Biodegradable Polyhydroxyalkanoates with a Different Set of Valerate Monomers: Chemical Structure and Physicochemical Properties.

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.

Antifungal activity of P3HB microparticles containing tebuconazole.

In this study, tebuconazole (TEB)-loaded poly-3-hydroxybutyrate (P3HB)-based microparticles were developed and comprehensively characterized. TEB-loaded microparticles with the initial loading amounts of the fungicide of 10, 25, and 50% of the polymer mass (TEB 10, TEB 25, and TEB 50%) were prepared using emulsion technique. Encapsulation efficiency of TEB varied from 59 to 86%. As the loading amount was increased, the average diameter of microparticles increased too, from 41.3 to 71.7 µm, while zeta potential was not influenced by TEB loading, varying between -32.6 and -35.7 mV. TEB was gradually released from the microparticles to the model medium, and after 60 d, from 25 to 43% of TEB was released depending on the content of the encapsulated fungicide. The data obtained from in vitro TEB release were fitted to different mathematical models. It was shown that the release profiles of TEB could be best explained by the Zero-order, Higuchi, and Hixson-Crowell models. The antifungal activity of the P3HB/TEB microparticles against phytopathogenic fungi Fusarium moniliforme and Fusarium solani was demonstrated by in vitro tests conducted in Petri dishes. Thus, hydrophobic agrochemicals (TEB) can be effectively encapsulated into P3HB microparticles to construct slow-release formulations.

Constructing sustained-release herbicide formulations based on poly-3-hydroxybutyrate and natural materials as a degradable matrix.

BACKGROUND: The purpose of the present study was to develop ecofriendly herbicide formulations. Its main aim was to develop and investigate slow-release formulations of herbicides (metribuzin, tribenuron-methyl, and fenoxaprop-P-ethyl) of different structure, solubility, and specificity, which were loaded into a degradable matrix of poly-3-hydroxybutyrate (P(3HB)) blended with available natural materials (peat, clay, and wood flour). RESULTS: Differences in the structure and physicochemical properties of the formulations were studied depending on the type of the matrix. Herbicide release and accumulation in soil were associated with the solubility of the herbicide. Fourier-transform infrared spectroscopy showed that no chemical bonds were formed between the components in the experimental formulations. Degradation of the formulations in agro-transformed soil in laboratory conditions was chiefly influenced by the shape of the specimens (granules or pellets) while the effect of the type of filler (peat, clay, or wood flour) was insignificant. The use of granules enabled more rapid accumulation of the herbicides in soil: their peak concentrations were reached after 3 weeks of incubation while the concentrations of the herbicides released from the pellets were the highest after 5-7 weeks. Loading of the herbicides into the polymer matrix composed of the slowly degraded P(3HB) and natural materials enabled both sustained function of the formulations in soil (lasting between 1.5 and ≥3 months) and stable activity of the otherwise rapidly inactivated herbicides such as tribenuron-methyl and fenoxaprop-P-ethyl. CONCLUSION: The experimental herbicide formulations enabled slow release of the active ingredients to soil. © 2019 Society of Chemical Industry.

Fungicidal activity of slow-release P(3HB)/TEB formulations in wheat plant communities infected by Fusarium moniliforme.

Fungicidal activity of experimental tebuconazole (TEB) formulations was investigated in laboratory soil ecosystems in wheat plant communities infected by Fusarium moniliforme. TEB was embedded in the matrix of poly-3-hydroxybutyrate, shaped as films and microgranules. These formulations were buried in the soil with wheat plants, and their efficacy was compared with that of commercial formulation Raxil and with the effect of pre-sowing treatment of seeds. In the experiment with the initially infected seeds and a relatively low level of natural soil infection caused by Fusarium fungi, the effects of the experimental P(3HB)/TEB formulations and Raxil were comparable. However, when the level of soil infection was increased by adding F. moniliforme spores, P(3HB)/TEB granules and films reduced the total counts of fungi and the abundance of F. moniliforme more effectively than Raxil. Seed treatment or soil treatment with Raxil solution showed an increase in the percentage of rot-damaged roots in the later stages of the experiment. In the early stage (between days 10 and 20), the percentage of rot-damaged roots in the soil with TEB embedded in the slowly degraded P(3HB) matrix was similar to that in the soil with Raxil. However, the efficacy of P(3HB)/TEB formulations lasted longer, and in later stages (between days 20 and 30), the percentage of rot-damaged roots in that group did not grow. In experiments with different TEB formulations and, hence, different fungicidal activities, the increase in plant biomass was 15-17 to 40-60% higher than in the groups where TEB was applied by using conventional techniques.

