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Obesity is a risk factor for type 2 diabetes mellitus (T2DM) and cardiovascular disease (CVD). Adipose tissue (AT) extracellular vesicles (EVs) could play a role in obesity and T2DM associated CVD progression via the influence of their specific cargo on gene expression in recipient cells. The aim of this work was to evaluate the effects of AT EVs of patients with obesity with/without T2DM on reverse cholesterol transport (RCT)-related gene expression in human monocyte-derived macrophages (MDMs) from healthy donors. AT EVs were obtained after ex vivo cultivation of visceral and subcutaneous AT (VAT and SAT, respectively). ABCA1, ABCG1, PPARG, LXRβ (NR1H2), and LXRα (NR1H3) mRNA levels in MDMs as well as in origine AT were determined by a real-time PCR. T2DM VAT and SAT EVs induced ABCG1 gene expression whereas LXRα and PPARG mRNA levels were simultaneously downregulated. PPARG mRNA levels also decreased in the presence of VAT EVs of obese patients without T2DM. In contrast ABCA1 and LXRβ mRNA levels tended to increase with the addition of obese AT EVs. Thus, AT EVs can influence RCT gene expression in MDMs during obesity, and the effects are dependent on T2DM status.

Introduction. Vitamin D deficiency may be a natural predictor of the onset of coronary heart disease (CHD) and myocardial infarction (MI) at a young age. The results of studies of the various variants association of the vitamin D receptor (VDR) gene with the risk of CHD are contradictory, which leads to the study of genetic variants of the VDR gene as predictors of the onset of the disease at the age of 45 years and younger in the Russian population. The objective was to determine the distribution of TaqI, BsmI and ApaI genotypes of the VDR gene variants and the level of vitamin D sufficiency in CHD patients with different age of onset of the disease and myocardial infarction, among residents of St. Petersburg. Methods and materials. The study included 410 CHD patients and 320 examined patients without CHD clinical signs of comparable age (p>0.05). All patients with CHD underwent coronary angiography. Typing of VDR gene variants was carried out by polymerase chain reaction and subsequent restriction analysis. Determination of the level of 25(OH)D blood serum was carried out by enzyme immunoassay. Results. The level of 25(OH)D in the blood serum of CHD patients was lower than in the control group (15.61±0.52 ng/ml and 20.82±0.69 ng/ml respectively; p=0.001). Severe 25(OH)D deficiency was detected more often in CHD patients and was associated with an increased risk of CHD (23 % and 8 % respectively; p=0.001, OR=3.54 (1.88÷6.67)). The normal level of 25(OH)D sufficiency was more often detected in patients from the comparison group than in CHD patients, and was associated with a decrease of CHD risk (16 % and 4 % respectively; p=0.0002, OR=OR=0,21 (0,09÷0,48)). The presence of the aa genotype and the a allele (ApaI), the bb genotype and the b allele of the VDR gene (BsmI) is associated with an increased risk of CHD and the onset of the disease and MI at the age of 45 years and younger. Conclusions. Severe 25(OH)D deficiency is typical for CHD patients and was associated with an increased risk of CHD. The presence of the aa genotype and the a allele (ApaI), the bb genotype and the b allele of the VDR gene (BsmI) is associated with an increased risk of CHD and with the onset of the diseases and myocardial infarction at a young age. The TaqI variant of the VDR gene is not associated with the risk of CHD.

