The self-plasticization, i.e., the increase in the polymer chains' mobility by including its monomer, has a major impact on a polymer's structural, thermal, and mechanical properties. In this study, differential scanning calorimetry (DSC), optical and Raman microscopies, thermo-mechanical analysis (TMA), size exclusion chromatography equipped with a multi-angle light scattering detector (SEC-MALS), and X-ray diffraction analysis (XRD) are used to investigate the effect of thermally induced self-plasticization of poly-(p-dioxanone), PDX, on the crystal growths from the amorphous and molten states. Significant changes in the crystallization behavior and mechanical properties of PDX are found only for samples self-plasticized at the depolymerization temperature (Td) above 150 °C. The intense self-plasticization leads to the decrease of the crystallization temperature, increase of the crystal growth rapidity, disappearance of the distinct α→α' polymorphic transition, reduction of the overall melting temperature, and segregation of the redundant monomer. Although the morphology of the crystalline phase has a major impact on the mechanical properties of PDX, the self-plasticization itself does not seem to result in any major changes in the magnitude, localization, or morphology of formed crystallites (these are primarily driven by the temperature of crystal growth). The manifestation of the variable activation energy concept is discussed for the present crystallization data.

• Klíčová slova
• crystallization, depolymerization, differential scanning calorimetry, polydioxanone, self‐plasticization,
• MeSH
• diferenciální skenovací kalorimetrie MeSH
• difrakce rentgenového záření MeSH
• dioxany * chemie   MeSH
• krystalizace * MeSH
• nízká teplota MeSH
• polymerizace * MeSH
• polymery * chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• dioxany * MeSH
• poly-4-dioxan-2-one MeSH Prohlížeč
• polymery * MeSH

The polyesters poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) used in various applications such as food packaging or 3D printing were depolymerized by biobased aliphatic alcohols-methanol and ethanol with the presence of para-toluenesulphonic acid (p-TSA) as a catalyst at a temperature of 151 °C. It was found that the fastest depolymerization is reached using methanol as anucleophile for the reaction with PLA, resulting in the value of reaction rate constant (k) of 0.0425 min-1 and the yield of methyl lactate of 93.8% after 120 min. On the other hand, the value of constant k for the depolymerization of PHB in the presence of ethanol reached 0.0064 min-1 and the yield of ethyl 3-hydroxybutyrate was of 76.0% after 240 min. A kinetics study of depolymerization was performed via LC-MS analysis of alkyl esters of lactic acid and 3-hydroxybutanoic acid. The structure confirmation of the products was performed via FT-IR, MS, 1H NMR, and 13C NMR. Synthesized alkyl lactates and 3-hydroxybutyrates were modified into polymerizable molecules using methacrylic anhydride as a reactant and potassium 2-ethylhexanoate as a catalyst at a temperature of 80 °C. All alkyl esters were methacrylated for 24 h, guaranteeing the quantitative yield (which in all cases reached values equal to or of more than 98%). The methacrylation rate constants (k') were calculated to compare the reaction kinetics of each alkyl ester. It was found that lactates reach afaster rate of reaction than 3-hydroxybutyrates. The value of k' for themethacrylated methyl lactate reached 0.0885 dm3/(mol·min). Opposite to this result, methacrylated ethyl 3-hydroxybutyrate's constant k' was 0.0075 dm3/(mol·min). The reaction rate study was conducted by the GC-FID method and the structures were confirmed via FT-IR, MS, 1H NMR, and 13C NMR.

• Klíčová slova
• alcoholysis, depolymerization, kinetics, methacrylation, poly(3-hydroxybutyrate), poly(lactic acid), polymerizable monomers,
• Publikační typ
• časopisecké články MeSH

Polystyrene (PS) is one of the most widely used synthetic polymers, with annual global production of around 20 million tons. However, its robust C─C backbone renders it highly recalcitrant to (bio)chemical depolymerization, and no sustainable re-/up-cycling method has yet been developed. Here, we establish a proof-of-concept for the efficient depolymerization of PS under mild aqueous conditions, using a laccase-mediator system (LMS) composed of Trametes versicolor laccase, 1-hydroxybenzotriazole (HBT), and ambient oxygen. To overcome substrate accessibility issues, PS is formulated into colloidally stable nanoparticles, promoting interfacial remote biocatalysis. Under such conditions, up to 99.9% decrease in molar mass is achieved from an initial PS of over 2 million g mol-1, synthesized by ab initio free-radical emulsion polymerization. This colloidal dispersion strategy is also effective for commercial PS and expanded PS waste processed by post-dispersion in surfactant-containing aqueous media. Mechanistic studies suggest that LMS-mediated depolymerization proceeds via HBT radical diffusion into PS nanoparticles, triggering hydrogen atom transfer (HAT)-based oxidation and β-scissions of PS chains. This approach provides an efficient method for PS depolymerization using aqueous conditions, ambient O2 and a native enzyme without harsh solvents or experimental conditions.

