Composite Polymer Granules Based on Poly-ε-Caprolactone and Montmorillonite Prepared by Solution-Casting and Melt Extrusion.

Eco-friendly polymer composites in the form of granules based on biodegradable polycaprolactone (PCL) with the inclusion of montmorillonite (MMT) from 5 to 50 wt% were prepared by solution-casting and melt extrusion. The physicochemical properties of the composite granules were studied using FTIR spectroscopy, XRDA, DSC, and TGA methods. The paper presents comparative values of crystallinity of composite granules which depend on the method of measuring (XRDA, DSC). It was shown that the crystallinity of PCL/MMT granules was affected by the preparation method and by the MMT content, and that with increase in MMT content, crystallinity increased by up to 61-67%. The change in crystallinity of the granules also affected its biodegradation in soil. At the end of exposure in soil, the mass loss for the granules prepared by solution-casting was more than 90%, whereas for the composite granules prepared by extrusion it was less than 60%. Applying melt extrusion enabled obtaining intercalated composites with predictable features, whereas only mixed-structure microcomposites could be prepared by solution-casting.

Aminolysis of Poly-3-Hydroxybutyrate in N,N-Dimethylformamide and 1,4-Dioxane and Formation of Functionalized Oligomers.

The degradation pattern of bacterial poly-3-hydroxybutyrate (PHB) in dimethylformamide (DMF) and dioxane solutions at 100 °C assisted by ethylenediamine, 1,4-diaminobutane and monoaminoethanol was studied. When diamines were introduced into the PHB solution in DMF in the amount of 1 mol of the reagent to 5 or 10 mol of PHB monomers, a rapid decrease in the molecular weight of the polymer was observed. The initial value of the weight average molecular weight (Mw) 840 kDa had decreased by 20-30 times within the first 10-20 min of the experiment, followed by its gradual decrease to several thousand Da. When a similar molar quantity of aminoethanol was added, the molecular weight decreased slower. PHB had been degrading much slower in the dioxane solution than in DMF. By varying the number of reagents, it was possible to reach stabilization of the Mw at 1000-3000 Da when using diamines and 8000-20,000 Da using aminoethanol. 1H NMR analysis of the oligomers revealed of amino and amido groups forming in their structure. From the opposite end of the polymer chain, residues of 3-hydroxybutyric, crotonic and isocrotonic acids were formed during degradation. Differential scanning calorimetry indicated that after oligomerization there was a decrease in the melting point from 178 °C to 140-170 °C depending on the decrease in the molecular weight. The method proposed can be used for obtaining aminated PHB oligomers.

Study of the Effect of Modified Aluminum Oxide Nanofibers on the Properties of PLA-Based Films.

To find out whether Al2O3 nanofiller is effective in improving the characteristics of polymer composites, composite polymer films based on biodegradable polylactide and epoxidized aluminum oxide nanofibers were obtained by solution casting. Surface morphology, mechanical and thermal properties of composites were studied by SEM, IR-Fourier spectroscopy, DSC and DMA. It was shown that, below and above the percolation threshold, the properties of the films differ significantly. The inclusion of alumina nanoparticles up to 0.2% leads to a plasticizing effect, a decrease in the crystallization temperature and the melting enthalpy and an increase in the tensile stress. An increase in the content of alumina nanoparticles in films above the percolation threshold (0.5%) leads to a decrease in the crystallinity of the films, an increase in stiffness and a drop in elasticity. Finding the percolation threshold of alumina nanoparticles in PLA films makes it possible to control their properties and create materials for various applications. The results of this study may have major significance for the commercial use of aluminum oxide nanofibers and can broaden the research field of composites.

Constructing slow-release formulations of herbicide metribuzin using its co-extrusion with biodegradable polyester poly-ε-caprolactone.

Different technologies to prepare long term pesticide forms include polymer coating, preparing composites and encapsulating pesticides in nanoparticles. A simple and low-cost method was proposed to obtain slow-release formulations by co-extrusion of a pesticide with a biodegradable polymer at a temperature above the melting points of both components. A herbicide metribuzin and low-melting polyester poly-ε-caprolactone were chosen for this work. Formulations containing 10%, 20%, and 40% herbicide were prepared. During 7 days of their exposition in water, it was released from 81% to 96% of initially loaded metribuzin; the highest release was detected for 40%-loaded forms. Biodegradation of the constructs and pesticide release were further studied in the model soil. Degradation rates of the specimens increased with an increase in pesticide content, from 9% to 20% over 14 weeks for the 10%/20%-loaded and the 40%-loaded specimens, respectively. The release of metribuzin reached, respectively, 37-38% and 55%. The herbicide content in soil was lower due to its partial degradation in soil; it reached 23-25% and 33%, respectively, from initially loaded into the polymer matrix. Release kinetics of metribuzin in water as in soil best fitted the First-order model. The used approach is promising for obtaining long-term release formulations for soil applications.

Production of Porous Films Based on Biodegradable Polyesters by the Casting Solution Technique Using a Co-Soluble Porogen (Camphor).

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.

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.

Constructing Slow-Release Fungicide Formulations Based on Poly(3-hydroxybutyrate) and Natural Materials as a Degradable Matrix.