Background. Olivopontocerebellar atrophy (OPCA) is a rare neurodegenerative disorder characterized by the continuously progressive course that combines the signs of cerebellar ataxia, parkinsonism, pyramidal syndrome, choreoathetosis, dementia, oculomotor dysfunction, affected peripheral nerves, and autonomic failure. Differential diagnosis is hampered by late onset of the disease in adulthood and older age, low prevalence in the population, non-specific nature, and slowly emerging symptoms. The paper investigates the clinical case of olivopontocerebellar atrophy that has been extremely difficult to verify. Aim. To attract attention of physicians of different specialties, primarily neurologists, psychiatrists, general practitioners, on the issue of rare neurodegenerative disorders, which are extremely difficult to verify in adulthood and older age. Methods. Medical history of female patient М., 68 years, who stayed at psychotherapy department. Assessment of the whole body, mental, and neurological status. Results. Considering the complaints of the patient and her relatives, the data of psychological and psychiatric assessment, neurological status, brain MRI, and no response to treatment with neurological and psychotherapeutic drugs, the following probable clinical diagnosis was established: “Congenital spinocerebellar ataxia of unspecified type (olivopontocerebellar atrophy)”. Conclusion. Early diagnosis of the OPCA clinical manifestations is extremely difficult, especially in elderly individuals, since the disorder occurs under the guise of age-related vascular changes in the brain matter and manifests itself in focal symptoms and mental function impairment. The history of the signs of prominent cognitive decline and multiple focal symptoms in the elderly patient, who is not excessive drinker and has no malignant hypertension or severe atherosclerosis, as well as any other background disease, requires exclusion of the disease vascular or degenerative origin. In the reported case, the combination of cerebellar ataxia and dementia constituted the core of clinical manifestations of the neurodegenerative process confirmed by brain imaging to exclude the conversion disorder.

The process of thermocatalytic conversion of pine ethanol lignin in supercritical ethanol was studied over NiCu/SiO2 and NiCuMo/SiO2 catalysts bearing 8.8 and 11.7 wt.% of Mo. The structure and composition of ethanol lignin and the products of its thermocatalytic conversion were characterized via 2D-HSQC NMR spectroscopy, GC-MC. The main aromatic monomers among the liquid products of ethanol lignin conversion were alkyl derivatives of guaiacol (propyl guaiacol, ethyl guaiacol and methyl guaiacol). The total of the monomers yield in this case was 12.1 wt.%. The temperature elevation up to 350 °C led to a slight decrease in the yield (to 11.8 wt.%) and a change in the composition of monomeric compounds. Alkyl derivatives of pyrocatechol, phenol and benzene were observed to form due to deoxygenation processes. The ratio of the yields of these compounds depended on the catalyst, namely, on the content of Mo in the catalyst composition. Thus, the distribution of monomeric compounds used in various industries can be controlled by varying the catalyst composition and the process conditions.

Introduction. Obesity is associated with a high risk of developing concomitant diseases such as: metabolic syndrome, type 2 diabetes mellitus (DM2), cardiovascular pathology. FABP4 (fatty acid binding protein) is the specific lipid chaperone and an important protein for the function of adipose tissue and is one of the adipocytokines secreted by adipose tissue.The objective of the study was to investigate the FABP4 gene expression in subcutaneous and visceral adipose tissue (SAT and VAT) in patients with obesity and DM2.Methods and materials. SAT and VAT samples were obtained during bariatric surgery (N=43, BMI>35): obese with DM2 (N=21), obese without DM2 (N=22). Samples for the control group without obesity (N=15, BMI

Introduction. Vitamin D deficiency may be an independent predictor of coronary heart disease (CHD) and the severity of coronary atherosclerosis. The results of studies of the association of various polymorphisms of the vitamin D receptor (VDR) gene with the risk and severity of CHD are contradictory, which necessitates the study of genetic variants of the VDR gene and the characteristics of the clinical course of CHD in the Russian population.The objective was to determine the distribution of genotypes of TaqI, BsmI and ApaI of polymorphic variants of the VDR gene and the level of vitamin D sufficiency in CHD patients with varying severity of CHD, residents of St. Petersburg.Methods and materials. The study included 407 CHD patients and 318 patients without clinical signs of CHD of comparable age (p>0.05). All CHD patients underwent coronary angiography. Typing of the VDR gene variants was performed by polymerase chain reaction and subsequent restriction analysis. Determination of the level of 25(OH)D blood serum was carried out by enzyme immunoassay.Results. Vitamin D deficiency was detected in 82 % of CHD patients, the content of 25(OH)D in blood serum was lower in CHD patients who had 2 or more myocardial infarctions (MI) than in those who had one MI (p=0.03). Vitamin D deficiency is associated with a 3.6-fold increased risk of multivessel disease (p=0.01). The presence of the aa genotype and the a allele (ApaI), the bb genotype and the b allele of the VDR gene (BsmI) is associated with an increased risk of CHD and the severity of atherosclerotic lesions of the coronary arteries.Conclusion. Vitamin D deficiency is typical for CHD patients and is associated with the severity of coronary atherosclerosis. The presence of aa genotype and a allele (ApaI polymorphism), bb genotype and b allele of the VDR gene (BsmI polymorphism) is associated with an increased risk of CHD and the severity of atherosclerotic lesions of the coronary arteries. TaqI polymorphism of the VDR gene is not associated with the risk of CHD.

