Search

The detailed experimental studies of the autothermal and steam reforming of model mixtures simulating the composition of commercial diesel fuel were carried out over Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic modules. The components of the diesel surrogates were n-hexadecane, o-xylene, and naphthalene as model compounds of aliphatics, mono-aromatics and diaromatics, respectively. It was shown that low reaction rate of diaromatics steam reforming facilitated increasing concentration of C1–C5 hydrocarbon by-products (primarily ethylene) in the gas phase, as well as formation of polyaromatic compounds by concurrent condensation reaction. These undesirable processes were responsible for increasing catalyst coking. Monoaromatic constituents hadn't any significant effect on the progress of undesirable side-reactions during autothermal and steam reforming of diesel surrogates.

Whole genome sequence from Acinetobacter baumannii isolate Ab-46-1632 reveals a novel KL144 capsular polysaccharide (CPS) biosynthesis gene cluster, which carries genes for d -glucuronic acid ( D -GlcA) and l -rhamnose ( l -Rha) synthesis. The CPS was extracted from Ab-46-1632 and studied by 1H and 13C NMR spectroscopy, including a two-dimensional 1H,13C HMBC experiment and Smith degradation. The CPS was found to have a hexasaccharide repeat unit composed of four l -Rhap residues and one residue each of d -GlcpA and N-acetyl- d -glucosamine ( D -GlcpNAc) consistent with sugar synthesis genes present in KL144. The K144 CPS structure was established and found to be related to those of A. baumannii K55, K74, K85, and K86. A comparison of the corresponding gene clusters to KL144 revealed a number of shared glycosyltransferase genes correlating to shared glycosidic linkages in the structures. One from the enzymes, encoded by only KL144 and KL86, is proposed to be a novel multifunctional rhamnosyltransfaerase likely responsible for synthesis of a shared α- l -Rhap-(1 → 2)-α-L-Rhap-(1 → 3)-L-Rhap trisaccharide fragment in the K144 and K86 structures.

Hydrotreatment of birch wood pyrolysis liquid (PL) was carried out at 350 °C and 6.0 MPa initial hydrogen pressure (RT) for 4 h in a batch autoclave using promising high-loading Ni-based catalysts stabilized by SiO2. Different additives (Cu, Mo, Cr, P) were used to modify the catalysts. The products in liquid organic (OPh) and aqueous phases (AqPh) after PL hydrotreatment were characterized by different methods, such as gas chromatography-mass spectrometry (GC–MS), Fourier-transform infrared (FTIR) spectroscopy, gel permeation chromatography (GPC), etc. Herein, the performance of the catalysts was evaluated by considering the yield and chemical composition of the products (gaseous phase, OPhs, AqPhs, and coke). For the MoCr-containing system, a higher yield of the aqueous phase with low O/C ratio was observed that could be explained by more effective hydrodeoxygenation of water-soluble compounds due to Ni-Mo-Cr solid solutions and coordinatively unsaturated Cry+ and Mox+ sites. P-modified NiCuMoP-SiO2 and NiCrP-SiO2 catalysts reveal more intense CO2 formation very likely due to decarboxylation over Ni3P particles, thus leading to the decrease in the oxygen content in organic phase to 14 wt.%. Fresh reduced catalysts were examined by CO chemisorption, X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM) to provide insights into the structure and morphology. High resistance to coke formation was evidenced according to CHNS analysis of spent samples, besides, the stability of catalysts was additionally assessed by X-ray diffraction.

In this study, new results of comparative research on autothermal reforming(ATR) of biofuels (hydrodeoxygenated biodiesel and long- stored biodiesel) over composite RhSC catalysts (0.24 wt.% Rh supported on structured Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl carrier) were obtained. The impact of fuel chemical composition on the catalyst performance was discussed. Hydrodeoxygenated biodiesel mainly consisted of heptadecane, other normal alkanes and small amounts of alkenes together with a portion of unreacted fatty acid ethers. RhSC exhibited syngas productivity of about 2.5 m3Lcat−1 h−1 (STP) at complete conversion of hydrodeoxygenated biodiesel without considerable by-products formation, at molar ratios O2/C = 0.54, H2O/C = 3, T =750 °C and GHSV =5000 h−1. The catalyst exhibited stable operation and no coke formation for at least 90 h on stream. Biodiesel after nine years storage, which was used in this study, contained methyl esters of saturated and unsaturated fatty acids and a large proportion of polymeric compounds. It was successfully demonstrated that even this aged biodiesel can be converted to synthesis gas over the developed Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl structured catalyst. Further optimization of the catalyst and reaction conditions (higher temperature, lower GHSV, catalyst doping by promoters) is required for reaching efficient reforming of the aged biodiesel. Nevertheless, it was demonstrated that biodiesel and hydrodeoxygenated biodiesel, which combine high energy density and renewability, were very attractive biofuels for fuel cell-based power unit applications.

The Rh/Ce0·75Zr0·25O2–δ-ƞ-Al2O3/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h−1. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h−1), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h−1. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h−1. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H2, CO, CO2), the reaction should be carried out at GHSV = 20,000 h−1. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.

