Abstract
Conformational analysis of the five-membered (furanose) rings of oligonucleotides commonly relies on the use of three-bond (vicinal) 1H-1H spin-coupling constants (3JHH) obtained from an analysis of 2D NMR cross-peaks (Schmitz et al 1990; Emsley et al 1993; Majumdar and Hosur 1992). For a HaCxCyHb fragment, the magnitude of 3JHa,Hb depends on the Cx-Cy torsion angle, with maximal coupling observed when Ha and Hb are eclipsed or antiperiplanar, and minimal coupling observed when these atoms are approximately orthogonal (Karplus 1959); in the ensuing years since this discovery, more refined Karplus relationships have been proposed that account for substitution and/or electronegativity effects at Cx and Cy on 3JHa,Hb (Haasnoot et al 1980).
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Altona C and Sundaralingam M (1972) Conformational analysis of the sugar ring in nucleosides and nucleotides. A new description using the concept of pseudorotation. J Am Chem Soc 94: 8205–8212
Bandyopadhyay T, Wu J and Serianni AS (1993) [l’-13c] 2’-deoxyribonucleosides: Structural and conformational insights derived from 13C-lH spin-coupling constants involving Cl’. J Org Chem 58: 5513–5517
Bock K, Lundt I and Pedersen C (1973) Assignment of anomeric structure to carbohydrates through geminal 13C-lH coupling constants. Tet Letters: 1037–1040
Bock K and Pedersen C (1975) A study of 13CH coupling constants in pentopyranoses and some of their derivatives. Acta Chem Scand Ser B B29: 258–264
Bock K and Pedersen C (1977) Two- and three-bond 13C-lH couplings in some carbohydrates. Acta Chem Scand Ser B B31: 354–358
Cano FH, Foces-Foces C, Jimenez-Barbero J, Alemany A, Bernabe M and Martin-Lomas M (1987) A conformational study of methyl β-cellobioside-d8 by 13C nuclear magnetic resonance spectroscopy: Dihedral angle dependence of 3Jc-H in 13C-O-C-lH arrays. J Org Chem 52: 3367–3372
Cyr N and Perlin AS (1979) The conformations of furanosides. A 13C nuclear magnetic resonance study. Can J Chem 57: 2504–2511
de Leeuw HPM, Haasnoot CAG and Altona C (1980) Empirical correlations between conformational parameters in β-D-fiiranoside fragments derived from a statistical survey of crystal structures of nucleic acid constituents. Isr J Chem 20: 108–126
Emsley L, Dwyer TJ, Spielmann HP and Wemmer DE (1993) Determination of DNA conformational features from selective two-dimensional NMR experiments. J Am Chem Soc 115: 7765–7771
Garrett EC and Serianni AS (1990a) Ab Initio molecular orbital calculations on carbohydrates: Conformational properties of deoxygenated furanose sugars, in Computer Modeling of Carbohydrate Molecules. French AD and Brady JW eds, ACS Symposium Series 430, American Chemical Society, Washington, DC pp 91–119
Garrett EC and Serianni AS (1990b) Ab Initio molecular orbital calculations on furanose sugars: A study with the 6–31G* basis set. Carbohydr Res 206: 183–191
Haasnoot CAG, de Leeuw FAAM and Altona C (1980) The relationship between proton-proton NMR coupling constants and substituent electronegativities I - An empirical generalization of the Karplus equation. Tetrahedron 36: 2783–2792
Hamer GK, Balza F, Cyr N and Perlin AS (1978) Experimental evidence of deviations from a Karplus-like relationship of vicinal carbon-proton coupling constants in some conformationally rigid carbohydrate derivatives. Can J Chem 56: 3109–3116
Hines JV, Varani G, Landry SM and Tinoco I Jr (1993) The stereospecific assignment of H5’ and H5” in RNA using two-bond carbon-proton scalar couplings. J Am Chem Soc, submitted for publication
Jardetzky O (1980) On the nature of molecular conformations inferred from high-resolution NMR. Biochem Biophvs Acta 621: 227–232
