Skip to main content

13C-1H Spin-Coupling Constants in Furanosyl Rings: Application to Oligonucleotide Structure Determination

  • Conference paper
NMR of Biological Macromolecules

Part of the book series: NATO ASI Series ((ASIH,volume 87))

  • 187 Accesses

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).

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Bock K, Lundt I and Pedersen C (1973) Assignment of anomeric structure to carbohydrates through geminal 13C-lH coupling constants. Tet Letters: 1037–1040

    Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Bock K and Pedersen C (1977) Two- and three-bond 13C-lH couplings in some carbohydrates. Acta Chem Scand Ser B B31: 354–358

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Cyr N and Perlin AS (1979) The conformations of furanosides. A 13C nuclear magnetic resonance study. Can J Chem 57: 2504–2511

    Article  CAS  Google Scholar 

  • 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

    Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Chapter  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Google Scholar 

  • Jardetzky O (1980) On the nature of molecular conformations inferred from high-resolution NMR. Biochem Biophvs Acta 621: 227–232

    CAS  Google Scholar 

  • Karplus M (1959) Contact electron-spin coupling of nuclear magnetic moments. J Chem Phys 30: 11–15

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Levitt M and Warshel A (1978) Extreme conformational flexibility of the furanose ring in DNA and RNA. J Am Chem Soc 100: 2607–2613

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Muller N and Pritchard DE (1959) C13 Splittings in proton magnetic resonance spectra I. Hydrocarbons J Chem Phys 31: 768–771

    CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Schwarcz J A, Cyr N and Perlin AS (1972) Orientational dependence of vicinal and geminal 13C-1H coupling. Can J Chem 50: 3667–3676

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints 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

Publish with us

Policies and ethics