Slow-release fungicide formulations (azoxystrobin, epoxiconazole, and tebuconazole) shaped as pellets and granules in a matrix of biodegradable poly(3-hydroxybutyrate) and natural fillers (clay, wood flour, and peat) were constructed. Infrared spectroscopy showed no formation of chemical bonds between components in the experimental formulations. The formulations of pesticides had antifungal activity against Fusarium verticillioides in vitro. A study of biodegradation of the experimental fungicide formulations in the soil showed that the degradation process was mainly influenced by the type of formulation without significant influence of the type of filler. More active destruction of the granules led to a more rapid accumulation of fungicides in the soil. The content of fungicides present in the soil as a result of degradation of the formulations and fungicide release was determined by their solubility. Thus, all formulations are able to function in the soil for a long time, ensuring gradual and sustained delivery of fungicides.

Constructing Slow-Release Formulations of Ammonium Nitrate Fertilizer Based on Degradable Poly(3-hydroxybutyrate).

The present study describes construction and investigation of experimental formulations of ammonium nitrate embedded in a matrix of degradable natural polymer poly-3-hydroxybutyrate [P(3HB)] and P(3HB) blended with wood flour shaped as tablets, some of them coated with P(3HB). Kinetics of ammonium release into soil as dependent on the composition of the polymer matrix was investigated in laboratory experiments. The rates of fertilizer release from formulations coated with a biopolymer layer were considerably (two months or longer) slower than the rates of fertilizer release from uncoated formulations, while release from polymer and composite (polymer/wood flour) formulations occurred with comparable rates. The use of the experimental formulations in laboratory ecosystems with wheat (Triticum aestivum L.) was more effective than application of free ammonium nitrate. The advantage of the slow-release fertilizer formulations is that they are buried in soil together with the seeds, and the fertilizer remains effective over the first three months of plant growth. The use of such slow-release formulations will reduce the amounts of chemicals released into the environment, which will curb their accumulation in food chains of ecosystems and mitigate their adverse effects on the biosphere.

Constructing Slow-Release Formulations of Metribuzin Based on Degradable Poly(3-hydroxybutyrate).

Experimental formulations of herbicide metribuzin embedded in matrices of degradable natural polymer poly(3-hydroxybutyrate) (P3HB) and its composites with poly(ethylene glycol) (PEG), poly-ε-caprolactone (PCL), and wood powder have been prepared in the form of pressed pellets containing 75% polymeric basis (pure P3HB or its composite with a second component at a ratio of 7:3) and 25% metribuzin. Incubation of formulations in soil laboratory systems led to the degradation of the matrix and herbicide release. The most active release of metribuzin (about 60% of the embedded herbicide over 35 days) was detected for the P3HB/PEG carrier compared to the P3HB, P3HB/wood, and P3HB/PCL forms (30-40%). Thus, the study shows that herbicide release can be controlled by the matrix formulation. Metribuzin formulations exerted a significant herbicidal effect on the plant Agrostis stolonifera, used as a weed plant model. Application of these long-term formulations will make it possible to reduce environmental release of chemicals, which will restrict the rate of their accumulation in trophic chains of ecosystems and abate their adverse effects on the biosphere.

Biodegradable poly-3-hydroxybutyrate as a fertiliser carrier.

BACKGROUND: Increasing use of mineral fertilisers can lead to accumulation of fertilisers in soil, water and foodstuffs. One of the approaches to preventing these problems is to develop controlled release forms of fertilisers. RESULTS: Experimental formulations of the nitrogen fertiliser urea loaded in a degradable matrix of the natural polymer poly-3-hydroxybutyrate (P3HB) in the form of films, pellets and coated granules were constructed and investigated. Nitrogen release into soil occurred as the polymer was degraded, and it was dependent on the geometry of the carrier and the amount of nitrogen loaded in it, showing that nitrogen release can last for 30 days or longer and that release rates can be controlled by varying the fabrication technique employed. P3HB/urea formulations have a favourable effect on the soil microbial community. The use of embedded urea has a beneficial influence on the growth of creeping bentgrass (Agrostis stolonifera) and lettuce (Latuca sativa) and reduces removal of nitrogen with drain water. CONCLUSION: The slow-release nitrogen formulations developed in this study can be buried in soil together with seeds preventing nitrogen deficiency. The use of such slow-release formulations can decrease the amounts of chemicals in the environment and prevent their adverse effects on the biosphere. © 2016 Society of Chemical Industry.

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.

BIOLUMBASE--the database of natural and transgenic bioluminescent organisms.

The Institute of Biophysics SB RAS hosts and maintains a specialized collection of luminous bacteria (CCIBSO 836) containing over 700 strains isolated in various regions of the world's oceans. The culture collection is a source of lux genes and biologically active substances. The wide application of bioluminescence in medicine and ecology has given importance to analysing information on the structure and functioning of bioluminescence systems in natural and transgenic microorganisms, as well as on their features that are closely interrelated with bioluminescence. The aims of our BIOLUMBASE database are: gathering information on microorganisms with lux genes, their analysis and free access, and distribution of this data throughout the global network. The database includes two sections, natural and transgenic luminous microorganisms, and is updated by our own experimental results, the published literature and internet resources. For the future, a publicly available internet site for BIOLUMBASE is planned. This will list the strains and provide comprehensive information on the properties and functions of luminous bacteria, the mechanisms of regulation of bioluminescence systems, constructs with lux genes, and applications of bioluminescence in microbiology, ecology, medicine and biotechnology. It is noteworthy that this database will also be useful for evaluation of biological hazards of transgenic strains. Users will be able to carry out bibliographic and strain searches starting from any feature of interest.