Obesity is a significant risk factor for the development of type 2 diabetes mellitus (T2DM). Adipose tissue dysfunction can affect the pool of circulating exosomal miRNAs, driving concomitant disease in obesity. These exosomal miRNAs can reflect adipose tissue functionality, thus serving as prognostic biomarkers for disease monitoring in case of T2DM. In the present study, we conducted NanoString microRNA profiling of extracellular vesicles (EVs) secreted by adipose tissue of obese patients (body mass index (BMI) > 35) without T2DM and nonobese individuals (BMI < 30) as a control group. Functional and pathway enrichment analysis showed that miRNAs associated with obesity in this study were implicated in insulin signaling and insulin resistance biological pathways. Further, these microRNAs were screened in serum EVs in the following groups: (1) obese patients with T2DM, (2) obese patients without T2DM, and (3) nonobese individuals as a control group. has-miR-551b-3p was shown to be downregulated in adipose tissue EVs, as well as in serum EVs, of patients with obesity without T2DM. At the same time, the serum exosomal hsa-miR-551b-3p content was significantly higher in obese patients with T2DM when compared with obese patients without T2DM and may be a potential biomarker of T2DM development in obesity.

Abstract Background Recent studies have focused on the potential role of epicardial adipose tissue (EAT) in the development of coronary artery disease (CAD). ABCA1 and ABCG1 transporters regulate cell cholesterol content and reverse cholesterol transport. We aimed to determine whether DNA methylation and mRNA levels of the ABCA1 and ABCG1 genes in EAT and subcutaneous adipose tissue (SAT) were associated with CAD. Methods Paired EAT and SAT samples were collected from 82 patients undergoing elective cardiac surgery either for coronary artery bypass grafting (CAD group, N = 66) or valve surgery (NCAD group, N = 16). ABCA1 and ABCG1 mRNA levels in EAT and SAT samples were analyzed using real time polymerase chain reaction, ABCA1 protein levels in EAT samples were assessed by western blotting. ABCA1 and ABCG1 DNA methylation analysis was performed in 24 samples from the CAD group and 9 samples from the NCAD group via pyrosequencing. Results DNA methylation levels in the ABCA1 promoter and ABCG1 cg27243685 and cg06500161 CpG sites were higher in EAT samples from patients with CAD compared with NCAD (21.92% vs 10.81%, p = 0.003; 71.51% vs 68.42%, p = 0.024; 46.11% vs 37.79%, p = 0.016, respectively). In patients with CAD, ABCA1 and ABCG1 DNA methylation levels were higher in EAT than in SAT samples (p

The reductive catalytic fractionation of flax shives in the presence of bimetallic NiRu catalysts supported on oxidized carbon materials (CM) such as mesoporous Sibunit and carbon mesostructured by KAIST (CMK-3) was studied. The catalysts based on CMK-3 were characterized by a higher surface area (1216 m2/g) compared to the ones based on Sibunit (315 m2/g). The catalyst supported on CMK-3 (10Ni3RuC400) was characterized by a more uniform distribution of Ni particles, in contrast to the Sibunit-based catalyst (10Ni3RuS450), on the surface of which large agglomerated particles (300–400 nm) were presented. The bimetallic catalysts were found to be more selective towards propanol-substituted methoxyphenols compared to monometallic Ru/C and Ni/C catalysts. A high yield of monomers (up to 26 wt%, including 17% 4-propanol guaiacol) was obtained in the presence of a 10Ni3RuC400 catalyst based on CMK-3.

