Photosensitive Layer-by-Layer Assemblies Containing Azobenzene Groups: Synthesis and Biomedical Applications

This review provides an overview of the syntheses of photosensitive layer-by-layer (LbL) films and microcapsules modified with azobenzene derivatives and their biomedical applications. Photosensitive LbL films and microcapsules can be prepared by alternate deposition of azobenzene-bearing polymers and counter polymers on the surface of flat substrates and microparticles, respectively. Azobenzene residues in the films and microcapsules exhibit trans-to-cis photoisomerization under UV light, which causes changes in the physical or chemical properties of the LbL assemblies. Therefore, azobenzene-functionalized LbL films and microcapsules have been used for the construction of photosensitive biomedical devices. For instance, cell adhesion on the surface of a solid can be controlled by UV light irradiation by coating the surface with azobenzene-containing LbL films. In another example, the ion permeability of porous materials coated with LbL films can be regulated by UV light irradiation. Furthermore, azobenzene-containing LbL films and microcapsules have been used as carriers for drug delivery systems sensitive to light. UV light irradiation triggers permeability changes in the LbL films and/or decomposition of the microcapsules, which results in the release of encapsulated drugs and proteins

Host-Guest Chemistry in Layer-by-Layer Assemblies Containing Calix[n]arenes and Cucurbit[n]urils: A Review

This review provides an overview of the synthesis of layer-by-layer (LbL) assemblies containing calix[n]arene (CA[n]) and cucurbit[n]uril (CB[n]) and their applications. LbL assemblies, such as thin films and microcapsules, containing selective binding sites have attracted considerable attention because of their potential use in separation and purification, sensors for ions and molecules, and controlled release. CA[n]-containing LbL films have been prepared using sulfonated CA[n] and cationic polymers to construct chemical sensors and molecular containers. CA[n]-containing LbL films deposited on the surface of a porous support are useful as ion-selective membranes that exhibit selective permeability to monovalent ions over multivalent ions. CB[n]s have been used as molecular glues for the construction of LbL films and microcapsules by taking advantage of the strong affinity of CB[n]s to aromatic compounds. CB[n]s form a stable 1:1:1 ternary complex with electron-rich and electron-deficient molecules in LbL films to stabilize the assemblies. CB[n]-containing LbL films can also be deposited on the surfaces of micro templates and nanopore membranes to construct microcapsules for controlled release and nanochannels for selective ion transport, respectively

Voltammetric Response of Alizarin Red S-Confined Film-Coated Electrodes to Diol and Polyol Compounds: Use of Phenylboronic Acid-Modified Poly(ethyleneimine) as Film Component

Alizarin red S (ARS) was confined in layer-by-layer (LbL) films composed of phenylboronic acid-modified poly(ethyleneimine) (PBA-PEI) and carboxymethylcellulose (CMC) to study the voltammetric response to diol and polyol compounds. The LbL film-coated gold (Au) electrode and quartz slide were immersed in an ARS solution to uptake ARS into the film. UV-visible absorption spectra of ARS-confined LbL film suggested that ARS formed boronate ester (ARS-PBS) in the film. The cyclic voltammetry of the ARS-confined LbL film-coated electrodes exhibited oxidation peaks at −0.50 and −0.62 V, which were ascribed to the oxidation reactions of ARS-PBS and free ARS, respectively, in the LbL film. The peak current at −0.62 V increased upon the addition of diol or polyol compounds such as L-dopa, glucose, and sorbitol into the solution, depending on the concentration, whereas the peak current at −0.50 V decreased. The results suggest a possible use of ARS-confined PBA-PEI/CMC LbL film-coated Au electrodes for the construction of voltammetric sensors for diol and polyol compounds

Alizarin Red S-Confined Layer-By-Layer Films as Redox-Active Coatings on Electrodes for the Voltammetric Determination of L-Dopa

The preparation of redox-active coatings is a key step in fabricating electrochemical biosensors. To this goal, a variety of coating materials have been used in combination with redox-active compounds. In this study, alizarin red S (ARS) was confined in layer-by-layer (LbL) films composed of poly(ethyleneimine) (PEI) and carboxymethylcellulose (CMC) to study the redox properties. A gold (Au) disc electrode coated with PEI/CMC LbL film was immersed in an ARS solution to uptake ARS into the film. ARS was successfully confined in the LbL film through electrostatic interactions. The cyclic voltammogram (CV) of ARS-confined PEI/CMC film-coated electrodes thus prepared exhibited redox waves in the potential range from −0.5 to −0.7 V originating from 9,10-anthraquinone moiety in ARS, demonstrating that ARS preserves its redox activity in the LbL film. An additional oxidation peak appeared around −0.4 V in the CV recorded in the solution containing phenylboronic acid (PBA), due to the formation of a boronate ester of ARS (ARS-PBA) in the film. The oxidation peak current at −0.4 V decreased upon addition of 3,4-dihydroxyphenylalanine (L-dopa) to the solution. Thus, the results suggest a potential use of the ARS-confined PEI/CMC films for constructing voltammetric sensors for L-dopa