With the purpose to replace expensive and significantly cytotoxic positively charged polypeptides in biodegradable capsules formed via Layer-by-Layer (LbL) assembly, multilayers of bovine serum albumin (BSA) and tannic acid (TA) are obtained and employed for encapsulation and release of model drugs with different solubility in water: hydrophilic-tetramethylrhodamine-isothiocyanate-labeled BSA (TRITC-BSA) and hydrophobic 3,4,9,10-tetra-(hectoxy-carbonyl)-perylene (THCP). Hydrogen bonding is proposed to be predominant within thus formed BSA/TA films. The TRITC-BSA-loaded capsules comprising 6 bilayers of the protein and polyphenol are benchmarked against the shells composed of dextran sulfate (DS) and poly-l-arginine (PARG) on degradability by two proteolytic enzymes with different cleavage site specificity (i.e., α-chymotrypsin and trypsin) and toxicity for murine RAW264.7 macrophage cells. Capsules of both types possess low cytotoxicity taken at concentrations equal or below 50 capsules per cell, and evident susceptibility to α-chymotrypsin resulted in release of TRITC-BSA. While the BSA/TA-based capsules clearly display resistance to treatment with trypsin, the assemblies of DS/PARG extensively degrade. Successful encapsulation of THCP in the TRITC-BSA/TA/BSA multilayer is confirmed, and the release of the model drug is observed in response to treatment with α-chymotrypsin. The thickness, surface morphology, and enzyme-catalyzed degradation process of the BSA/TA-based films are investigated on a planar multilayer comprising 40 bilayers of the protein and polyphenol deposited on a silicon wafer. The developed BSA/TA-based capsules with a protease-specific degradation mechanism are proposed to find applications in personal care, pharmacology, and the development of drug delivery systems including those intravenous injectable and having site-specific release capability.

Fast lipid peroxidation in emulsified oils results in carcinogens formation and product rancidity. Prevention of oxidative degradation in oil-in-water emulsion has been achieved by encapsulating of each droplet of dispersed phase in antioxidant multilayer coating shell. The fabrication comprised placing a surface-active ionic emulsifier at the oil/water interface followed by stepwise alternate adsorption a biocompatible polyelectrolyte and antioxidant layers. Uncoupled polyelectrolyte macromolecules and antioxidant were thoroughly removed from formulation, thus the protection was entirely attributed to the droplets' shell. The experiments were performed using linseed oil, the richest source of highly unstable omega-3 alpha linolenic essential fatty acid. Bovine serum albumin (BSA) was exploited as an anionic emulsifier. The biodegradable coating shell was formed of poly-l-arginine (PARG) and dextran sulfate (DS) applied as a polycation and a polyanion respectively. Tannic acid (TA) known as a natural antioxidant and possessing antimicrobial properties was used as a protective remedy. Oil microdroplets coated with TA-containing shell displayed physical-chemical and mechanical stability in aqueous phase and over freeze-drying process as determined by ζ-potential measurements, dynamic light scattering (DLS), and confocal laser scanning microscopy (CLSM). Oxidation of emulsified oil was monitored by formation of malondialdehyde (MDA) in the samples quantified by Thiobarbituric Acid Reactive Substances (TBARS) assay. Coating shell with an incorporated layer of TA effectively suppressed oxidation in water-dispersed oil droplets and affected iron-catalyzed oxidation over 15 days of incubation at 37 °C in 0.3 mM FeBr2 solution. Antioxidant activity of TA-containing shell assembled around each oil droplet was found to be higher than that of mixed tocopherols (MT) added to linseed oil in concentration of 10000 ppm.

Layer-by-layer assembled shells are prospective candidates for encapsulation, stabilization, storage, and release of fragrances. A shell comprising four alternative layers of a protein and a polyphenol is employed to encapsulate the dispersed phase of a fragrance-containing oil-in-water emulsion. The model fragrance used in this work consists of 10 ingredients, covering a range of typically employed aroma molecules, all premixed in equal mass and with sunflower oil acting as the base. The encapsulated emulsion is stable after 2 months of storage at 4 °C as revealed by static light scattering and confocal laser scanning microscopy. Gas chromatography/mass spectrometry data show that the encapsulation efficiency of 8 out of 10 fragrance ingredients depends on the water solubility: the less water-soluble an ingredient, the more of it is encapsulated. The amount of these fragrance ingredients remaining encapsulated decreases linearly upon emulsion incubation at 40 °C and the multilayer shell does not hinder their release. The other two fragrance ingredients having the lowest saturation vapor pressure demonstrate sustained release over 5 days of incubation at 40 °C. The composition of released fragrance remains almost constant over 3 days of incubation, upon further incubation it becomes enriched with these two ingredients when others start to be depleted.

Single‐wall carbon nanotubes modified by anionic polyelectrolyte molecules are embedded into the shells of microcapsules. Carbon nanotubes serve as rigid rods in a softer polymeric capsule, which forms a free‐standing shell upon treatment with glutaraldehyde and subsequent drying. The embedded carbon nanotubes exhibit a broad absorption in the UV–near‐infrared part of the spectrum, and that allows point‐wise activation and opening of the microcapsules by laser. Raman signal analysis shows changes of carbon‐nanotube‐specific lines after high‐power laser irradiation, which is characteristic of the formation of disordered carbonlike structures. These polyelectrolyte/carbon nanotube composite capsules represent a novel light‐addressable type of microcontainers.

Microcapsules, made of biodegradable polymers, containing magnetite nanoparticles with tunable contrast in both the T1 and T2 MRI modes, were successfully prepared using a layer-by-layer approach. The MRI contrast of the microcapsules was shown to depend on the distance between magnetite nanoparticles in the polymeric layers, which is controlled by their concentration in the microcapsule shell. A fivefold increase in the average distance between the nanoparticles in the microcapsule shell led to a change in the intensity of the MR signal of 100% for both the T1 and T2 modes. Enzyme treatment of biodegradable shells resulted in a change of the microcapsules' MRI contrast. In vivo degradation of nanocomposite microcapsules concentrated in the liver after intravenous injection was demonstrated by MRI. This method can be used for the creation of a new generation of drug delivery systems, including drug depot, with combined navigation, visualization and remote activated release of bioactive substances in vivo.

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Targeted cell delivery via magnetically sensitive microcapsules of an applied magnetic field would advance localized cell transplantation therapy, by which healthy cells can be introduced into tissues to repair damaged or diseased organs. In the present research, we implement magnetically sensitive cells via an uptake of microcapsules containing magnetic nanoparticles in their walls. As is shown in an example of the MA-104 cell line, the magnetic polyelectrolyte multilayer capsules have no toxicity effect on the cells after internalization. Microscopy methods have been used to evaluate the uptake of capsules by the cells. Magnetically sensitive cells are retained in the capillary flow when the magnetic gradient field is applied (<200 T m-1), but they proliferate at the site of retention for several days after the magnet is removed. As an example of cell manipulation, we have demonstrated a novel methodology for cell sheet isolation and transfer using cells impregnated with magnetic microcapsules. A weak enzyme treatment is used to facilitate tissue engineering assemblies by cell monolayer deposition. This type of cell monolayer assembly has provided a 3D tissue engineering construction using an externally applied magnetic field, which is modelled in this study. The approach presented in this work opens perspectives for preclinical studies of tissue and organ repair.

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