New insights into the role of sediments in microplastic inputs from the Northern Dvina River (Russia) to the White and Barents Seas.

The Northern Dvina River is one of the main sources of microplastic pollution entering to the White and Barents Seas. The coastal and bottom sediments of this river play an important role as a transfer link of microplastics. With Py-GC/MS and µFT-IR methods, it was found that the sediments contain up to 350 mg/kg or 650 particles/kg of microplastic (dry weight). The unique hydrologic conditions of the river branching area contribute to the formation of a microplastic pollution hotspot. The hotspot accumulates >30 % of microplastic pollution, mainly ABS plastic particles smaller than 0.3 mm with roughness and cracks, which increases the hazard class (from II to IV) of microplastic pollution. Obtained data and high annual variability of pollution indicates that this area acts as a place of accumulation, degradation and gradual release of microplastics into the White and Barents Seas, i.e. into the Arctic region.

Biophysical Characterization and Cytocompatibility of Cellulose Cryogels Reinforced with Chitin Nanowhiskers.

Polysaccharide-based cryogels are promising materials for producing scaffolds in tissue engineering. In this work, we obtained ultralight (0.046-0.162 g/cm3) and highly porous (88.2-96.7%) cryogels with a complex hierarchical morphology by dissolving cellulose in phosphoric acid, with subsequent regeneration and freeze-drying. The effect of the cellulose dissolution temperature on phosphoric acid and the effect of the freezing time of cellulose hydrogels on the structure and properties of the obtained cryogels were studied. It has been shown that prolonged freezing leads to the formation of denser and stronger cryogels with a network structure. The incorporation of chitin nanowhiskers led to a threefold increase in the strength of the cellulose cryogels. The X-ray diffraction method showed that the regenerated cellulose was mostly amorphous, with a crystallinity of 26.8-28.4% in the structure of cellulose II. Cellulose cryogels with chitin nanowhiskers demonstrated better biocompatibility with mesenchymal stem cells compared to the normal cellulose cryogels.

Features of the Chemical Composition and Structure of Birch Phloem Dioxane Lignin: A Comprehensive Study.

Understanding the chemical structure of lignin in the plant phloem contributes to the systematics of lignins of various biological origins, as well as the development of plant biomass valorization. In this study, the structure of the lignin from birch phloem has been characterized using the combination of three analytical techniques, including 2D NMR, Py-GC/MS, and APPI-Orbitrap-HRMS. Due to the specifics of the phloem chemical composition, two lignin preparations were analyzed: a sample obtained as dioxane lignin (DL) by the Pepper's method and DL obtained after preliminary alkaline hydrolysis of the phloem. The obtained results demonstrated that birch phloem lignin possesses a guaiacyl-syringyl (G-S) nature with a unit ratio of (S/G) 0.7-0.9 and a higher degree of condensation compared to xylem lignin. It was indicated that its macromolecules are constructed from ß-aryl ethers followed by phenylcoumaran and resinol structures as well as terminal groups in the form of cinnamic aldehyde and dihydroconiferyl alcohol. The presence of fatty acids and flavonoids removed during alkaline treatment was established. Tandem mass spectrometry made it possible to demonstrate that the polyphenolic components are impurities and are not incorporated into the structure of lignin macromolecules. An important component of phloem lignin is lignin-carbohydrate complexes incorporating xylopyranose moieties.

Chitin Cryogels Prepared by Regeneration from Phosphoric Acid Solutions.

Cryogelation is a developing technique for the production of polysaccharide materials for biomedical applications. The formation of a macroporous structure during the freeze-drying of polysaccharide solutions creates biomaterials suitable for tissue engineering. Due to its availability, biocompatibility, biodegradability, and non-toxicity, chitin is a promising natural polysaccharide for the production of porous materials for tissue engineering; however, its use is limited due to the difficulty of dissolving it. This work describes the preparation of cryogels using phosphoric acid as the solvent. Compared to typical chitin solvents phosphoric acid can be easily removed from the product and recovered. The effects of chitin dissolution conditions on the structure and properties of cryogels were studied. Lightweight (ρ 0.025-0.059 g/cm3), highly porous (96-98%) chitin cryogels with various heterogeneous morphology were produced at a dissolution temperature of 20 ± 3 °C, a chitin concentration of 3-15%, and a dissolution time of 6-25 h. The crystallinity of the chitin and chitin cryogels was evaluated by 13C CP-MAS NMR spectroscopy and X-ray diffractometry. Using FTIR spectroscopy, no phosphoric acid esters were found in the chitin cryogels. The cryogels had compressive modulus E values from 118-345 kPa and specific surface areas of 0.3-0.7 m2/g. The results indicate that chitin cryogels can be promising biomaterials for tissue engineering.

Bordered Pit Formation in Cell Walls of Spruce Tracheids.

