Orestovia-like plants are of great scientific and practical interest for various fields of natural science, forming the most ancient unique Devonian Barzas coals in the Kuznetsk Basin, Russia. However their natural affinity (higher plants or algae) remains disputable. This work studies Barzas compressions of Orestovia-like plants from the standpoint of chemosystematics. We proposed to use the aromatic biopolymer lignin, which is included in all higher terrestrial plants, as a marker of organic matter. To prove the presence of lignin and establish its structure, a complex of physical and chemical methods was used: FTIR and EPR spectroscopy, pyrolytic gas chromatography-mass spectrometry, scanning electron microscopy, X-ray fluorescence and X-ray phase analysis. Based on the obtained results, we found the presence of transformation products of compositionally homogeneous pcoumaric protolignin in the substance of plant remains. The obtained data do not exclude the validity of the hypothesis that the Devonian Orestovia-like plants belong to higher plants.

The paper discusses the challenges associated with utilizing different plant waste materials to create novel sorbents based on cellulose. The work aims to provide new data on the structure and sorption properties of polysaccharide samples in relation to toxicants such as mycotoxin T-2 and radionuclide uranium-238. The research employed X-ray diffraction, FTIR, low-temperature nitrogen adsorption, and methods of wood chemistry. The paper presents the results of a study on several polysaccharides, such as cellulose, β-glucan, and lichenin. A new approach for obtaining numerical data from X-ray diffraction patterns was proposed and applied to the analysis of cellulose samples from wheat straw, rye, and oats. Taking cereal celluloses as an example, it was suggested that there might be several types of structurally ordered elements at the supramolecular level. The degree of crystallinity of cellulose samples was calculated. The results show that the degree of crystallinity is 0.23 for wheat cellulose, 0.30 for rye cellulose, and 0.14 for oat cellulose. The study examined the sorption properties of lichenin and cellulose for mycotoxin T-2 under conditions simulating the gastrointestinal tract of mammals. It was found that at pH 2 (as in a stomach), wheat straw absorbs 73

The study of the value of lignin for biomedical use is generating growing interest. For the first time, the safety and biological efficacy of lignin from the stems of the oat Avena sativa L. were studied, necessary for a preliminary assessment of its biomedical potential, have been studied. In vitro experiments, a sample of oat lignin exhibited cytotoxicity to the HeLa, A549, and HT-29 cancer cell lines, depending on the concentration. At maximum concentrations 125 and 150 μg/ml, it reduced their survival and increased the level of reactive oxygen species. In vivo experiments, a sample of oat lignin, with acute (from 5 to 250 mg/kg body weight) and chronic (300, 1200 and 2000 mg/kg body weight) administration, did not have a toxic or genotoxic effect on the organs of mice. The biological efficacy of the oat lignin was manifested in activation of repair processes in bone marrow and thyroid gland, a decrease in the level of abnormal spermatozoa in males, stimulation of reproductive performance of females and in increase in research activity and a decrease in the level of anxiety in animals. The results indicate the prospects for further study of the medical and biological potential lignin of the oat.

It has been experimentally established that samples of low-layer graphene, synthesized by carbonization of plant materials (lignin, cellulose, and spruce bark) under conditions of self-propagating high-temperature synthesis, are effective sorbents for mycotoxin T-2 under conditions simulating the environment in the gastrointestinal tract of mammals, and are capable of irreversibly sorb at least 94.6% of mycotoxin with a sorption capacity of 1 mg of mycotoxins per 1 g of sorbent. Key words: few-layer graphene, self-propagating high-temperature synthesis, specific surface area, mycotoxin sorption. Keywords: few-layer graphene, self-propagating high-temperature synthesis, specific surface, sorption of mycotoxins.

The results of the study of carbon nanomaterials (CNM) synthesized by carbonation of lignocellulose biomass under conditions of self- propagating high- temperature synthesis (SHS) are presented. For the first time, it was proposed to use stems of Sosnovsky hogweed for the production of CNM. The influence of the choice of raw materials and synthesis conditions on the sorption characteristics of the samples was evaluated. It is shown that as a result of carbonization of biopolymers under the conditions of the SHS process, a cardinal transformation of the initial matter occurs, as evidenced by the results of chemical analysis and data obtained by scanning electron microscopy. By the method of low- temperature nitrogen adsorption, the fact of the formation of a developed surface- porous structure, with a specific area two orders of magnitude larger than the surface area of the initial plant biomass, has been established. The main regularities of the processes of adsorption from aqueous media with a low concentration (0.625 mu g/ml) of uranium were established. It was found that carbon nanomaterials samples are characterized by a strong retention of U(VI), a significant amount of which (67-70 %) is not desorbed either by water or aqueous solutions of CH3COONH4 and HCI (1 M). The relationship between the parameters of the surface- porous structure and adsorption- desorption indicators has been established. The obtained results indicated a high innovative potential of CNM.

