Conceptualization and Investigation of Multicomponent Polymer Networks as Prospective Corticosteroid Carriers.

Dexamethasone (DXM) is a highly potent and long-acting synthetic glucocorticoid with anti-inflammatory, anti-allergic, and immunosuppressive effects. However, the systemic application of DXM can cause undesirable side effects: sleep disorders, nervousness, heart rhythm disorders, heart attack, and others. In the present study, multicomponent polymer networks were developed as potential new platforms for the dermal application of dexamethasone sodium phosphate (DSP). First, a copolymer network (CPN) comprising hydrophilic segments of different chemical structures was synthesized by applying redox polymerization of dimethyl acrylamide onto poly(ethylene glycol) in the presence of poly(ethylene glycol) diacrylate (PEGDA) as a crosslinker. On this basis, an interpenetrating polymer network structure (IPN) was obtained by introducing a second network of PEGDA-crosslinked poly(N-isopropylacrylamide). Multicomponent networks obtained were characterized by FTIR, TGA, and swelling kinetics in different solvents. Both CPN and IPN showed a high swelling degree in aqueous media (up to 1800 and 1200%, respectively), reaching the equilibrium swelling within 24 h. Additionally, IPN showed temperature-responsive swelling in an aqueous solution as the equilibrium swelling degree decreased considerably with an increase in the temperature. In order to evaluate the networks' potential as drug carriers, swelling in DSP aqueous solutions of varied concentration was investigated. It was established that the amount of encapsulated DSP could be easily controlled by the concentration of drug aqueous solution. In vitro DSP release was studied in buffer solution (BS) with pH 7.4 at 37 °C. The results obtained during DSP loading and release experiments proved the feasibility of the developed multicomponent hydrophilic polymer networks as effective platforms for potential dermal application.

Blending Approach Preparation of PVA-g-PMA Films with Embedded "Green" Synthesized Silver Nanoparticles for Acetone Optical Detection.

The blending approach (also known as the ex-situ approach) was used for the deposition of thin composite films comprising poly(vinyl alcohol-graft-methyl acrylate) (PVA-g-PMA) and silver nanoparticles (AgNPs). Firstly, the copolymer aqueous dispersion was synthesized through the redox polymerization of methyl acrylate (MA) on poly(vinyl alcohol) (PVA) using ammonium cerium (IV) nitrate as the initiator. Then, AgNPs were synthesized through a "green" method using the water extract of lavender based on by-products of the essential oil industry, and then they were blended with the polymer. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to determine nanoparticle size, along with their stability over time in suspension, during the 30-day period. Thin films of the PVA-g-PMA copolymer, with different AgNP volume fractions varying between 0.008 and 0.260%, were deposited via the spin-coating method on Si substrates, and their optical properties were explored. UV-VIS-NIR spectroscopy and non-linear curve fitting were used for the determination of the refractive index, extinction coefficient, and thickness of the films, while photoluminescence measurements at room temperature were conducted for studying the emission of the films. The concentration dependence of film thickness was observed and showed that thickness increased linearly from 31 nm to 75 nm when the nanoparticles' weight content increased from 0.3 wt% to 2.3 wt%. The sensing properties toward acetone vapors were tested in a controlled atmosphere by measuring reflectance spectra before and during exposure to the analyte molecules in the same film spot; the swelling degree of films was calculated and compared to the corresponding undoped samples. It was shown that the concentration of AgNPs of 1.2 wt% in the films is optimal for the enhancement of the sensing response toward acetone. The influence of AgNPs on the films' properties was revealed and discussed.

Poly(l-Lactide) Liquid Crystals with Tailor-Made Properties Toward a Specific Nematic Mesophase Texture.

