Polyhydroxyalkanoates (PHAs) are a family of polyesters produced by many microbial species. These naturally occurring polymers are widely used in tissue engineering because of their in vivo degradability and excellent biocompatibility. The best studied among them is poly(3-hydroxybutyrate) (PHB) and its copolymer with 3-hydroxyvaleric acid (PHBV). Despite their superior properties, PHB and PHBV suffer from high crystallinity, poor mechanical properties, a slow resorption rate, and inherent hydrophobicity. Not only are PHB and PHBV hydrophobic, but almost all members of the PHA family struggle because of this characteristic. One can overcome the limitations of microbial polyesters by modifying their bulk or surface chemical composition. Therefore, researchers have put much effort into developing methods for the chemical modification of PHAs. This paper explores a rarely addressed topic in review articles—chemical methods for modifying the structure of PHB and PHBV to enhance their suitability as biomaterials for tissue engineering applications. Different chemical strategies for improving the wettability and mechanical properties of PHA scaffolds are discussed in this review. The properties of PHAs that are important for their applications in tissue engineering are also discussed.

In this study, lithium borohydride (LiBH₄) reduction was used to modify the surface chemistry of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibers. Although the most common reaction employed in the surface treatment of polyester materials is hydrolysis, it is not suitable for fiber modification of bacterial polyesters, which are highly resistant to this type of reaction. The use of LiBH₄ allowed the formation of surface hydroxyl groups under very mild conditions, which was crucial for maintaining the fibers’ integrity. The presence of these groups resulted in a noticeable improvement in the surface hydrophilicity of PHBV, as revealed by contact angle measurements. After the treatment with a LiBH₄ solution, the electrospun PHBV fibrous mat had a significantly greater number of viable osteoblast-like cells (SaOS-2 cell line) than the untreated mat. Moreover, the results of the cell proliferation measurements correlated well with the observed cell morphology. The most flattened SaOS-2 cells were found on the surface that supported the best cell attachment. Most importantly, the results of our study indicated that the degree of surface modification could be controlled by changing the degradation time and concentration of the borohydride solution. This was of great importance since it allowed optimization of the surface properties to achieve the highest cell-proliferation capacity.

This study presents an in-depth molecular and structural characterization of novel biopolyesters developed under the trademark Bluepha^®. The primary aim was to elucidate the relationship between chemical structure, chain architecture, and material properties of these biopolyesters to define their potential applications across various sectors. Proton nuclear magnetic resonance (¹H NMR) analysis identified the biopolyesters as poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] (PHBH) copolymers, containing 4% and 10% molar content of hydroxyhexanoate (HH) units, respectively. Mass spectrometry analysis of PHBH oligomers, produced via controlled thermal degradation, further confirmed the chemical structure and molecular architecture of the PHBH samples. Additionally, multistage electrospray ionization mass spectrometry (ESI-MS/MS) provided insights into the chemical homogeneity and arrangement of comonomer units within the copolyester chains, revealing a random distribution of hydroxyhexanoate (HH) and hydroxybutyrate (HB) units along the PHBH chains. X-ray diffraction (XRD) patterns demonstrated partial crystallinity in the PHBH samples. The thermal properties, including glass transition temperature (T_g), melting temperature (T_m), and melting enthalpy (ΔH_m), were found to be lower in PHBH than in poly(R)-3-hydroxybutyrate (PHB), suggesting a broader application potential for the tested PHBH biopolyesters.

The optical properties, electronic structure and morphology of thin films of the polymer donor PTB7-Th blended with either the fullerene acceptor PC70BM or the non-fullerene acceptor ZY-4Cl were systematically investigated to evaluate their annealing-induced evolution. Thin films were characterized using UV–Vis–NIR absorption spectroscopy, spectroscopic ellipsometry, ATR-FTIR spectroscopy, atomic force microscopy (AFM), and nano-IR analysis. In situ stepwise thermal annealing revealed distinct changes in absorption edge parameters, indicating thermally induced modifications in the electronic structure of the blend films. Ellipsometric analysis showed that elevated temperatures significantly affect the refractive index and extinction coefficient spectra. AFM measurements demonstrated markedly different surface morphology evolution for the two blend systems, with pronounced needle-shaped crystallites formation observed in PTB7-Th:ZY-4Cl films after annealing at 100 °C. Nano-IR characterization identified these crystallites as predominantly PTB7-Th, indicating phase separation driven by thermal treatment. The combined optical and structural results reveal distinct annealing-induced changes in the blend. Finally, BHJ solar cells, based on PTB7-Th:PC70BM and PTB7-Th:ZY-4Cl active layers, were fabricated, and their photovoltaic response was demonstrated.

This study developed a technical task associated with the formation of welded joints based on biodegradable polymers and their subsequent physicochemical characterization. The primary objective was to establish the effect of the welding process and modification of natural poly(3-hydroxybutyrate) (PHB) with N,N-dibutylundecenoylamide (DBUA) as a plasticizing agent on the structure and properties of PHB-based biopolymer materials as well as the process and structure of welded joints formation using ultrasonic welding technique. The weldability of biodegradable layers based on PHB and PHB/DBUA mixture was ultrasonically welded and optimized using a standard Branson press-type installation. The effect of the DBUA plasticizer and welding process on the structure of PHB-based biodegradable material was investigated using scanning electron microscopy, X-ray diffraction, FT-IR spectroscopy, differential scanning calorimetry, and thermomechanical analysis. The results confirmed that the DBUA acted as an effective plasticizer of PHB, contributing to lower crystallinity of the PHB/DBUA mixture (63%) in relation to the crystallinity degree of pure PHB film (69%). Ultrasonic welding resulted in an additional increase (approximately 8.5%) in the degree of crystallinity in the PHB/DBUA in relation to the initial PHB/DBUA mixture. The significant shift toward lower temperatures of the crystallization and melting peaks of PHB modified with DBUA were observed using DSC concerning pure PHB. The melt crystallization process of PHB was affected by welding treatment, and a shift toward higher temperature was observed compared with the unwelded PHB/DBUA sample. The butt-welded joints of biodegradable PHB/DBUA materials made using the ultrasonic method tested for tensile strength have damaged the area immediately outside the joining surface.