Vadim B. Krylov's research while affiliated with N. D. Zelinsky Institute of Organic Chemistry and other places

Publications (77)

Article
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A method was developed for the conjugation of aminopropyl spacer-bearing carbohydrates with epoxy groups on the crown of nanoparticles consisting of a copolymer of N-vinyl-2-pyrrolidone and allyl glycidyl ether in basic buffer, opening prospects for the design of vectorized nanocomposite drug forms. A conjugate of the above copolymer and trisacchar...
Article
A biosensor based on the analyte-induced aggregation of functionalized nanoparticles recorded using two optical signals of different physical nature is developed. The hydrodynamic diameter of the conjugates, measured by the dynamic light scattering (DLS) method, and the counting rate of scattered light pulses, proportional to the elastic static sca...
Article
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The polysaccharide mannan is the main surface antigen of the cell wall of Candida fungi, playing an important role in the pathogenesis of diseases caused by these mycopathogens. Mannan has a complex, comb-like structure and includes a variety of structural units, with their combination varying depending on the Candida species and strain. Glucomanna...
Article
The COVID-19 pandemic has revealed the new forms of invasive fungal infections. Without timely diagnosis and treatment, mortality reaches 100%. We analyzed 31 observed cases of invasive mucormycosis and aspergillosis in patients with COVID-19 to identify risk factors, the time sequence of the onset of clinical symptoms, and diagnostic features. Maj...
Article
The regimens of anticancer therapy have been intensified and methods of high-dose chemotherapy (HDCT) have been introduced for recent years which made it possible to achieve significant progress in the results of tumor treatments. Intensification of chemotherapy regimens in cancer patients leads to the emergence of risk factors of invasive candidia...
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Unlike pyranoside cycles which are generally characterized by strictly defined conformational preferences, furanosides are flexible and may adopt a wide range of available conformations. During our previous studies, conformational changes of galactofuranoside cycles upon total sulfation were described computationally, using a simple Hartree–Fock (H...
Article
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Monoclonal antibody EBCA-1 is used in the sandwich immune assay for the detection of circulating Candida mannan in blood sera samples for the diagnosis of invasive candidiasis. To reinvestigate carbohydrate specificity of EBCA-1, a panel of biotinylated oligosaccharides structurally related to distinct fragments of Candida mannan were loaded onto a...
Article
β-(1→3)-d-Glucan is a branched polysaccharide present in the inner layer of the cell wall of various representatives of the fungal kingdom. Therefore, this polysaccharide is considered as a common marker for the laboratory diagnosis of mycoses of various etiologies. However, low concentration of β-(1→3)-d-glucan in biological fluids (∼40 pg mL−1) r...
Article
The synthesis of vicinally branched trisaccharide composed from two D-galactofuranoside residues attached via β-(1→2)- and β-(1→3)-linkages to α-D-galactopyranoside unit has been performed for the first time. Reported trisaccharide represents the described in 2017 moiety of galactoxylomannan – capsular polysaccharide of opportunistic fungal pathoge...
Chapter
This self-review covers the application of various computational methods for the investigation of carbohydrate reactivity. Since this topic cannot be investigated properly without paying attention to conformational behaviour of sugar molecules, some aspects of the theoretical conformational analysis are also discussed.
Article
Infections caused by Enterococcus spp., are a major concern in the clinical setting. In Enterococcus faecalis, the capsular polysaccharide diheteroglycan (DHG), composed of ß-D-galactofuranose-(1→3)-ß-D-glucopyranose repeats, has been described as an important virulence factor and as a potential vaccine candidate against encapsulated strains. Synth...
Article
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Methodologies to identify epitopes or ligands of the fungal cell wall polysaccharides influencing the immune response of human pathogens have to date been imperfect. Using the galactomannan (GM) of Aspergillus fumigatus as a model, we have shown that synthetic oligosaccharides of distinct structures representing key fragments of cell wall polysacch...
