Characterization of the complex formation of 1,6-anhydro-ß-maltose and potassium ions using NMR spectroscopy and single-crystal X-ray crystallography.

The formation of a complex between 1,6-anhydro-ß-maltose and potassium ions was characterized using (1)H, (13)C and (39)K NMR spectroscopy and single-crystal X-ray crystallography. In the NMR study, the spin-lattice relaxation times (T(1)) of C1, C3, C5, C6, and C5' significantly decreased in the presence of potassium ions, and (39)K-T(1) also decreased in the presence of 1,6-anhydro-ß-maltose, indicating complex formation. In a crystal, both 8- and 9-coordination structures, corresponding to the distorted capped pentagonal bipyramidal structure and the capped hexagonal bipyramidal structure, respectively, were identified. A potassium ion was positioned in the center of each bipyramidal structure.

Characterization of the complex formation of 1,6-anhydro-beta-maltotriose with potassium using 1H and 39K NMR spectroscopy.

The (1)H and (39)K longitudinal relaxation times (T(1)) and (1)H diffusion coefficients were measured to investigate the complex formation of 1,6-anhydro-beta-maltotriose and potassium ions. Although the (1)H-T(1) values of H3', H5', H1'' and H4'' decreased in the presence of potassium ions, (1)H chemical shifts and (1)H diffusion coefficients did not show significant changes. The long-range coupling constants of (3)J(C-H) around the glycosyl bonds did not show significant changes either. In the measurements of (39)K spectra, the (39)K signal obviously broadened and the (39)K-T(1) values decreased in the presence of 1,6-anhydro-beta-maltotriose, indicating the complex formation of 1,6-anhydro-beta-maltotriose and potassium ions. These results indicate that the conformation and molecular volume were unaffected in the complex formation.

Specific interactions between silver(I) ions and cytosine-cytosine pairs in DNA duplexes.

Very specific binding of the Ag(i) ion unexpectedly stabilized DNA duplexes containing the naturally occurring cytosine-cytosine (C-C) mismatch-base pair; because the C-C pair selectively binds to the Ag(i) ion, we developed a DNA-based Ag(i) sensor that employed an oligodeoxyribonucleotide containing C-C pairs used for Ag(i) binding sites.

Characterization of the malate-aluminum(III) complex using 1H and 27Al NMR spectroscopy.

Structural elucidation of a malate-aluminum(III) complex has been carried out using 1H and 27Al NMR spectroscopy. The 1H chemical shift perturbation clearly indicated the interaction between malate and Al(III) ion. The measurements of 27Al NMR and 1H-13C HSQC spectra demonstrated that the major form of a complex comprised two equivalent malate ions and two unequivalent Al(III) ions. With this constraint, an equilibrium geometry of the complex was proposed by a semi-empirical molecular orbital calculation.

MercuryII-mediated formation of thymine-HgII-thymine base pairs in DNA duplexes.

The very specific binding of the HgII ion unexpectedly and significantly stabilizes naturally occurring thymine-thymine base mispairing in DNA duplexes. Following this finding, we prepared DNA duplexes containing metal-mediated base pairs at the desired sites, as well as novel double helical architectures consisting only of thymine-HgII-thymine pairs.

Spectroscopic characterization of 2-isopropylmalic acid-aluminum(III) complex.

Spectroscopic elucidation of a 2-isopropylmalic acid (2-iPMA)-aluminum(III) complex has been carried out using (1)H, (13)C and (27)Al NMR spectroscopy, diffusion-ordered NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS). 2-iPMA is secreted by Saccharomyces cerevisiae and can dissolve Al(III) in the culture medium. The (1)H chemical shift perturbation and (1)H DOSY clearly indicated the formation of the 2-iPMA-Al(III) complex. The measurements of (13)C and (27)Al NMR spectroscopy and ESI-MS demonstrated that the major form of a complex is comprised four 2-iPMA and two Al(III) species. This compound is expected to possess strong Al(III)-detoxification capability.

Observation of 1,6-anhydro-beta-maltose and 1,6-anhydro-beta-D-glucopyranose complexed with rubidium by NMR spectroscopy and electrospray ionization mass spectrometry.

