A direct, low-cost method to determine the concentration of lactose is an important goal with possible impact in various types of industry. In this study, a biosensor is reported that exploits the specific interaction between lactose and the enzyme β-galactosidase (β-Gal) normally employed to process lactose into glucose and galactose for lactose-intolerant people. The biosensor was made with β-Gal immobilized in layer-by-layer (LbL) films with the polyelectrolyte poly(ethylene imine) (PEI) and poly(vinyl sufonate) (PVS) on an indium tin oxide (ITO) electrode modified with a layer of Prussian Blue (PB). With an ITO/PB/(PEI/PVS) 1 (PEI/β-Gal) 30 architecture, lactose could be determined with an amperometric method with sensitivity of 0.31 μA mmol −1 cm −2 and detection limit of 1.13 mmol L −1, which is sufficient for detecting lactose in milk and for clinical exams. Detection occurred via a cascade reaction involving glucose oxidase titrated as electrolytic solution in the electrochemical cell, while PB allowed for operation at 0.0 V versus saturated calomel electrode, thus avoiding effects from interfering species. Sum-frequency generation spectroscopy data for the interface between the LbL film and a buffer containing lactose indicated that β-Gal lost order, which is the first demonstration of structural effects induced by the molecular recognition interaction with lactose.
Dermal drug release systems are an important area of research because they can be applied to the skin in a non-invasive procedure using a lower concentration of drugs. In this study, we have developed two types of Layer-by-Layer (LbL) films for releasing emodin (EM). In one system, EM was intercalated with poly(ethylenimine) PEI and poly(vinyl sufonate) (PVS) polyelectrolytes, forming (PEI/PVS)(PEI/EM); in another, EM was incorporated in liposomes obtained by mixing dipalmitoyl phosphatidyl glycerol (DPPG) and palmitoyl oleoyl phosphatidyl glycerol (POPG) lipids, forming (PEI/PVS)(PEI/DPPG-POPG-EM). UV-vis and FTIR spectroscopies were used to characterize the LbL films. These showed that the depositions of material by LbL were efficient, with increases in the absorbance of each bilayer evidencing the presence of EM in the film. The (PEI/PVS)(PEI/EM) and (PEI/PVS)(PEI/DPPG-POPG-EM) films released EM in three and five days, respectively. The cyclic voltammetry (CV) assay of the (PEI/PVS)(PEI/EM) results are in agreement with UV-vis measurements, which suggest that EM was protonated in acid environments, while the CV of (PEI/PVS)(PEI/DPPG-POPG-EM) demonstrated distinct protonation behaviour for EM within the inner liposome structure, even in acid solutions. Therefore, this study presents two systems based on LbL films and provides additional details about the release of EM from these films to create a viable alternative for transdermal applications.
Herein, we present the synthesis of linear photochromic norbornene polymers bearing spiropyran side groups (poly(SP-R)) and their assembly into layer-by-layer (LbL) films on glass substrates when converted to poly(MC-R) under UV irradiation. The LbL films were composed of bilayers of poly(allylamine hydrochloride) (PAH) and poly(MC-R), forming (PAH/poly(MC-R)) coatings. The merocyanine (MC) form presents a significant absorption band in the visible spectral region, which allowed tracking of the LbL deposition process by UV-vis spectroscopy, which showed a linear increase of the characteristic MC absorbance band with increasing number of bilayers. The thickness and morphology of the (PAH/poly(MC-R)) films were characterized by ellipsometry and scanning electron microscopy, respectively, with a height of ∼27.5 nm for the first bilayer and an overall height of ∼165 nm for the (PAH/poly(MC-R)) multilayer film. Prolonged white light irradiation (22 h) resulted in a gradual decrease of the MC band by 90.4 ± 2.9% relative to the baseline, indicating the potential application of these films as coatings for photocontrolled delivery systems.
Due to their reversible diol-binding ability, phenylboronic acid (BA) derivatives have gained considerable interest for the development of saccharide sensors and drug delivery systems. In particular, BA-containing polymers have been used for the realisation of sugar-responsive layerby-layer (LbL) films. Herein, a LbL system based on cationic BA-homopolymers (PBA) is presented, and its subsequent sugar-induced disassembly is described. The BA-linear polymers (PBA) were intercalated with poly(vinylsulfonic acid, sodium salt) to form (PBA/PVS)n film assemblies. Different orientations of the boronic acid substituent (ortho-, meta-and para-) in the PBA polymer were investigated for their influence on the LbL assembly. The rate of disassembly in the presence of glucose or fructose was analyzed by UV-vis spectroscopy. Additionally, the PVS component was replaced by an anionic fluorophore, pyranine (PYR), which allowed the assembly and disassembly to be monitored by fluorescence.
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