Search PubMed⌕ Search

Biomedical subjects

M Kainosho

Publications and source records attributed to M Kainosho.

87 records · Page 5Linked to original sources

Detection of proton-acceptor sites of hydrogen bonding in adenine X uracil base pairs by the use of 15N magnetic resonance.

2',3',5'-Tri-O-acetyl[1,3,7,9,amino-15N]adenosine(ac3Ado) and its 8-2H and 8-bromo derivatives (ac3[8-2H]Ado and ac3br8Ado) were synthesized from 95% 15N-enriched adenosine which was obtained by microbial fermentation. The chemical shifts and nuclear Overhauser effects of 15N NMR of the adenosine derivatives were measured by changing the concentration of the mixed 1-cyclohexyluracil (cHxUra) in chloroform. The limiting shift of each 15N resonance was calculated by using the association constants obtained from proton magnetic resonances of the ac3Ado/cHxUra and ac3br8Ado/cHxUra systems. From the quantitative analysis of the 15N chemical shifts of the N-1 and N-7 atoms it could be concluded that ac3Ado X cHxUra dimers prefer the Hoogsteen-type pair while the Watson-Crick-type pairs are predominant in the ac3br8Ado X cHxUra dimers. The N-3 atom, which does not locate at the interaction site, showed a fairly large induced shift. Thus the induced shift of 15N resonance by association does not always mean the involvement of the corresponding nucleus to the interaction site. The effect of intermolecular hydrogen bonding on the nuclear Overhauser enhancement of the 15N-7 resonance was observed in the ac3[8-2H]Ado/cHxUra mixture. The presence of the Hoogsteen-type hydrogen bonding was proposed by the use of 15N NMR spectra. The present information will be useful for the elucidation of non-Watson-Crick-type base-pair interaction in transfer TNA and oligonucleotides.

Adenine↗

The structure of permetin A, a new polypeptin type antibiotic produced by Bacillus circulans.

The structure of permetin A(I), an antibiotic substance produced by Bacillus circulans AJ 3902, has been elucidated as a cyclic acyl peptide by means of the mass and nuclear magnetic resonance spectroscopic techniques. (Formula: see text.) The structure was found to be the same as polypeptin A(II) except that L-Thr in II is replaced by L-Ser in I. Details of the structural determination are given for the permetin A itself as well as for the hydrolyzed permetin A. (Formula: see text.)

Anti-Bacterial Agents↗

An 15N NMR study of adenine-uracil base pair in a non-aqueous solvent.

[1,3,7,9,10-15N]-2',3',5'-Tri-O-acetyl adenosine (A) and its 8-D and 8-Br derivatives (AD and ABr) were prepared from 95% 15N enriched adenosine obtained from microbial fermentation. The chemical shifts and nuclear Overhauser effects of 15N resonances were measured as a function of the concentration of the mixed 1-cyclohexyluracil. The limiting shift of each 15N resonance was calculated and the structure of the A-U dimer was estimated. From the shifts of 15N-1 and 15N-7 signals it is determined that ABr-U dimers prefer the Watson-Crick type hydrogen bond while the Hoogsteen type pairs are predominant in the A-U dimers.

Adenine↗

The formation and annealing of structural defects in lipid bilayer vesicles.

It is shown that sonication of phospholipid-water dispersions below the crystalline leads to liquid crystalline phase transition temperature (Tc) produces bilayer vesicles with structural defects within the bilayer membrane, which permit rapid permeation of ions and catalyze vesicle-vesicle fusion. These structural defects are annihilated simply by annealing the vesicle suspension above Tc. The rate of annealing was found to be slow, of the order of an hour for T = 3 degrees C above Tc, but annealing is complete within 10 min for T = 10 degrees C above Tc. It is proposed that these structural defects are fault-dislocations in the bilayer structure, which arise from a population defect in the distribution of the lipid molecules between the outer and inner monolayers, when small bilayer fragments reassemble to form the small bilayer vesicles during the sonication procedure. Such a population defect can only be remedied by lipid transport via the inside in equilibrium outside flip-flop mechanism, which would account for the slow kinetics of annealing observed even at 3 degrees C above the phase transition.

Binding Sites↗

The interpretation of proton magnetic resonance linewidths for lecithin dispersions. Effect of particle size and chain packing.

Two previously reported theoretical treatments of the effect of sonication on the PMR spectrum of phospholipid bilayer membranes have led to divergent conclusions regarding the effects of sonication on the structure of the bilayer membrane. In this report these two theoretical treatments will be critically reviewed, and it will be shown that only the theory of Seiter and Chan (Seiter, C.H.A. and Chan, S.I. (1973) J. Am. Chem. Soc. 95, 7541-7553) yields predictions which are in agreement with experiment. Analysis of available and newly acquired NMR results for sonicated bilayer vesicles of different sizes, both above and below the thermal phase transition, indicates that sonication does disrupt the regular molecular packing of the phospholipid molecules in these systems.

Binding Sites↗