Piezoelectric and Dielectric Electrospun Fluoropolymer Membranes for Oral Mucosa Regeneration: A Comparative Study.

Wound healing of the oral mucosa is an urgent problem in modern dental surgical practice. This research article presents and compares the findings of the investigations of the structural, physicochemical, and biological characteristics of two types of polymeric membranes used for the regeneration of oral mucosa. The membranes were prepared from poly(tetrafluoroethylene) (PTFE) and a copolymer of vinylidene fluoride and tetrafluoroethylene (VDF-TeFE) and analyzed via scanning electron microscopy, atomic force microscopy, X-ray diffraction analysis, and Fourier transform infrared spectroscopy. Investigation results obtained indicate that both types of membranes are composed of thin fibers: (0.57 ± 0.25) µm for PTFE membranes and (0.43 ± 0.14) µm for VDF-TeFE membranes. Moreover, the fibers of VDF-TeFE membranes exhibit distinct piezoelectric properties, which are confirmed by piezoresponse force microscopy and X-ray diffraction. Both types of membranes are hydrophobic: (139.7 ± 2.5)° for PTFE membranes and (133.5 ± 2.0)° for VDF-TeFE membranes. In vitro assays verify that both membrane types did not affect the growth and division of mice fibroblasts of the 3T3-L1 cell line, with a cell viability in the range of 88-101%. Finally, in vivo comparative experiments carried out using Wistar rats demonstrate that the piezoelectric VDF-TeFE membranes have a high ability to regenerate oral mucosa.

Composite Ferroelectric Membranes Based on Vinylidene Fluoride-Tetrafluoroethylene Copolymer and Polyvinylpyrrolidone for Wound Healing.

Wound healing is a complex process and an ongoing challenge for modern medicine. Herein, we present the results of study of structure and properties of ferroelectric composite polymer membranes for wound healing. Membranes were fabricated by electrospinning from a solution of vinylidene fluoride/tetrafluoroethylene copolymer (VDF-TeFE) and polyvinylpyrrolidone (PVP) in dimethylformamide (DMF). The effects of the PVP content on the viscosity and conductivity of the spinning solution, DMF concentration, chemical composition, crystal structure, and conformation of VDF-TeFE macromolecules in the fabricated materials were studied. It was found that as PVP amount increased, the viscosity and conductivity of the spinning solutions decreased, resulting in thinner fibers. Using FTIR and XRD methods, it was shown that if the PVP content was lower than 50 wt %, the VDF-TeFE copolymer adopted a flat zigzag conformation (TTT conformation) and crystalline phases with ferroelectric properties were formed. Gas chromatography results indicated that an increase in the PVP concentration led to a higher residual amount of DMF in the material, causing cytotoxic effects on 3T3L1 fibroblasts. In vivo studies demonstrated that compared to classical gauze dressings impregnated with a solution of an antibacterial agent, ferroelectric composite membranes with 15 wt % PVP provided better conditions for the healing of purulent wounds.

Site-specific release of reactive oxygen species from ordered arrays of microchambers based on polylactic acid and carbon nanodots.

Non-destructive, controllable, remote light-induced release inside cells enables studying of time- and space-specific surface-mediated delivery of bioactive compounds, which is an important approach in a wide range of biomedical tasks, especially those related to the control of cell growth, regenerative medicine, and self-disinfecting structures such as catheters. In this regard, the elaboration of encapsulation and controlled release of oxidative species is in high demand due to its versatile applications. One of the obvious candidates for such species is hydrogen peroxide. However, the delivery of hydrogen peroxide to the site of interest with high temporal and spatial precision remains challenging due to the active and unstable nature of the substance. We hereby present an approach to encapsulate and store a hydrogen peroxide-containing solid compound (sodium percarbonate) in the free-standing arrays of biopolymer-based microchambers. In this regard, we use solid-state encapsulation enabling high payload ability, followed by isolated storage in order to prevent contact of the cargo with water. Monitoring of the release profiles reveals the encapsulation of sodium percarbonate with little leakage for up to 24 hours. Microchambers are fabricated with predetermined size and spatial distribution, which allows the release of extremely small amounts of cargo (10-30 pg) with high spatial accuracy. Microchambers are made of polylactic acid and functionalized by carbon nanodots, which provide biocompatibility and biodegradability of the whole system together with responsiveness towards NIR light. These chambers facilitate both ultrasound-assisted burst release and laser-driven carbon nanoparticle-assisted precise release of extremely small, controlled amounts of a few picograms of hydrogen peroxide in submerged conditions. Microchambers loaded with sodium percarbonate provided adhesion and high viability of mouse fibroblasts over 24 h of exposure. The developed system opens an exciting avenue for prospective delivery routes in a number of areas such as wound healing by time and site-specific release.