• Klíčová slova
• Biocatalysis, Laccase, Latex, Polystyrene, Upcycling,
• Publikační typ
• časopisecké články MeSH

UNLABELLED: Actin cytoskeleton is a vital cellular structure primarily known for controlling cell integrity, division and expansion. Here we present a proteomic dissection of Arabidopsis roots treated by actin depolymerizing agent latrunculin B. Pharmacological disintegration of the actin cytoskeleton by latrunculin B caused downregulation of several proteins involved in the actin organization and dynamics. Moreover, this approach helped to identify new protein candidates involved in gene transcription, due to the altered abundance of proteins involved in mRNA nuclear export. Finally, latrunculin B negatively affected the abundance of abscisic acid (ABA) responsive proteins. SIGNIFICANCE: This article substantially contributes to the current knowledge about the importance of actin organization and dynamics in proteome remodelling. We employed gel based and gel free proteomic analyses and identified several new protein candidates and protein networks linking actin dynamics to the gene transcription and to the ABA response in Arabidopsis.

• Klíčová slova
• ABA responsive proteins, Actin cytoskeleton, Arabidopsis root, Latrunculin B, Proteomics, mRNA export,
• MeSH
• aktiny chemie   metabolismus   MeSH
• Arabidopsis chemie   MeSH
• bicyklické sloučeniny heterocyklické farmakologie   MeSH
• kořeny rostlin chemie   MeSH
• kyselina abscisová fyziologie   MeSH
• mikrofilamenta účinky léků   MeSH
• polymerizace účinky léků   MeSH
• proteiny huseníčku analýza   chemie   metabolismus   MeSH
• proteom analýza   účinky léků   MeSH
• proteomika metody   MeSH
• thiazolidiny farmakologie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• aktiny MeSH
• bicyklické sloučeniny heterocyklické MeSH
• kyselina abscisová MeSH
• latrunculin B MeSH Prohlížeč
• proteiny huseníčku MeSH
• proteom MeSH
• thiazolidiny MeSH

Optimal conditions for isotachophoretic separation of carboxymethyl-D-glucoses formed by acidic depolymerization of carboxymethylcellulose were found. 6-O-carboxymethyl-D-glucose, 2-O-carboxymethyl-D-glucose and 3-O-carboxymethyl-D-glucose were identified and determined in the reaction mixture after carboxymethylcellulose hydrolysis. Relative reactivity of hydroxy groups in the glucopyranose unit of cellulose decreased in the following order: O(6)H greater than O(2)H much greater than O(3)H. This was found to be in agreement with the data published by other authors.

• MeSH
• elektroforéza metody   MeSH
• hydrolýza MeSH
• methylcelulosa analogy a deriváty   MeSH
• methylglukosidy analýza   MeSH
• methylglykosidy analýza   MeSH
• sodná sůl karboxymethylcelulosy analýza   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• methylcelulosa MeSH
• methylglukosidy MeSH
• methylglykosidy MeSH
• sodná sůl karboxymethylcelulosy MeSH

The integrity of the actin cytoskeleton is essential for plant immune signalling. Consequently, it is generally assumed that actin disruption reduces plant resistance to pathogen attack. Here, we demonstrate that actin depolymerization induced a dramatic increase in salicylic acid (SA) levels in Arabidopsis thaliana. Transcriptomic analysis showed that the SA pathway was activated due to the action of isochorismate synthase (ICS). The effect was also confirmed in Brassica napus. This raises the question of whether actin depolymerization could, under particular conditions, lead to increased resistance to pathogens. Thus, we explored the effect of pretreatment with actin-depolymerizing drugs on the resistance of Arabidopsis thaliana to the bacterial pathogen Pseudomonas syringae, and on the resistance of an important crop Brassica napus to its natural fungal pathogen Leptosphaeria maculans. In both pathosystems, actin depolymerization activated the SA pathway, leading to increased plant resistance. To our best knowledge, we herein provide the first direct evidence that disruption of the actin cytoskeleton can actually lead to increased plant resistance to pathogens, and that SA is crucial to this process.