A complex of 1,6-anhydro-beta-maltose with rubidium and that of 1,6-anhydro-beta-D-glucopyranose with rubidium were characterized using 87Rb NMR spectroscopy, diffusion-ordered NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS). Although subtle differences were observed in the 1H chemical shifts of 1,6-anhydro-beta-maltose in between the presence and absence of rubidium in deuterium oxide, measurements of the spin-lattice relaxation time (T1) of the 87Rb nucleus, the diffusion coefficients of 1,6-anhydro-beta-maltose using 1H DOSY and ESI-MS indicated the complex formation of 1,6-anhydro-beta-maltose with rubidium. The complex formation with rubidium was also identified for 1,6-anhydro-beta-D-glucopyranose using NMR and ESI-MS techniques.

Practical aspects of ROESY experiments for identification of bound waters in the cyclic tetrasaccharide.

ROESY pulse sequences are presented and evaluated to identify bound waters in the cyclic tetrasaccharide. The first experiment incorporated the double-pulsed field gradient spin-echo (DPFGSE) for selective water excitation at the initial portion of the pulse sequence. Although long, shaped pulses were used in DPFGSE to achieve the highly selective excitation of water resonance that is very close to resonances of the cyclic tetrasaccharide, the approach was not effective because of the loss of sensitivity. Concomitant use of long delays and moderate length of shaped pulses in the portion of DPFGSE gained more sensitivity. A simple approach incorporating spin-echo with long delays instead of DPFGSE also afforded a sensitive spectrum. Practical aspects of these ROESY experiments are illustrated using the cyclic tetrasaccharide cyclo-{-->6}-alpha-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->6)-alpha-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->).

Identification of bound water molecules in the cyclic tetrasaccharide, cyclo-{-->6}-alpha-d-Glcp-(1-->3)-alpha-D-Glcp-(1-->6)-alpha-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->).

A structural characterization of bound water molecules in the cyclic tetrasaccharide, cyclo-{-->6}-alpha-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->6)-alpha-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->), was carried out by NMR spectroscopy. H-1', 2'-OH, H-3', and 4'-OH of the 3-O-glycosylated residue and H-1 of the 6-O-glycosylated residue were found to cross-relax with protons of bound waters using the double-pulsed field-gradient spin-echo ROESY experiment. In the crystal structure, one water molecule is located in the center of the plate, and its temperature factor is very low, indicating that this water molecule is an intrinsic component.

Oxidation of 3-C-(2-amino-2-deoxy-D-glucopyranosyl)-1-propene compounds and the structure of 3-C-(2-amino-2-deoxy-D-glucopyranosyl)-1,2-propanediol derivatives for a synthesis of 2,3-didehydro-2,7-dideoxy-N-acetylneuraminic acid.

Oxidation of 5-acetamido-4,8-anhydro-1,2,3,5-tetradeoxy-D-glycero-D-ido-non-1-enitol [3-C-(2-amino-2-deoxy-beta-D-glucopyranosyl)-1-propene] was studied to search for preparative routes to aminodeoxy didehydro nonulosonic acid derivatives. Since only moderate chiral induction was observed with osmium tetroxide dihydroxylation as well as with peracid epoxidation, the catalytic asymmetric dihydroxylation conditions were applied to give the stereocontrolled formation of 1,2-propanediol derivatives. The structures of these diastereoisomeric 1,2-propanediol derivatives were determined by X-ray crystallographic analyses. The formation of diastereoisomeric 1,2-propanediols also varied with the nature of 2-substituent on the aminodoexy glycosyl moiety. Thus 5-acetamido-4,8-anhydro-3,5-dideoxy-D-erythro-L-ido-nonitol [(2S)-3-C-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-1,2-propanediol] was obtained predominantly up to 70% from 3-C-(2-acetamido-2-deoxyglycosyl)-1-propene by the use of ADmixbeta reagent. The (2S)-propanediol derivative was transformed in a five-step reaction sequence to 2,3-didehydro-2,7-dideoxy-N-acetylneuraminic acid.