Efficacy of embedded metribuzin and tribenuron-methyl herbicides in field-grown vegetable crops infested by weeds.

The purpose of the present study was to investigate the efficacy of the experimental formulations of the metribuzin (MET) and tribenuron-methyl (TBM) herbicides embedded in the matrix of degradable poly-3-hydroxybutyrate blended with wood flour in field-grown tomato and beet crops infested by weeds. There is a necessity to develop environmentally friendly and effective means to protect plants because of the shortcomings of the free herbicide forms such as the environmentally unsafe spray application of solutions and suspensions of the widespread metribuzin and tribenuron-methyl herbicides, removal from soil during watering events and rains, and transport to natural aquatic environments, where the herbicides accumulate in the trophic chains of biota. Free TBM is also rapidly inactivated in soil and metabolized to nontoxic products in plants. The efficacy of experimental formulations of metribuzin and tribenuron-methyl embedded in the matrix of degradable poly-3-hydroxybutyrate blended with wood flour was tested in field-grown tomato and beet crops infested with weeds. Application of metribuzin resulted in the highest productivity of tomatoes (2.3 kg/m2) and table beet (3.4 kg/m2), improved biometric parameters of tomato fruits and beet roots, and caused reduction in nitrate nitrogen concentrations in them. The mode of herbicide delivery did not affect sugar contents, but application of both metribuzin and tribenuron-methyl induced a 1.7-fold and 1.4-fold, respectively, increase in vitamin C concentrations in tomato fruits and beet roots relative to the vegetables grown on the subplots treated with free herbicides and the intact plants. Embedded herbicides can be used as preemergence herbicides in the field. Fig. a Graphical abstract.

Efficacy of Slow-Release Formulations of Metribuzin and Tribenuron Methyl Herbicides for Controlling Weeds of Various Species in Wheat and Barley Stands.

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.

Biological effects of the free and embedded metribuzin and tribenuron-methyl herbicides on various cultivated weed species.

The present study addresses the herbicidal activity and biological effects of the metribuzin (MET) and tribenuron-methyl (TBM) herbicides used to control various weed species (Amaranthus retroflexus, Sinapis arvensis, and Leucanthemum maximum). The effects of the free herbicides and the herbicides embedded in granules of degradable polymer poly-3-hydroxybutyrate [P(3HB)] blended with birch wood flour were compared. Metribuzin, regardless of the form, caused 100% mortality of the three weeds by day 21. The herbicidal activity of tribenuron-methyl was lower than that of metribuzin, but the embedded TBM was superior to the free herbicide in the length and strength of its action on the weeds. Both metribuzin forms dramatically decreased the main parameters of fluorescence: maximum quantum yield of photosystem-II [Y(II)max], maximum quantum yield of non-photochemical quenching [Y(NPQ)max], and maximum rate of non-cyclic electron transport [ETRmax] and concentrations of chlorophyll a and b. The effect of the embedded TBM on the photosynthetic activity of the weeds was lower in the first two weeks of the growth of herbicide-treated plants but lasted longer than the effect of the free TBM and increased over time. Embedding of metribuzin in the matrix of degradable blend did not decrease its herbicidal activity.

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.

The effect of the chemical composition and structure of polymer films made from resorbable polyhydroxyalkanoates on blood cell response.

Four PHA types were synthesized in the culture of Cupriavidus eutrophus B-10646 under special conditions, poly(3­hydroxybutyrate) [P(3HB)] and of copolymers, which contained 3HB monomers and 4­hydroxybutyrate (4HB), 3­hydroxyvalerate (3HV), or 3­hydroxyhexanoate (3HHx). All copolymers had the Mw of about 550-670 kDa, and the homopolymer P(3HB) had a significantly higher Mw - 920 kDa. P(3HB­co­4HB) and P(3HB­co­3HHx) had the lowest Cx (42 and 49%) while P(3HB­co­3HV) and P(3HB) exhibited higher Cx values (76%). Polymer films were prepared from different PHAs. Electron microscopy showed differences in the surface microstructure of the films. Films prepared from the P(3HB) were more hydrophobic and the arithmetic mean surface roughness of 71-75 nm, than the copolymer films, which were hydrophilic (57-60°) and had considerably higher roughness (158-177 nm). Blood parameters (hemoglobin and hemolysis) and response of the cells (erythrocytes, platelets, and monocytes) were studied in experiments with blood directly contacting the surface of the films of PHAs with different compositions. Cultivation of blood cells on polymer films did not cause any adverse effects on adhesion and morphology of all cell types. Results of studying blood cell response suggested that the films made from low-crystallinity copolymers containing 4­hydroxybutyrate and 3­hydroxyhexanoate were the best for contact with blood.

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.

Bio-functionalization of phytogenic Ag and ZnO nanobactericides onto cellulose films for bactericidal activity against multiple drug resistant pathogens.