An advanced fabrication technology of reaction-bonded SiC is developed, which includes the preparation of a C/SiC preform by repeated cycles of phenolic resin impregnation and pyrolysis, followed by infiltration with silicon melt. The use of different number of impregnation stages provides control of carbon content in the preform and the corresponding SiC content in final ceramics. The effect of the impregnation number on the preform characteristics and ceramics composition, thermal and mechanical properties are investigated comprehensively. With an increase of impregnation number up to four, SiC fraction in the ceramics enlarges to 93 vol%, thermal conductivity and Young’s modulus increase to 186 W/(m∙K) and 427 GPa respectively, which are superior to most reaction-bonded SiC. Flexural strength (225 MPa) and thermal expansion coefficient (2∙10−6 K-1) are not dependent on the impregnation number. The obtained results provide an opportunity to design and fabricate reaction-bonded SiC ceramics with a given set of properties.

We report a novel family of natural lipoglycopeptides produced by Streptomyces sp. INA-Ac-5812. Two major components of the mixture, named gausemycins A and B, were isolated, and their structures were elucidated. The compounds are cyclic peptides with a unique peptide core and several remarkable structural features, including unusual positions of d-amino acids, lack of the Ca2+ -binding Asp-X-Asp-Gly (DXDG) motif, tyrosine glycosylation with arabinose, presence of 2-amino-4-hydroxy-4-phenylbutyric acid (Ahpb) and chlorinated kynurenine (ClKyn), and N-acylation of the ornithine side chain. Gausemycins have pronounced activity against Gram-positive bacteria. Mechanistic studies highlight significant differences compared to known glyco- and lipopeptides. Gausemycins exhibit only slight Ca2+ -dependence of activity and induce no pore formation at low concentrations. Moreover, there is no detectable accumulation of cell wall biosynthesis precursors under treatment with gausemycins.

The specific features of the sorption activity of silver nanoparticles (AgNPs) on biodegradable polymers of natural (collagen) and artificial (polyamide 6.6) origin have been established. The ability has been demonstrated for resorbable fibers of natural origin to more actively adsorb AgNPs with sizes from 1 to 10 nm during the first hour and stronger hold them on the surface during the first day of exposure to argogel. During the first hour of incubation of these polymers in a gel composition containing AgNPs obtained by the method of cavitation-diffusion photochemical reduction, their higher sorption activity was revealed in the size range from 1 to 10 nm in relation to the polyfilament synthetic material. After 24 h of exposure, a significant increase in the fraction of small AgNPs already on collagen fibers was observed, which was also accompanied by a significantly lower (19 times) content of AgNPs with a diameter above 40 nm on the catgut.

In this work, it has been shown that aliphatic C–H oxidations by bioinspired catalyst systems Mn aminopyridine complex/H2O2/carboxylic acid in acetonitrile afford predominantly a mixture of the cor...

A capsular polysaccharide was isolated from cells of opportunistic bacterial pathogen Acinetobacter baumannii strain MAR 55–66. According to carbohydrate analysis and 1H and 13C NMR spectroscopy, it is composed of heptasaccharide repeating units, which include five l-rhamnose (Rha) residues and one residue each of d-glucuronic acid (GlcA) and N-acetyl-d-glucosamine (GlcNAc). For structural analysis of this polysaccharide, the Smith degradation, depolymerization with a recombinant endo-glycosidase from a specific bacteriophage, and selective solvolysis with CF3CO2H were applied. The two last methods resulted in formation of the same linear heptasaccharide, which was subjected to the following chemical modifications: borohydride reduction, β-elimination with alkali, and partial acid hydrolysis. The resulting oligosaccharides were isolated by gel-permeation chromatography, and their structures were established by 1H and 13C NMR spectroscopy including 2D 1H-1H and 1H-13C NMR correlation experiments, as well as high-resolution electrospray ionization mass spectrometry. Based on the data obtained, the structure of the branched heptasaccharide repeating unit containing three Rha residues and one GlcNAc residue in the main chain along with two Rha residues and one GlcA residue in the side chain was established. The polysaccharide studied belongs to a group of structurally similar capsular polysaccharides of A. baumannii, which are built up of branched oligosaccharide repeating units that include four or five l-Rha residues and one residue each of d-GlcA and d-GlcNAc.

The synthesis of a vicinally branched trisaccharide composed of two d-galactofuranoside residues attached viaβ-(1 → 2)- and β-(1 → 3)-linkages to the α-d-galactopyranoside unit has been performed for the first time. The reported trisaccharide represents the galactoxylomannan moiety first described in 2017, which is the capsular polysaccharide of the opportunistic fungal pathogen Cryptococcus neoformans responsible for life-threatening infections in immunocompromised patients. The NMR-data reported here for the synthetic model trisaccharide are in good agreement with the previously assessed structure of galactoxylomannan and are useful for structural analysis of related polysaccharides. The target trisaccharide as well as the constituent disaccharides were analyzed by a combination of computational and NMR methods to demonstrate good convergence of the theoretical and experimental results. The results suggest that the furanoside ring conformation may strongly depend on the aglycon structure. The reported conformational tendencies are important for further analysis of carbohydrate-protein interaction, which is critical for the host response toward C. neoformans infection.

The composition and structure of the cell wall glycopolymers of Paenarthrobacter species (P. aurescens VKM Ac-1105T, P. histidinovorans VKM Ac-1978T, and P. nicotinovorans VKM Ac-1988T, previously assigned to the genus Arthrobacter) were studied. All strains under study were found to contain a neutral polysaccharide, (1 → 6)-linked β-D-galactofuranan with the 2,3-diacetamido-2,3-dideoxy-α-glucopyranose (α-GlcpNAc3NAc) residues that glycosylate most of the hydroxyl groups at C-2 of galactofuranose. Acid hydrolysates of the cell walls contained galactose, glucose, arabinose, glucosamine, and galactosamine. The polysaccharide structure was established by chemical and NMR spectroscopic methods. The galactofuranan structure has not been previously described for representatives of other Actinobacteria genera. The data obtained expand our understanding of the chemical structure of microbial cell walls and may be used in taxonomy of actinobacteria, especially to differentiate at the phenotype level and to justify the description of new genera in the family Micrococcaceae.