This paper presents the liquid crystal (LC) properties of poly(l-lactide) (PLLA). Mesophase behavior is investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The performed analyses confirm that pressed PLLA films exhibit the unique capability of self-assembling into a nematic mesophase under the influence of mechanical pressure, temperature, and time. It was originally demonstrated that the chiral nematic mesophase can be obtained by introducing fine powders into the polymer. Based on the research conducted, it was proved that the pressed PLLA films have a chiral nematic mesophase with a nematic-to-isotropic phase transition and a large mesophase stability range overlapping the temperature of the human body, which can persist for years at ambient temperature. The obtained films show tailor-made properties toward a nematic mesophase with a specific texture, including colored planar texture of the chiral nematic mesophase and blue-phase (BP) LC texture. The BP, described for the first time in plain PLLA, occurred over a wider than usual temperature range of stability between isotropic and chiral nematic thermotropic phases (ΔT ≈ 9 °C), which is an advantage of the obtained polymer material, in addition to ease of preparation. This opens up new prospects for advanced photonic green applications.

Flexible and Transparent Polymer-Based Optical Humidity Sensor.

Thin spin-coated polymer films of amphiphilic copolymer obtained by partial acetalization of poly (vinyl alcohol) are used as humidity-sensitive media. They are deposited on polymer substrate (PET) in order to obtain a flexible humidity sensor. Pre-metallization of substrate is implemented for increasing the optical contrast of the sensor, thus improving the sensitivity. The morphology of the sensors is studied by surface profiling, while the transparency of the sensor is controlled by transmittance measurements. The sensing behavior is evaluated through monitoring of transmittance values at different levels of relative humidity gradually changing in the range 5-95% and the influence of up to 1000 bending deformations is estimated by determining the hysteresis and sensitivity of the flexible sensor after each set of deformations. The successful development of a flexible sensor for optical monitoring of humidity in a wide humidity range is demonstrated and discussed.

Optical Sensing of Humidity Using Polymer Top-Covered Bragg Stacks and Polymer/Metal Thin Film Structures.

Thin films with nanometer thicknesses in the range 100-400 nm are prepared from double hydrophilic copolymers of complex branched structures containing poly(N,N-dimethyl acrylamide) and poly(ethylene oxide) blocks and are used as humidity sensitive media. Instead of using glass or opaque wafer for substrates, polymer thin films are deposited on Bragg stacks and thin (30 nm) sputtered Au-Pd films thus bringing color for the colorless polymer/glass system and enabling transmittance measurements for humidity sensing. All samples are characterized by transmittance measurements at different humidity levels in the range from 5% to 90% relative humidity. Additionally, the humidity induced color change is studied by calculating the color coordinates at different relative humidity using measured spectra of transmittance or reflectance. A special attention is paid to the selection of wavelength(s) of measurements and discriminating between different humidity levels when sensing is performed by measuring transmittance at fixed wavelengths. The influence of initial film thickness, sensor architecture, and measuring configuration on sensitivity is studied. The potential and advantages of using top covered Bragg stacks and polymer/metal thin film structures as humidity sensors with simple optical read-outs are demonstrated and discussed.

Ecotoxicological impact of selected polyethylenimines toward their potential application as nitrogen fertilizers with prolonged activity.

Poly(2-oxazoline) polymers have found extensive application in the preparation of microcapsules for biomedical purposes. However, there is a scarcity of information related to their ecotoxicological assessment. Therefore, in this study, we focused on the ecotoxicity of selected polyethylenimines (PEIs) including poly(2-ethyl-2-oxazoline) (PEtOx) as an N-acyl-substituted PEI, linear polyethylenimine (LPEI) and branched polyethylenimine (BPEI). Oat (a monocotyledon) (Avena sativa) and radish (a dicotyledon) (Raphanus sativus) were selected as the representative plants, which are recommended by the Organization for Economic Cooperation and Development (OECD) 208 as the standard to test for plant growth. Shoot and root length, fresh and dry matter, level of total nitrogen in green parts of the plants, as well as total chlorophyll and carotenoids were determined. Phytotoxicity of all the tested parameters was dependent on the concentration of the examined polymers in the soil as well as on the time of their incubation in the soil. According to our results, the amount of nitrogen in green parts of the plants was increased compared to the control plants, which revealed the uptake of the plant-available form of nitrogen released from the tested PEIs. This was especially true for the plants treated with LPEI. Ecotoxicological impact of the incubated polymers in the soil against marine bacteria Allivibrio fischeri proved that, the all tested polyethylenimines may be classified as not harmful to aquatic microorganisms.

