Oligomers of poly-3-hydroxybutyrate (PHB) were prepared by aminolysis of high molecular weight PHB with ethylenediamine and 1,4-diaminobutane. Polymer-oligomer blends (10, 30, and 50% content of the oligomers) were prepared as films by solution casting. As the content of oligomers increased, a gradual increase in the hydrophilicity of the polymer surface was observed, resulting reflected in the water contact angle decrease from 84° to 72–76°. In addition, a moderate decrease in elongation at break, Young's modulus, and tensile strength for the blends were observed as more oligomer was added to the film. Finally, the viability of NIH-3T3 mouse fibroblasts was higher compared to intact PHB when growing in non-prepared polymer/oligomer mixtures. These findings confirm the benefits of the introduction of a hydrophilic functionalized oligomer into the PHB matrix in terms of improving the biocompatibility of the resulting polymer/oligomer blends.

The results of the study of plastic composites from degradable poly(3-hydroxybutyrate) P(3HB) and cellulose-containing natural materials of various origins are presented. For the first time, P(3HB) composites filled with bacterial nanocellulose (BNC) or wood (Pinus sibirica) flour (WF) were produced by melt pressing at 170 °C and 2000 Pa. The influence of the filler type and amount (30, 40, 50, 70 and 90 wt

The properties, features of thermal behavior and crystallization of copolymers containing various types of valerate monomers were studied depending on the set and ratio of monomers. We synthesized and studied the properties of three-component copolymers containing unusual monomers 4-hydroxyvalerate (4HV) and 3-hydroxy-4-methylvalerate (3H4MV), in addition to the usual 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) monomers. The results showed that P(3HB-co-3HV-co-4HV) and P(3HB-co-3HV-co-3H4MV) terpolymers tended to increase thermal stability, especially for methylated samples, including an increase in the gap between melting point (Tmelt) and thermal degradation temperature (Tdegr), an increase in the melting point and glass transition temperature, as well as a lower degree of crystallinity (40–46%) compared with P(3HB-co-3HV) (58–66%). The copolymer crystallization kinetics depended on the set and ratio of monomers. For terpolymers during exothermic crystallization, higher rates of spherulite formation (Gmax) were registered, reaching, depending on the ratio of monomers, 1.6–2.0 µm/min, which was several times higher than the Gmax index (0.52 µm/min) for the P(3HB-co-3HV) copolymer. The revealed differences in the thermal properties and crystallization kinetics of terpolymers indicate that they are promising polymers for processing into high quality products from melts.

The results of constructing 3D scaffolds from degradable poly(3-hydrosbutyrpate-co-3-hydroxyvalerate) using FDM technology and studying the structure, mechanical properties, biocompatibility in vitro, and osteoplastic properties in vivo are presented. In the process of obtaining granules, filaments, and scaffolds from the initial polymer material, a slight change in the crystallization and glass transition temperature and a noticeable decrease in molecular weight (by 40%) were registered. During the compression test, depending on the direction of load application (parallel or perpendicular to the layers of the scaffold), the 3D scaffolds had a Young’s modulus of 207.52 ± 19.12 and 241.34 ± 7.62 MPa and compressive stress tensile strength of 19.45 ± 2.10 and 22.43 ± 1.89 MPa, respectively. SEM, fluorescent staining with DAPI, and calorimetric MTT tests showed the high biological compatibility of scaffolds and active colonization by NIH 3T3 fibroblasts, which retained their metabolic activity for a long time (up to 10 days). The osteoplastic properties of the 3D scaffolds were studied in the segmental osteotomy test on a model defect in the diaphyseal zone of the femur in domestic Landrace pigs. X-ray and histological analysis confirmed the formation of fully mature bone tissue and complete restoration of the defect in 150 days of observation. The results allow us to conclude that the constructed resorbable 3D scaffolds are promising for bone grafting.

The properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) P(3HB-co-3HHx) copolymers with different ratios of monomers synthesized by the wild-type strain Cupriavidus necator B-10646 on sugars, and an industrial sample from Kaneka synthesized by the recombinant strain C. necator NSDG-ΔfadB1 on soybean oil, were studied in a comparative aspect and in relation to poly(3-hydroxybutyrate) P(3HB). The copolymer samples, regardless of the synthesis conditions or the ratio of monomers, had reduced values of crystallinity degree (50-60%) and weight average molecular weight (415-520 kDa), and increased values of polydispersity (2.8-4.3) compared to P(3HB) (70-76%, 720 kDa, and 2.2). The industrial sample had differences in its thermal behavior, including a lower glass transition temperature (-2.4 °C), two peaks in its crystallization and melting regions, a lower melting point (Tmelt) (112/141 °C), and a more pronounced gap between Tmelt and the temperature of thermal degradation (Tdegr). The process, shape, and size of the spherulites formed during the isothermal crystallization of P(3HB) and P(3HB-co-3HHx) were generally similar, but differed in the maximum growth rate of the spherulites during exothermic crystallization, which was 3.5-3.7 μm/min for P(3HB), and 0.06-1.25 for the P(3HB-co-3HHx) samples. The results from studying the thermal properties and the crystallization mechanism of P(3HB-co-3HHx) copolymers are important for improving the technologies for processing polymer products from melts.

A series of films was obtained from blends of poly-3-hydroxybutyrate (PHB) and poly-s-caprolactone (PCL). The structure, physical, mechanical and biological properties of the films were studied, depending on the ratio of the components. The microscopic structure of mixed films was determined by the main component of the blend: the films were porous with a predominance of PHB and relatively smooth with a predominance of PCL. The highest values of elongation at break (229-269%), as well as the local maximum values of tensile strength (14-15 MPa) were noted for blends with 5-25% PHB content. At PHB content of 25% and 75%, local maxima of Young’s modulus were observed (507 and 655 MPa, respectively). When the ratio of the components in the blend was equal (50:50 by weight), the films were heterogeneous and had the lowest values of mechanical strength (ultimate strength and elongation at break were 3 MPa and 15.5%, respectively). A study of the biocompatibility of mixed films in a culture of NIH 3T3 mouse fibroblasts based on determination of the number of adhered cells in the MTT test showed the absence of cytotoxic action, as well as high adhesion and cell proliferation, in some cases exceeding the data for films from pure PHB and PCL. This demonstrates the suitability of PHB-PCL blends for the production of cell carriers for tissue engineering and other reconstructive technologies.

The efficacy of slow-release formulations of tribenuron-methyl (TBM) embedded in the matrix of degradable poly(3-hydroxybutyrate) blended with birch wood flour [polymer/wood flour/herbicide 50/30/20 wt.%] was compared with the efficacy of TBM as the active ingredient of the Mortira commercial formulation, which was applied as post-emergence spray to treat spring wheat cv. Novosibirskaya 15. The study was conducted in Central Siberia (in the environs of the city of Krasnoyarsk, Russia) from May to August 2020. The biological efficacy of the embedded TBM was 92.3%, which was considerably higher than the biological efficacy of the Mortira formulation used as the post-emergence spray (15.4%). The embedding of TBM into degradable blended matrix enabled long-duration functioning of this unstable herbicide in soil. The sensitivity of weed plants to TBM differed depending on the species. TBM was more effective against A. retroflexus and A. blitoides, which were killed at an earlier stage, than against C. album and G. aparine, whose percentage increased in the earlier stage and which were controlled by the herbicide less effectively and at later stages. On the plot treated with the embedded herbicide, the parameters of the wheat yield structure were the best, and the total yield was the highest: 3360 ± 40 kg/ha versus 3250 ± 50 kg/ha in the group of plants sprayed with the Mortira formulation. The grain produced in all groups was of high quality and was classified as Grade 1 food grain. The highest quality parameters (grain hectoliter mass, gluten, and protein contents) were obtained in the group of plants treated with the embedded herbicide. The study of the embedded TBM confirmed the high efficacy of the experimental formulation.

