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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    European biophysics journal 19 (1990), S. 73-78 
    ISSN: 1432-1017
    Schlagwort(e): DNA hydrodynamics ; Cross relaxation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Physik
    Notizen: Abstract Proton-proton relaxation rate constants depend on the angle between the internuclear vector and the principal axis of rotation in symmetric top molecules. It is possible to determine to rotational correlation times of the equivalent ellipsoid for DNA fragments from a knowledge of the axial ratio and the cross-relaxation rate constant for the cytosine H6-H5 vectors. The cross-relaxation rate constants for the cytosine H6-H5 vectors have been measured in the 14-base-pair sequence dGCTGTTGACAATTA.dTAATTGTCAACAGC at four temperatures. The results, along with literature data for DNA fragments ranging from 6 to 20 base pairs can be accounted for by a simple hydrodynamic equation based on the formalism of Woessner (1962). The measured cross-relaxation rate constant is independent of position in the sequence and is consistent with the absence of large amplitude internal motions on the Larmor time scale. All the data can be described by a simple hydrodynamic model, which accounts for the rotational anisotropy of the DNA fragments and allows the correlation time for end-over-end tumbling to be determined if the approximate rise per base pair is known. This is the correlation time that dominates the spectral density functions for internucleotide vectors and is significantly different from that calculated for a sphere of the same hydrodynamic volume for fragments containing more than about 14 base pairs. This method therefore allows NOE intensities used for structure calculation of nucleic acids to be treated more rigorously.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    European biophysics journal 17 (1989), S. 221-232 
    ISSN: 1432-1017
    Schlagwort(e): Cross relaxation ; DNA dynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Physik
    Notizen: Abstract The conformations and internal dynamics of the deoxyriboses of d(CGTACG)2 have been determined by NMR measurements at 15°C. The conformations of the sugars were determined using coupling constants and time-dependent NOE measurements. The J-splitting patterns of the H1′, H2′ and H2″ resonances show that the sugars exist as mixtures of conformations near C2′ endo (south) and C3′ endo (north). The population of the south conformation was larger for the purines than for the pyrimidines. The overall tumbling time of the molecule in 2H2O was determined from measurements of the cross relaxation rate constant for the H6-H5 vectors of the two cytosine residues. Order parameters were determined for the H1′-H2″, H2′-H2″ and H2′-H3′ vectors from measurements of cross relaxation rate constants, making use of multi-spin analysis of the NOE build up rates. These order parameters are weakly dependent of the base sequence, and except for the terminal Cyt 1 residue, the H2′-H2″ and H2′-H3′ vectors are near unity, indicating the absence of rapid pseudorotation on the nanosecond time scale. However, the order parameter for the H1′-H2″ vector is significantly smaller than expected for rapid pseudorotation indicating the presence of other motions of the sugars. This motion must be about an effective axis parallel to the H2′-H″ vector, and to occur with an angular fluctuation of about 30°. The results show that to obtain highly refined structures for nucleic acids by NMR the effects of spin diffusion and motional averaging cannot be ignored.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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