KL55, KL74, and KL85 capsular polysaccharide (CPS) biosynthesis loci in Acinetobacter baumannii BAL_204, BAL_309, and LUH5543 genomes, respectively, are related and each contains genes for l -Rhap and d -GlcpA synthesis. The CPSs were isolated and studied by sugar analysis, Smith degradation, and 1H and 13C NMR spectroscopy. The K55 and K74 CPSs are built up of branched octasaccharide repeats (K units) containing one residue each of d -GlcpA and d -GlcpNAc and six residues of l -Rhap. The K55 unit differs from the K74 unit in the linkage between D-GlcpA and an l -Rhap residue in the K unit (1 → 3 versus 1 → 2) and linkage between K units. However, most K units in the isolated K74 CPS were modified by β-elimination of a side-chain α- l -Rhap-(1 → 3)-α- l -Rhap disaccharide from position 4 of GlcA to give 4-deoxy- l -threo-hex-4-enuronic acid (1:~3 ratio of intact and modified units). The K85 CPS has a branched heptasaccharide K unit similar to the K74 unit but with one fewer α- l -Rhap residue in the side chain. In contrast to previous findings on A. baumannii CPSs, each K locus includes fewer glycosyltransferase (Gtr) genes than the number required to form all linkages in the K units. Hence, one Gtr appears to be multifunctional catalysing formation of two 1 → 2 and one 1 → 3 linkages between the l -Rha residues.

Lipopolysaccharide (LPS) of a new Pantoea agglomerans strain P324 was studied by chemical and biological methods. Mild acid hydrolysis of the LPS resulted in lipid A and O-specific polysaccharide (OPS) fractions. Studies by negative-ion mode HR ESI mass spectrometry showed heterogeneity of the lipid A, the major form being a hexa-acylated derivative containing biphosphorylated GlcN disaccharide, four 14:0 (3-OH), one 18:0, and one 12:0 residues. The following structure of the OPS was elucidated by chemical, NMR and computational methods: →3)-α-L-Rhap-(1→4)-α-D-Glcp-(1→. The P. agglomerans P324 LPS showed medium level of toxic and pyrogenic activities. Structural components of the LPS exhibited varying effects on the activity of Bacillus peptidases. Thus, the OPS and lipid A played a significant role in the hydrolysis of fibrin by Bacillus proteases but did not affect the activity of protease 2 of B. thuringiensis IMV B-7465 and protease 1 of B. thuringiensis IMV B-7324. Hydrolysis of elastin was intensified by core oligosaccharide and lipid A. Hydrolysis of collagen in the presence of the isolated fractions was accompanied by the inhibition of activity as compared to the native LPS.

The liquid fraction of tire pyrolysis products was comprehensively analyzed by gas chromatography–mass spectrometry and two-dimensional gas chromatography. The direct (nonpolar–polar) и and inverse (polar–nonpolar) column combinations were used. The inverse combination allows efficient separation of alkanes and alkenes. Aliphatic hydrocarbons constitute no more than 24 wt % of the liquid fraction, with the remainder being aromatic, mainly monoaromatic, compounds. The sulfur content of the liquid fraction is about 0.7 wt %; sulfur is mainly present in the form of thiophene derivatives.

A denitrifying bacterium Pseudomonas veronii A-6-5 was isolated from a deep aquifer contaminated with nitrates and uranium. The O-polysaccharide (OPS) was isolated by mild acid degradation of the lipopolysaccharide of P. veronii A-6-5 and studied using sugar analysis and 1D and 2D 1H and 13C NMR spectroscopy. The trisaccharide O-repeating unit was found to have the following structure: [Formula: see text] [Formula: see text] where Hb is 3-hydroxybutanoyl. The genome of P. veronii A-6-5 was sequenced and a respective OPS gene cluster was identified. Functions of the proteins encoded in the gene cluster, including the enzymes involved in the O-polysaccharide biosynthesis and glycosyl transferases, were putatively assigned by comparison with available database sequences. Formation of a new coordination bond between uranyl and the O-polysaccharide from P. veronii A-6-5 was demonstrated using FTIR spectroscopy; it may affect uranyl migration in the groundwaters due to its immobilization on microbial biofilms. Applied importance of this work is that the structure of the O-polysaccharide of a strain isolated from uranium-contaminated groundwater was determined and the character of interaction between the polysaccharide and the uranyl ion was established. The data obtained are of importance for development of the biotechnologies for treatment of uranium-contaminated groundwater and activated sludge.

The serological classification scheme of the opportunistic Proteus bacilli includes a number of Proteus penneri strains. The tested P. penneri 4034-85 strain turned out to be serologically distinguished in ELISA and Western blotting. The O-polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of this strain and studied by sugar and methylation analyses and dephosphorylation along with 1H and 13C NMR spectroscopy, including 2D 1H,1H COSY, TOCSY, ROESY, 1H,13C HSQC, HMBC, and HSQC-TOCSY experiments, The O-polysaccharide was found to have a linear repeating unit containing glycerol 1-phosphate and two residues each of Gal and GlcNAc. The following O-polysaccharide structure was established, which, to our knowledge, is unique among known bacterial polysaccharide structures.