Purpose: To synthesize and investigate polyhydroxyalkanoates (PHAs) with different monomer composition and percentages and polymer films prepared from them. Results: Various PHAs: homopolymer poly-3-hydroxybutyrate P(3HB) and 2-, 3-, and 4-component copolymers comprising various combinations of 3-hydroxybutyrate (3HB), 3-hydroxyvalerate (3HV), 4-hydroxybutyrate (4HB), and 3-hydroxyhexanoate (3HHx) monomers were synthesized under specialized conditions. Relationships were found between the monomer composition of PHAs and their molecular-weight and thermal properties and degree of crystallinity. All copolymers had decreased weight average molecular weights, Mw (to 390-600 kDa), and increased values of polydispersity (3.2-4.6) compared to the P(3HB). PHA copolymers showed different thermal behavior: an insignificant decrease in Tmelt and the presence of the second peak in the melting region and changes in parameters of crystallization and glass transition. At the same time, they retained thermostability, and the difference between Tmelt and Tdegr was at least 100-120 degrees C. Incorporation of 4HB, 3HV, and 3HHx monomer units into the 3-hydroxybutyrate chain caused changes in the amorphous to crystalline ratio and decreased the degree of crystallinity (Cx) to 20-40%. According to the degree to which the monomers reduced crystallinity, they were ranked as follows: 4HB - 3HHx - 3HV. A unique set of films was produced; their surface properties and physical/mechanical properties were studied as dependent on PHA composition; monomers other than 3hydroxybutyrate were found to enhance hydrophilicity, surface development, and elasticity of polymer films. Conclusion: An innovative set of PHA copolymers was synthesized and solution-cast films were prepared from them; the copolymers and films were investigated as dependent on polymer chemical composition. Results obtained in the present study contribute to the solution of a critical issue of producing degradable polymer materials. (C) 2021 Elsevier B.V. All rights reserved.

The herbicidal activity of long-acting formulations of metribuzin and tribenuron methyl herbicides embedded in granules prepared from a mixture of degradable poly(3-hydroxybutyrate) and birch wood flour was studied in laboratory-grown weeds of various species and in wheat Triticum aestivum and barley Hordeum vulgare stands infested by weeds. The constructed formulations effectively suppressed all species of weeds studied. The biological effectiveness of herbicide formulations toward intact plants in wheat and barley stands infested with weeds was close to 100%, which was significantly higher than the effect of their free forms. The more effective suppression of weeds by embedded herbicides was beneficial for the growth of crops whose aboveground biomass was 8-13 to 20% greater than that of the crops in the treatments with free herbicides. Embedded metribuzin and tribenuron methyl exhibit sustained and pronounced herbicidal activity and are effective for pre-emergence soil application for crops infested with weeds of various species.

Composite films and nonwoven mats of the poly-3-hydroxybutyrate and chitosan natural polymers were prepared and investigated. DSC and FTIR techniques were used to confirm that P(3HB) blending with chitosan resulted in a decrease in P(3HB) crystallinity to 47% and 62% in the films and nonwoven mats, respectively. Scanning electron microscopy showed that addition of chitosan induced changes in the surface morphology of the composite films and a reduction in the diameter of ultrafine fibers in the nonwoven mats from 800 nm to 460 nm. The values of water contact angle for films (53 degrees) and nonwoven mats (50.6 degrees) suggested that chitosan enhanced hydrophilic properties and moisture absorption capacity of the composite materials. On the other hand, P(3HB) showed its reinforcing ability and improved the physical/mechanical properties of chitosan. The work included studies of in vitro biodegradation of the composite specimens and their ability to maintain cell growth and attachment in NIH 3T3 fibroblast culture. (c) 2020 Published by Elsevier B.V.

Composite films and nonwoven mats of the poly-3-hydroxybutyrate and chitosan natural polymers were prepared and investigated. DSC and FTIR techniques were used to confirm that P(3HB) blending with chitosan resulted in a decrease in P(3HB) crystallinity to 47% and 62% in the films and nonwoven mats, respectively. Scanning electron microscopy showed that addition of chitosan induced changes in the surface morphology of the composite films and a reduction in the diameter of ultrafine fibers in the nonwoven mats from 800 nm to 460 nm. The values of water contact angle for films (53°) and nonwoven mats (50.6°) suggested that chitosan enhanced hydrophilic properties and moisture absorption capacity of the composite materials. On the other hand, P(3HB) showed its reinforcing ability and improved the physical/mechanical properties of chitosan. The work included studies of in vitro biodegradation of the composite specimens and their ability to maintain cell growth and attachment in NIH 3T3 fibroblast culture.