The aim of the study was to investigate whether visual stimuli have the same potency to increase electroencephalography (EEG) delta wave power density during non-rapid eye movement (NREM) sleep as do auditory stimuli that may be practical in the treatment of some sleep disturbances. Nine healthy subjects underwent two polysomnography sessions—adaptation and experimental—with EEG electrodes positioned at Fz–Cz. Individually adjusted auditory (pink noise) and visual (light-emitting diode (LED) red light) paired 50-ms signals were automatically presented via headphones/eye mask during NREM sleep, shortly (0.75–0.90 s) after the EEG wave descended below a preset amplitude threshold (closed-loop in-phase stimulation). The alternately repeated 30-s epochs with stimuli of a given modality (light, sound, or light and sound simultaneously) were preceded and followed by 30-s epochs without stimulation. The number of artifact-free 1.5-min cycles taken in the analysis was such that the cycles with stimuli of different modalities were matched by number of stimuli presented. Acoustic stimuli caused an increase (p < 0.01) of EEG power density in the frequency band 0.5–3.0 Hz (slow waves); the values reverted to baseline at post-stimuli epochs. Light stimuli did not influence EEG slow wave power density (p > 0.01) and did not add to the acoustic stimuli effects. Thus, dim red light presented in a closed-loop in-phase fashion did not influence EEG power density during nocturnal sleep.

Noble metal-based catalysts are widely used to intensify the processes of reductive fractionation of lignocellulose biomass. In the present investigation, we proposed for the first time using the inexpensive NiCuMo/SiO2 catalyst to replace Ru-, Pt-, and Pd-containing catalysts in the process of reductive fractionation of abies wood into bioliquids and cellulose products. The optimal conditions of abies wood hydrogenation were selected to provide the effective depolymerization of wood lignin (250 °C, 3 h, initial H2 pressure 4 MPa). The composition and structure of the liquid and solid products of wood hydrogenation were established. The NiCuMo/SiO2 catalyst increases the yield of bioliquids (from 36 to 42 wt%) and the content of alkyl derivatives of methoxyphenols, predominantly 4-propylguaiacol and 4-propanolguaiacol. A decrease in the molecular mass and polydispersity (from 1870 and 3.01 to 1370 Da and 2.66, respectively) of the liquid products and a threefold increase (from 9.7 to 36.8 wt%) in the contents of monomer and dimer phenol compounds were observed in the presence of the catalyst. The solid product of catalytic hydrogenation of abies wood contains up to 73.2 wt% of cellulose. The composition and structure of the solid product were established using IRS, XRD, elemental and chemical analysis. The data obtained show that the catalyst NiCuMo/SiO2 can successfully replace noble metal catalysts in the process of abies wood reductive fractionation into bioliquids and cellulose.

The physicochemical properties of binary systems are of great importance for the application of the latter. We report on the investigation of an ammonium sulfamate–urea binary system with different component ratios using a combination of experimental (FTIR, XRD, TGA/DSC, and melting point) and theoretical (DFT, QTAIM, ELF, RDG, ADMP, etc.) techniques. It is shown that, at a temperature of 100 °C, the system under study remains thermally and chemically stable for up to 30 min. It was established using X-ray diffraction analysis that the heating time barely affects the X-ray characteristics of the system. Data on the aggregate states in specified temperature ranges were obtained with thermal analysis and determination of the melting point. The structures of the ammonium sulfamate–urea system with different component ratios were optimized within the density functional theory. The atom-centered density matrix propagation calculation of the ammonium sulfamate–urea system with different component ratios was performed at temperatures of 100, 300, and 500 K. Regardless of the component ratio, a regular increase in the potential energy variation (curve amplitude) with an increase in temperature from 100 to 500 K was found.