The present study describes the synthesis of silver and zinc oxide nanobactericides from the phytogenic source Bupleurum aureum. The synthesized nanobactericides were characterized and evaluated for bio-functionalization onto bacterial cellulose membrane which was synthesized by Komagataeibacterxylinus B-12068 culture strain. The synthesis of nanobacterides were initially confirmed using UV-Visible spectroscopy which indicated localized surface resonance (LSPR) peaks at 415 nm for silver nanobactericides and 280 nm for zinc nanobactericides. The nature of the capping agent for synthesized nanobactericides was predicted using FTIR which confirmed the presence of functional moieties. XRD analysis revealed their crystalline nature while morphological characteristics were studied using TEM which confirmed the polydispersity of nanobactericides with the average size in the range of 20-25 nm. The nanobactericides were tested for their antimicrobial activity against seven multi-drug resistant pathogens which were clinically isolated from patients suffering from a myriad of microbial infections. The tested pathogens had antimicrobial resistance to ten different antibiotics and have been reported to be the major cause of nosocomial infections. The nanobactericides displayed significant activity against the test pathogens. Silver nanobactericides showed the highest activity against Escherichia coli strain 55 with a 24 mm zone of inhibition while zinc oxide nanobactericides displayed the highest activity against methicillin-resistant Staphylococcus aureus (MRSA) with a 20 mm inhibition zone. The bio- functionalized cellulose films (BCF) were characterized using SEM along with physicochemical analysis. The BCF's were evaluated for antibacterial activity against test pathogens which resulted in marked antimicrobial potential against multi-drug resistant bacteria and therefore has the potential to be utilized as an efficient alternative to counter drug resistant pathogens.

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.

Poly(3-hydroxybutyrate)/metribuzin formulations: characterization, controlled release properties, herbicidal activity, and effect on soil microorganisms.

Slow-release formulations of the herbicide metribuzin (MET) embedded in the polymer matrix of degradable poly-3-hydroxybutyrate [P(3HB)] in the form of microparticles, films, microgranules, and pellets were developed and tested. The kinetics of polymer degradation, MET release, and accumulation in soil were studied in laboratory soil microecosystems with higher plants. The study shows that MET release can be controlled by using different techniques of constructing formulations and by varying MET loading. MET accumulation in soil occurs gradually, as the polymer is degraded. The average P(3HB) degradation rates were determined by the geometry of the formulation, reaching 0.17, 0.12, 0.04, and 0.05 mg/day after 60 days for microparticles, films, microgranules, and pellets, respectively. The herbicidal activities of P(3HB)/MET formulations and commercial formulation Sencor Ultra were tested on the Agrostis stolonifera and Setaria macrocheata plants. The parameters used to evaluate the herbicidal activity were plant density and the weight of fresh green biomass measured at days 10, 20, and 30 after sowing. All P(3HB)/MET formulations had pronounced herbicidal activity, which varied depending on MET loading and the stage of the experiment. In the early phases of the experiment, the herbicidal effect of P(3HB)/MET formulations with the lowest MET loading (10 %) was comparable with that of the commercial formulation. The herbicidal effect of P(3HB)/MET formulations with higher MET loadings (25 and 50 %) at later stages of the experiment were stronger than the effect of Sencor Ultra.

Constructing herbicide metribuzin sustained-release formulations based on the natural polymer poly-3-hydroxybutyrate as a degradable matrix.

Polymer poly(3-hydroxybutyrate) [P(3HB)] has been used as a matrix in slow-release formulations of the herbicide metribuzin (MET). Physical P(3HB)/MET mixtures in the form of solutions, powders, and emulsions were used to construct different metribuzin formulations (films, granules, pellets, and microparticles). SEM, X-Ray, and DSC proved the stability of these formulations incubated in sterile water in vitro for long periods of time (up to 49 days). Metribuzin release from the polymer matrix has been also studied. By varying the shape of formulations (microparticles, granules, films, and pellets), we were able to control the release time of metribuzin, increasing or decreasing it.

Characterization of biodegradable poly-3-hydroxybutyrate films and pellets loaded with the fungicide tebuconazole.

Biodegradable polymer poly(3-hydroxybutyrate) (P3HB) has been used as a matrix to construct slow-release formulations of the fungicide tebuconazole (TEB). P3HB/TEB systems constructed as films and pellets have been studied using differential scanning calorimetry, X-ray structure analysis, and Fourier transform infrared spectroscopy. TEB release from the experimental formulations has been studied in aqueous and soil laboratory systems. In the soil with known composition of microbial community, polymer was degraded, and TEB release after 35 days reached 60 and 36 % from films and pellets, respectively. That was 1.23 and 1.8 times more than the amount released to the water after 60 days in a sterile aqueous system. Incubation of P3HB/TEB films and pellets in the soil stimulated development of P3HB-degrading microorganisms of the genera Pseudomonas, Stenotrophomonas, Variovorax, and Streptomyces. Experiments with phytopathogenic fungi F. moniliforme and F. solani showed that the experimental P3HB/TEB formulations had antifungal activity comparable with that of free TEB.

An in vivo study of osteoplastic properties of resorbable poly-3-hydroxybutyrate in models of segmental osteotomy and chronic osteomyelitis.

A series of 3D implants and filling materials prepared from powdered biodegradable polymers, polyhydroxyalkanoates (PHAs), have been designed for the purposes of reparative osteogenesis. The 3D implants are made of resorbable polymer of hydroxybutyric acid (poly-3-hydroxybutyrate, P3HB) and a composite of this polymer with hydroxyapatite (HA) (P3HB/HA). The properties of the implants were studied in vivo in a model of segmental osteotomy and compared with commercial material Bio-Oss(®). All implants containing P3HB as the main component facilitate reconstructive osteogenesis. P3HB and P3HB/HA show pronounced osteoplastic properties; their in vivo degradation is slow and corresponds to the growth of a new bone tissue, facilitating normal reparative osteogenesis. Also, powdered P3HB and P3HB/tienam can be used as filling materials for osteoplasty of bone cavities infected by Staphylococcus aureus. Biodegradable 3D implants and P3HB-based filling materials show pronounced osteoplastic properties and degrade in vivo at a slow rate, enabling normal reparative osteogenesis.