Catalytic autothermal reforming (ATR) of a number of hydrocarbon fuels was studied over composite RhCZ-S catalyst (0.24 wt% Rh supported on structured Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl carrier). Iso-octane and n-hexadecane as model compounds of gasoline and diesel fuel, respectively, showed similar properties in ATR process, indicating weak influence of molecular weight and branching degree of liquid alkanes on catalyst performance. Biodiesel ATR characteristics were similar to those of n-hexadecane ATR, as the utilized biodiesel predominantly contained alkanes, being products of fatty acid tail fragments hydrogenation. Even in the case of gasoline ATR, sufficient amount of monoaromatics did not influence a lot on the catalyst performance. Diesel ATR showed rather different situation: the catalyst tended to lose activity due to coking, and incomplete fuel conversion was observed. Analysis of unreacted fuel revealed bi- and polyaromatic compounds (mainly naphtalenes and antracenes) were difficult to convert.

Lipopolysaccharide (LPS) of Ochrobactrum cytisi IPA7.2, a bacterium isolated from the roots of Solanum tuberosum L., was extracted from dry bacterial cells and chemically characterized. The O-specific polysaccharide was obtained by mild acid hydrolysis of the LPS and studied by sugar analysis and 1H and 13C NMR spectroscopy, including 1H,1H COSY, 1H,1H TOCSY, 1H,1H ROESY, 1H,13C HSQC, and 1H,13C HMBC experiments. The polysaccharide was linear and consisted of trisaccharide repeating units of the following structure: Download : Download high-res image (36KB) Download : Download full-size image A putative O-antigen gene cluster of O. cytisi IPA7.2 was identified and found to be consistent with the O-specific polysaccharide structure. The LPS of Ochrobactrum cytisi IPA7.2 promoted the growth of potato microplants in vitro.

Highly polar capillary columns with liquid stationary phases (LSPs) based on dicationic quinolinium ionic liquids (ILs) are studied. These ILs are characterized by high polarity and strong dipole–dipole and π–π interactions in a linear free energy relationship model, and can separate complex mixtures (containing aromatic hydrocarbons, phenols, catechols, and hydroquinones) that are problematic for columns with conventional LSPs. It is shown that the high thermal stability of dicationic quinolinium ILs allows to perform chromatographic separation up to a temperature of at least 300°C, which is impossible for any conventional polar and highly polar LSPs. The thermal stability of the studied LSPs is virtually independent of the structure of a dicationic quinolinium IL and the length of an alkyl bridge.

Two stable operating mode, which were called “jet” and “bell” mode, were observed for Hall thrusters. These modes are distinguished from each other by the shape of the plasma plume and the anode efficiency. This paper presents the results of the measurements of the high-frequency floating potential oscillations using a Langmuir probe and of the relative erosion rate of boron nitride ceramic (BN) insulators using passive optical diagnostics in the “jet” and “bell” modes. The studies were carried out for the Hall thruster with the diameter of the middle line of 77 mm and power up to 2.5 kW.

Two glycosyl 1-phosphate polymers containing monoglycosyl 1-phosphate, -6)-α-D-Glcp-(1-P., and diglycosyl 1-phosphate, -6)-α-D-GalpNAc-(1→6)-α-D-GlcpNAc-(1-P., in the repeating unit were identified in the cell wall of Glutamicibacter protophormiae VKM Ac-2104T (formerly, Arthrobacter protophormiae). The structures of these polymers were described for the first time in prokaryotes. Teichulosonic acid, the third identified polymer, with 3-deoxy-D-glycero-α-D-galacto-non-2-ulopyranosonic acid (Kdn) and β-D-glucopyranose residues in the main chain, →6)-β-D-Glcp-(1→8)-α-Kdn-(2→, has been previously detected in a number of actinobacteria. The structures of these glycopolymers were established based on the results of chemical analysis and one-dimensional 1H, 13C, and 31P NMR spectroscopy using two-dimensional homonuclear (1H,1H COZY, TOCSY, ROESY) and heteronuclear (1H,13C HSQC, HSQC-TOCSY, HMBC, and 1H,31P HMBC) techniques.

The structures of three cell wall glycopolymers of the phytopathogen Rathayibacter tritici VKM Ac-1603T (family Microbacteriaceae, order Micrococcales, class Actinobacteria) were established by chemical methods and NMR spectroscopy. Polymer 1 is a branched rhamnomannan with the repeating unit →3)-α-[β-D-Xylp-(1→2)]-D-Manp-(1→2)-α-D-Rhap-(1→3)-α-D-Manp-(1→2)-α-D-Rhap-(1→; polymer 2 is a linear rhamnomannan with the repeating unit →2)-α-D-Manp-(1→2)-α-D-Rhap-(1→3)-α-D-Manp-(1→2)-α-D-Rhap-(1→; polymer 3 is a branched teichuronic acid containing monosaccharide residues GlcA, Gal, Man, and Glc at a 1:1:1:5 ratio (see the text for the structures). It has been demonstrated that representatives of four Rathayibacter species studied to date (R. tritici VKM Ac-1603T, R. iranicus VKM Ac-1602T, R. toxicus VKM Ac-1600 and “Rathayibacter tanaceti” VKM Ac-2596) contain differing patterns of phosphate-free glycopolymers. At the same time, the above Rathayibacter strains have a common property — the presence of rhamnomannans with D-rhamnose. These rhamnomannans may be linear or branched and differing in the positions of glycosidic bonds and side substituents. The presence in the cell wall of rhamnomannans with D-rhamnose may serve as useful chemotaxonomic marker of the genus Rathayibacter.

