Ivetta Aramovna Varyan

In the present research, a new type of biomimetic material loaded with chlorophyll derivatives (CpDs) for photodynamic therapy based on poly(3-hydroxybutyrate) (PHB) was fabricated by the electrospinning method. Such matrices showed great potential for the advanced delivery of photodynamic therapeutic reagents to targeted regions and options for prolonged local application. The key morphological characteristics of fibrous materials were investigated. It was found that incorporation of CpDs leads to a change in the average fiber diameter from 3.5 µm to 2.1 µm, increasing porosity from 80% to 90% and accompanied by an over 3-fold increased proportion of open pores. Moreover, the CpD application facilitated fine hydrophilicity tuning, allowing an increase of this parameter up to 10% under different conditions, neutralizing the hydrophobic nature of the matrix polymer and photosensitizer. Moreover, changes in physical properties, supramolecular structure, photosensitizing effect, and singlet oxygen generation were investigated. The data obtained show that the proposed materials are great examples of convenient and reliable carriers for advanced PDT. The results obtained demonstrate high antimicrobial activity in the presence of irradiation as well as noticeable efficacy against carcinoma, both light and dark.

To obtain data on the effects of ozonolysis on the structural and dynamic parameters of ultrafine fibers based on the binary compositions of poly-(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) with varying ratios of polymer components ranging from 0/100 to 100/0 mass%, produced by electrospinning, a study was conducted. The morphology and structural–dynamic characteristics of the ultrafine fibers were examined. Comprehensive research was carried out, combining thermophysical measurements (DSC), dynamic measurements using an electron paramagnetic resonance (EPR) technique, scanning electron microscopy, and infrared spectroscopy. The influence of the mixture’s composition and ozonolysis on the degree of crystallinity of PHB and the molecular mobility of the TEMPO radical (tetramethylpiperidine-1-oxyl) in the amorphous regions of the PHB/PVP fiber material was demonstrated. The low-temperature maximum on the DSC thermograms provided information about the fraction of hydrogen bonds in the mixed compositions, allowing for the enthalpy of thermal destruction of these bonds in both the original and oxidized samples to be determined. The study showed significant changes in the degree of crystallinity of PHB, the enthalpy of hydrogen bond destruction, molecular mobility, moisture absorption of the compositions, and the activation energy of rotational diffusion in the amorphous regions of the PHB/PVP mixed compositions. It was established that within the 50/50% PHB/PVP ratio, an inversion transition occurs from the dispersion material to the dispersion medium. Ozonolysis induces a sharp change in the material’s structure. The conducted research provided the first opportunity to assess the impact of ozonolysis on the structural and dynamic characteristics of PHB/PVP ultrafine fibers at a molecular level. These materials may serve as a therapeutic system for controlled drug delivery.

The problem of polymer waste (plastic waste) is one of the most acute environmental problems of our time

The control of the quantities of multi-tonnage polymers, in particular, making them biodegradable, is an urgent task. This study suggests a new approach in the application of natural rubber (NR) as an initiator of biodegradation of low-density polyethylene (LDPE) in soil. The study examines the structure, properties and rates of biodegradation of thin LDPE films with different content of NR. Such methods as fourier transform infrared spectroscopy (FTIR), electron paramagnetic resonance (EPR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscope (SEM), atomic force microscopy (AFM), gel-permeation chromatography (GPC), and acoustic microscopy were used for the most complete characterization of NR/LDPE composite systems. It was shown for the first time that at concentrations above 30%, NR is able to form an interpenetrating structure with the LDPE matrix, which has a decisive effect on the initiation of biodegradation during exposure in soil. Thus, the composition with 50% natural rubber exhibits the highest mass loss. The sample with 50% natural rubber content lost 70% of its mass, while the one with 40% NR content lost 38%. Furthermore, after soil burial, a significant decrease in crystallinity was observed: from 39.5% to 31.5% for the 90/10 composition and from 39.1% to 24.2% for the 50/50 composition. The results obtained are confirmed by a noticeable decrease in the molecular weight characteristics of LDPE.

This work is devoted to the electrospinning of biocompatible fibrous matrixes for microbial wound therapy. The problem of treating staphylococcal-infected wounds remains urgent. In this study, we propose a new approach to the use of the chlorophyll (Chl) and poly-3-hydroxybutyrate (PHB) composite system in the treatment of infected wounds. The structure and properties of the electrospun polymer matrix based on PHB modified with various concentrations of Chl was investigated by SEM, confocal microscopy, DSC, EPR. The release rate, fluorescence, and antimicrobial activity of Chl incorporated into PHB were studied. The high efficiency of the developed materials was shown with the participation of laboratory animals.