Abstract Omentin-1 and fatty acid-binding protein 4 (FABP4) are adipose tissue adipokines linked to obesity-associated cardiovascular complications. The aim of this study was to investigate epicardial adipose tissue (EAT) omentin-1 and FABP4 gene expression in obese and non-obese patients with coronary artery disease (CAD). Omentin-1 and FABP4 mRNA levels in EAT and paired subcutaneous adipose tissue (SAT) as well as adipokine serum concentrations were assessed in 77 individuals (61 with CAD; 16 without CAD (NCAD)). EAT FABP4 mRNA level was decreased in obese CAD patients when compared to obese NCAD individuals (p=0.001). SAT FABP4 mRNA level was decreased in CAD patients compared to NCAD individuals without respect to their obesity status (p=0.001). Omentin-1 mRNA level in EAT and SAT did not differ between the CAD and NCAD groups. These findings suggest that omentin-1 gene expression in adipose tissue is not changed during CAD; downregulated FABP4 gene expression in SAT is associated with CAD while EAT FABP4 gene expression is decreased only in obesity-related CAD.

Reductive catalytic fractionation (RCF) has emerged as an effective lignin-first biorefinery strategy to depolymerize lignin into tractable fragments in high yields. Herein, we propose the RCF of spruce wood over a Ru/C bifunctional catalyst in the medium of ethanol and molecular hydrogen to produce monomeric phenolic compounds from lignin, polyols from hemicelluloses, and microcrystalline cellulose. This contribution attempts to elucidate the role of the Ru/C bifunctional catalysts characteristics. The results clarify the particular effect of the carbon support acidity, catalyst grain size, content and dispersion of Ru on the effectiveness of lignin and hemicelluloses extraction and the yields of liquid and gaseous products. The most efficient catalysts for RCF of spruce wood, providing high yields of the monomeric phenols, glycols, and solid product with content of cellulose up to 90 wt%, bear 3 wt% of Ru with a dispersion of 0.94 based on an acidic oxidized graphite-like carbon support Sibunit®, and having a grain size of 56–94 μm. The Ru/C catalysts intensify the reactions of hydrodeoxygenation of liquid products from lignin. The main phenolic monomers are 4-propyl guaiacol, 4-propenyl guaiacol, and 4-propanol guaiacol. We explored the effect of the process temperature and time on the yield and composition of the liquid, solid, and gaseous products of spruce wood RCF. The optimal trade-off between the yields of phenolic monomers (30.0 wt%). polyols (18.6 wt%) and the solid product containing 84.4 wt% of cellulose is reached at 225 °C and 3 h over the most acidic Ru/C catalyst.

In this study, hemicelluloses of aspen wood (Pópulus trémula) were obtained by oxidative delignification in an acetic acid-water-hydrogen peroxide medium at temperatures of 70–100 °C and a process time of 1–4 h. The maximum polysaccharide yield of up to 9.68 wt% was reported. The composition and structure of the hemicelluloses were studied using a complex of physicochemical methods: gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, 2D nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The xylose, mannose, galactose, and glucose monomer units were identified in the hemicelluloses by gas chromatography. The weight average molecular weight Mw of the products determined by gel permeation chromatography was found to range within 8932–33,142 g/mol. The reported Fourier-transform spectra of the hemicelluloses contain all the bands characteristic of heteropolysaccharides; a weak lignin absorption signal in the spectra at 1500–1510 cm−1 is attributed to a minor content of phenolic fragments in the structure of the obtained hemicelluloses. The use of thermogravimetric analysis established that the hemicelluloses isolated from aspen wood are resistant against heating to temperatures of up to 90–100 °C and, upon further heating up to 400 °C, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses was examined using the compounds that mimic free radicals (1,1-diphenyl-2-picrylhydrazyl) and hydroxyl radicals (salicylic acid). It was found that the activity of all polysaccharides in neutralizing DPPH and hydroxyl radicals is lower than the absorption capacity of vitamin C at all the tested concentrations (0.5, 2, and 5 mg/mL) and attains 81.7 and 82.9%, respectively.