Article
Using 3-O-benzoyl-4,6-O-di-tert-butylsilylidene-2-azido-2-deoxy-selenogalactoside, biotinylated oligo-α-(1→4)-D-galactosamines comprising from 2 to 6 GalN units were prepared for the first time together with their N-acetylated derivatives. The combination of blocking groups used herein provided stereocontrol for the α-stereospecific glycosylation,...
Chapter
The cell wall of pathogenic fungi is highly important for the development of fungal infections and is the first cellular component to interact with the host immune system. The fungal cell wall is mainly built up of different polysaccharides representing ligands for pattern recognition receptors (PRRs) on immune cells and antibodies. Purified fungal...
Article
Galactomannan (GM) is a specific polysaccharide antigen of opportunistic mold fungi of the genus Aspergillus. The detection of GM in patients’ biological fluids is a reliable criterion for the diagnosis of invasive pulmonary aspergillosis, a severe disease. In this report, we evaluated the analytical capabilities of the fluorescence polarization im...
Article
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The incidence and prevalence of serious fungal infections is rising, especially in immunosuppressed individuals. Moreover, co-administration of antibiotics and immunosuppressants has driven the emergence of new multidrug-resistant pathogens. The significant increase of multidrug-resistant pathogens, together with their ability to form biofilms, is...
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Aspergillus fumigatus and A. flavus are the fungal pathogens responsible for most cases of invasive aspergillosis (IA). Early detection of the circulating antigen galactomannan (GM) in serum allows the prompt application of effective antifungal therapy, thus improving the survival rate of IA patients. However, the use of monoclonal antibodies (mAbs...
Article
Polysulfated carbohydrates play an important role in many biological processes because of their ability to bind to various protein receptors such as different growth factors, blood coagulation factors, adhesion lectins etc. Precise information about spatial organization of sulfated derivatives is of high demand for molecular modelling of such inter...
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Klebsiella pneumoniae Is a Gram‐negative pathogenic bacterium that emerges a challenge for modern medicine due to intensively rising multi‐drug resistance. Specific LPS O‐chains represent promising targets for development of vaccines for immunoprophylaxis or immunotherapy of K. pneumoniae‐caused diseases. Herein, the synthesis of di‐, tetra‐, and h...
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β-(1→3)-D-Glucan is an essential component of the fungal cell wall. Mouse monoclonal antibodies (mAbs) against synthetic nona-β-(1→3)-D-glucoside conjugated with bovine serum albumin (BSA) were generated using hybridoma technology. The affinity constants of two selected mAbs, 3G11 and 5H5, measured by a surface plasmon resonance biosensor assay usi...
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The studies on the recently discovered pyranoside-into-furanoside rearrangement have led us to conformational investigations of furanosides upon their total sulfation. Experimental NMR data showed that in some cases drastic changes of the ring conformation occurred while sometimes only the conformation of the exocyclic C4–C5 linkage changed. Herein...
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Insulin and lysozyme share the common features of being prone to aggregate and having biomedical importance. Encapsulating lysozyme and insulin in micellar nanoparticles probably would prevent aggregation and facilitate oral drug delivery. Despite the vivid structural knowledge of lysozyme and insulin, the environment-dependent oligomerization (dim...
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Ab initio calculations of fully O-sulfated model monosaccharides, including common hexoses (glucose, galactose, fucose, and mannose) and pentoses (arabinose and xylose), were performed to study the energetic properties of the recently discovered pyranoside-into-furanoside (PIF) rearrangement. It was shown that the per-O-sulfated derivatives of fura...
Article
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Great progresses have been made in the recent years in the detection of circulating galactofuranose-bearing molecules for the diagnosis of aspergillosis. However, the test used in the clinical practice is hampered by the occurrence of false positives. A glycoarray with dozens of oligosaccharides structurally related to the Aspergillus fumigatus gal...
Article
Laboratory animals (the California rabbit) were immunized with natural preparations of Saccharomyces cerevisiae and Candida krusei yeasts. The resulting sera have been analyzed with ligand libraries constructed from synthetic oligosaccharides related to the main carbohydrate components of the fungal cell wall. It is shown that the antibodies in the...
