15N NMR spectroscopy 28—solvent effects on the 15N13C coupling constants of amides, imides, ureas and polypeptides

The 15N13C coupling constants of 15N-enriched acetamide, N-acetylglycine anilide, phthalimide, α,α′-bisphthalimido-p-xylene, N-methyl-N′-phenylurea, poly-L-alanine and poly-L-valine were measured in various solvents. It was found that the 15N13C coupling constants depend largely on the nature of the solvent. Increasing acidity leads to higher one-bond and lower two-bond coupling constants. A change of concentration does not have any influence on the 15N13C couplings while a large increase in temperature leads to a slightly lower 1J(NC). It is concluded that solvent effects may limit the use of 15N13C coupling constants for the elucidation of solvent-induced conformational changes.

[1]  H. Kricheldorf 15N NMR spectroscopy 24—chemical shifts and coupling constants of α-amino acid N-carboxyanhydrides and related heterocycles† , 1980 .

[2]  H. Kricheldorf 15N NMR spectroscopy 26 coil-helix transition of poly-L-ornithine , 1980, Polymer Bulletin.

[3]  H. Kricheldorf Helical poly(L‐alanine) in trifluoroacetic acid , 1979 .

[4]  M. Llinás,et al.  Signs of heteronuclear spin–spin coupling constants in 15N‐acetamide , 1979 .

[5]  T. Ohki,et al.  Salt‐induced conformational change of random copolymers (Lys50Tyr50)n and (Lys50Phe50)n studied by 1H‐ and 13C‐nuclear magnetic resonances. Aggregation behavior of helical segments , 1979 .

[6]  H. Rüterjans,et al.  NMR investigations on alanyl-[15% 13C, 95% 15N]-proline: 15N chemical shifts and 13C15N coupling constants , 1978 .

[7]  H. Kricheldorf 15N NMR spectroscopy, 9. Solvent effects on polypeptides and polyamides , 1978 .

[8]  Y. Inoue,et al.  13C and 1H NMR studies of helix‐coil transition of poly(β‐benzyl‐L‐aspartate) and poly(γ‐benzyl‐L‐glutamate): Behavior in nonprotonating solvent mixtures, and origin of solvent‐induced chemical shift , 1977 .

[9]  R. Komoroski,et al.  A nuclear magnetic resonance study of the helix–coil transition of poly(L‐glutamic acid) , 1977, Biopolymers.

[10]  H. R. Kricheldorf Mechanismus der NCA‐Polymerisation, 4. Synthese und Reaktionen von N‐Acyl‐NCA , 1977 .

[11]  T. Venanzi,et al.  Relationship between /sup 15/N/sup 13/C coupling constants and hybridization , 1976 .

[12]  T. Venanzi,et al.  Theory and calculation of carbon-nitrogen spin-spin coupling constants , 1976 .

[13]  John D. Roberts,et al.  NITROGEN-15 MAGNETIC RESONANCE SPECTROSCOPY. II. COUPLING CONSTANTS. , 1964 .

[14]  F. Bovey NMR observations of polypeptide conformations , 1974 .

[15]  J. Pople,et al.  Approximate self-consistent molecular orbital theory of nuclear spin coupling. I. Directly bonded carbon-hydrogen coupling constants , 1970 .

[16]  R. Gillespie,et al.  A NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF THE PROTONATION OF AMIDES IN FLUOROSULPHURIC ACID , 1963 .