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At least 199 records · Page 11Linked to original sources
PubMed2001

Fe(III) coordination properties of two new saccharide-based enterobactin analogues: methyl 2,3,4-tris-O-[N-[2,3-di(hydroxy)benzoyl-glycyl]-aminopropyl]-alpha-D-glucopyranoside and methyl 2,3,4-tris-O-[N-[2,3-di-(hydroxy)-benzoyl]-aminopropyl]-alpha-D-glucopyranoside.

The synthesis of two saccharide-based enterobactin analogues, methyl 2,3,4-tris-O[-N[2,3-di(hydroxy)benzoyl-glycyl]-aminopropyl]-alpha-D-glucopyranoside (H(6)L(A)) and methyl 2,3,4-tris-O-[N-[2,3-di(hydroxy)benzoyl]-aminopropyl]-alpha-D-glucopyranoside (H(6)L(B)), are reported along with their pK(a) values, Fe(III) binding constants, and aqueous solution speciation as determined by spectrophotometric and potentiometric titration techniques. Use of a saccharide platform to synthesize a hexadentate triscatechol chelator provides some advantages over other approaches to enterobactin models, including significant water solubility, resistance to hydrolysis, and backbone chirality which may provide favorable recognition and availability to cells. The protonation constants for the catechol ligand hydroxyl moieties were determined for both ligands and found to be significantly different, which is attributed to the differences in the spacer chain of the two triscatechols. Proton dependent Fe(III)-ligand equilibrium constants were determined using a model involving the sequential protonation of the Fe(III)-ligand complex. These results were used to calculate the formation constants, log beta(110) = 41.38 for Fe(III)-H(6)L(A) and log beta(110) = 46.38 for Fe(III)-H(6)L(B). The calculated pM values of 28.6 for H(6)L(A) and 28.3 for H(6)L(B) indicate that these ligands possess Fe(III) affinities comparable to or greater than other enterobactin models and are thermodynamically capable of removing Fe(III) from transferrin.

Algorithms↗
PubMed2003

Fe(III) coordination properties of a new saccharide-based exocyclic trihydroxamate analogue of ferrichrome.

The coordination chemistry of a saccharide-based ferrichrome analogue, 1-O-methyl-2,3,4-tris-O-[4-(N-hydroxy-N-methylcarbamoyl)-n-butyrate]-alpha-d-glucopyranoside (H(3)L), is reported, along with its pK(a) values, Fe(III) and Fe(II) chelation constants, and aqueous-solution speciation as determined by spectrophotometric and potentiometric titration techniques. The use of a saccharide platform to synthesize a hexadentate trihydroxamic acid chelator provides some advantages over other approaches to ferrichrome models, including significant water solubility and hydrogen-bonding capability of the backbone that can potentially provide favorable receptor recognition and biological activity. The pK(a) values for the hydroxamate moieties were found to be similar to those of other trihydroxamates. Proton-dependent Fe(III)-H(3)L and Fe(II)-H(3)L equilibrium constants were determined using a model involving the sequential protonation of the iron(III)- and iron(II)-ligand complexes. These results were used to calculate the formation constants, log beta(110) = 31.86 for Fe(III)L and 12.1 for Fe(II)L(-). The calculated pFe value of 27.1 indicates that H(3)L possesses an Fe(III) affinity comparable to or greater than those of ferrichrome and other ferrichrome analogues and is thermodynamically capable of removing Fe(III) from transferrin. E(1/2) for the Fe(III)L/Fe(II)L(-) couple was determined to be -436 mV from quasi-reversible cyclic voltammograms at pH = 9, and the pH-dependent E(1/2) profile was used to determine the Fe(II)L(-) protonation constants.

Algorithms↗
PubMed2003

Microenvironmental polarity control of electron-transfer photochirogenesis. Enantiodifferentiating polar addition of 1,1-diphenyl-1-alkenes photosensitized by saccharide naphthalenecarboxylates.