Lipopolysaccharide (LPS), localized in the outer leaflet of the outer membrane, serves as the major surface component of the Gram-negative bacterial cell envelope responsible for the activation of the host’s innate immune system. Variations of the LPS structure utilized by Gram-negative bacteria promote survival by providing resistance to components of the innate immune system and preventing recognition by TLR4. This review summarizes studies of the biosynthesis of Yersinia pseudotuberculosis complex LPSs, and the roles of their structural components in molecular mechanisms of yersiniae pathogenesis and immunogenesis.

The K17 capsular polysaccharide (CPS) produced by Acinetobacter baumannii G7, which carries the KL17 configuration at the capsule biosynthesis locus, was isolated and studied by chemical methods along with one- and two-dimensional 1H and 13C NMR spectroscopy. Selective cleavage of the glycosidic linkage of a 2,4-diacetamido-2,4,6-trideoxy- d -glucose ( d -QuiNAc4NAc) residue by (i) trifluoroacetic acid solvolysis or (ii) alkaline β-elimination (NaOH-NaBH4) of the 4-linked D-alanine amide of a 2-acetamido-2-deoxy- d -galacturonic acid residue ( d -GalNAcA6DAla) yielded trisaccharides that were isolated by Fractogel TSK HW-40 gel-permeation chromatography and identified by using NMR spectroscopy and high-resolution electrospray ionization mass spectrometry. The following structure was established for the trisaccharide repeat (K unit) of the CPS: →4)- α -d -GalpNAcA6 d Ala-(1 → 4)- α -d -GalpNAcA-(1 → 3)- β- d -QuipNAc4NAc-(1 → . The presence of the itrA1 gene coding for the initial glycosylphosphotransferase in the KL17 gene cluster established the first sugar of the K unit as d -QuipNAc4NAc. KL17 includes genes for three transferases that had been annotated previously as glycosyltransferases (Gtrs). As only two Gtrs are required for the K17 structure and one d -GalpNAcA residue is modified by a d -alanine amide, these assignments were re-assessed. One transferase was found to belong to the ATPgrasp_TupA protein family that includes d -alanine- d -alanine ligases, and thus was renamed Alt1 ( al anine t ransferase). Alt1 represents a novel family that amidate the carboxyl group of d -GalpNAcA or d -GalpA.

Capsular polysaccharide (CPS), isolated from Acinetobacter baumannii LUH5549 carrying the KL32 capsule biosynthesis gene cluster, was studied by sugar analysis, Smith degradation, and one- and two-dimensional 1H and 13C NMR spectroscopy. The K32 CPS was found to be composed of branched pentasaccharide repeats (K units) containing two residues of β-D-GalpNAc and one residue of β-D-GlcpA (β-D-glucuronic acid) in the main chain and one residue each of β-D-Glcp and α-D-GlcpNAc in the disaccharide side chain. Consistent with the established CPS structure, the KL32 gene cluster includes genes for a UDP-glucose 6-dehydrogenase (Ugd3) responsible for D-GlcA synthesis and four glycosyltransferases that were assigned to specific linkages. Genes encoding an acetyltransferase and an unknown protein product were not involved in CPS biosynthesis. Whilst the KL32 gene cluster has previously been found in the global clone 2 (GC2) lineage, LUH5549 belongs to the sequence type ST354, thus demonstrating horizontal gene transfer between these lineages.

O antigen is a polysaccharide chain of a lipopolysaccharide on the outer membrane of Gram-negative bacteria. O-antigen-based serotyping and molecular typing are widely used for epidemiological and surveillance purposes. Two polysaccharides were isolated by Sephadex G-50 gel-permeation chromatography following mild acid degradation of the lipopolysaccharide of Escherichia albertii EA046 assigned to serotype O9. The polysaccharide eluted first was considered as the O-antigen. It was composed of tetrasaccharide repeating units containing two residues of d -Man and one residue each of d -Gal and d -GlcNAc as well as glycerol phosphate. It had the following unique structure which was established by NMR spectroscopy applied to the initial and dephosphorylated polysaccharides: The polysaccharide eluted from the gel second was identified as a mannan with a → 3)-β- d -Manp-(1 → 2)-α- d -Manp-(1 → 2)-α- d -Manp-(1 → trisaccharide repeating unit. In E. albertii EA046, two polysaccharide gene clusters were found at a chromosomal locus flanked by the conserved galF gene and the histidine synthesis operon (his). They were suggested to drive the biosynthesis of the O-antigen by the Wzy/Wzy-dependent pathway and the mannan by the Wzm/Wzt-dependent pathway. The mannan shares the structure and gene cluster with a polysaccharide isolated earlier from the lipopolysaccharide of Escherichia coli O8.

The present work was devoted to the investigation of highly polar capillary columns with stationary phases based on ionic liquids (IL) with cyanopropyl-containing cations. Five imidazole and quinolinium cyanopropyl-containing ILs have been studied. Their high polarity has been demonstrated. The measured Abraham selectivity has demonstrated an increase in specific types of interaction comparing to noncyanopropyl analogs. High thermal stability up to 300°C has been shown, especially for dicationic ILs. Examples of separation for one-dimensional and two-dimensional gas chromatography have been shown.