Human industrial activity is accompanied by the formation of vast volumes of water contaminated with radionuclides, including radium-226, which create serious danger to people. Graphene nanostructures are among the most promising materials for purifying water from radionuclides. This work has been devoted to investigating the efficiency of few-layer graphene synthesized under conditions of self-propagating high-temperature synthesis from cellulose and wastes of the woodworking industry (technical lignin, tree bark) for purifying water from radium-226. The key advantage of the method chosen for synthesis of few-layer graphene is the possibility to synthesize large volumes of the material at an acceptable cost, which is extremely important for industrial applications. It has been found that the synthesized samples of few-layer graphene can efficiently purify water from radium-226 (the degree of sorption is higher than 99

This article presents results of our study of the structural organization of macromolecules of natural lignins isolated from some coniferous and deciduous plants. The main feature of lignin as a polymer is the polyvariability at all levels of structural organization. The study showed that the studied samples were very individual and differed in the content of functional groups, elemental composition, and structural units of the guaiacyl, syringyl, and p-hydroxyphenyl types. Acacia lignin has the most interesting chemical structure, since p-hydroxyphenyl structures are absent in the macromolecule of this biopolymer. The molecular properties of the acacia and spruce lignins are investigated by the methods of high-speed sedimentation, translational diffusion and viscosimetry. It were determined the molecular weight of fractions, the scaling coefficients of the Mark-Kuhn-Houwink equation, fractal dimension df and the value of the Tsvetkov-Klenin hydrodynamic invariant. Based on the analysis of the hydrodynamic behavior and topological structure of macromolecules, it was concluded that acacia lignin was a star-shaped polymer, and spruce lignin was a randomly branched polymer. The studied lignins have interesting and promising biomedical properties. The main feature of lignins is their high antioxidant activity (AOA), which is comparable with the activity of well-known low molecular weight antioxidants. It was shown that lignins from acacia and walnut wood were characterized by the highest AOA. In addition, lignins have excellent sorption properties against the extremely toxic aflatoxin B1 produced by the so-called "yellow mold"(fungi of the genus Aspergillus flavus). The lignin from walnut wood with the index of irreversible adsorption of AF reaching 68.4% should be considered the most effective.

The topological structure of the macromolecules of lignins isolated from oat husk and fir wood was studied by means of macromolecular hydrodynamic methods. The macromolecular properties were analyzed by evaluating the intrinsic viscosity and coefficients of the translational diffusion and the sedimentation velocity of the lignins in dilute dimethylformamide solutions. The average molecular weights (MDη) and polydispersity parameters were calculated based on the results of the fractionation, as follows: Mw = 14.6 × 103, Mn = 9.0, and Mw/Mn = 1.62 for lignins from fir wood and Mw = 14.9 Mn = 13.5 and Mw/Mn = 1.1 for lignins from oat husks. The fractal analysis of the lignin macromolecules allowed us to identify the distinctive characteristics of the fractal and topological structures of these lignins. The measurements indicated that the fractal dimension (df) values of the guaiacyl-syringyl lignins from oat husks were between 1.71 and 1.85, while the df of a typical guaiacyl lignin from fir wood was ~2.3. Thus, we determined that the lignin macromolecules of oat husks belong to the diffusion-limited aggregation-type cluster–cluster class of fractals of the Meakin–Kolb type, with a predominance of characteristics common to a linear configuration. The lignins of softwood fir trees exhibited a branched topological structure, and they belong to the diffusion-limited aggregation-type particle–cluster class of fractals of the Witten–Sander type. Lignins from oat husks have the linear topology of macromolecules while the macromolecules of the lignins from fir wood can be characterized as highly branched polymers.

The protein-polysaccharide complex is a unique biocomposite (based on algal cellulose) produced by marine brown algae. It has an amorphous-crystalline mesoporous structure with a large number of active functional groups capable of acting as sorption centers. In the framework of this study, the sorption of uranium and thorium by samples of the protein-polysaccharide complex and algal cellulose of two macrophyte species: Laminaria digitata and Saccharina latissima were studied. It was established that both sorbents bound uranium and thorium with different efficiency: 80–84

Orestovia -like plants were dominants in the formation of Devonian coals, among the most ancient in Earth’s history. A complex study of them was conducted, clarifying the possibilities of chemosystematics for Paleozoic fossil plants. The morphology and material composition of plant compressions are described. EPR spectroscopy has shown the presence of paramagnetic properties in the studied compressions, a specific feature of lignins and products of their transformation. The method of pyrolytic chromato-mass spectrometry revealed the aromatic nature of organic matter, structurally similar to lignin and built exclusively from p -coumaric units.