Enantiodifferentiating polar photoaddition of alcohol to 1,1-diphenylpropene and 1,1-diphenyl-1-butene sensitized by saccharide naphthalene(di)carboxylates was performed in nonpolar to polar solvents containing methanol, ethanol, or 2-propanol as the nucleophile to give the corresponding anti-Markovnikov alcohol adduct, that is, 1,1-diphenyl-2-alkoxy-propane and -butane in low-to-good chemical yields, depending on the sensitizer, chiral auxiliary, alcohol, solvent, and temperature employed. The excited state and intermediate involved, the reaction and enantiodifferentiation mechanism operating, and the factors controlling chemical and optical yields were elucidated from the photochemical and stereochemical outcomes under various conditions and also from the sensitizer and exciplex fluorescence quenching experiments and the molecular orbital calculations. A new strategy was developed to overcome the normally accepted tradeoff between the chemical and optical yields. This is made possible by employing protected saccharides as chiral auxiliaries and running the photoreactions not in a nonpolar but in a low-polarity solvent such as diethyl ether, which jointly enhance the "microenvironmental" polarity around the sensitizer to facilitate electron transfer, keeping the intimate interactions between the chiral sensitizer and substrate within the exciplex intermediate. By optimizing these factors, we obtained the photoadduct in enantiomeric excesses of up to 58%, which is the highest ever reported for a photosensitized bimolecular enantiodifferentiating reaction.

Journal Article↗
PubMed2003

De novo asymmetric bio- and chemocatalytic synthesis of saccharides - stereoselective formal O-glycoside bond formation using palladium catalysis.

A novel integrated bio- and chemocatalytic approach to the de novo catalytic asymmetric synthesis of saccharides has been developed. Acetoxypyranones obtained enantiopure by enzymatic resolution have been shown to undergo highly stereoselective palladium-catalyzed formal O-glycoside bond formation. The combination of these protocols can be applied to the iterative asymmetric catalytic synthesis of saccharides.

Acetals↗
PubMed2003

Remarkably size-regulated cell invasion by artificial viruses. Saccharide-dependent self-aggregation of glycoviruses and its consequences in glycoviral gene delivery.

We here report a novel example of artificial glycoviral vectors constructed via number- and size-controlled gene (pCMVluc, 7040 bp) coating with micellar glycocluster nanoparticles (GNPs) of calix[4]resorcarene-based macrocyclic glycocluster amphiphiles having eight or five saccharide moieties with terminal alpha-glucose (alpha-Glc), beta-glucose (beta-Glc), or beta-galactose (beta-Gal) residues. The resulting glycoviruses are compactly packed (approximately 50 nm) and well charge-shielded (zeta approximately equal 0 mV), undergo saccharide-dependent (alpha-Glc > beta-Gal >> beta-Glc) self-aggregation, and transfect cell (Hela and HepG2) cultures as triggered by the pinocytic form of endocytosis. The semilogarithmic linear size-activity correlation suggests that size-restricted pinocytosis (<100 nm) is effective only for monomeric viruses. The activities of oligomeric and otherwise poorly active beta-Gal-functionalized viruses toward hepatic HepG2 cells are approximately 10(2)-times higher than expected on the size basis, owing to the receptor-mediated specific pathway involving the asialoglycoprotein receptors on the hepatic cell surfaces. The scope and prospect of artificial glycoviruses are discussed.

Calixarenes↗
PubMed2004

Saccharide-dependent induction of chiral helicity in achiral synthetic hydrogen-bonding oligomers.

Conformational transitions of biopolymers are well-known to be affected by noncovalent interactions with small molecules. We found that synthetic polymers, poly- and oligo(meta-ethynylpyridine)s, are guided to helical structures by uncharged hydrogen-bonding interactions with saccharides enclosed in the inner sphere of the polymers. Circular dichroism (CD) studies revealed that chirality of saccharide was transferred to the helical sense of the polymers. Among the n-octyl pyranosides of naturally important hexoses, beta-glucoside induced CDs most effectively. Size-regulated 18-mer and longer oligomers also showed the induced CDs similar to those for the polymers. Furthermore, native monosaccharides were extracted into less polar organic solvent with the help of the polymers, inducing similar CD signals.

Carbohydrates↗
PubMed2005

Double-modification of lectin using two distinct chemistries for fluorescent ratiometric sensing and imaging saccharides in test tube or in cell.

The site-selective incorporation of two different fluorophores into a naturally occurring protein (lectin, a sugar-binding protein) has been successfully carried out using two distinct orthogonal chemical methods. By post-photoaffinity labeling modification, Con A, a glucose- and mannose-selective lectin, was modified with fluorescein in the proximity of the sugar binding site (Tyr100 site), and the controlled acylation reaction provided the site-selective attachment of coumarin at Lys114. In this doubly modified Con A, the fluorescein emission changed upon the binding to the corresponding sugars, such as the glucose or mannose derivatives, whereas the coumarin emission was constant. Thus, the doubly modified Con A fluorescently sensed the glucose- and mannose-rich saccharides in a ratiometric manner while retaining the natural binding selectivity and affinity, regardless of the double modification. On the benefit of the ratiometric fluorescent analysis using two distinct probes, the sugar trimming process of a glycoprotein can be precisely monitored by the engineered Con A. Furthermore, the doubly modified Con A can be used not only for the convenient fluorescent imaging of saccharides localized on a cell surface, such as the MCF-7, a breast cancer cell having rich high-mannose branch, but also for the ratiometric fluorescent sensing of the glucose concentration inside HepG2 cells. These results demonstrated that the semisynthetic lectin modified doubly by two distinct chemistries is superior to the singly modified one in function, and thus, it may be potentially useful in cell, as well as in test tube.