Hydrogenation of flax shives in ethanol over bifunctional Ni/C catalysts at 225 °C has been studied. It has been shown that the 10% Ni/C catalyst enhances the yield of monomeric products from 1.1 to 9.7 wt %, decreases the solid product content from 45 to 35 wt %, and increases the degree of delignification to 91%. The main monomeric compounds obtained during hydrogenation are propyl guaiacol and propenyl guaiacol. It has been established that an increase in the mass transfer intensity via increasing the stirring rate or decreasing the catalyst grain size leads to an increase in the total yield of monomeric compounds and the propanol guaiacol yield. Alkaline and acid pretreatment increases the cellulose content in the solid product from 42 to 73 wt %. The proposed sequential scheme of the transformation and formation of monomeric products over the bifunctional nickel catalyst is lignin—coniferyl alcohol—4-propanol guaiacol—4-propenyl guaiacol—4-propyl guaiacol.

Soda lignin is a by-product of the soda process for producing cellulose from grassy raw materials. Since a method for the industrial processing of lignin of this type is still lacking, several research teams have been working on solving this problem. We first propose a modification of soda lignin with sulfamic acid over solid catalysts. As solid catalysts for lignin sulfation, modified carbon catalysts (with acid sites) and titanium and aluminum oxides have been used. In the elemental analysis, it is shown that the maximum sulfur content (16.5 wt%) was obtained with the Sibunit-4® catalyst oxidized at 400 °C. The incorporation of a sulfate group has been proven by the elemental analysis and Fourier-transform infrared spectroscopy. The molecular weight distribution has been examined by gel permeation chromatography. It has been demonstrated that the solid catalysts used in the sulfation process causes hydrolysis reactions and reduces the molecular weight and polydispersity index. It has been established by the thermal analysis that sulfated lignin is thermally stabile at temperatures of up to 200 °C. According to the atomic force microscopy data, the surface of the investigated film consists of particles with an average size of 50 nm. The characteristics of the initial and sulfated β-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3–4 h and temperatures of 90–100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark–Kuhn–Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33–1.01 and 1.57–472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm−1 (C–O–C and C–O–H), 1738 cm−1 (ester C=O), 1375 cm−1 (–C–CH3), 1243 cm−1 (–C–O–), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.

Betulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst®15 solid acid catalyst. It has been shown that this catalyst remains stable when being repeatedly (up to four cycles) used and ensures obtaining of sulfated betulin with a sulfur content of ~10%. The introduction of the sulfate group into the betulin molecule has been proven by Fourier-transform infrared, ultraviolet-visible, and nuclear magnetic resonance spectroscopy. The Fourier-transform infrared (FTIR) spectra contain absorption bands at 1249 and 835–841 cm−1; in the UV spectra, the peak intensity decreases; and, in the nuclear magnetic resonance (NMR) spectra, of betulin disulfate, carbons С3 and С28 are completely shifted to the weak-field region (to 88.21 and 67.32 ppm, respectively) with respect to betulin. Using the potentiometric titration method, the product of acidity constants K1 and K2 of a solution of the betulin disulfate H+ form has been found to be 3.86 × 10–6 ± 0.004. It has been demonstrated by the thermal analysis that betulin and the betulin disulfate sodium salt are stable at temperatures of up to 240 and 220 °C, respectively. The density functional theory method has been used to obtain data on the most stable conformations, molecular electrostatic potential, frontier molecular orbitals, and mulliken atomic charges of betulin and betulin disulfate and to calculate the spectral characteristics of initial and sulfated betulin, which agree well with the experimental data.

