The Effect of Pyrolysis Temperature and the Source Biomass on the Properties of Biochar Produced for the Agronomical Applications as the Soil Conditioner.

Biochar is a versatile carbon-rich organic material originating from pyrolyzed biomass residues that possess the potential to stabilize organic carbon in the soil, improve soil fertility and water retention, and enhance plant growth. For the utilization of biochar as a soil conditioner, the mutual interconnection of the physicochemical properties of biochar with the production conditions used during the pyrolysis (temperature, heating rate, residence time) and the role of the origin of used biomass seem to be crucial. The aim of the research was focused on a comparison of the properties of biochar samples (originated from oat brans, mixed woodcut, corn residues and commercial compost) produced at different temperatures (400-700 °C) and different residence times (10 and 60 min). The results indicated similar structural features of produced biochar samples; nevertheless, the original biomass showed differences in physicochemical properties. The morphological and structural analysis showed well-developed aromatic porous structures for biochar samples originated from oat brans, mixed woodcut and corn residues. The higher pyrolysis temperature resulted in lower yields; however, it provided products with higher content of organic carbon and a more developed surface area. The lignocellulose biomass with higher contents of lignin is an attractive feedstock material for the production of biochar with potential agricultural applications.

Properties and structure of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) filaments for fused deposition modelling.

Fused deposition modelling (FDM) is a process of additive manufacturing allowing creating of highly precise complex three-dimensional objects for a large range of applications. The principle of FDM is an extrusion of the molten filament and gradual deposition of layers and their solidification. Potential applications in pharmaceutical and medical fields require the development of biodegradable and biocompatible thermoplastics for the processing of filaments. In this work, the potential of production of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)) filaments for FDM was investigated in respect to its thermal stability. Copolymer P(3HB-co-4HB) was biosynthesised by Cupriavidus malaysiensis. Rheological and mechanical properties of the copolymer were modified by the addition of plasticizers or blending with poly(lactic acid). Thermal stability of mixtures was studied employing thermogravimetric analysis and rheological analyses by monitoring the time-dependent changes in the complex viscosity of melt samples. The plasticization of P(3HB-co-4HB) slightly hindered its thermal degradation but the best stabilization effect was found in case of the copolymer blended with poly(lactic acid). Overall, rheological, thermal and mechanical properties demonstrated that the plasticized P(3HB-co-4HB) is a potential candidate of biodegradable polymer for FDM processes.

How the Supramolecular Nature of Lignohumate Affects Its Diffusion in Agarose Hydrogel.

Lignohumate, as an industrially produced analog of natural humic substances, is studied from the point of view of its diffusion properties. This work focuses on its permeation ability, important in agricultural and horticultural applications, connected with its penetration into plant organs as leaves and roots. The hydrogel based on agarose was used as a model material for the diffusion of lignohumate. Two types of experiments were realized: the diffusion of lignohumate in the hydrogel diffusion couple and the diffusion of lignohumate from its solution into hydrogel. The diffusion coefficient of lignohumate in the hydrogel was determined and used for the modelling of the time development of concentration profiles. It was found that the model agrees with experimental data for short times but an accumulation of lignohumate in front of the interface between donor and acceptor hydrogels was observed after several days. The particle size distribution of lignohumate and changes in the E4/E6 ratio used as an indicator of molecular weight of humic substances were determined. The results showed that the supramolecular structure of lignohumate can react sensitively to actual changes in its environs and thus affect their mobility and permeability into different materials. A filtration effect at the interface can be observed as an accompanying phenomenon of the re-arrangement in the lignohumate secondary structure.

Enzymatic Hydrolysis of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) Scaffolds.

Polyhydroxyalkanoates (PHAs) are hydrolyzable bio-polyesters. The possibility of utilizing lignocellulosic waste by-products and grape pomace as carbon sources for PHA biosynthesis was investigated. PHAs were biosynthesized by employing Cupriavidus necator grown on fructose (PHBV-1) or grape sugar extract (PHBV-2). Fifty grams of lyophilized grape sugar extract contained 19.2 g of glucose, 19.1 g of fructose, 2.7 g of pectin, 0.52 g of polyphenols, 0.51 g of flavonoids and 7.97 g of non-identified rest compounds. The grape sugar extract supported the higher production of biomass and modified the composition of PHBV-2. The biosynthesized PHAs served as matrices for the preparation of the scaffolds. The PHBV-2 scaffolds had about 44.2% lower crystallinity compared to the PHBV-1 scaffolds. The degree of crystallinity markedly influenced the mechanical behavior and enzymatic hydrolysis of the PHA scaffolds in the synthetic gastric juice and phosphate buffer saline solution with the lipase for 81 days. The higher proportion of amorphous moieties in PHBV-2 accelerated enzymatic hydrolysis. After 81-days of lasting enzymatic hydrolysis, the morphological changes of the PHBV-1 scaffolds were negligible compared to the visible destruction of the PHBV-2 scaffolds. These results indicated that the presence of pectin and phenolic moieties in PHBV may markedly change the semi-crystalline character of PHBV, as well as its mechanical properties and the course of abiotic or enzymatic hydrolysis.

Active biodegradable packaging films modified with grape seeds lignin.

