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We previously reported that layer-by-layer (LbL) film prepared by a combination of 2,2,6,6-tetramethylpiperidinyl N-oxyl (TEMPO)-modified polyacrylic acid (PAA) and polyethyleneimine (PEI) were decomposed by application of an electric potential. However, there have been no reports yet for other polycationic species. In this study, LbL films were prepared by combining various polycationics (PEI, poly(allylamine hydrochloride) (PAH), poly(diallydimethylammonium chloride) (PDDA), and polyamidoamine (PAMAM) dendrimer) and TEMPO-PAA, and the decomposition of the thin films was evaluated using cyclic voltammetry (CV) and constant potential using an electrochemical quartz crystal microbalance (eQCM). When a potential was applied to an electrode coated on an LbL thin film of polycations and TEMPO-PAA, an oxidation potential peak (Epa) was obtained around +0.6 V vs. Ag/AgCl in CV measurements. EQCM measurements showed the decomposition of the LbL films at voltages near the Epa of the TEMPO residues. Decomposition rate was 82% for the (PEI/TEMPO-PAA)5 film, 52% for the (PAH/TEMPO-PAA)5 film, and 49% for the (PDDA/TEMPO-PAA)5 film. It is considered that the oxoammonium ion has a positive charge, and the LbL films were decomposed due to electrostatic repulsion with the polycations (PEI, PAH, and PDDA). These LbL films may lead to applications in drug release by electrical stimulation. On the other hand, the CV of the (PAMAM/TEMPO-PAA)5 film did not decompose. It is possible that the decomposition of the thin film is not promoted, probably because the amount of TEMPO-PAA absorbed is small. [ABSTRACT FROM AUTHOR]

Insulin-containing microcapsules were prepared by a layer-by-layer (LbL) deposition of poly(allylamine hydrochloride) (PAH) and polyanions, such as poly(styrenesulfonate) (PSS), poly(vinyl sulfate) (PVS), and dextran sulfate (DS) on insulin-containing calcium carbonate (CaCO3) microparticles. The CaCO3 core was dissolved in diluted HCl solution to obtain insulin-containing hollow microcapsules. The microcapsules were characterized by scanning electron microscope (SEM) and atomic force microscope (AFM) images and ζ-potential. The release of insulin from the microcapsules was faster at pH 9.0 and 7.4 than in acidic solutions due to the different charge density of PAH. In addition, insulin release was suppressed when the microcapsules were constructed using PAH with a lower molecular weight, probably owing to a thicker shell of the microcapsules. The results suggested a potential use of the insulin-containing microcapsules for developing insulin delivery systems. [ABSTRACT FROM AUTHOR]

pH is one of the most important properties associated with an aqueous solution and various pH measurement techniques are available. In this study, Azure A-modified poly(methacrylic acid) (AA-PMA) was synthesized used to prepare a layer-by-layer deposited film with poly(allylamine hydrochloride) (PAH) on a glassy carbon electrode via electrostatic interactions and the multilayer film-immobilized electrode was used to measure pH. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurement were performed. Consequently, the oxidation potential of AA on the electrode changed with pH. As per Nernst's equation, because H+ ions are involved in the redox reaction, the peak potential shifted depending on the pH of the solution. The peak potential shifts are easier to detect by DPV than CV measurement. Accordingly, using electrochemical responses, the pH was successfully measured in the pH range of 3 to 9, and the electrodes were usable for 50 repeated measurements. Moreover, these electrochemical responses were not affected by interfering substances. [ABSTRACT FROM AUTHOR]