Some O-polysaccharides (O-antigens) of the lipopolysaccharides of bacteria of the genus Cronobacter contain 3-deoxy-d-manno-oct-2-ulosonic acid. O-Polysaccharides of Cronobacter turicensis G3874 and Cronobacter muytjensii G3886 containing this unit were found to be structurally related to each other and to those of Cronobacter dublinensis HPB 3169 and Cronobacter sakazakii G2706 (serotype O5) studied earlier. The O-polysaccharides differ in the N-acyl group on a 3-amino-3,6-dideoxy-d-glucose residue [(R)-3-hydroxybutanoyl vs. acetyl] or in the presence or absence of the O-acetyl group on an l-rhamnose residue only. Structures of the new O-antigens were established by chemical methods and by 1D and 2D 1H and 13C NMR spectroscopy applied to polysaccharides and pentasaccharides obtained by mild alkaline O-deacylation and mild acid hydrolysis of the isolated lipopolysaccharides, respectively.

The work provides the study of quinolinium ionic liquids (ILs)—a new class of stationary phases for capillary gas chromatography (GC). Quinolinium ILs were shown to have new attractive properties. ...

Mild acid degradation of the lipopolysaccharide of Yersinia kristensenii C-134 afforded a glycerol teichoic acid-like O-polysaccharide, which was studied by sugar analysis, O-deacetylation and dephosphorylation along with 1D and 2D NMR spectroscopy. The following structure of the O-polysaccharide was established: This structure is related to those of other Y. kristensenii O-polysaccharides studied earlier. The O-antigen gene cluster of Y. kristensenii С-134 was analyzed and found to be consistent with the O-polysaccharide structure established.

The absorption activity of silver nanoparticles (AgNPs) on the surface of fibers of natural and artificial origin is estimated. In addition, it is determined that the sorption activity of natural or artificial fibers with respect to silver nanoparticles depends on their size, fabrication method, and properties of the gelling agent. It is found that the highest absorption of silver nanoparticles is observed when using natural silk fibers, which possess a significantly higher activity as compared with an artificial fiber (fluoroex).

It has been established that indicators of the intensity of chemiluminescence in the native and muscle cellized tissues of rat muscular organs, as well as in their decellularized matrices, can serve as one of the express criteria that allows, along with ultrastructural analysis, to quantify the viability of cell structures in biological samples of the diaphragm.

In the course of developing an assay to identify genes responsible for antibiotic resistance in gram-negative bacteria, it has been found that standard (not DNA-free) Taq DNA polymerases were contaminated with blaTEM gene fragments that varied in length and quantities. The complete blaTEM gene sequence was either absent or was detected in infinitesimal amounts. We developed an approach to avoid false-positive findings caused by contaminating blaTEM gene sequences in conventional polymerases. The method is based on selection of a target sequence to be detected within the blaTEM gene in such a way that the chosen sequence is amplified with primers incapable of amplifying contaminating DNA sequences of the polymerase.

O-specific polysaccharide was obtained by mild acid hydrolysis of the lipopolysaccharide of plant-growth-promoting rhizobacteria Azospirillum doebereinerae GSF71T and studied by sugar analysis along with 1H and 13C NMR spectroscopy, including 2D 1H,1H COSY, TOCSY, ROESY, 1H,13C HSQC, and HMBC experiments. It was established that the polysaccharide is linear and consists of tetrasaccharide repeating units with the following structure.

Lipopolysaccharide (LPS) was extracted from dry bacterial cells of plant-growth-promoting bacterium Azospirillum brasilense SR8 (IBPPM 5). The O-specific polysaccharide (OPS) was obtained by mild acid hydrolysis of the lipopolysaccharide and studied by sugar analysis, 1H and 13C NMR spectroscopy, including 1H,1H COSY, TOCSY, ROESY, and 1H,13C HSQC and HMBC experiments, computational NMR-based structure analysis, and Smith degradation. The OPS was shown to contain two types of repeating units of the following structure: Both OPS structures are present in A. brasilense 54, from which structure 1 has been reported earlier (Fedonenko et al., 2011), whereas to our knowledge structure 2 has not been hitherto found in bacterial saccharides. Treatment of wheat seedling roots with LPS of A. brasilense SR8 increased the number of root hair deformations as compared to seedlings grown without LPS, but had no effect on adsorption of the bacteria to the root surface. A. brasilense SR8 was able to utilize LPS of several structurally related Azospirillum strains.

The pectins were isolated from sterile stems of E. arvense (EA, yield 5.9%) and E. sylvaticum (ES, yield 4.8%) (Equisetaceae) using ammonium oxalate extraction after preliminary treatment with dilute HCl (рH 4.0). The pectins possessed high molecular weight (Mw, 340–360 kDa), high GalA content (ca. 85%), low degrees of methyl-esterification (14–16%) and acetylation (3–8%). NMR analysis indicated extensive regions of partially methyl-etherified and 3-O-acetylated HG and minor regions of low branched RG in the fragment isolated after hydrolysis of pectin EA by pectinase. Pectin EA produced a higher viscosity solution, formed a stronger and more rigid ionotropic hydrogel than pectin ES. The pectins scavenged DPPH and hydroxyl radicals, but not the superoxide radical and hydrogen peroxide. Phenolic compounds (0.11 and 0.23%) associated with polysaccharide moieties were apparently responsible for the differences in the anti-DPPH scavenging activity of pectins EA and ES (63 and 49%). The findings suggested that pectin from E. arvense should be more perspective than pectin from E. sylvaticum on their use as components of wound healing remedies.