Porous films have been prepared from degradable polymers-poly-3-hydroxybutyrate (PHB), poly-ε-caprolactone (PCL) and a blend of these polymers (1:3)-by adding porogen (camphor) to the polymer solution at 10%, 30% or 50% of the total mass of the polymer and porogen, and leaching it out afterwards. After the rinse, camphor content in films decreased to about 0.025%. The structure, physical/mechanical and biological properties of the films were investigated as dependent on their composition and porosity, which varied depending on the amount of camphor added. The surface of PHB films was porous, the PCL films were relatively smooth, and the PHB/PCL films had an intermediate structure. The addition of camphor increased the thickness (from 35 to 45 µm, from 40 to 80 µm and from 20 to 65 µm for PHB, PCL and PHB/PCL, respectively) and porosity (from 4.2(±3.6)% to 50.0(±12.8)%, from 6.4(±5.5)% to 54.5(±6.0)% and from 4.9(±4.8)% to 51.5(±5.8)%, respectively) of the films. The introduction (and removal) of 10% camphor into the PHB and PHB/PCL films led to an approximately twofold increase in the polar component of the free surface energy (from 5.4 ± 0.38 to 11.8 ± 1.33 and from 2.7 ± 0.13 to 5.2 ± 0.09 mN/m, respectively) but in other cases, on the contrary, a decrease in this indicator was registered. The increase of camphor addition from 0% to 50% gradually impaired mechanical properties of the films: so, Young's modulus decreased from 3.6 to 1.8 GPa, from 0.30 to 0.12 GPa and from 0.50 to 0.20 GPa for PHB, PCL and PHB/PCL, respectively. At the same time, the water vapor transmission rate considerably increased from 197.37 ± 23.62 to 934.03 ± 114.34 g/m2/d for PHB films; from 1027.99 ± 154.10 to 7014.62 ± 280.81 g/m2/d for PCL films; and from 715.47 ± 50.08 to 4239.09 ± 275.54 g/m2/d for PHB/PCL films. Results of biocompatibility testing in the culture of NIH 3T3 mouse fibroblast cells showed that for the most of experimental samples cell adhesion and proliferation were comparable or superior to the corresponding parameters on the initial nonporous films. The best results were obtained for PHB films where at Day 3 of the experiment the registered cell density for experimental samples arrived at 2.66(±0.26) × 105 cells/cm2 versus 1.29(±0.33) × 105 cells/cm2 in the control. So, the proposed method can be used to construct highly porous cell scaffolds for cellular engineering.

Biodegradable poly-3-hydroxybutyrate [P(3HB)] and birch wood flour (as filler) were used to prepare powdered blends and then pellets and granules. Pellets were produced by cold pressing of polymer and filler powders; granules were produced from the powders wetted with ethanol. The properties of the initial P(3HB) and filler and the blends thereof were studied using IR spectroscopy, differential scanning calorimetry, X-ray analysis, and electron microscopy. No chemical bonds between the components were revealed; the blends were physical mixtures. The degree of crystallinity of the blends was lower than that of the initial polymer, suggesting different crystallization kinetics of the blends. The introduction of increasing amounts of filler into the polymer progressively decreased the mechanical strength of the pellets, as confirmed by a decrease in Young’s modulus. The resulting composite, based on biodegradable polymers and wood flour, is a promising nontoxic material for the production of wood-based panels for the construction industry and the manufacture of furniture in place of materials produced using toxic polyester resins

A strain of acetic acid bacteria, Komagataeibacter xylinus B-12068, was studied as a source for bacterial cellulose (BC) production. The effects of cultivation conditions (carbon sources, temperature, and pH) on BC production and properties were studied in surface and submerged cultures. Glucose was found to be the best substrate for BC production among the sugars tested; ethanol concentration of 3% (w/v) enhanced the productivity of BC. Optimization of medium and cultivation conditions ensures a high production of BC on glucose and glycerol, up to 2.4 and 3.3 g/L/day, respectively. C/N elemental analysis, emission spectrometry, SEM, DTA, and X-ray were used to investigate the structure and physical and mechanical properties of the BC produced under different conditions. MTT assay and SEM showed that native cellulose membrane did not cause cytotoxicity upon direct contact with NIH 3T3 mouse fibroblast cells and was highly biocompatible.