Karplus M (1959) Contact electron-spin coupling of nuclear magnetic moments. J Chem Phys 30: 11–15
Lancelot G, Chanteloup L, Beau J-M and Thuong NT (1993) Selectively 13C-enriched DNA: 13C and 1H Assignments of the Lac operator by two-dimensional relayed HMQC experiments. J Am Chem Soc 115: 1599–1560
Levitt M and Warshel A (1978) Extreme conformational flexibility of the furanose ring in DNA and RNA. J Am Chem Soc 100: 2607–2613
Majumdar A and Hosur RV (1992) Simulation of 2D NMR spectra for determination of solution conformations of nucleic acids. Prog NMR Spec 24: 109–158
Montelione GT, Winkler ME, Rauenbuehler P and Wagner G (1989) Accurate measurements of long-range heteronuclear coupling constants from homonuclear 2D NMR spectra of isotope-enriched proteins. J Mag Reson 82: 198–204
Muller N and Pritchard DE (1959) C13 Splittings in proton magnetic resonance spectra I. Hydrocarbons J Chem Phys 31: 768–771
Nikonowicz EP, Sirr A, Legault P, Jucker FM, Baer LM and Pardi A (1992) Preparation of 13C and 15N labeled RNAs for heteronuclear multidimensional NMR studies. Nucl Acids Res 20: 4507–4513
Pearlman DA and Kim S-H (1985) Conformational studies of nucleic acids II. The conformational energetics of commonly occurring nucleosides. J Biomol Struct Dyn 3: 99–125
Rinkel LJ and Altona C (1987) Conformational analysis of the deoxyribofuranose ring in DNA by means of sums of proton-proton coupling constants: A graphical method. J Biomol Struct Dyn 4: 621–649
Salazar M, Federoff OY, Miller JM, Ribeiro NS and Reid BR (1993) The DNA strand in DNA. RNA hybrid duplexes is neither B-form nor A- form in solution. Biochemistry 32: 4207–4215
Schmitz U, Zon G and James TL (1990) Deoxyribose conformation in [d(GTATATAC]2: Evaluation of sugar pucker by simulation of double- quantum-filtered COSY cross-peaks. Biochemistry 29: 2357–2368
Schwarcz J A, Cyr N and Perlin AS (1972) Orientational dependence of vicinal and geminal 13C-1H coupling. Can J Chem 50: 3667–3676
Schwarcz JA, Cyr N and Perlin AS (1975) Orientational effects and the sign of two-bond 13C-1H coupling. Can J Chem 53: 1872–1875
Serianni AS and Barker R (1984) [13C]-Enriched tetroses and tetrofuranosides: An evaluation of the relationship between NMR parameters and furanosyl ring conformation. J Org Chem 49: 3292–3300
Tvaroska I, Hricovini M and Petrakova E (1989) An attempt to derive a new Karplus-type equation of vicinal proton-carbon coupling constants for C-O-C-H segments of bonded atoms. Carbohydr Res 189: 359–362
Varani G and Tinoco I Jr (1991) Carbon assignments and heteronuclear coupling constants for an RNA oligonucleotide from natural abundance 13C-!H correlated experiments. J Am Chem Soc 113: 9349–9354
Westhof E and Sundaralingam M (1983) A method for the analysis of puckering disorder in five-membered rings: The relative mobilities of furanose and proline rings and their effects on polynucleotide and polypeptide backbone flexibility. J Am Chem Soc 105: 970–976
Wu J and Serianni AS (1993) [l3C]-Labeled oligodeoxyribonucleotides: A solution study of a CCAAT-containing sequence at the NF-I recognition site of human adenovirus. Submitted for publication
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1994 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Serianni, A.S. (1994). 13C-1H Spin-Coupling Constants in Furanosyl Rings: Application to Oligonucleotide Structure Determination. In: Stassinopoulou, C.I. (eds) NMR of Biological Macromolecules. NATO ASI Series, vol 87. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-79158-1_16
Download citation
DOI: https://doi.org/10.1007/978-3-642-79158-1_16
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-79160-4
Online ISBN: 978-3-642-79158-1
eBook Packages: Springer Book Archive