Article
Biotinylated hepta-, nona- and undeca-α-(1→3)-D-glucosides representing long oligosaccharides of α-(1→3)-D-glucan, one of the major components of the cell walls of the fungal pathogen Aspergillus fumigatus, were synthesized for the first time via a blockwise strategy. Convergent assembly of the α-(1→3)-D-glucan chains was achieved by glycosylation...
Article
Brush rabbits were immunized with injections prepared from the fungi Aspergillus fumigatus, Aspergillus niger, and Aspergillus repens. A library of synthetic biotinylated oligosaccharides containing the key fragments of antigenic polysaccharides of the fungal cell wall—galctomannan, α- and β-glucans, mannan, and chitin—was used to analyze carbohydr...
Data
Electrophoretic and western blot analyses of monoclonal antibodies 7B8 and 8G4. (A) Coomassie blue stained 12% SDS–PAAG electrophoretic analysis of purified mAb 7B8 and mAb 8G4 in reducing conditions. (B) Western blot analysis of mAb 7B8 and mAb 8G4 fractionated by 12.5% SDS-PAAG electrophoresis in reducing conditions and developed with alkaline ph...
Data
Luck of binding of monoclonal antibodies 7B8 and 8G4 to selected bacterial cells. Fixed cells were incubated with mAbs 7B8 and 8G4. (A) Bacterial DNA was stained with DAPI. (B) Binding of mAbs with bacterial cells was identified with Alexa Fluor 488 conjugated anti-mouse IgG antibodies staining in confocal microscopy. (B) Scale bar 10 μm. (TIF)
Article
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A panel of specific monoclonal antibodies (mAbs) against synthetic pentasaccharide β-D-Galf-(1→5)-[β-D-Galf-(1→5)]3-α-D-Manp, structurally related to Aspergillus fumigatus galactomannan, was generated using mice immunized with synthetic pentasaccharide-BSA conjugate and by hybridoma technology. Two selected mAbs, 7B8 and 8G4, could bind with the in...
Article
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The synthesis of model oligosaccharides related to antigenic galactomannans of the dangerous fungal pathogen Aspergillus fumigatus has been performed employing pyranoside-into-furanoside (PIF) rearrangement and controlled O(5) → O(6) benzoyl migration as key synthetic methods. The prepared compounds along with some previously synthesized oligosacch...
Article
The carbohydrate specificity of antibodies obtained by immunizing laboratory animals with immunogens prepared from the Aspergillus fumigatus cell wall was analyzed using the library of biotinylated synthetic oligosaccharides. It has been shown that the main part of antipolysaccharide antibodies recognizes galactomannan in the studied immunogens wit...
Article
The electrospray ionization high-resolution mass spectra of biotinylated hexaethylene glycol–spacered molecular probes bearing biologically relevant carbohydrate moieties in positive and negative modes were recorded and interpreted. Collisionally induced decay mass spectra (positive mode) revealed different patterns depending on the charge of the p...
Article
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The study is oriented at the in vitro evaluation of the immunobiological activity and efficacy of synthetically prepared isomeric pentasaccharides representing fragments of Aspergillus fumigatus cell-wall galactomannan and containing β-(1→5)-linked tetragalactofuranoside chain attached to O-6 (GM-1) or O-3 (GM-2) of a spacer-armed mannopyranoside r...
Article
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The study is oriented at the in vitro evaluation of the immunobiological activity and efficacy of synthetically prepared isomeric pentasaccharides representing fragments of Aspergillus fumigatus cell-wall galactomannan and containing β-(1→5)-linked tetra-galactofuranoside chain attached to O-6 (gM-1) or O-3 (gM-2) of a spacer-armed mannopyranoside...
Article
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Organic systems still dominate several traditional areas of chemical science and well-known applications, such as the synthesis of pharmaceutical compounds and drugs. However, a fascinating trend has appeared recently to combine pure organic systems into advanced molecular architectures and to create hybrid molecular systems. These interdisciplinar...
