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.

The nitroxyl radical of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) can electro-oxidize not only alcohols but also amines. However, TEMPO has low activity in a neutral aqueous solution due to the large steric hindrance around the nitroxyl radical, which is the active site. Therefore, nortropine N-oxyl (NNO) was synthesized to improve the catalytic ability of TEMPO and to investigate the electrolytic oxidation effect on amines from anodic current changes. Ethylamine, diethylamine, triethylamine, tetraethylamine, isopropylamine, and tert-butylamine were investigated. The results indicated that TEMPO produced no response current for any of the amines under physiological conditions; however, NNO did function as an electrolytic oxidation catalyst for diethylamine, triethylamine, and isopropylamine. The anodic current depended on amine concentration, which suggests that NNO can be used as an electrochemical sensor for amine compounds. In addition, electrochemical detection of lidocaine, a local anesthetic containing a tertiary amine structure, was demonstrated using NNO with a calibration curve of 0.1–10 mM.

Quantifying drug concentrations in vivo quickly and easily is possible using electrochemical methods. The present study describes the electrochemical detection of vancomycin (VCM) and other antibiotics from the current obtained using nitroxyl radicals as electrocatalysts. Nortropine N-oxyl (NNO), which is more active than 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), a typical nitroxyl radical compound, produced greater current values for drugs with intramolecular hydroxy groups and secondary and tertiary amines. However, because the catalytic action of NNO is inactivated by primary amines in the substrate, VCM and teicoplanin with primary amines could not be detected. TEMPO was less active than NNO but not inactivated against primary amines. Therefore, electrochemical sensing of vancomycin was done using 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl (A-TEMPO), which has a greater oxidation capacity than TEMPO due to its electron-withdrawing groups. As a result, the current of A-TEMPO increased in the low concentration range of VCM as compared to TEMPO. This method also was able to quantify VCM in the concentration range of 10–100 μM, which is an important concentration range for drug monitoring in blood.

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.

[Ag(cytidine)₂]⁺ formation can be utilized for controlling the redox potential of the Ag⁺/Ag couple.

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.