Karplus equation for NMR coupling constants

E467020

The Karplus equation for NMR coupling constants is an empirical relationship that links three-bond scalar coupling values between nuclei to the dihedral angle between them, enabling the determination of molecular conformations from NMR data.

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Statements (49)

Predicate Object
instanceOf NMR parameter correlation
conformational analysis tool
empirical relationship
appliesTo H–C–C–H dihedral angles
three-bond couplings across a single bond
vicinal proton–proton couplings
assumes coupling constant is periodic in dihedral angle
maximum coupling near 180 degrees
minimum coupling near 90 degrees
calibratedBy experimental NMR data
quantum chemical calculations
category NMR structural restraints
empirical structure–property relationships
dependsOn dihedral angle θ between coupled nuclei
empirical parameters A, B, and C
describes 3J spin–spin coupling constants
three-bond scalar coupling constants
field nuclear magnetic resonance spectroscopy
physical chemistry
structural chemistry
hasVariant Karplus equation for 3J(HN,Hα) in proteins NERFINISHED
Karplus-like equations for heteronuclear couplings
generalized Karplus equation NERFINISHED
historicalContext introduced in the 1950s
involves cosine-squared angular dependence
periodicity of 360 degrees in θ
limitation accuracy decreases for highly substituted systems
does not explicitly include dynamic averaging
parameters are system-dependent
mathematicalForm J = A cos²(θ) + B cos(θ) + C
namedAfter Martin Karplus NERFINISHED
parameter A
B
C
predicts magnitude of 3J coupling constants
relatedTo J-coupling based structure refinement
Ramachandran plot analysis in proteins
relates 3J coupling constants to dihedral angles
NMR coupling constants to molecular conformation
sensitivityTo bond geometry
electronegativity of substituents
substituent effects
usedFor conformational analysis of organic molecules
determining dihedral angles from NMR data
peptide and protein structure determination
protein backbone torsion angle estimation
validating molecular dynamics simulations
usedIn solid-state NMR adaptations
solution-state NMR spectroscopy

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Martin Karplus hasWork Karplus equation for NMR coupling constants