• MeSH
• aktiny metabolismus   MeSH
• Arabidopsis metabolismus   mikrobiologie   MeSH
• Ascomycota patogenita   MeSH
• Brassica napus metabolismus   mikrobiologie   MeSH
• intramolekulární transferasy metabolismus   MeSH
• kyselina salicylová metabolismus   MeSH
• nemoci rostlin mikrobiologie   MeSH
• proteiny huseníčku metabolismus   MeSH
• Pseudomonas syringae patogenita   MeSH
• regulace genové exprese u rostlin fyziologie   MeSH
• signální transdukce fyziologie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• aktiny MeSH
• intramolekulární transferasy MeSH
• isochorismate synthase MeSH Prohlížeč
• kyselina salicylová MeSH
• proteiny huseníčku MeSH

TfCa, a promiscuous carboxylesterase from Thermobifida fusca, was found to hydrolyze polyethylene terephthalate (PET) degradation intermediates such as bis(2-hydroxyethyl) terephthalate (BHET) and mono-(2-hydroxyethyl)-terephthalate (MHET). In this study, we elucidated the structures of TfCa in its apo form, as well as in complex with a PET monomer analogue and with BHET. The structure-function relationship of TfCa was investigated by comparing its hydrolytic activity on various ortho- and para-phthalate esters of different lengths. Structure-guided rational engineering of amino acid residues in the substrate-binding pocket resulted in the TfCa variant I69W/V376A (WA), which showed 2.6-fold and 3.3-fold higher hydrolytic activity on MHET and BHET, respectively, than the wild-type enzyme. TfCa or its WA variant was mixed with a mesophilic PET depolymerizing enzyme variant [Ideonella sakaiensis PETase (IsPETase) PM] to degrade PET substrates of various crystallinity. The dual enzyme system with the wild-type TfCa or its WA variant produced up to 11-fold and 14-fold more terephthalate (TPA) than the single IsPETase PM, respectively. In comparison to the recently published chimeric fusion protein of IsPETase and MHETase, our system requires 10% IsPETase and one-fourth of the reaction time to yield the same amount of TPA under similar PET degradation conditions. Our simple dual enzyme system reveals further advantages in terms of cost-effectiveness and catalytic efficiency since it does not require time-consuming and expensive cross-linking and immobilization approaches.

• Publikační typ
• časopisecké články MeSH

Anthropogenic climate change, principally induced by the large volume of carbon dioxide emission from the global economy driven by fossil fuels, has been observed and scientifically proven as a major threat to civilization. Meanwhile, fossil fuel depletion has been identified as a future challenge. Lignocellulosic biomass in the form of organic residues appears to be the most promising option as renewable feedstock for the generation of energy and platform chemicals. As of today, relatively little bioenergy comes from lignocellulosic biomass as compared to feedstock such as starch and sugarcane, primarily due to high cost of production involving pretreatment steps required to fragment biomass components via disruption of the natural recalcitrant structure of these rigid polymers; low efficiency of enzymatic hydrolysis of refractory feedstock presents a major challenge. The valorization of lignin and cellulose into energy products or chemical products is contingent on the effectiveness of selective depolymerization of the pretreatment regime which typically involve harsh pyrolytic and solvothermal processes assisted by corrosive acids or alkaline reagents. These unselective methods decompose lignin into many products that may not be energetically or chemically valuable, or even biologically inhibitory. Exploring milder, selective and greener processes, therefore, has become a critical subject of study for the valorization of these materials in the last decade. Efficient alternative activation processes such as microwave- and ultrasound irradiation are being explored as replacements for pyrolysis and hydrothermolysis, while milder options such as advanced oxidative and catalytic processes should be considered as choices to harsher acid and alkaline processes. Herein, we critically abridge the research on chemical oxidative techniques for the pretreatment of lignocellulosics with the explicit aim to rationalize the objectives of the biomass pretreatment step and the problems associated with the conventional processes. The mechanisms of reaction pathways, selectivity and efficiency of end-products obtained using greener processes such as ozonolysis, photocatalysis, oxidative catalysis, electrochemical oxidation, and Fenton or Fenton-like reactions, as applied to depolymerization of lignocellulosic biomass are summarized with deliberation on future prospects of biorefineries with greener pretreatment processes in the context of the life cycle assessment.