Biodegradable packaging materials represent one possible solution for how to reduce the negative environmental impact of plastics. The main idea of this work was to investigate the possibility of utilizing grape seed lignin for the modification of polyhydroxyalkanoates with the use of its antioxidant capacity in packaging films. For this purpose, polymeric films based on the blend of high crystalline poly(3-hydroxybutyrate) (PHB) and amorphous polyhydroxyalkanoate (PHA) were prepared. PHB/PHA films displayed Young modulus of 240 MPa, tensile strength at a maximum of 6.6 MPa and elongation at break of 95.2%. The physical properties of PHB/PHA films were modified by the addition of 1-10 wt% of grape seeds lignin (GS-L). GS-L lignin showed a high antioxidant capacity: 238 milligrams of Trolox equivalents were equal to one gram of grape seeds lignin. The incorporation of grape seeds lignin into PHB/PHA films positively influenced their gas barrier properties, antioxidant activity and biodegradability. The values of oxygen and carbon dioxide transition rate of PHB/PHA with 1 wt% of GS-L were 7.3 and 36.3 cm3 m-2 24 h 0.1 MPa, respectively. The inhibition percentage of the ABTS radical determined in PHB/PHA/GS-L was in the range of 29.2% to 100% depending on the lignin concentration. The biodegradability test carried out under controlled composting environment for 90 days showed that the PHB/PHA film with 50 w/w% of amorphous PHA reached the degradability degree of 68.8% being about 26.6% higher decomposition than in the case of neat high crystalline PHB film. The degradability degree of PHA films in compost within the tested period reflected the modification of the semi-crystalline character and varied with the incorporated lignin. From the toxicological point of view, the composts obtained after biodegradation of PHA films proved the non-toxicity of PHB/PHA/GS-L materials and its degradation products showed a positive effect on white mustard (Sinapis alba L.) seeds germination.

Characterization of humic acids in a continuous-feeding vermicomposting system with horse manure.

The increasing numbers of kept horses create problems with processing horse manure as important local waste. This work was focused on horse manure vermicomposting in a real-field continuous-feeding system under controlled conditions, and on the complex study of the maturity and stability of the produced vermicompost. Commonly used simple indicators such as the C/N ratio, N-NH4+/N-NO3- ratio, DOC or ion exchange capacity, and also more advanced spectroscopic and thermoanalytic techniques were used and applied on the humic substances isolated from the vermicompost during its maturation (12 months in total). When compared with the original horse manure, vermicomposting decreased the aliphatic, protein-like, and polysaccharide humic components, whereas vermicomposting increased the aromaticity and contents of oxygen-containing functional groups. The typical tryptophan-like fluorophores in the manure, corresponding to the freshly produced organic matter of biological or microbial origin, were progressively transformed to humic-like fluorophores during vermicomposting. The most thermally labile humic fraction disappeared quickly during the very early vermicomposting stages. The results of spectroscopic and thermogravimetric analyses suggest that stable and mature vermicompost was produced after 6-9 months of vermicomposting, which was also supported by biologically-based maturity indicators.

Drug Release Kinetics of Electrospun PHB Meshes.

Microbial poly(3-hydroxybutyrate) (PHB) has several advantages including its biocompatibility and ability to degrade in vivo and in vitro without toxic substances. This paper investigates the feasibility of electrospun PHB meshes serving as drug delivery systems. The morphology of the electrospun samples was modified by varying the concentration of PHB in solution and the solvent composition. Scanning electron microscopy of the electrospun PHB scaffolds revealed the formation of different morphologies including porous, filamentous/beaded and fiber structures. Levofloxacin was used as the model drug for incorporation into PHB electrospun meshes. The entrapment efficiency was found to be dependent on the viscosity of the PHB solution used for electrospinning and ranged from 14.4-81.8%. The incorporation of levofloxacin in electrospun meshes was confirmed by Fourier-transform infrared spectroscopy and UV-VIS spectroscopy. The effect of the morphology of the electrospun meshes on the levofloxacin release profile was screened in vitro in phosphate-buffered saline solution. Depending upon the morphology, the electrospun meshes released about 14-20% of levofloxacin during the first 24 h. The percentage of drug released after 13 days increased up to 32.4% and was similar for all tested morphologies. The antimicrobial efficiency of all tested samples independent of the morphology, was confirmed by agar diffusion testing.

What keeps polyhydroxyalkanoates in bacterial cells amorphous? A derivation from stress exposure experiments.

Polyhydroxyalkanoates (PHA) are storage polymers accumulated by numerous prokaryotes in form of intracellular granules. Native PHA granules are formed by amorphous polymer which reveals considerably higher elasticity and flexibility as compared to crystalline pure PHA polymers. The fact that bacteria store PHA in amorphous state has great biological consequences. It is not clear which mechanisms protect amorphous polymer in native granules from transition into thermodynamically favorable crystalline state. Here, we demonstrate that exposition of bacterial cells to particular stressors induces granules aggregation, which is the first but not sufficient condition for PHA crystallization. Crystallization of the polymer occurs only when the stressed bacterial cells are subsequently dried. The fact that both granules aggregation and cell drying must occur to induce crystallization of PHA indicates that both previously suggested hypotheses about mechanisms of stabilization of amorphous state of native PHA are valid and, in fact, both effects participate synergistically. It seems that the amorphous state of the polymer is stabilized kinetically by the low rate of crystallization in limited volume in small PHA granules and, moreover, water present in PHA granules seems to function as plasticizer protecting the polymer from crystallization, as confirmed experimentally for the first time by the present work.