second order phase transition between collapsed state phases, from relatively frozen to a fluctuating phase. Our analysis of the data around 30 degrees C indicates that the critical point of gel volume transition belongs to the so-called mean-field universality class, as predicted in Onuki [Phys. Rev. A 38, 2192 (1988)] and by Golubovic and Lubensky [Phys. Rev. Lett. 63, 1082 (1989)]. The relaxation time for the equilibrium swelling critically depends on the temperature and diverges near 60 degrees C, where both fluorescence intensity and the volume of the gel change drastically and indicate the discontinuous volume phase transition. The swelling kinetics of the critical gel during the discontinuous volume phase transition can be modeled best with the first term in the expansion of the Li-Tanaka equation for a long initial period of the swelling time.     

Effect of amino acid surfactants on phase transition of poly(N-isopropylacrylamide) gel

The volume phase transition behavior of a poly(N-isopropylacrylamide) gel (NIPA gel) in solutions of N-acyl amino acid surfactants were studied as a function of surfactant concentration. The addition of a surfactant beyond the critical micelle concentration (cmc) produced elevation in the transition temperature of the NIPA gel and its swelling. The changes in the volume phase transition temperature and in the swelling of the NIPA gel became more significant with the decreasing size of the amino acid side chain. This result could almost be explained only by the binding amount of surfactant onto the NIPA gel regardless of molecular structure of the amino acid. The binding amount increased in the order of sodium N-lauroyl-glycinate>-alaninate>-valinate>-leucinate>or=-phenylalaninate. For an N-acyl amino acid surfactant to bind onto the NIPA gel, to increase the transition temperature, and to facilitate swelling of the gel, the steric hindrance of the amino acid side chain was more effective than its hydrophobicity.     

Tailoring thermoresponsive nanostructured poly(N-isopropylacrylamide) hydrogels made with poly(acrylamide) nanoparticles

The thermoresponsive behavior and mechanical properties of nanostructured hydrogels, which consist of poly(acrylamide) nanoparticles embedded in a cross-linked poly(N-isopropylacrylamide) hydrogel matrix, are reported here. Nanostructured hydrogels exhibit a tuned volume phase transition temperature (T _VPT), which varies with nanoparticle content in the range from 32 up to 39–40 °C. Moreover, larger equilibrium water uptake, faster swelling and de-swelling rates, and larger equilibrium swelling at 25 °C were obtained with nanostructured hydrogels compared with those of conventional ones. Elastic and Young’s moduli were larger than those of conventional hydrogels at similar swelling ratios. The tuned T _VPT and the de-swelling rate were predicted with a modified Flory–Rehner equation coupled with a mixing rule that considers the contribution of both polymers. These behaviors are explained by a combination of hydrophilic/hydrophobic interactions and by the controlled inhomogeneities (nanoparticles) introduced by the method of synthesis.     

Lower critical solution temperature sensitivity to structural changes in poly(N‐isopropyl acrylamide) homopolymers

The effect of the molecular weight on the lower critical solution temperature (LCST) has been discussed extensively, where LCST increased with molar mass, decreased or kept constant, which leads to confusion. This work is focused on the preparation of poly(N‐isopropyl acrylamide) homopolymers, obtained in a wide molecular weights range. The LCST behavior is analyzed by calorimetry and rheology, and a deep study of molecular features is carried out for a better knowledge of the influence of various parameters involved on LCST. Finally, the molecular weight trend is observed, and its influence on LCST is compared with the effect of other parameters as polymer concentration in water, end‐group effect, and tacticity. It is observed that other parameters such tacticity and end‐group effect will affect the LCST behavior over molecular weight, if this one is not high enough. Furthermore, the study of the LCST ranges will be a useful tool for analyzing the molecular weight trends. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1386–1393     

Water and drug transport in radiation-crosslinked poly(2-methoxyethylacrylate-co-dimethyl acrylamide) and poly(2-methoxyethylacrylate-co-acrylamide) hydrogels

Hydrogels of poly(N,N′-dimethylacrylamide-co-2-methoxyethylacrylate) and poly(acrylamide-co-2-methoxyethylacrylate) have been synthesized by radiation polymerization in dimethylformamide solution with trimethylolpropane trimethacrylate as a crosslinker. In this work, some investigations on the in vitro release of gentamicin sulphate, an antibiotic entrapped in the hydrogels, are reported. The kinetics of drug release from hydrogels matrices were examined and the results indicate that the release for the proposed geometry practically occurs in the first 24 h. The fractional cumulative release of the drug from the DMAA/MOEA matrices is linear when plotted against the square root of time, pointing out a Fickian process. On the other hand, AAm/MOEA matrices showed an initial non-Fickian behaviour, probably indicating a comparable rates of Fickian diffusion and polymer relaxation.     

