AbstractpH-sensitive nanoclay composite hydrogels based on N-isopropylacrylamide (NIPA) were synthesized by copolymerization with cationic and anionic comonomers. Laponite nanoclay particles served as multifunctional crosslinkers, producing hydrogels with exceptionally high mechanical strengths, as measured by elongation at break. Cationic copolymer gels based on NIPA and dimethylaminoethylmethacrylate were prepared by aqueous free radical polymerization, adopting a procedure reported by Haraguchi (Adv Mater 2002, 14, 1120-1124. Without modification, this technique failed to produce anionic copolymer gels of NIPA and methacrylic acid due to flocculation of clay particles. Three methods were conceived to incorporate acidic MAA into nanoclay hydrogels. First, NIPA was copolymerized with acidic comonomer under dilute conditions, producing hydrogels with good pH-sensitivity but weak mechanical characteristics. Second, NIPA was copolymerized with methyl methacrylate, which was then hydrolyzed to generate acid sidegroups, yielding hydrogels that were much stronger but less pH sensitive. Third, NIPA was copolymerized with an acid comonomer following modification of the nanoclay surface with pyrophosphate ions. The resulting hydrogels exhibited both strong pHsensitivities at 37 °C and excellent tensile properties. Optical transparency changed during polymerization, depending on hydrophobicity of the components. This work increases the diversity and functionality of nanoclay hydrogels, which display certain mechanical advantages over conventionally crosslinked hydrogels.

No abstract

Phenylboronic acids are a class of compounds that bind glucose and other sugars. When polymerized into hydrogels, they provide a convenient nonenzymatic means for sensing glucose concentration, provided competing sugars are present at negligible concentrations. In this paper we provide a comprehensive study of swelling of hydrogels containing methacrylamidophenylboronic acid (MPBA), as a function of pH and concentration of either glucose or fructose. In one set of hydrogels, MPBA is substituted at 20 mol· % in a polyacrylamide hydrogel [p(MPBA-co-AAm)], while in a second set of hydrogels, 20 mol· % MPBA is supplemented with 20 mol· % of N-3-(dimethylaminopropyl methacrylamide) [p(MPBA-co-DMP-co-AAm)]. Swelling curves are markedly different for fructose and glucose, and for the two sets of hydrogels. While fructose alters swelling by binding and contributing to the ionization of MPBA, glucose does the same, but it also can form crosslinking bridges between separate chains, leading to hydrogel shrinkage. While the [p(MPBA-co-AAm)] hydrogels behaved as polyacids, swelling monotonically with increasing pH, the [p(MPBA-co-DMP-co-AAm)] hydrogels exhibited polyampholyte behavior, with swelling minima at intermediate pH values.

Summary:We are investigating an autonomous glucose-driven hydrogel/enzymebased device prototype for rhythmic, pulsed delivery of gonadotropin releasing hormone (GnRH). The device employs a pH-sensitive hydrogel membrane in conjunction with the enzyme glucose oxidase. This system delivers GnRH in rhythmic pulses when exposed to a constant level of glucose. These pulses result from autonomous pH oscillations inside the device that are created by an unstable nonlinear feedback between hydrogel permeability to glucose and production of acid by glucose oxidase. Previous versions of this prototype utilized p(N-isopropylacrylamide-co-methylacrylic acid) p(NIPA-co-MAA) hydrogels, with 10 mol% MAA incorporated. With this membrane, which undergoes a volume transition (VT) near pH 5, pH oscillations centered around pH 5 are observed. This range is too low to sustain oscillations in physiologically buffered media. To shift the operating pH of oscillations closer to physiologic pH, we have sought ways to increase the pH of the volume transition. In this study we show that increasing the side chain length of the a-alkylacrylic acid (RAA) comonomer enhances the overall hydrophobicity of the copolymer, and shifts the VT pH closer to physiological pH values. We also demonstrate the ability of such membranes to affect an alkaline shift in the range of oscillations in the prototype oscillator device.