Biosensing Techniques↗
PubMed2002

Hydroxymethyl group conformation in saccharides: structural dependencies of (2)J(HH), (3)J(HH), and (1)J(CH) spin-spin coupling constants.

Experimental and theoretical methods have been used to correlate (2)J(HH) and (3)J(HH) values within the exocyclic hydroxymethyl groups (CH(2)OH) of saccharides with specific molecular parameters, and new equations are proposed to assist in the structural interpretation of these couplings. (3)J(HH) depends mainly on the C-C torsion angle (omega) as expected, and new Karplus equations derived from J-couplings computed from density functional theory (DFT) in a model aldopyranosyl ring are in excellent agreement with experimental values and with couplings predicted from a previously reported general Karplus equation. These results confirm the reliability of DFT-calculated (1)H-(1)H couplings in saccharides. (2)J(HH) values depend on both the C-C (omega) and C-O (theta) torsions. Knowledge of the former, which may be derived from other parameters (e.g., (3)J(HH)), allows theta to be evaluated indirectly from (2)J(HH). This latter approach complements more direct determinations of theta from (3)J(HCOH) and potentially extends these more conventional analyses to O-substituted systems lacking the hydroxyl proton. (1)J(CH) values within hydroxymethyl fragments were also examined and found to depend on r(CH), which is modulated by specific bond orientation and stereoelectronic factors. These latter factors could be largely, but not completely, accounted for by C-C and C-O torsional variables, leading to only semiquantitative treatments of these couplings (details discussed in the Supporting Information). New equations pertaining to (2)J(HH) and (3)J(HH) have been applied to the analysis of hydroxymethyl group J-couplings in several mono- and oligosaccharides, yielding information on C5-C6 and/or C6-O6 rotamer populations.

Carbohydrate Conformation↗
PubMed1999

Saccharide Libraries as Potential Templates for Regio- and Chiroselective Introduction of Two Functional Groups into [60]Fullerene.

This paper reports regio- and chiroselective introduction of two boronic acid groups into [60]fullerene controlled by a saccharide used as a template molecule. The double [4+2] cycloadditions between [60]fullerene and 1:2 saccharide-boronic acid complexes 6-9 afforded [60]fullerene-bisadducts 12. Their structures were identified on the basis of (1)H and (13)C NMR, UV-vis, and CD spectroscopy, mass spectrometry, and chiral HPLC analysis. When 3-O-methyl-D-glucose (4) was used as the template molecule, high regioselectivity was achieved which gave trans-4 isomer 12a as a main isomer in 72.5% yield. The chiro- as well as regioselective preparation of e isomer 12c was attained in 81.4% ee from the 55.7% yield racemic mixture by the reaction using the D-mannitol-3,4-carbonate template (3). When the enantiomers, D-threitol (D-2) and L-threitol (L-2) were used as the templates, cis-3 isomers 12b and ent-12b with opposite chirality were yielded in 44.2 and 45.2% ee, respectively. On the other hand, 1-O-methyl-alpha-D-mannopyranoside template (5) featured nonselective cycloaddition.

Journal Article↗
PubMed2005

Lipid phase transition in saccharide-coated cholate-containing liposomes: coupling to the surrounding matrix.

We performed FTIR measurements on cholate-containing liposomes (CCL) embedded in saccharide (trehalose or sucrose) matrixes with different contents of residual water. We obtained information on the CCL phase transition following the thermal evolution (310-70 K) of the IR spectrum of the carbonyl moieties of phospholipids in the frequency range 4225-4550 cm(-1). Furthermore, we simultaneously followed the thermal evolution of the water association band, which gave information on the behavior of the surrounding water-saccharide matrix. The analysis revealed a small sub-band of the water association band present in CCL but not in cholate-free liposomes, the thermal evolution of which is tightly coupled to that of the spectrum of the carbonyl moieties of phospholipids. We suggest that this band arises from water molecules, which are inserted within the lipidic structure, in the region located at the border between the hydrophilic and the hydrophobic moieties of phospholipids in the presence of cholic acid. Such water molecules could be responsible for the peculiar flexibility and hydrophilicity of CCL. Following Giuffrida et al. (J. Phys. Chem. B 2003, 107, 13211-13217), we also performed a Spectra Distance analysis, which enabled us to detect an overall liposomes-matrix structural coupling.