Revisiting the thermosensitivity of poly(acrylamide-co-diacetone acrylamide)

The lower critical solution temperature （LCST） behavior of poly（acrylamide-co-diacetone acrylamide） （poly（AM-co-DAM）） copolymer in aqueous solutions was studied. The results demonstrate the LCST linearly decreases as the molar fraction of DAM （fDAM） increases. In the range of fDAM 〈 0.36, the transmittance increases as fDAM decreases because the more hydrophilic copolymer chains can form looser aggregates with a lower refractive index. The transmittance exhibits a minimum when fDAM is less than 0.28 as the chains form micelle-like structure with a size smaller than the wavelength. The LCST decreases with the initial polymer concentration, but it levels off when the polymer concentration is high enough. Moreover, no hysteresis can be observed in the change of transmittance during the heating-cooling process because no additional hydrogen bonds are formed in the collapsed state due to the steric hindrance of the large side groups in DAM units.     

Molecular chain properties of poly (N-isopropyl acrylamide)

A series of poly( N-isopropyl acrylamide) (PNIPAM) samples with molecular weight ranging from 2.23×10~4 to 130×10~4 and molecular weight distribution M_w/M_n≤1.28 were obtained by free radical polymerization and repeat precipitation fractionation. The molecular weight M_w, second virial coefficient A_2 as well as the mean-square-root radius of gyration 〈S~2〉 for PNIPAM samples in tetrahydrofuran (THF) were determined by light scattering, and the relations were estimated at A_2 ∞ M_w~0.25) and 〈S~2〉~(1/2)=1.56×10~(-9) M_w~(0.56). The intrinsic viscosity for THF solution and methanol solution of PNIPAM samples was measured and the Mark-Houwink equations were obtained as [η]=6.90×10~(-5) M~(0/73) (THF solution) and [η]=1.07×10~(-4) M~(0.71) (methanol solution). The above results indicate that both THF and methanol are good solvents for PNIPAM. The limit characteristic ratio C_∞ for PNIPAM in the two solutions was determined to be 10.6 by using Kurata-Stockmayer equation, indicating that the f     

Production of poly(chlorosulfostyrene) by synthesis in a gel

Synthesis in a gel as a method for the preparation of poly(chlorosulfostyrene) by treating polystyrene with chlorosulfonic acid was proposed, which makes it possible to obtain a polymer with a total degree of functionalization of sulfo and chlorosulfo groups up to 1.0. The possibility of regulating the degree of chlorosulfonation in the range from 50 to 100% was shown. The composition and structure of the products of polymer-analogous transformations were characterized by elemental analysis, FTIR spectroscopy, and thermogravimetry with IR identification of the decomposition products. Chlorosulfonation in the gel makes it possible to achieve a high degree of functionalization even at lower temperatures, at room temperature, and at less time than compared with known methods.     

Engineering a sharp physiological transition state for poly(n‐isopropylacrylamide) through structural control

Poly(N‐isopropylacrylamide) (pNIPAAm), a well‐studied, biologically inert polymer that undergoes a sharp aqueous thermal transition at 32 °C, has been a subject of widespread interest for possible biological applications. A major hindrance to its successful application is due to the difficulty of maintaining a sharp transition when the polymer is modified for a physiological transition temperature, especially in isotonic solutions. Current copolymer blends raise the transition temperature but also make the transition significantly broader. We have combined the use of reversible addition‐fragmentation chain transfer (RAFT) polymerization with tacticity control to synthesize well‐defined pNIPAAm that demonstrates sharp transitions under physiological conditions. By selecting a RAFT agent with appropriate end groups, controlling molecular weight, and increasing the racemo diad content, we were able to increase the thermal transition temperature of pure pNIPAAm to a sharp transition at 37.6 °C under isotonic conditions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of poly(2-amino-2-methylpropyl)acrylamide,poly(2-amino-2-methylbutyl)acrylamide,and copolymers of polyacrylamide

Polyacrylamides possessing an amino group at the terminus of the branch chain as the potential site for amino acid and/or nucleic acid base grafting have been prepared. This type of polyacrylamide would provide a substantial spacing distance between the polymer main chain and pendant groups. Poly(2-amino-2-methylpropyl)acrylamide (PDMPA) and optically active poly(2-amino-2-methylbutyl)acrylamide (PDMBA) were characterized using vapor phase osmometry (VPO), gel permeation chromatography (GPC), and dilute solution viscometry. In addition, copolymers of poly(2-amino-2-methylpropyl)acrylamide with N-vinylpyrrolidinone, N-vinylimidazole, and H(5)-vinylimidazole, were prepared.