Carbodiimide additive to control hydrolytic stability and biodegradability of PLA

Enhanced durability of bio-based polylactic acid (PLA) is one of the prerequisites to be a considered as alternative to petroleum-based polymers in long time application. The effect of bis(2,6-diisopropylphenyl)carbodiimide (BDICDI) additive in various concentration on the extent of hydrolytic stabilization and subsequent degradation kinetics of PLA was studied in the process of abiotic hydrolysis and microbial decomposition under composting conditions. The study showed that BDICDI acts as an efficient stabilizer suppressing the hydrolytic scission of ester bonds of PLA in both degradation processes tested, especially at concentrations above 1.5% w/w. Within the stabilization period which strongly depends on concentrations of BDICDI, suppression of hydrolytic degradation also triggered preservation of thermal and mechanical properties. After the period of stabilization as the dose of stabilizer is depleted, probably via reaction with water molecules and carboxylic groups, the material was hydrolyzed at a comparable or even slightly higher rate than pure PLA. By applying the appropriate amount of BDICDI, the approximate duration of stabilization could be set to suit the desired requirements of the final product. © 2016 Elsevier Ltd15-08287Y, GACR, Czech Science FoundationCzech Science Foundation [15-08287Y]; Ministry of Education, Youth and Sports of the Czech Republic [LO1504]; Internal Grant Agency of the Tomas Bata University in Zlin [IGA/CPS/2016/004

Photodegradation and biodegradation of poly(lactic) acid containing orotic acid as a nucleation agent

Orotic acid is a natural heterocyclic compound that acts as a nucleation agent in poly(lactic acid) (PLA). PLA materials with increasing orotic acid content were prepared and characterized. It was found that crystallinity of about 28% was reached with 0.3% content of the agent. Further enhancement in the content of the agent did not provoke any additional significant increase of crystallinity. Subsequently, it was investigated whether the orotic acid content affected photodegradation of PLA and, in the next phase, its biodegradation. The results of rheological measurements showed that the compound slightly accelerates photodegradation of the material, which was accompanied by the cleavage of PLA chains. Previous photodegradation was shown to accelerate the subsequent biodegradation by shortening the lag phase of the process, where the explanation is probably in the reduction of the polymer molecular weight during the photodegradation. Moreover, the presence of orotic acid in both initial and photodegraded samples was found to influence biodegradation positively by shortening the lag phase and increasing the observed maximal rate of the biodegradation. © 2019 by the authors.Tomas Bata University in Zlin, Internal Grant Agency [IGA/FT/2018/009, IGA/FT/2019/011

Melt viscoelastic assessment of Poly(Lactic Acid) composting: Influence of UV Ageing

This study is devoted to the degradation pathway (bio, photo degradation and photo/bio) of Poly(Lactic acid) PLA polymers by means of melt viscoelasticity. A comparison was made between three PLA polymers with different microstructures (L, D stereoisomers). Biodegradability was determined during composting by burying the polymer films in compost at 58 _C. Melt viscoelasticity was used to assess the molecular evolution of the materials during the composting process. Viscoelastic data were plotted in the complex plane. We used this methodology to check the kinetics of the molecular weight decrease during the initial stages of the degradation, through the evolution of Newtonian viscosity. After a few days in compost, the Newtonian viscosity decreased sharply, meaning that macromolecular chain scissions began at the beginning of the experiments. However, a double molar mass distribution was also observed on Cole-Cole plots, indicating that there is also a chain recombination mechanism competing with the chain scission mechanism. PLA hydrolysis was observed by infra-red spectroscopy, where acid characteristic peaks appeared and became more intense during experiments, confirming hydrolytic activity during the first step of biodegradation. During UV ageing, polymer materials undergo a deep molecular evolution. After photo-degradation, lower viscosities were measured during biodegradation, but no significant differences in composting were found. © 2018 by the authors

Occurrence and analysis of thermophilic poly(butylene adipate-co-terephthalate)-degrading microorganisms in temperate zone soils