Influence of Macromolecular Architecture on the Optical and Humidity-Sensing Properties of Poly(N,N-Dimethylacrylamide)-Based Block Copolymers.

The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such as triblock, star-shaped, and branched were synthesized. The copolymers were characterized using conventional spectroscopic techniques as well as methods for characterization of copolymer macromolecular characteristics in solution, namely size-exclusion chromatography and static light scattering. Thin films of the copolymers of nanometer scale thickness were deposited on silicon substrates by the spin-coating method. The refractive index and extinction coefficient of the copolymer films were calculated from the reflectance spectra by using non-linear curve fitting methods and the composition-structure-optical properties relationships were evaluated. Humidity-sensing properties of the films were studied by measuring reflectance spectra of the films at a relative humidity range from 5 to 95%RH. The implementation of the copolymer films as optical sensors of humidity is justified and discussed.

pH-Sensitive cationic copolymers of different macromolecular architecture as potential dexamethasone sodium phosphate delivery systems.

This paper describes the synthesis and characterization of cationic copolymers with different macromolecular architecture and drug delivery properties of the corresponding dexamethasone sodium phosphate (DSP)-loaded systems. Copolyelectrolytes comprising poly[2-(acryloyloxy)ethyl] trimethylammonium chloride (PAETMAC) and poly(ethylene glycol) blocks as well as a tri-arm star-shaped PAETMAC were synthesized using cerium(IV) ion-mediated polymerization method. The obtained copolyelectrolytes and corresponding ionic associates with DSP have been characterized by (1)H NMR, Fourier Transform Infrared spectroscopy, and differential scanning calorimetry. The average diameter, size distribution, and ζ-potential of the copolymers and DSP-copolymer ionic associates were determined by dynamic light scattering, and particles were visualized by scanning electron microscopy and transmission electron microscopy. The biocompatibility and cytotoxicity of obtained copolymers were determined. In vitro drug release experiments were carried out to estimate the ability of the obtained nanoparticles for sustained release of DSP for a period of 24 h.

Evaluation of poly(2-ethyl-2-oxazoline) containing copolymer networks of varied composition as sustained metoprolol tartrate delivery systems.

Segmented copolymer networks (SCN) based on poly(2-ethyl-2-oxazoline) and containing 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and/or methyl methacrylate segments have been evaluated as potential sustained release systems of the water soluble cardioselective ß-blocker metoprolol tartrate. The structure and properties of the drug carriers were investigated by differential scanning calorimetry, attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. Swelling kinetics of SCNs in various media was followed, and the conditions for effective MT loading were specified. MT-loaded SCNs with drug content up to 80 wt.% were produced. The release kinetics of metoprolol tartrate from the systems was studied and it was shown that the conetworks of different structure and composition are able to sustain the metoprolol tartrate release without additional excipients.

Polyester-based (bio)degradable polymers as environmentally friendly materials for sustainable development.

This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields.

Study of the potential of amphiphilic conetworks based on poly(2-ethyl-2-oxazoline) as new platforms for delivery of drugs with limited solubility.

Thermoresponsive amphiphilic conetworks comprising poly(2-ethyl-2-oxazoline) (PEtOx), 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate segments have been studied as new platforms for delivery of drug with limited solubility. Series of conetworks of varied composition were synthesized and swelling kinetics in aqueous media and ethanol were followed. The platforms were loaded with the hydrophobic drug ibuprofen by swelling in its ethanol solution. The structure and properties of the drug carriers were investigated by scanning electron microscopy and differential scanning calorimetry. The release kinetics profiles of ibuprofen from the studied platform were established. The investigation proved the feasibility of the PEtOx-based amphiphilic conetworks as highly effective platforms for sustained ibuprofen delivery.