Studies of carbon nanomaterials (CNM) synthesized from lignocellulosic biomass, and natural and technical lignins were carried out. For the first time, we suggested using stems of Sosnovsky hogweed, one of the most aggressive and poisonous invasive plant species, to produce CNM. The influence of the choice of raw materials and synthesis conditions on the sorption and surface-porous characteristics of the samples was evaluated. The main regularities of adsorption processes from aqueous media with a low concentration (0.625 μg/ml) of uranium were established. We found that strong retention of uranium characterizes carbonized biopolymers (CBP) samples, a significant amount of which (67–70%) is not desorbed either by water or aqueous solutions of CH3COONH4 and HCI (1 M). In addition, we found out that the carbon nanomaterials we synthesized can adsorb mycotoxin T-2. The obtained results indicated a high innovative potential of CNM.

The proposed work is in line with current trends in the development of nature-like technologies and is devoted to analyzing the chemical structure and searching for new ways to use lignins for biomedical applications. Lignins are interesting biopolymers of the plant origin whose structural organization is multivariate and largely depends on the biological species of the plant. The objects of the study are lignins isolated from the stems of several species of annual and perennial plants. Characterization of lignins using FTIR, Py–GC/MS, EPR and 13C NMR spectroscopy revealed differences in the chemical structure of these biopolymers. The processes of adsorption/desorption of mycotoxins T-2 and aflatoxin B2 (AFB2) were studied under conditions of in vitro modeling of the digestive system of mammals. The relationship between the parameters of surface-porous structure, chemical structure, and lignin adsorption parameters has been revealed. We have determined that the best adsorbents of mycotoxins are lignins with a high content of active functional groups, namely carboxyl groups and phenolic groups. The highest value of strong adsorption of aflatoxin B2 and mycotoxin T-2 could be characterized by a sample of lignin isolated from walnut wood. The analysis of the totality of data on the adsorption capacity and parameters of the structural organization of lignins at the chemical, macromolecular and morphological levels allows concluding that chemisorption mechanisms play the most important role in the implementation of strong adsorption of mycotoxins. The antioxidant activity of lignins was evaluated. The results of the study of structural–chemical, antioxidant and adsorption properties in relation to various mycotoxins indicate a high biomedical potential of natural lignins.

Уважаемые коллеги!Благодарим Вас за проявленный интерес к Четвертой российской конференции «Графен: молекула и 2D кристалл» и желание принять участие в её работе.Конференция проходит в научно-образовательном центре города Новосибирска -Академгородке.Мероприятие посвящено актуальным направлениям исследований и разработок в области углеродных и низкоразмерных материалов.Проведение конференции поможет координации усилий ученых в решении современных проблем материаловедения и привлечению молодых исследователей для решения актуальных научных задач.Оргкомитет выражает особую благодарность НГУ, Центру компетенций НТИ «Моделирование и разработка новых функциональных материалов с заданными свойствами», компаниям «Диаэм», «НТ-МДТ Спектрум Инструментс» и корпорации "Графеновая Долина" за финансовую поддержку и журналам Аналитика, Наноиндустрия и РЭНСИТ за информационную поддержку.Искренне надеемся, что пребывание в Новосибирском Академгородке и в стенах Новосибирского государственного университета оставит множество положительных эмоций и

This paper presents our studies of chemical and topological structure of lignin macromolecules isolated from herbaceous plants of various botanical origins. The elemental, monomeric, and functional composition of biopolymers by 13С-NMR spectroscopy, electron paramagnetic resonance, FTIR spectroscopy and Py-GC/MS spectrometry were determined. The antioxidant properties and determined structural-chemical correlations were evaluated. The results of a study of the topological structure of one of the most promising from a biomedical point of view sample of Rhodiola rosea lignin are presented. For the first time, it is proved that this lignin belongs to the class of star-shaped polymers. The geroprotective properties of Rhodiola rosea lignin were studied, and the fact of increasing lifespan of model animal Drosophila melanogaster flies was established. In the first time the effect of lignin from the stems of oats Avena sativa on the cognitive abilities of laboratory mice was studied. The obtained data indicate an improvement in the activity of the brain and central nervous system of model animals with regular preventive administration of lignin.

The proposed literature review is in line with current trends in the development of nature-like technologies and is devoted to the analysis of the chemical structure and the search for new ways to use lignins for biomedical applications. Lignins are unique biopolymers of plant origin, the structural organization of which is multivariate and largely depends on the biological species of the plant. Fundamental structural and chemical studies are increasingly clarifying our understanding of the macromolecules structure of this key plant biopolymer, and the study of various taxonomic origins lignins shows to what extent evolution and natural variability have led to a complication of the chemical structure of macromolecules, including through the inclusion of "unconventional" phenolic monomers. This suggests that lignins contain much more structural units than the three monolignol variants described in lignin chemistry textbooks. As a result, as the analysis of the literature data shows, the very definition of lignin continues to expand and refine. Currently, there is a dramatic increase in interest in lignin-based materials, mainly due to their diverse beneficial properties, such as biodegradability, reactivity, biocompatibility, low toxicity and a wide range of biological activity. One of the main objectives of this article is to identify and discuss the mechanisms of biological action of lignins on living organisms to assess the biomedical potential and substantiate the possibility of their use as innovative drugs of antioxidant, radioprotective and geroprotective action. Finding new ways to use lignins is necessary to meet the challenges of maintaining health and improving the quality and duration of people's lives.