The ubiquity and character of thermophilic poly(butylene adipate-co-terephthalate) (PBAT)-degrading microorganisms in soils were investigated and compared to the process in an industrial composting plant. PBAT degraders were sought in 41 temperate zone soils. No mesophilic degraders were found by the employed method, but roughly 102 colony-forming units (CFUs) of thermophilic degraders per gram of soil were found in nine soils, and after an enrichment procedure, the PBAT-degrading consortia were isolated from 30 out of 41 soils. Thermophilic actinomycetes, Thermobispora bispora in particular, together with bacilli proved to be the key constituents of the isolated and characterized PBAT-degrading consortia, with bacilli comprising from about 30% to over 90% of the retrieved sequences. It was also shown that only consortia containing both constituents were able to decompose PBAT. For comparison, a PBAT film together with two types of PBAT/starch films were subjected to biodegradation in compost and the degrading microorganisms were analyzed. Bacilli and actinobacteria were again the most common species identified on pure PBAT film, especially at the beginning of biodegradation. Later, the composition of the consortia on all three tested materials became very similar and more diverse. Since waste containing PBAT-based materials is often intended to end up in composting plants, this study increases our confidence that thermophilic PBAT degraders are rather broadly present in the environment and the degradation of the material during the composting process should not be limited by the absence of specific microorganisms. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.Internal Grant of Tomas Bata University in Zlin [IGA/FT/2020/005, IGA/FT/2020/009

Structure characterization and biodegradation rate of poly(ε-caprolactone)/starch blends

The present paper focuses on the effects of blending poly (ε-caprolactone) (PCL) with thermoplastic starch (TPS) on the final biodegradation rate of PCL/TPS blends, emphasizing the type of environment in which biodegradation takes place. The blends were prepared by melt-mixing the components before a two-step processing procedure, which strongly affects the degree of plasticization and therefore the final material morphology, as was detailed in the previous work, was used for the thermoplastic starch. The concentration row of pure PCL over PCL/TPS blends to pure TPS was analyzed for biodegradation in two different environments (compost and soil), as well as from a morphological, thermomechanical, rheological, and mechanical point of view. The morphology of all the samples was studied before and after biodegradation. The biodegradation rate of the materials was expressed as the percentage of carbon mineralization, and significant changes, especially after exposure in soil, were recorded. The crystallinity of the measured samples indicated that the addition of thermoplastic starch has a negligible effect on PCL-crystallization. The blend with 70% of TPS and a co-continuous morphology demonstrated very fast biodegradation, with the initial rate almost identical to pure TPS in both environments while the 30% TPS blend exhibited particle morphology of the starch phase in the PCL matrix, which probably resulted in a dominant effect of the matrix on the biodegradation course. Moreover, some molecular interaction between PCL and TPS, as well as differences in flow and mechanical behavior of the blends, was determined. © Copyright © 2020 Nevoralová, Koutný, Ujčić, Starý, Šerá, Vlková, Šlouf, Fortelný and Kruliš.MH CR [NV15-31269A]; Technology Agency of the CR [TE01020118, TN01000008]; Ministry of Education, Youth and Sports of the CR, program NPU I [POLYMAT LO1507

Genotypic and phenotypic detection of polyhydroxyalkanoate production in bacterial isolates from food

Polyhydroxyalkanoates (PHAs) are widely used in medical and potentially in other applications due to their biocompatibility and biodegradability. Understanding PHA biosynthetic pathways may lead to the detection of appropriate conditions (substrates) for producing a particular PHA type by a specific microbial strain. The aim of this study was to establish a method enabling potentially interesting PHA bacterial producers to be found. In the study, all four classes of PHA synthases and other genes involved in PHA formation (fabG, phaA, phaB, phaG, and phaJ) were detected by PCR in 64 bacterial collection strains and food isolates. Acinetobacter, Bacillus, Cupriavidus, Escherichia, Klebsiella, Lelliottia, Lysinibacillus, Mammaliicoccus, Oceanobacillus, Pantoea, Peribacillus, Priestia, Pseudomonas, Rahnella, Staphylococcus, and Stenotrophomonas genera were found among these strains. Fructose, glucose, sunflower oil, and propionic acid were utilized as carbon sources and PHA production was detected by Sudan black staining, Nile blue staining, and FTIR methods. The class I synthase and phaA genes were the most frequently found, indicating the strains’ ability to synthesize PHA from carbohydrates. Among the tested bacterial strains, the Pseudomonas genus was identified as able to utilize all tested carbon sources. The Pseudomonas extremorientalis strain was determined as a prospect for biotechnology applications. © 2023 by the authors.IGA/FT/2022/00

Comprehensive biodegradation analysis of chemically modified poly(3-hydroxybutyrate) materials with different crystal structures