Ultrafine fibers from poly(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) and their blends with different component ratios in the range of 0/100 to 100/0 wt.% were obtained, and their structure and dynamic properties were studied. The polymers were obtained via electrospinning in solution mode. The structure, morphology, and segmental dynamic behavior of the fibers were determined using optical microscopy, SEM, EPR, DSC, and IR spectroscopy. The low-temperature maximum on the DSC endotherms provided information on the state of the PVP hydrogen bond network, which made it possible to determine the enthalpies of thermal destruction of these bonds. The PHB/PVP fiber blend ratio significantly affected the structural and dynamic parameters of the system. Thus, at low concentrations of PVP (up to 9%) in the structure of ultra-fine fibers, the distribution of this polymer occurs in the form of tiny particles, which are crystallization centers, which causes a significant increase in the degree of crystallinity (χ) activation energy (E_act) and slowing down of molecular dynamics (τ). At higher concentrations of PVP, loose interphase layers were formed in the system, which caused a decrease in these parameters. The strongest changes in the concentration of hydrogen bonds occurred when PVP was added to the composition from 17 to 50%, which was due to the formation of intermolecular hydrogen bonds both in PVP and during the interaction of PVP and PHB. The diffusion coefficient of water vapor in the studied systems (D) decreased as the concentration of glassy PVP in the composition increased. The concentration of the radical decreased with an increase in the proportion of PVP, which can be explained by the glassy state of this polymer at room temperature. A characteristic point of the 50/50% mixture component ratio was found in the region where an inversion transition of PHB from a dispersion material to a dispersed medium was assumed. The conducted studies made it possible for the first time to conduct a comprehensive analysis of the effect of the component ratio on the structural and dynamic characteristics of the PHB/PVP fibrous material at the molecular scale.

This work is devoted to the creation of biocompatible fibrous materials with a high antimicrobial effect based on poly-3-hydroxybutyrate (PHB) and chlorophyll (Chl). The data obtained show the possibility of obtaining fibrous materials from PHB and Chl by electrospinning methods. The obtained electrospun matrices were investigated by the SEM, DSC and FTIR methods. Various key properties of the matrices were evaluated, including hydrophilicity and mechanical strength, as well as photodynamic and light-dependent antimicrobial effects against the conditionally pathogenic microorganism Staphylococcus aureus. The results demonstrate a significant improvement in electrospinning properties for a concentration of 0.5% Chl and a reduction in fiber formation defects, as well as an increase in the strength of nonwovens. It was found that the antimicrobial potential of Chl-PHB (with concentrations of Chl of 1.25 and 1.5%) is higher than that of Chl in free form. It was also determined that irradiation increases the inhibitory effect of Chl, both in free form and in the form of a complex with a polymer.

Electrospun ultrathin fibers based on binary compositions of polylactide (PLA) and poly(ε-caprolactone) (PCL) with the various content from the polymer ratio from 0/100 to 100/0 have been explored. Combining thermal (DSC) and spectropy (ESR) techniques, the effect of biopolymer content on the characteristics of the crystal structure of PLA and PCL and the rotative diffusion of the stable TEMPO radical in the intercrystallite areas of PLA/PCL compositions was shown. It was revealed that after PLA and PCL blending, significant changes in the degree of crystallinity of PLA, PCL segment mobility, sorption of the Tempo probe, as well as its activation energy of rotation in the intercrystalline areas of PLA/PCL fibers, were evaluated. The characteristic region of biopolymers’ composition from 50/50 to 30/70% PLA/PCL blend ratio was found, where the inversion transition of PLA from dispersive medium to dispersive phase where an inversion transition is assumed when the continuous medium of the PLA transforms into a discrete phase. The performed studies made it possible, firstly, to carry out a detailed study of the effect of the system component ratio on the structural and dynamic characteristics of the PLA/PCL film material at the molecular level.

Electrospun ultrathin fibers based on binary compositions of polylactide (PLA) and poly(ε-caprolactone) (PCL) with different ratios of polymer components from 0/100 to 100/0 wt. % were studied. Using a combination of thermal (DSC) and relaxation (EPR) measurements, the effect of biopolymers content on the characteristics of the crystal structure of PLA and PCL and the diffusive rotational mobility of the stable TEMPO radical in the amorphous regions of PLA/PCL compositions was shown. It was revealed that after PLA and PCL blending, significant changes in the degree of crystallinity of PLA, PCL segmental mobility, sorption capacity of the radical as well as activation energy of rotational diffusion in the amorphous regions of PLA/PCL composition are observed. The characteristic region of biopolymers’ composition from 50/50 to 30/70 % PLA/PCL blends ratio was found, where the inversion transition of PLA from dispersive medium to dispersive phase where an inversion transition is assumed when the continuous medium of the PLA transforms into a discrete phase. The performed studies made it possible for the first time to carry out a comprehensive analysis of the effect of the system component ratio on the structural and dynamic characteristics of the PLA/PCL film material at the molecular level.