Modification of PCL Scaffolds by Reactive Magnetron Sputtering: A Possibility for Modulating Macrophage Responses.

Direct current (DC) reactive magnetron sputtering is as an efficient method for enhancing the biocompatibility of poly(ε-caprolactone) (PCL) scaffolds. However, the PCL chemical bonding state, the composition of the deposited coating, and their interaction with immune cells remain unknown. Herein, we demonstrated that the DC reactive magnetron sputtering of the titanium target in a nitrogen atmosphere leads to the formation of nitrogen-containing moieties and the titanium dioxide coating on the scaffold surface. We have provided the possible mechanism of PCL fragmentation and coating formation supported by XPS results and DFT calculations. Our preliminary biological studies suggest that DC reactive magnetron sputtering of the titanium target could be an effective tool to control macrophage functional responses toward PCL scaffolds as it allows to inhibit respiratory burst while retaining cell viability and scavenging activity.

Fabrication of PLA/CaCO3 hybrid micro-particles as carriers for water-soluble bioactive molecules.

We propose the use of polylactic acid/calcium carbonate (PLA/CaCO3) hybrid micro-particles for achieving improved encapsulation of water-soluble substances. Biodegradable porous CaCO3 microparticles can be loaded with wide range of bioactive substance. Thus, the formation of hydrophobic polymeric shell on surface of these loaded microparticles results on encapsulation and, hence, sealing internal cargo and preventing their release in aqueous media. In this study, to encapsulate proteins, we explore the solid-in-oil-in-water emulsion method for fabricating core/shell PLA/CaCO3 systems. We used CaCO3 particles as a protective core for encapsulated bovine serum albumin, which served as a model protein system. We prepared a PLA coating using dichloromethane as an organic solvent and polyvinyl alcohol as a surfactant for emulsification; in addition, we varied experimental parameters such as surfactant concentration and polymer-to-CaCO3 ratio to determine their effect on particle-size distribution, encapsulation efficiency and capsule permeability. The results show that the particle size decreased and the size distribution narrowed as the surfactant concentration increased in the external aqueous phase. In addition, when the CaCO3/PLA mass ratio dropped below 0.8, the hybrid micro-particles were more likely to resist treatment by ethylenediaminetetraacetic acid and thus retained their bioactive cargos within the polymer-coated micro-particles.

Polylactic Acid Sealed Polyelectrolyte Multilayer Microchambers for Entrapment of Salts and Small Hydrophilic Molecules Precipitates.

Efficient depot systems for entrapment and storage of small water-soluble molecules are of high demand for wide variety of applications ranging from implant based drug delivery in medicine and catalysis in chemical processes to anticorrosive systems in industry where surface-mediated active component delivery is required on a time and site specific manner. This work reports the fabrication of individually sealed hollow-structured polyelectrolyte multilayer (PEM) microchamber arrays based on layer-by-layer self-assembly as scaffolds and microcontact printing. These PEM chambers are composed out of biocompatible polyelectrolytes and sealed by a monolayer of hydrophobic biocompatible and biodegradable polylactic acid (PLA). Coating the chambers with hydrophobic PLA allows for entrapment of a microair-bubble in each chamber that seals and hence drastically reduces the PEM permeability. PLA@PEM microchambers are proven to enable prolonged subaqueous storage of small hydrophilic salts and molecules such as crystalline NaCl, doxicycline, and fluorescent dye rhodamine B. The presented microchambers are able to entrap air bubbles and demonstrate a novel strategy for entrapment, storage, and protection of micropackaged water-soluble substances in precipitated form. These chambers allow triggered release as demonstrated by ultrasound responsiveness of the chambers. Low-frequency ultrasound exposure is utilized for microchamber opening and payload release.

Patterned Microstructure Fabrication: Polyelectrolyte Complexes vs Polyelectrolyte Multilayers.

Polyelectrolyte complexes (PEC) are formed by mixing the solutions of oppositely charged polyelectrolytes, which were hitherto deemed "impossible" to process, since they are infusible and brittle when dry. Here, we describe the process of fabricating free-standing micro-patterned PEC films containing array of hollow or filled microchambers by one-step casting with small applied pressure and a PDMS mould. These structures are compared with polyelectrolyte multilayers (PEM) thin films having array of hollow microchambers produced from a layer-by-layer self-assembly of the same polyelectrolytes on the same PDMS moulds. PEM microchambers "cap" and "wall" thickness depend on the number of PEM bilayers, while the "cap" and "wall" of the PEC microchambers can be tuned by varying the applied pressure and the type of patterned mould. The proposed PEC production process omits layering approaches currently employed for PEMs, reducing the production time from ~2 days down to 2 hours. The error-free structured PEC area was found to be significantly larger compared to the currently-employed microcontact printing for PEMs. The sensitivity of PEC chambers towards aqueous environments was found to be higher compared to those composed of PEM.