Article
High-resolution electrospray ionization mass spectra (MS and MS/MS) of a series of glycoconjugates containing biotin and oligomannuronopyranosyl residues linked via a hexaethylene glycol spacer were recorded in the positive and negative ion modes and interpret. In collision activation mass spectra of the positively charged ions (CID MS²), two serie...
Article
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Interactions between human lysozyme (HL) and the lipopolysaccharide (LPS) of Klebsiella pneumoniae O1, a causative agent of lung infection, were identified by surface plasmon resonance. To characterize the molecular mechanism of this interaction, HL binding to synthetic disaccharides and tetrasaccharides representing one and two repeating units, re...
Article
A gene that encodes fucoidanase ffa2 in the marine bacterium Formosa algae strain KMM 3553(T) was cloned, and the protein (FFA2) was produced in Escherichia coli Recombinant fucoidanase FFA2 was purified, and the biochemical properties of this enzyme were studied. The amino acid sequence of FFA2 showed 57% identity with known fucoidanase FcnA from...
Article
An efficient strategy for synthesis of spacer-armed tetrasaccharide related to galactan I of Klebsiella pneumoniae was reported employing newly developed acid-free conditions for pyranoside-into-furanoside (PIF) rearrangement of a digalactoside bearing 4-pentenyl group at anomeric position. The 4-pentenyl aglycon was successfully used both as a lea...
Article
Distortion of the ring conformation in β-gluco- and β-xylopyranosides upon their per-O-sulfation was observed. In the case of glucose, a conformation intermediate between 3,OB and ³S1 was found, while complete ⁴C1→¹C4 inversion was detected in xylopyranoside. The conformational changes were evidenced experimentally by measuring intra-ring ¹H–¹H cou...
Article
A new pyranoside-into-furanoside (PIF) rearrangement of selectively protected galactopyranosides, followed by controlled O(5) → O(6) benzoate migration, gives either 5-OH or 6-OH products. It has been applied for the synthesis of four oligosaccharides related to the galactomannan from Aspergillus fumigatus. The assembly of target oligosaccharides c...
Article
Here, we report the biochemical characterization of a novel α-L-fucosidase with broad substrate specificity (FpFucA) isolated from the mycelial fungus Fusarium proliferatum LE1. Highly purified α-L-fucosidase was obtained from several chromatographic steps after growth in the presence of L-fucose. The purified α-L-fucosidase appeared to be a monome...
Article
The pyranoside-into-furanoside (PIF) rearrangement was recently reported as a useful tool for the synthesis of furanoside-containing complex oligosaccharides. Until now, this transformation has only been described for some protected allyl-β-d-galactosides and one l-fucoside. In this communication its applicability is expanded. The formation of fura...
Article
The driving force for the constant improvement and development of new synthetic methodologies in carbohydrate chemistry is a growing demand for biologically important oligosaccharide ligands and neoglycoconjugates thereof for numerous biochemical investigations such as cell-to-pathogen interactions, immune response, cell adhesion, etc. Here we repo...
Article
The paper deals with the comparison of different theoretical methods for the calculation of stabilization energies of glycosyl cations from fucofuranoside glycosyl donors containing different protecting groups at atom O(3). The experimental and calculated data on stereoselectivity of glycosylation were compared. The formation of the stabilized glyc...
Article
Sulfated polysaccharides, fucoidans, from brown algae are built up mainly of α-l-fucopyranosyl units and form a group of natural biopolymers with a wide spectrum of biological activities. Systematic synthesis of oligosaccharides representing fucoidans' fragments gives molecular probes for detecting pharmacophores within fucoidan polysaccharide chai...
Article
Synthesis, theoretical conformational analysis (molecular mechanics and DFT calculations) and NMR spectral data including the (13)C-NMR glycosylation effects for six pairs of isomeric furanosyl-(1→3)-pyranosides with different anomeric and absolute configurations of furanosyl units as well as configurations of C2 and C4 in the pyranoside units are...