Phenylboronic acid-bearing polyamidoamine dendrimer (PBA-PAMAM)/poly(vinyl alcohol) (PVA) multilayer films were prepared through the layer-by-layer (LbL) deposition of PBA-PAMAM solution and PVA solution. PBA-PAMAM/PVA films were constructed successfully through the formation of boronate ester bonds between the boronic acid moiety in PBA and 1,3-diol units in PVA. When the (PBA-PAMAM/PVA)5 films were immersed in rose bengal (RB) solution, RB was adsorbed onto the LbL films. The amount of RB adsorbed was higher in the LbL films immersed in acidic solution than in basic solution. The release of RB from the LbL films was also promoted in the basic solution, while it was suppressed in the acidic solution. The boronic acid ester is oxidized to phenol by hydrogen peroxide (H2O2) and the carbon-boron bond is cleaved, so that the (PBA-PAMAM/PVA)5 films can be decomposed by immersion in H2O2 solution. Therefore, when RB-adsorbed (PBA-PAMAM/PVA)5 films were immersed in H2O2 solution, the release of RB was moderately promoted when the solution was weakly acidic. [ABSTRACT FROM AUTHOR]

Glucose-sensitive films were prepared through the layer-by-layer (LbL) deposition of hemin-modified poly(ethyleneimine) (H-PEI) solution and DNA solution (containing glucose oxidase (GOx)). H-PEI/DNA + GOx multilayer films were constructed using electrostatic interactions. The (H-PEI/DNA + GOx)5 film was then partially decomposed by hydrogen peroxide (H2O2). The mechanism for the decomposition of the LbL film was considered to involve more reactive oxygen species (ROS) that were formed by the reaction of hemin and H2O2, which then caused nonspecific DNA cleavage. In addition, GOx present in the LbL films reacts with glucose to generate hydrogen peroxide. Therefore, decomposition of the (H-PEI/DNA + GOx)5 film was observed when the thin film was immersed in a glucose solution. (H-PEI/DNA + GOx)5 films exposed to a glucose solution for periods of 24, 48 72, and 96 h indicated that the decomposition of the film increased with the time to 9.97%, 16.3%, 23.1%, and 30.5%, respectively. The rate of LbL film decomposition increased with the glucose concentration. At pH and ionic strengths close to physiological conditions, it was possible to slowly decompose the LbL film at low glucose concentrations of 1–10 mM. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2)-sensitive layer-by-layer films were prepared based on combining phenyl boronic acid (PBA)-modified poly(allylamine) (PAH) with shikimic acid (SA)-modified-PAH through boronate ester bonds. These PBA-PAH/SA-PAH multilayer films could be prepared in aqueous solutions at pH 7.4 and 9.0 in the presence of NaCl. It is believed that the electrostatic repulsion between the SA-PAH and PBA-PAH was diminished and the formation of ester bonds between the SA and PBA was promoted in the presence of NaCl. These films readily decomposed in the presence of H2O2 because the boronate ester bonds were cleaved by an oxidation reaction. In addition, SA-PAH/PBA-PAH multilayer films combined with glucose oxidase (GOx) were decomposed in the presence of glucose because GOx catalyzes the oxidation of D-glucose to generate H2O2. The surfaces of CaCO3 microparticles were coated with PAH/GOx/(SA-PAH/PBA-PAH)5 films that absorbed insulin. A 1 mg quantity of these particles released up to 10 μg insulin in the presence 10 mM glucose under physiological conditions. [ABSTRACT FROM AUTHOR]

Thin films were prepared using layer-by-layer (LbL) deposition of Nafion (NAF) and polycations such as poly(allylamine hydrochloride) (PAH), poly(ethyleneimine) (PEI), and poly(diallydimethylammonium chloride) (PDDA). Insulin was then adsorbed on the NAF-polycation LbL films by immersion in an insulin solution. The NAF-polycation LbL films were characterized using a quartz crystal microbalance and an atomic force microscope. The release of insulin from the LbL films was characterized using UV-visible adsorption spectroscopy and fluorescence emission spectroscopy. The greatest amount of insulin was adsorbed on the NAF-PAH LbL film. The amount of insulin adsorbed on the (NAF/PAH)5NAF LbL films by immersion in a 1 mg mL−1 insulin solution at pH 7.4 was 61.8 µg cm−2. The amount of insulin released from the LbL films was higher when immersed in insulin solutions at pH 2.0 and pH 9.0 than at pH 7.4. Therefore, NAF-polycations could be employed as insulin delivery LbL films under mild conditions and as an insulin release control system according to pH change. [ABSTRACT FROM AUTHOR]