For the first time, the fractionation of birch wood into microcrystalline cellulose, xylose and methoxyphenols is suggested based on the integration of alkali-acid pretreatments and hydrogenation in ethanol over a bifunctional Ru/C catalyst. It is established that removal of hemicelluloses during pretreatments of birch wood influences the yields of the liquid, gaseous and solid products of the non-catalytic and catalytic hydrogenation of pretreated samples in ethanol at 225 °C. The bifunctional Ru/carbon catalyst affects in different ways the conversion and yields of products of hydrogenation of the initial and acid- and alkali-pretreated birch wood. The most noticeable influence is characteristic of the hydrogenation of the acid-pretreated wood, where in contrast to the non-catalytic hydrogenation, the wood conversion and the yields of liquid products increase but the yields of the solid and gaseous products decrease. GC-MS, gel permeation chromatography and elemental analysis were used for characterization of the liquid product composition. The molecular mass distribution of the liquid products of hydrogenation of the initial and pretreated wood shifts towards the low-molecular range in the presence of the catalyst. From the GC-MS data, the contents of monomer compounds, predominantly 4-propylsyringol and 4-propanolsyringol, increase in the presence of the ruthenium catalyst. The solid products of catalytic hydrogenation of the pretreated wood contain up to 95 wt% of cellulose with the structure, similar to that of microcrystalline cellulose.

Xanthan is an important polysaccharide with many beneficial properties. Sulfated xanthan derivatives have anticoagulant and antithrombotic activity. This work proposes a new method for the synthesis of xanthan sulfates using sulfamic acid. Various N-substituted ureas have been investigated as process activators. It was found that urea has the greatest activating ability. BBD of xanthan sulfation process with sulfamic acid in 1,4-dioxane has been carried out. It was shown that the optimal conditions for the sulfation of xanthan (13.1 wt% sulfur content) are: the amount of sulfating complex per 1 g of xanthan is 3.5 mmol, temperature 90 °C, duration 2.3 h. Sulfated xanthan with the maximum sulfur content was analyzed by physicochemical methods. Thus, in the FTIR spectrum of xanthan sulfate, in comparison with the initial xanthanum, absorption bands appear at 1247 cm−1, which corresponds to the vibrations of the sulfate group. It was shown by GPC chromatography that the starting xanthan gum has a bimodal molecular weight distribution of particles, including a high molecular weight fraction with Mw > 1000 kDa and an LMW fraction with Mw < 600 kDa. It was found that the Mw of sulfated xanthan gum has a lower value (~612 kDa) in comparison with the original xanthan gum, and a narrower molecular weight distribution and is characterized by lower PD values. It was shown by thermal analysis that the main decomposition of xanthan sulfate, in contrast to the initial xanthan, occurs in two stages. The DTG curve has two pronounced peaks, with maxima at 226 and 286 °C.

The process of sulfation of arabinogalactan—a natural polysaccharide from Larix sibirica Ledeb.—with sulfamic acid in 1,4-dioxane using different activators has been studied for the first time. The dynamics of the molecular weight of sulfated arabinogalactan upon variation in the temperature and time of sulfation of arabinogalactan with sulfamic acid in 1,4-dioxane has been investigated. It has been found that, as the sulfation time increases from 10 to 90 min, the molecular weights of the reaction products grow due to the introduction of sulfate groups without significant destruction of the initial polymer and sulfation products. Sulfation at 95 °C for 20 min yields the products with a higher molecular weight than in the case of sulfation at 85 °C, which is related to an increase in the sulfation rate; however, during the further process occurring under these conditions, sulfation is accompanied by the destruction and the molecular weight of the sulfated polymer decreases. The numerical optimization of arabinogalactan sulfation process has been performed. It has been shown that the optimal parameters for obtaining a product with a high sulfur content are a sulfamic acid amount of 20 mmol per 1 g of arabinogalactan, a process temperature of 85 °C, and a process time of 2.5 h.

Thermal conversion of flax shives was studied in sub- and supercritical ethanol medium at 225 and 250 °C in the presence of the bifunctional catalyst 3% Ru/C. The use of 3% Ru/C catalyst in the process of thermal conversion of flax shives in supercritical ethanol was found to increase the conversion of the shives by 27% and the yield of liquid products by 10%. The use of 3% Ru/C catalyst in sub- and supercritical ethanol led to the destruction of both lignin and cellulose. The degree of delignification in the non-catalytic thermal conversion increased upon transition from subcritical (225 °C) to supercritical (250 °C) conditions. Main monomeric products of the thermal conversion process were guaiacylpropene or guaiacylpropane depending on the process temperature. In the presence of Ru/C catalyst, the molecular weight distribution was shifted towards an increase in the content of monomeric compounds in the liquid products.