Cholates↗
PubMed2001

Novel porphyrin-cryptand cyclic systems: receptors for saccharide recognition in water.

Two macrocyclic porphyrin sandwich systems, 4 and 5, together with the linear compound 6 have been prepared and examined as saccharide receptors. The cyclic porphyrin-cryptand conjugates 4 and 5 bind saccharides efficiently in highly competitive media with a preference for trisaccharides probably due to a complementary topology of hydrophobic and hydrophilic solvating regimes with respect to the sugar guests.

Bridged Bicyclo Compounds, Heterocyclic↗
PubMed2005

A rigid C3v-symmetrical host for saccharide recognition: 1,3,5-tris(2-hydroxyaryl)-2,4,6-trimethylbenzenes.

A rigid C(3v)-symmetrical host molecule, syn-1,3,5-tris(2-hydroxy-5-pentylphenyl)-2,4,6-trimethylbenzene, was readily obtained via Suzuki coupling and thermal atropisomerization. The host molecule effectively associated with various saccharides by multipoint hydrogen bonds, whereas its anti-atropisomer and analogue lacking in methyl groups showed much weaker association with saccharides. Thermodynamic analyses suggested that the difference of the association strength was caused by entropic factors.

Benzene Derivatives↗
PubMed2005

Computational studies of 13C NMR chemical shifts of saccharides.

The (13)C NMR chemical shifts for alpha-D-lyxofuranose, alpha-D-lyxopyranose (1)C(4), alpha-D-lyxopyranose (4)C(1), alpha-D-glucopyranose (4)C(1), and alpha-D-glucofuranose have been studied at ab initio and density-functional theory levels using TZVP quality basis set. The methods were tested by calculating the nuclear magnetic shieldings for tetramethylsilane (TMS) at different levels of theory using large basis sets. Test calculations on the monosaccharides showed B3LYP(TZVP) and BP86(TZVP) to be cost-efficient levels of theory for calculation of NMR chemical shifts of carbohydrates. The accuracy of the molecular structures and chemical shifts calculated at the B3LYP(TZVP) level is comparable to those obtained at the MP2(TZVP) level. Solvent effects were considered by surrounding the saccharides by water molecules and also by employing a continuum solvent model. None of the applied methods to consider solvent effects was successful. The B3LYP(TZVP) and MP2(TZVP)(13)C NMR chemical shift calculations yielded without solvent and rovibrational corrections an average deviation of 5.4 ppm and 5.0 ppm between calculated and measured shifts. A closer agreement between calculated and measured chemical shifts can be obtained by using a reference compound that is structurally reminiscent of saccharides such as neat methanol. An accurate shielding reference for carbohydrates can be constructed by adding an empirical constant shift to the calculated chemical shifts, deduced from comparisons of B3LYP(TZVP) or BP86(TZVP) and measured chemical shifts of monosaccharides. The systematic deviation of about 3 ppm for O(1)H chemical shifts can be designed to hydrogen bonding, whereas solvent effects on the (1)H NMR chemical shifts of C(1)H were found to be small. At the B3LYP(TZVP) level, the barrier for the torsional motion of the hydroxyl group at C(6) in alpha-D-glucofuranose was calculated to 7.5 kcal mol(-1). The torsional displacement was found to introduce large changes of up to 10 ppm to the (13)C NMR chemical shifts yielding uncertainties of about +/-2 ppm in the chemical shifts.

Carbon Isotopes↗
PubMed2006

A fluorescent water-soluble naphthalimide-based receptor for saccharides with highest sensitivity in the physiological pH range.

A new water-soluble fluororeactand for the optical detection of saccharides is presented. We have combined the functional naphthalimide fluorophore with the well-known ability of boronic acids to bind to the diol moiety of saccharides. The fluororeactand exhibits sensitivity in the mM range, absorbance and emission in the visible spectral range, large Stokes' shift and fluorescence increase in the physiological pH range.

Carbohydrates↗
PubMed1972

Protein-polysaccharide biosynthesis. Membrane-bound saccharides.