Whole genome sequences of two Acinetobacter baumannii clinical isolates, 48-1789 and MAR24, revealed that they carry the KL106 and KL112 capsular polysaccharide (CPS) biosynthesis gene clusters, respectively, at the chromosomal K locus. The KL106 and KL112 gene clusters are related to the previously described KL11 and KL83 gene clusters, sharing genes for the synthesis of l-rhamnose (l-Rhap) and 6-deoxy-l-talose (l-6dTalp). CPS material isolated from 48-1789 and MAR24 was studied by sugar analysis and Smith degradation along with one- and two-dimensional 1H and 13C NMR spectroscopy. The structures of K106 and K112 oligosaccharide repeats (K units) l-6dTalp-(1→3)-D-GlcpNAc tetrasaccharide fragment share the responsible genes in the respective gene clusters. The K106 and K83 CPSs also have the same linkage between K units. The KL112 cluster includes an additional glycosyltransferase gene, Gtr183, and the K112 unit includes α l-Rhap side chain that is not found in the K106 structure. K112 further differs in the linkage between K units formed by the Wzy polymerase, and a different wzy gene is found in KL112. However, though both KL106 and KL112 share the atr8 acetyltransferase gene with KL83, only K83 is acetylated.

The KL26 gene cluster responsible for the synthesis of the K26 capsular polysaccharide (CPS) of Acinetobacter baumannii includes rmlBDAC genes for l -rhamnose ( l -Rhap) synthesis, tle to generate 6-deoxy- l -talose ( l -6dTalp) from l -Rhap, and a manC gene for D -mannose ( D -Manp) that is rare in Acinetobacter CPS. K26 CPS material was isolated from A. baumannii isolate KZ-1098, and studied by sugar analysis, Smith degradation, and one and two-dimensional 1H and 13C NMR spectroscopy before and after O-deacetylation with aqueous ammonia. The following structure of the branched hexasaccharide repeating unit of the CPS was established: → 2 ) − β − D − Man p − 1 → 4 − β − D − Glc p − 1 → 3 − α − L − 6 dTal p − 1 → 3 − β − D − Glc p NAc − ( 1 → 3 ↑ 1 4 │ Ac α − L − Rha p − 2 ← 1 − α − D − Glc p The structural depolymerase of phage vB_AbaP_APK26 cleaved selectively the β-GlcpNAc-(1 → 2)-α-Manp linkage in the K26 CPS formed by WzyK26 to give monomer, dimer, and trimer of the CPS repeating unit, which were characterized by high-resolution electrospray ionization mass spectrometry as well as 1H and 13C NMR spectroscopy. The wzyK26 gene responsible for this linkage and the manC gene were only found in six A. baumannii genomes carrying KL26 and one carrying the novel KL148 gene cluster, indicating the rare occurrence of β-GlcpNAc-(1 → 2)-α-Manp in A. baumannii CPS structures. However, K26 shares a β- d -Glcp-(1 → 3)-α- l -6dTalp-(1 → 3)-β- d -GlcpNAc trisaccharide fragment with a group of related A. baumannii CPSs that have varying patterns of acetylation of l -6dTalp.

An O-specific polysaccharide (OPS) was isolated from the lipopolysaccharide of Pseudomonas mediterranea strain C5P1rad1, the causal agents of tomato pith necrosis and Chrysanthemum stem rot, and studied by one- and two-dimensional 1 H and 13 C NMR spectroscopy. The following structure of the trisaccharide repeating unit of the OPS was established, which, to our knowledge, is unique among the known bacterial polysaccharide structures: →4)-β- d -Man p NAc3NAcA-(1 → 4)-β- d -Man p NAc3NAcA-(1 → 3)-α- d -Qui p NAc4NAc-(1→ where QuiNAc4NAc and ManNAc3NAcA indicate 2,4-diacetamido-2,4,6-trideoxyglucose and 2,3-diacetamido-2,3-dideoxymannuronic acid, respectively. Pre-treatment of leaves with LPS or OPS preparations at 250 and 50 μg mL −1 did not inhibit development of a hypersensitivity reaction induced by P. mediterranea C5P1rad1 on tobacco, tomato and chrysanthemum plants. The same preparations at 250 μg mL −1 partially prevented elicitation of the hypersensitivity reaction by Pseudomonas syringae KVPT7RC on chrysanthemum but not tobacco and tomato.

Acinetobacter baumannii, a nonfermentative, Gram-negative, aerobic bacterium, is one of the most significant nosocomial pathogens. The pathogenicity of A. baumannii is based on the cooperative action of many factors, one of them being the production of capsular polysaccharides (CPSs) that surround bacterial cells with a thick protective layer., Acinetobacter baumannii is one of the most clinically important nosocomial pathogens. The World Health Organization refers it to its “critical priority” category to develop new strategies for effective therapy. This microorganism is capable of producing structurally diverse capsular polysaccharides (CPSs), which serve as primary receptors for A. baumannii bacteriophages carrying polysaccharide-degrading enzymes. In this study, eight novel bacterial viruses that specifically infect A. baumannii strains belonging to K2/K93, K32, K37, K44, K48, K87, K89, and K116 capsular types were isolated and characterized. The overall genomic architecture demonstrated that these viruses are representatives of the Friunavirus genus of the family Autographiviridae. The linear double-stranded DNA phage genomes of 41,105 to 42,402 bp share high nucleotide sequence identity, except for genes encoding structural depolymerases or tailspikes, which determine the host specificity. Deletion mutants lacking N-terminal domains of tailspike proteins were cloned, expressed, and purified. The structurally defined CPSs of the phage bacterial hosts were cleaved with the specific recombinant depolymerases, and the resultant oligosaccharides that corresponded to monomers or/and dimers of the CPS repeats (K units) were isolated. Structures of the derived oligosaccharides were established by nuclear magnetic resonance spectroscopy and high-resolution electrospray ionization mass spectrometry. The data obtained showed that all depolymerases studied were glycosidases that specifically cleave the A. baumannii CPSs by the hydrolytic mechanism, in most cases, by the linkage between the K units. IMPORTANCE Acinetobacter baumannii, a nonfermentative, Gram-negative, aerobic bacterium, is one of the most significant nosocomial pathogens. The pathogenicity of A. baumannii is based on the cooperative action of many factors, one of them being the production of capsular polysaccharides (CPSs) that surround bacterial cells with a thick protective layer. Polymorphism of the chromosomal capsule loci is responsible for the observed high structural diversity of the CPSs. In this study, we describe eight novel lytic phages which have different tailspike depolymerases (TSDs) determining the interaction of the viruses with corresponding A. baumannii capsular types (K types). Moreover, we elucidate the structures of oligosaccharide products obtained by cleavage of the CPSs by the recombinant depolymerases. We believe that as the TSDs determine phage specificity, the diversity of their structures should be taken into consideration as selection criteria for inclusion of certain phage candidates in the cocktail designed to control A. baumannii with different K types.