Article
Ab initio methods were compared for modeling the transformation of pyranosides into furanosides occurring during the exhaustive sulfation of the pyranoside substrate in the presence of a strong acid. Six basis sets differed by the presence or absence of diffusion and polarization functions were studied: 6-31G, 6-31G*, 6-31+G, 6-31+G*, 6-31++G, and...
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Aspergillus fumigatus is a very common fungus with high pathogenic potential for immunosuppressed hospital patients. A. fumigatus galactomannan, being the part of its cell wall, is considered as a promising candidate for vaccine and diagnostic test-systems. In this article we report the convergent synthesis of pentasaccharide fragments of the galac...
Article
Great interest in natural furanoside-containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside-into-furanoside (PIF) rearrangement permitting the transformation of selectively O-substituted pyranosides into the corresponding furanosides is r...
Article
Enterococcus faecalis is one of most important nosocomial and often multi-antibiotic resistant pathogens responsible for infections that are difficult to treat. Previously, a cell-wall polysaccharide termed diheteroglycan (DHG) was isolated and characterized as a promising vaccine candidate. However, the configuration of its lactic acid (LA) residu...
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Anionic fucose-containing polysaccharides (fucoidans of brown seaweeds, sulfated fucans and fucosylated chondroitin sulfates of invertebrates) are attracting a rapidly growing research interest due to different types of their biological activity discovered in recent years. In particular, algal fucoidans are characterized by large structural variati...
Article
A family of fifteen glycoclusters based on a cyclic oligo-(1→6)-β-D-glucosamine core has been designed as potential inhibitors of the bacterial lectin LecA with various valencies (from 2 to 4) and linkers. Evaluation of their binding properties towards LecA has been performed by a combination of hemagglutination inhibition assays (HIA), enzyme-link...
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Three structurally different fucoidans from the brown seaweeds Saccharina latissima (SL), Fucus vesiculosus (FV), and Cladosiphon okamuranus (CO), two chemically modified fucoidans with a higher degree of sulfation (SL-S, CO-S), and a synthetic totally sulfated octasaccharide (OS), related to fucoidans, were assessed on anticoagulant and antithromb...
Article
Three hyperbranched dendrimers (polyglycidols) and the corresponding sulfated derivatives, differing in the average molecular weight, were synthesized. The compounds obtained were characterized in detail by mass spectrometry and 1H and 13C NMR spectroscopy, enabling estimation of the sizes of the corresponding molecules. Assignment of signals and i...
Article
Natural glycosaminoglycan heparin remains the most commonly prescribed anticoagulant for hospitalized patients in modern medical practice. Unfortunately, its administration can be accompanied by a series of clinical side effects, including thrombocytopenia and bleeding. This determines the urgency of the development of alternative anticoagulant dru...
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The extracellular domain of Notch contains epidermal growth factor (EGF) repeats that are extensively modified with different O-linked glycans. O-Fucosylation is essential for receptor function, and elongation with N-acetylglucosamine, catalyzed by members of the Fringe family, modulates Notch activity. Only recently, genes encoding enzymes involve...
Article
Chondroitin sulfates isolated from cartilage of five marine fish species: Atlantic salmon (Salmo salar), Greenland shark (Somniosus microcephalus), blackmouth catshark (Galeus melastomus), birdbeak dogfish (Deania calcea), and Arctic skate (Amblyraja hyperborea), were characterized in detail by 1H and 13C NMR spectroscopy. The complete signal assig...
Article
The synthesis of per-O-sulfated derivatives of di-, tetra-, hexa-, octa-, dodeca-, and hexadecafucosides related to natural fucoidans of different types has been performed with the use of previously reported acid-promoted protocol for per-O-sulfation of polyols by SO(3) complexes. During the treatment of (1→3)-linked oligofucosides under these cond...
Article
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Persulfated derivatives of natural polyhydroxy compounds, such as lignans secoisolariciresinol, and isolariciresinol, flavonoid dihydroquercetin, and myo-inositol, have been synthesized. The ability of these compounds to inhibit the intrinsic pathway of blood coagulation (APTT-test) and to reduce the activity of coagulation factor Xa in the presenc...