This work presents a comprehensive analysis of the biodegradation of polyhydroxybutyrate (PHB) and chemically modified PHB with different chemical and crystal structures in a soil environment. A polymer modification reaction was performed during preparation of the chemically modified PHB films, utilizing 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane as a free-radical initiator and maleic anhydride. Films of neat PHB and chemically modified PHB were prepared by extrusion and thermocompression. The biological agent employed was natural mixed microflora in the form of garden soil. The course and extent of biodegradation of the films was investigated by applying various techniques, as follows: a respirometry test to determine the production of carbon dioxide through microbial degradation; scanning electron microscopy (SEM); optical microscopy; fluorescence microscopy; differential scanning calorimetry (DSC); and X-ray diffraction (XRD). Next-generation sequencing was carried out to study the microbial community involved in biodegradation of the films. Findings from the respirometry test indicated that biodegradation of the extruded and chemically modified PHB followed a multistage (2-3) course, which varied according to the spatial distribution of amorphous and crystalline regions and their spherulitic morphology. SEM and polarized optical microscopy (POM) confirmed that the rate of biodegradation depended on the availability of the amorphous phase in the interspherulitic region and the width of the interlamellar region in the first stage, while dependence on the size of spherulites and thickness of spherulitic lamellae was evident in the second stage. X-ray diffraction revealed that orthorhombic α-form crystals with helical chain conformation degraded concurrently with β-form crystals with planar zigzag conformation. The nucleation of PHB crystals after 90 days of biodegradation was identified by DSC and POM, a phenomenon which impeded biodegradation. Fluorescence microscopy evidenced that the crystal structure of PHB affected the physiological behavior of soil microorganisms in contact with the surfaces of the films.Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT; Horizon 2020, (862910); Univerzita Tomáše Bati ve Zlíně, UTB, (IGA/FT/2022/006, IGA/FT/2023/002)European Union's Horizon 2020 Research and Innovation Program [862910]; Internal Grant Agency of Tomas Bata University in Zlin [IGA/FT/2023/002, IGA/FT/2022/006]; Ministry of Education, Youth and Sports of the Czech Republic [90254

Biodegradable polyesters and low molecular weight polyethylene in soil: Interrelations of material properties, soil organic matter substances, and microbial community

Conventional and also biodegradable polymer microplastics have started to be broadly present in the environment, if they end up in soil, they may influence both abiotic and biotic soil properties. In this study, the interactions of polyethylene wax together with three biodegradable polyesters PLA, PHB and PBAT with a soil matrix were investigated over a 1-year incubation period. Soil organic matter content was measured using UV-VIS, the microbial biomass amount was measured using qPCR, the mineralisation of polymers was measured using UGA 3000, the surface of polymers was observed with SEM, live/dead microorganisms were determined by fluorescent microscopy and microbial consortia diversity was analyzed using NGS. The amount of humic substances was generally higher in incubations with slowly degrading polyesters, but the effect was temporary. The microbial biomass grew during the incubations; the addition of PHB enhanced fungal biomass whereas PE wax enhanced bacterial biomass. Fungal microbial consortia diversity was altered in incubations with PHB and PBAT. Interestingly, these two polyesters were also covered in biofilm, probably fungal. No such trend was observed in a metagenomic analysis of bacteria, although, bacterial biofilm was probably formed on the PE520 surface. Different methods confirmed the effect of certain polymers on the soil environment

Evaluation of the Financial Situation in the Firm and Proposals to its Improvement

The bachelor thesis focuses on evaluation of financial situation of the company TM Stav, spol. s.r.o. and proposals to its improvement for period 2016-2020. This work is divided into three parts – theoretical, analytic and practical. In the theoretical part are implied theoretical basis about financial analysis. Analytic part contains analysis present condition of the company. Practical part is focusing on proposals to improve current situation of the company TM Stav, spol. s.r.o

Evaluation of the Financial Situation in the Firm and Proposals to its Improvement

The bachelor thesis focuses on evaluation of financial situation of the company TM Stav, spol. s.r.o. and proposals to its improvement for period 2016-2020. This work is divided into three parts – theoretical, analytic and practical. In the theoretical part are implied theoretical basis about financial analysis. Analytic part contains analysis present condition of the company. Practical part is focusing on proposals to improve current situation of the company TM Stav, spol. s.r.o