Non-edible cellulose-containing biomass is a promising and abundant feedstock for simple sugar production. This study presents the results of different cellulose-containing materials (CCM) hydrolysis experiments with P. verruculosum enzyme complexes in laboratory conditions. Among the non-pretreated substrates, only a few had a relatively high convertibility—soy bean husks (31%) and sugar beat pulp (20%)—while wheat straw, oat husks, sunflower peals, and corn stalks had a low convertibility of 3% to 12%. This indicates that a major part of CCM needs pretreatment. Steam-exploded (with Ca(OH)2) soy bean and oat husks (76% and 58%), fine ball-milled aspen wood and nitric acid-pretreated aspen wood (62% and 78%), and steam-exploded (with sulfuric acid) corn stalks (55%) had a high convertibility. Woody biomass pretreated with pulp and paper mills also had a high convertibility (56–78%)—e.g., never dried kraft hardwood and softwood pulp (both bleached and unbleached). These results demonstrate that effective cellulose-containing material processing into simple sugars is possible. Simple sugars derived from CCM using P. verruculosum preparation are a promising feedstock for the microbiological production of biofuels (bioethanol and biobutanol), aminoacids, and organic acids (e.g., lactic acid for polylactic acid production).

The cell wall of Clavibacter michiganensis subsp. michiganensis VKM Ас-1403Т (family Microbacteriaceae, class Actinobacteria) contains two polysaccharides. The first one is neutral (1 → 6) linked galactofuranan in which every second galactofuranose residue in the main chain substituted at position 3 by side trisaccharide, β-D-GlcpNAc-(1 → 3)-α-L-Rhap-(1 → 2)-α-D-Fucp-(1 →. The second polymer is pyruvylated galactomannan with the repeating unit, →3)-α-D-Galp-(1 → 3)-α-D-[4,6-S-Pyr]-Manp-(1 → 3)-α-D-Manp-(1 →. The cell wall glycopolymer structures were established by chemical and NMR spectroscopic methods. The obtained results provide new data on the cell wall composition of plant pathogenic species of the genus Clavibacter and can promote understanding the molecular mechanisms involved in colonization and infection of plants.

We report a novel family of natural lipoglycopeptides produced by Streptomyces sp. INA-Ac-5812. Two major components of the mixture, named gausemycins A and B, were isolated, and their structures were elucidated. The compounds are cyclic peptides with a unique peptide core and several remarkable structural features, including unusual positions of D-amino acids, lack of the Ca2+ -binding Asp-X-Asp-Gly (DXDG) motif, tyrosine glycosylation with arabinose, presence of 2-amino-4-hydroxy-4- phenylbutyric acid (Ahpb) and chlorinated kynurenine (ClKyn), N-acylation of the ornithine side chain. These major components of the peptide antibiotic family have pronounced activity against Gram-positive bacteria. The mechanism of action of gausemycins was explored by a number of methods, showing significant differences compared to glycopeptides and related lipopeptides. For example, gausemycins exhibit no Ca2+ -dependence of antimicrobial activity and induce no pore formation at low concentrations. Moreover, there is no detectable accumulation of cell wall biosynthesis precursors under treatment with gausemycins.

Aerobic gram-negative bacterium Acinetobacter baumannii has recently become one of the most relevant pathogens associated with hospital-acquired infections worldwide. A. baumannii produces a capsule around the cell, which represents a thick viscous layer of structurally variable capsular polysaccharide (CPS). The capsule protects the bacteria against unfavorable environmental factors and biological systems, including bacteriophages and host immune system. Many A. baumannii phages have structural depolymerases (tailspikes) that specifically recognize and digest bacterial CPS. In this work, we studied the interaction of tailspike proteins of four lytic depolymerase-carrying phages with A. baumannii CPS. Depolymerases of three bacteriophages (Fri1, AS12, and BS46) were identified as specific glycosidases that cleave the CPS of A. baumannii strains 28, 1432, and B05, respectively, by the hydrolytic mechanism. The gp54 depolymerase from bacteriophage AP22 was characterized as a polysaccharide lyase that cleaves the CPS of A. baumannii strain 1053 by β-elimination at hexuronic acid (ManNAcA) residues.

The phase complex is found and the chemical interaction is studied in the composition polyhedra of a quinary reciprocal system based on halides, metavanadates, and molybdates of lithium and potassium. The compositions of low-melting mixtures were determined for the possible use as electrolytes for chemical power sources and heat-storage materials.