• Klíčová slova
• biorefinery, depolymerization, greener oxidation, life cycle analysis, lignocellulosic biomass, mild pretreatment,
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH

Lignocellulose is a major biopolymer in plant biomass with a complex structure and composition. It consists of a significant amount of high molecular aromatic compounds, particularly vanillin, syringeal, ferulic acid, and muconic acid, that could be converted into intracellular metabolites such as polyhydroxyalkanoates (PHA) and hydroxybutyrate (PHB), a key component of bioplastic production. Several pre-treatment methods were utilized to release monosaccharides, which are the precursors of the relevant pathway. The consolidated bioprocessing of lignocellulose-capable microbes for biomass depolymerization was discussed in this study. Carbon can be stored in a variety of forms, including PHAs, PHBs, wax esters, and triacylglycerides. From a biotechnology standpoint, these compounds are quite adaptable due to their precursors' utilization of hydrogen energy. This study lays the groundwork for the idea of lignocellulose valorization into value-added products through several significant dominant pathways.

• Klíčová slova
• bioplastics production, consolidated bioprocessing, kitchen waste, lignocellulose depolymerization, polyhydroxyalkanoates (PHA), renewable aromatics,
• MeSH
• biomasa MeSH
• biopolymery chemie   metabolismus   MeSH
• lignin * chemie   metabolismus   MeSH
• odpadní produkty MeSH
• polyhydroxyalkanoáty chemie   biosyntéza   metabolismus   MeSH
• potraviny MeSH
• ztráty potravin a plýtvání s nimi MeSH
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH
• Názvy látek
• biopolymery MeSH
• lignin * MeSH
• lignocellulose MeSH Prohlížeč
• odpadní produkty MeSH
• polyhydroxyalkanoáty MeSH
• ztráty potravin a plýtvání s nimi MeSH

The actin cytoskeleton plays a central part in the dynamic organization of eukaryotic cell structure. Nucleation of actin filaments is a crucial step in the establishment of new cytoskeletal structures or modification of existing ones, providing abundant targets for regulatory processes. A substantial part of our understanding of actin nucleation derives from studies on yeast and metazoan cells. However, recent advances in structural and functional genome analysis in less traditional models, such as plants or Dictyostelium discoideum, provide an emerging picture of an evolutionarily conserved core of at least two actin nucleation mechanisms, one mediated by the Arp2/3 complex and the other one by the formin-based module. A considerable degree of conservation is found also in the systems controlling the balance between filamentous and globular actin (profilin, actin-depolymerizing factor/cofilin) and even in certain regulatory aspects, such as the involvement of Rho-related small GTPases. Identification of such conserved elements provides a prerequisite for the characterization of evolutionarily variable aspects of actin regulation which may be responsible for the rich morphological diversity of eukaryotic cells.

• MeSH
• aktiny genetika   fyziologie   ultrastruktura   MeSH
• Arabidopsis genetika   fyziologie   MeSH
• biologická evoluce MeSH
• biologické modely MeSH
• cytoskeletální proteiny fyziologie   MeSH
• Dictyostelium fyziologie   MeSH
• faktory depolymerizující aktin MeSH
• kontraktilní proteiny fyziologie   MeSH
• mikrofilamenta fyziologie   MeSH
• mikrofilamentové proteiny fyziologie   MeSH
• profiliny MeSH
• protein 2 související s aktinem MeSH
• proteiny huseníčku MeSH
• Rho proteiny vázající GTP fyziologie   MeSH
• výměnné faktory guaninnukleotidů fyziologie   MeSH
• zvířata MeSH
• Check Tag
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• přehledy MeSH
• Názvy látek
• aktiny MeSH
• cytoskeletální proteiny MeSH
• faktory depolymerizující aktin MeSH
• kontraktilní proteiny MeSH
• mikrofilamentové proteiny MeSH
• PRF1 protein, Arabidopsis MeSH Prohlížeč
• profiliny MeSH
• protein 2 související s aktinem MeSH
• proteiny huseníčku MeSH
• Rho proteiny vázající GTP MeSH
• výměnné faktory guaninnukleotidů MeSH