The process of pit formation in plants still has various questions unaddressed and unknown, which opens up many interesting and new research opportunities. The aim of this work was elucidation of the mechanism for the formation of bordered pits of the spruce (Picea abies (L.) Karst.) tracheid with exosomes participation and mechanical deformation of the cell wall. Sample sections were prepared from spruce stem samples after cryomechanical destruction with liquid nitrogen. The study methods included scanning electron microscopy and enzymatic treatment. Enzymatic treatment of the elements of the bordered pit made it possible to clarify the localization of cellulose and pectin. SEM images of intermediate stages of bordered pit formation in the radial and tangential directions were obtained. An asynchronous mechanism of formation of bordered-pit pairs in tracheids is proposed. The formation of the pit pair begins from the side of the initiator cell and is associated with enzymatic hydrolysis of the secondary cell wall and subsequent mechanical deformation of the primary cell walls. Enzymatic hydrolysis of the S1 layer of the secondary cell wall is carried out by exosome-delivered endoglucanases.

Analysis of the functional group composition of the spruce and birch phloem lignin.

In this article, the functional group composition of the spruce (Pícea ábies) and birch (Bétula péndula) phloem lignin is described. The features of the chemical structure were studied by analyzing dioxane lignin using the elemental analysis, UV-Vis, FT-IR, and 1D NMR spectroscopy. For comparison, samples of xylem dioxane lignin isolated from the corresponding wood species were also analyzed. FT-IR spectroscopy data suggest that the lignins of birch phloem and xylem are similar in chemical structure. However, there are differences in absorption bands in the spectra of spruce dioxane lignin, which indicate the opposite. Quantitative analysis of the functional group composition was performed using 13C and 31P NMR data. It was found that free phenolic hydroxyl groups of catechol and p-hydroxyphenyl types are dominated in the composition of spruce phloem lignin. Birch phloem lignin has a qualitative and quantitative composition of functional groups characteristic of hardwood lignins. However, the content of G-units is greater than S-units, in contrast to the birch xylem lignin, where S-units predominate. The revealed differences are relevant from the point of view of plant physiology. The practical significance of the study is connected with understanding the reactivity of lignins when considering the chemical processing of tree bark.

Exosomes in the phloem and xylem of woody plants.

MAIN CONCLUSION: Exosomes in the secondary phloem and secondary xylem of angiosperms and gymnosperms have physiological roles in the storage and transport of endoglucanases. Knowledge of plant extracellular vesicles (EVs) is limited by their presence in the apoplastic fluid of seeds and leaves. The contents of plant EVs and their biological functions are unclear. The aim of the present study was to expand our knowledge of EVs in woody plants. Sample splits were prepared from branch and stem samples from angiosperms and gymnosperms after cryomechanical destruction with liquid nitrogen. The study methods included scanning electron (SEM), atomic force microscopy (AFM), endoglucanase activity measurement. EVs visualized on the internal layers of the cell walls proved to be exosomes according to their diameter (65-145 nm). SEM revealed cup-shaped structures characteristic of exosomes in a dry state. Plant exosomes in the form of globules in the native state were visualized for the first time by AFM. Exosomes were present both in the active and dormant cambium. Erosion zones were observed at the sites of exosome localization. The activity of endo-1,4-ß-glucanase was detected in Picea xylem, while the RNA level was very low, suggesting that endo-1,4-ß-glucanases were preserved in the exosomes. There are grounds to assert that endo-1,4-ß-glucanases delivered by exosomes participated in pit cavity formation in the S1 layer of xylary fibres. A possible mechanism of endo-1,4-ß-glucanase action in the biosynthesis of the secondary wall is proposed. These results demonstrate that the physiological role of the exosomes in the phloem and xylem is the storage and transport of endo-1,4-ß-glucanases participating in cell wall remodeling in woody plants. Present study expands our knowledge about plant exosomes.

Fish hosts, glochidia features and life cycle of the endemic freshwater pearl mussel Margaritifera dahurica from the Amur Basin.

Margaritiferidae is a small freshwater bivalve family with 16 species. In spite of a small number of taxa and long-term history of research, several gaps in our knowledge on the freshwater pearl mussels still exist. Here we present the discovery of host fishes for Margaritifera dahurica, i.e. Lower Amur grayling, sharp-snouted lenok, and blunt-snouted lenok. The host fishes were studied in rivers of the Ussuri Basin. The identification of glochidia and fish hosts was confirmed by DNA analysis. The life cycle of M. dahurica and its glochidia are described for the first time. The SEM study of glochidia revealed that the rounded, unhooked Margaritifera dahurica larvae are similar to those of the other Margaritiferidae. Margaritifera dahurica is a tachytictic breeder, the larvae of which attach to fish gills during the Late August - September and finish the metamorphosis in June. Ancestral host reconstruction and a review of the salmonid - pearl mussel coevolution suggest that the ancestral host of the Margaritiferidae was a non-salmonid fish, while that of the genus Margaritifera most likely was an early salmonid species or their stem lineage. The overfishing of lenoks and graylings appears to be the most significant threat for this rare mussel species.

Juniper wood structure under the microscope.

MAIN CONCLUSION: The investigations confirm the physicochemical nature of the structure and self-assembly of wood substance and endorse its application in plant species. The characteristic morphological features, ultra-microstructure, and submolecular structure of coniferous wood matrix using junipers as the representative tree were investigated by scanning electron (SEM) and atomic-force microscopy (AFM). Novel results on the specific composition and cell wall structure features of the common juniper (Juniperus Communis L.) were obtained. These data confirm the possibility of considering the wood substance as a nanobiocomposite. The cellulose nanofibrils (20-50 nm) and globular-shaped lignin-carbohydrate structures (diameter of 5-60 nm) form the base of such a nanobiocomposite.