Membrane-bound saccharides obtained from ear cartilage from rabbits recovering from papain injection were examined for glycosyl acceptor properties, alkali lability, molecular size and degree of sulphation. Although considerable glucuronosyl transfer from UDP-glucuronic acid could be demonstrated, less than one-third could be identified as representing chondroitin linkage formation; there was little or no effect of molecular size on acceptor properties. Approximately one-half of the membrane-associated chondroitin-like saccharide chains are solubilized by alkali, whereas one-half require proteolysis for solubilization. These fractions are analytically indistinguishable and both contain xylose and galactose as well as uronic acid and sulphated N-acetyl-galactosamine. All fragments that were examined contained stoicheiometric amounts of axial sulphate ester, strongly suggesting a close relationship between chain extension and sulphation.

Animals↗
PubMed1981

Glycoprotein biosynthesis in animal cells grown in suspension culture. Assembly of lipid-linked saccharides and formation of protein-bound 'high-mannose' oligosaccharides.

Glycoprotein biosynthesis was studied with mouse L-cells grown in suspension culture. Glucose-deprived cells incorporated [3H]mannose into 'high-mannose' protein-bound oligosaccharides and a few relatively high-molecular-weight lipid-linked oligosaccharides. The latter were retained by DEAE-cellulose and turned over quite slowly during pulse--chase experiments. Increased heterogeneity in size of lipid-linked oligosaccharides developed during prolonged glucose deprivation. Sequential elongation of lipid-linked oligosaccharides was also observed, and conditions that prevented the assembly of the higher lipid-linked oligosaccharides also prevented the formation of the larger protein-bound 'high-mannose' oligosaccharides. In parallel experiments, [3H]mannose was incorporated into a total polyribosome fraction, suggesting that mannose residues were transferred co-translationally to nascent protein. Membrane preparations from these cells catalysed the assembly from UDP-N-acetyl-D-[6-3H]glucosamine and GDP-D-[U-14C]mannose of polyisoprenyl diphosphate derivatives whose oligosaccharide moieties were heterogeneous in size. Elongation of the N-acetyl-D-[6-3H]glucosamine-initiated glycolipids with mannose residues produced several higher lipid-linked oligosaccharides similar to those seen during glucose deprivation in vivo. Glucosylation of these mannose-containing oligosaccharides from UDP-D-[6-3H]glucose was restricted to those of a relatively high molecular weight. Protein-bound saccharides formed in vitro were mainly smaller in size than those assembled on the lipid acceptors. These results support the involvement of lipid-linked saccharides in the synthesis of asparagine-linked glycoproteins, but show both in vivo and in vitro that protein-bound 'high-mannose' oligosaccharide formation can occur independently of higher lipid-linked oligosaccharide synthesis.

Animals↗
PubMed1999

Enzymatic synthesis of alpha3'sialylated and multiply alpha3fucosylated biantennary polylactosamines. A bivalent [sialyl diLex]-saccharide inhibited lymphocyte-endothelium adhesion organ-selectively.

Multifucosylated sialo-polylactosamines are known to be high affinity ligands for E-selectin. PSGL-1, the physiological ligand of P-selectin, is decorated in HL-60 cells by a sialylated and triply fucosylated polylactosamine that is believed to be of functional importance. Mimicking some of these saccharide structures, we have synthesized enzymatically a bivalent [sialyl diLex]-glycan, Neu5Acalpha2-3'Lexbeta1-3'Lexbeta1-3'(Neu5Acalpha2-3'Lexbeta1-3Lexbe ta1-6')LN [where Neu5Ac is N-acetylneuraminic acid, Lex is the trisaccharide Galbeta1-4(Fucalpha1-3)GlcNAc and LN is the disaccharide Galbeta1-4GlcNAc]. Several structurally related, novel polylactosamine glycans were also constructed. The inhibitory effects of these glycans on two L-selectin-dependent, lymphocyte-to-endothelium adhesion processes of rats were analysed in ex-vivo Stamper-Woodruff binding assays. The IC50 value of the bivalent [sialyl diLex]-glycan at lymph node high endothelium was 50 nm, but at the capillaries of rejecting cardiac allografts it was only 5 nm. At both adhesion sites, the inhibition was completely dependent on the presence of fucose units on the sialylated LN units of the inhibitor saccharide. These data show that the bivalent [sialyl diLex]-glycan is a high affinity ligand for L-selectin, and may reduce extravasation of lymphocytes at sites of inflammation in vivo without severely endangering the normal recirculation of lymphocytes via lymph nodes.

Amino Sugars↗