Efficacy of tebuconazole embedded in biodegradable poly-3-hydroxybutyrate to inhibit the development of Fusarium moniliforme in soil microecosystems.

BACKGROUND: An important line of research is the development of a new generation of formulations with targeted and controlled release of the pesticide, using matrices made from biodegradable materials. In this study, slow-release formulations of the fungicide tebuconazole (TEB) have been prepared by embedding it into the matrix of poly-3-hydroxybutyrate (P3HB) in the form of films, microgranules and pellets. RESULTS: The average rates of P3HB degradation were determined by the geometry of the formulation, reaching, for 63 days, 0.095-0.116, 0.081-0.083 and 0.030-0.055 mg day-1 for films, microgranules and pellets respectively. The fungicidal activity of P3HB/TEB against the plant pathogen Fusarium moniliforme was compared with that of the commercial formulation Raxil Ultra. A pronounced fungicidal effect of the experimental P3HB/TEB formulations was observed in 2-4 weeks after application, and it was retained for 8 weeks, without affecting significantly the development of soil aboriginal microflora. CONCLUSION: TEB release can be regulated by the process employed to fabricate the formulation and the fungicide loading, and the TEB accumulates in the soil gradually, as the polymer is degraded. The experimental forms of TEB embedded in the slowly degraded P3HB can be used as a basis for developing slow-release fungicide formulations. © 2016 Society of Chemical Industry.

Effects of intracellular poly(3-hydroxybutyrate) reserves on physiological-biochemical properties and growth of Ralstonia eutropha.

Microbial polyhydroxyalkanoates (PHAs), because of their well studied complex physiology and commercial potential, are vehicles for carbon and potential storage reduction for many microbial species. Even with the wealth of studies about microbial PHAs in the scientific literature, polymer accumulation and degradation are still not comprehensively understood. Poly(3-hydroxybutyrate) (P3HB) granule formation and polymer mobility were studied here in the bacterium Ralstonia eutropha strain B5786 in autotrophic cultures. Electron microscopy studies revealed decreasing cell size concomitant with enlargement of size and number of intracellular granules, and inhibition of cell division during intracellular polymer production. Activities of key P3HB biosynthetic enzymes demonstrated correlations with each other during polymer accumulation, suggesting an intricately regulated P3HB cycle in autotrophically grown R. eutropha cells.

Cell growth and accumulation of polyhydroxyalkanoates from CO2 and H2 of a hydrogen-oxidizing bacterium, Cupriavidus eutrophus B-10646.

Synthesis of polyhydroxyalkanoates (PHAs) by a new strain of Cupriavidus - Cupriavidus eutrophus B-10646 - was investigated under autotrophic growth conditions. Under chemostat, at the specific flow rate D=0.1h(-1), on sole carbon substrate (CO2), with nitrogen, sulfur, phosphorus, potassium, and manganese used as growth limiting elements, the highest poly(3-hydroxybutyrate) [P(3HB)] yields were obtained under nitrogen deficiency. In batch autotrophic culture, in the fermenter with oxygen mass transfer coefficient 0.460 h(-1), P(3HB) yields reached 85% of dry cell weight (DCW) and DCW reached 50 g/l. Concentrations of supplementary PHA precursor substrates (valerate, hexanoate, γ-butyrolactone) and culture conditions were varied to produce, for the first time under autotrophic growth conditions, PHA ter- and tetra-polymers with widely varying major fractions of 3-hydroxybutyrate, 4-hydroxybutyrate, 3-hydroxyvalerate, and 3-hydroxyhexanoate monomer units. Investigation of the high-purity PHA specimens showed significant differences in their physicochemical and physicomechanical properties.