The physicochemical properties such as the degree of crystallinity and temperature and molecularmass characteristics of a number of polyhydroxyalkanoates of various chemical composition synthesized on a complex carbon substrate by bacteria Cupriavidus eutrophus В10646 have been investigated. Two-, three-, and four-component copolymer samples have different sets and ratios of monomers with various lengths of carbon chains: 3-hydroxybutyrate (3HB), 4-hydroxybutyrate (4HB), 3-hydroxyvalerate (3HV), 3-hydroxyhexanoate (3HH), 3-hydroxy-4-methyl valerate (3H4MV), and diethylene glycol (DEG). It has been shown that weight-average molar mass М w and polydispersity vary in a wide range with no correlation existing with the composition of copolymer polyhydroxyalkanoates and that thermal stability is preserved in the temperature interval between the melting temperature and the thermal degradation temperature from 100 to 120–140°С. The composition and ratio of monomers most notably affect the degree of crystallinity of polyhydroxyalkanoates. Significant differences between the degrees of crystallinity of three- and four-component polyhydroxyalkanoates have been found for the first time. The degree of crystallinity for copolymers P(3HB/3HV/4HB) is 9–22%, and the degree of crystallinity for copolymers P(3HB/3HV/3HH) and P(3HB/3GV/3H4MV) is 41–63%; this value is close to the degree of crystallinity for diblock copolymers P(3HB)/DEG, which is 56–69%. For the four-component copolymers P(3HB/3GV/4HB/3HH), the degree of crystallinity is 30–41%. The values of М w for the copolymers P(3HB/DEG) are inhomogeneous and the polymers contain fractions uneven with respect to molecular mass: a high-molecular-mass polymer (М w from 2700 to 4900 kDa) and a low-molecular-mass polymer (М w = 46–167 kDa). For the copolymers P(3HB)/DEG and P(3HB/3HV/3H4MV), two peaks are observed in the region of melting with the gap between these peaks being 4–20°С. All of the types of copolymer samples, regardless of the monomer ratio, show an increase in elongation at break against the background of a decrease in tensile stress and Young’s modulus, with these effects being pronounced to different extents. On the whole, the properties of multicomponent polyhydroxyalkanoates differ appreciably.

The rheology of solutions of polyhydroxyalkanoates in chloroform and dichloromethane was studied. The dynamic viscosity of solutions depended on type of solvent and PHA. The polymer solutions with increase of temperature behave as Newtonian fluids. Dynamic viscosity was increasing with the concentration of polymer in solution, regardless of the solvent. Solutions of PHAs in descending order of magnitude of dynamic viscosity can be positioned in the following order: P(3HB) – P(3HB-3HV) – P(3GB-3HH) – P(3HB-4HB). The magnitude of the dynamic viscosity of solutions based on chloroform in 3-3,5 times higher than that of solutions based on dichloromethane at identical concentration and temperature. The obtained values of dynamic viscosity have demonstrated the dependence of rheological parameter on the chemical composition of the polymer, and the characteristics of solvent (composition, temperature, and concentration)

Fibrous scaffolds from polymer solutions of poly-3-hydroxybutyrate, polylactide and polyglycolide, and copolymer of poly(lactide-glycolide) were obtained using electrostatic shaping with one or two feeding capillaries on one collecting manifold and their characteristics were studied. The spatial distribution of fibers having different chemical structure in layers of fibrous scaffolds occurred when two feeding capillaries were used. The composition of polymer solutions influenced on the hydrophilic-hydrophobic properties of fibrous scaffolds, regardless of the method of electrostatic molding