Studies have shown that exposure to organophosphates (OPs) is associated with increased frequency of gastrointestinal diseases. In order to evaluate the effect of dysfunction of detoxification system on the development of gastrointestinal pathology, we studied «esterase status» (activity of acetylcholinesterase, butyrylcholinesterase and paraoxonase 1 (PON1)) among workers at the plants providing storage and disposal of OPs. The enzymatic activity of PON1 was significantly increased in individuals who had prolonged direct contact with the OPs. It was shown that among all gastrointestinal diseases included in this study PON1 activity was increased in patients with chronic esophagitis and chronic gastritis as compared to workers without gastrointestinal diseases (p

Flax shive is the main waste (up to 70 wt %) in the production of flax fiber. It represents the lignified parts of the flax stem mainly in the form of small straws. Complex processing of such wastes is a significant problem due to the heterogeneity of the chemical structure of lignin. This article presents the results of reductive catalytic fractionation (RCF) of flax shive in ethanol and isopropanol at elevated temperatures (225–250 °C) in the presence of a bifunctional catalyst (Ru/C) and molecular hydrogen. This provides solvolytic depolymerization of lignin and hemicelluloses presented in flax shive. Catalytic hydrogenation effectively stabilizes the formed lignin intermediates and prevents repolymerization reactions producing the lignin fraction with a high degree of depolymerization. RCF of flax shive produces solid products with a high cellulose content and liquid products consisting mainly of monophenolic compounds. Furthermore, the effect of different characteristics (the ruthenium content, particle size, and support acidity) of the bifunctional catalysts containing ruthenium nanoparticles supported on mesoporous, graphite-like carbon material Sibunit®-4 on the yield and composition of the products of hydrogenation of flax shive in sub- and super-critical ethanol has been studied. Bifunctional catalysts Ru/C used in the RCF of flax shive increase its conversion from 44 to 56 wt % and the yield of monophenols from 1.1 to 10.2 wt % (based on the weight of lignin in the sample). Using the best Ru/C catalyst containing 3% of Ru on oxidized at 400 °C carbon support, the high degree of delignification (up to 79.0%), cellulose yield (up to 67.2 wt %), and monophenols yield (up to 9.5 wt %) have been obtained.

Objective: to estimate contribution of C(-344)T version of aldosterone synthase CYP11B2 gene in risk of metabolic syndrome (MS) and atrial fibrillation (AF) for inhabitants of the Northwest region of Russia. Material and methods: 199 patients with MS, 103 from them with AF and 267 healthy persons. Identification of C-344T gene of CYP11B2 aldosterone sinthase has been performed by means of PCR method with restriction analysis. Results: in MS carriership of TT (-344) genotype met more often than in control: 33.2 % and 24.3 %, respectively (p = 0.04). Carriership of TT (-344) genotype increases risk of MS: OR = 1.54 (95 % CI 1.03-2.32) and was not associated with an increased risk of AF. Conclusion: association of TT(-344) genotype of CYP11B2 gene with risk of metabolic syndrome for inhabitants of the Northwest region ofRussia is revealed.

Apolipoprotein A-I is a key structure protein of antiatherogenic high density lipoproteins (HDL). The aim of the study was to investigate the relationship between (-75)G/A and 83C/T polymorphic variants of apolipoprotein A-I gene (APOA1) and the plasma lipid profile in the population of Saint-Petersburg. Allele T83 of APOA1 gene was found to be associated with the reduced risk of atherosclerosis development among Saint-Petersburg inhabitants. The study demonstrates that allele T83 of APOA1 gene is associated with higher plasma HDL cholesterol levels (p