Natural lignins play a key physiological role in plant responses to various biotic and abiotic stresses throughout the life cycle of a plant organism. Radiation influence is a powerful anthropogenic factor that can disrupt the normal functioning of plants, which are forced to adapt to changing environmental conditions. This work was aimed at assessing the effect of radiation factors on the chemical structure of stress lignins from aspen stands that have passed the main stages of ontogeny in radioactively contaminated areas. As a result of our research the chemical composition of stress lignins, the quantitative ratios of guaiacyl, syringyl, and p-coumaric structural units, as well as main types of intermonomer bonds, were determined. Radioactive stress resulted in changing chemical structure of lignins expressed in the increasing quantity of syringyl units and decreasing proportion of guaiacyl and p-coumaric units. In the paper a novel estimation of the quantity of intermonomer ether bonds, substructures of resinol, phenylcoumaran, and dibenzodioxocin was presented. It was determined that radiation stress leads to increasing number of ether bonds and decreasing number of other types of intermonomer bonds. Conclusions about the effect of exogenous radiation factors on the chemical structure of stress lignins were confirmed by the results of correlation analysis of experimental data. The results on the stress lignin structure are relevant from the perspective of plant physiology. For the first time, data on the paramagnetic and antioxidant properties of stress lignins have been obtained, which might result in new ways of practical use of lignins.

In this paper we report novel comparative structural-chemical studies of chemofossils from Paleozoic and Mesozoic seeds. The chemofossils had well-preserved organic matter with a high content of carbon and oxygen. It is shown that the high preservation of the coats of Paleozoic seeds resulted from the reducing environment of their fossilization, which is confirmed by the presence of inclusions of pyrite. IR and EPR spectra of the samples indicate that the chemofossils were of an aromatic nature, and the structural fragments had oxygen-containing functional groups. The Early Carboniferous seeds coats have paramagnetic properties conditioned by the presence of phenoxyl radicals. The chemical structure of the samples was reconstructed using pyrolytic chromatography-mass spectrometry and it was shown that the Early Carboniferous and Cretaceous seeds coats included relicts of different types of lignins. The lignin nature of the studied samples was confirmed by EPR signals of phenoxyl radicals with characteristics typical of natural lignins. We concluded that the Early Carboniferous seed coats contain unmethoxylated polymers of p-coumaric-catechyl type.

A comprehensive study of dispersed Early Carboniferous seeds has been carried out to test the possibilities of using chemosystematics for Paleozoic fossils. This has involved their morphology; the ultrastructure of ion thinned sections and their material. The results of analysis of the FTIR and EPR spectra indicate that the key structural unit of the substance is the phenyl propane structure. The presence of relict lignin ( p ‑coumaric type) was established by structural-chemical analysis using pyrolytic chromatomass-spectrometry. Lignins of this type are unknown in modern plants. The concentration of phenoxyl radicals is 2–3 orders of magnitude higher in the samples than in modern lignins.

Currently, there is a tendency to deepen the mycotoxin problem, which is associated with the global warming and environmental pollution. The results of a study of the sorption capacity of adsorbents samples based on natural materials diatomites and lignins in relation to mycotoxin T-2 are presented. The chemical composition of diatomites of the Inzensk deposit before and after modification is given and the parameters of the surface-porous structure of the samples are established. The isotherms of adsorption and desorption of nitrogen on the surface of diatomites were studied and for the first time it was shown that they belong to the type IV(a) acording to IUPAC classification. The distribution of pores by size was studied and it was established that a significant proportion of the pore space of diatomites are mesopores with an average width of 7–12 nm. The highest adsorption rates of mycotoxin T-2 were established for a diatomite sample subjected to acid modification. Data on the adsorption of mycotoxin T-2 by samples of lignins isolated from the wood of birch Betula verrucosa, stems of rye Secale sp. and cabbage Brassica oleracea are given. The results of the determination of functional groups, elemental and monomeric composition of lignins are presented. It has been established that the adsorption capacity of drugs depends mainly on the peculiarities of the chemical structure of the studied samples. The highest adsorption rates of mycotoxin T-2 are established for lignin isolated from cabbage stems. Comparison of mycotoxin T-2 adsorption, surface porous structure parameters and chemical structure of various samples leads to the conclusion that for both diatomites and lignins, the chemisorption process plays the most important role.