Effect of Drug Encapsulation and Hydrothermal Exposure on the Structure and Molecular Dynamics of the Binary System Poly(3-hydroxybutyrate)-chitosan

Abstract

In this work, film materials based on binary compositions of poly-(3-hydroxybutyrate) (PHB) and chitosan with different ratios of polymer components in the range from 0/100 to 100/0 wt. % were studied. Using a combination of thermal (DSC) and relaxation (EPR) measurements, the influence of the encapsulation temperature of the drug substance (DS) of dipyridamole (DPD) and moderately hot water (at 70 °C) on the characteristics of the PHB crystal structure and the diffusion rotational mobility of the stable TEMPO radical in the amorphous regions of the PHB/chitosan compositions is shown. The low-temperature extended maximum on the DSC endotherms made it possible to obtain additional information about the state of the chitosan hydrogen bond network. This allowed us to determine the enthalpies of thermal destruction of these bonds. In addition, it is shown that when PHB and chitosan are mixed, significant changes are observed in the degree of crystallinity of PHB, degree of destruction of hydrogen bonds in chitosan, segmental mobility, sorption capacity of the radical, and the activation energy of rotational diffusion in the amorphous regions of the PHB/chitosan composition. The characteristic point of polymer compositions was found to correspond to the ratio of the components of the mixture 50/50%, for which the inversion transition of PHB from dispersed material to dispersion medium is assumed. Encapsulation of DPD in the composition leads to higher crystallinity and to a decrease in the enthalpy of hydrogen bond breaking, and it also slows down segmental mobility. Exposure to an aqueous medium at 70 °C is also accompanied by sharp changes in the concentration of hydrogen bonds in chitosan, the degree of PHB crystallinity, and molecular dynamics. The conducted research made it possible for the first time to conduct a comprehensive analysis of the mechanism of action of a number of aggressive external factors (such as temperature, water, and the introduced additive in the form of a drug) on the structural and dynamic characteristics of the PHB/chitosan film material at the molecular level. These film materials have the potential to serve as a therapeutic system for controlled drug delivery.

Electrospun Polylactide—Poly(ε-Caprolactone) Fibers: Structure Characterization and Segmental Dynamic Response

“…Along with widely used methods such as NMR, mechanic or dielectric dynamic spectroscopy, thermophysical execution, and IR (FTIR, ATR, and Raman) spectroscopy, the spin-probing ESR spectroscopy technique presents an extremely responsive approach to the reliable exploration of segmental mobility in petrol-and bio-based polymer blend systems [40,41]. Earlier, the authors investigated a series of individual and blended biopolymers on the base of poly(3-hydroxybutyrate) [PHB] by the above-mentioned ESR method to elucidate the role of segmental dynamics in annealing, hydrothermal aging, ozonolysis, as well as for water and drug diffusion in the PHB-based films and electrospun fibers [42][43][44]. The correlation among thermophysical phenomena, diffusivity, and segmental dynamics has stimulated us to transfer the focus of academic consideration from PHB blends to PLA ones.…”