title: Geometry of multiple-spin systems as reflected in 13C-{1H} dipolar spectra measured at Lee-Goldburg cross-polarization.
abstract: Theoretical calculation and analysis of (13)C-{(1)H} dipolar spectra of small-size spin clusters is presented. Dipolar spectra simulated using the time-independent average Hamiltonian are compared with the dipolar profiles obtained by 2D and 3D (1)H-(13)C correlation experiments employing Lee-Goldburg off-resonance cross-polarization (LG-CP). It is demonstrated that the structural parameters such as interatomic distances as well as mutual orientation of internuclear vectors can be derived from the dipolar profiles of simple spin clusters. Simplified analysis of the dipolar spectra based on isolated-like spin-pair approach can be used only if interacting spin cluster is reduced to the three-spin system in which the angle between both internuclear vectors ranges from 45 degrees to 135 degrees . For other local arrangements of spin systems the produced dipolar spectra must be analyzed with high caution. Contributions of all interacting spins to dipolar evolution of (13)C magnetization are mutually mixed and cannot be easily separated. However, simplification of the dipolar spectra is achieved by selective excitation. Enhanced selectivity of LG-CP transfer due to the initial (1)H chemical-shift-evolution period makes it possible to construct the dipolar spectra from (1)H-(13)C cross-peak intensities for every detected (1)H-(13)C spin-pair. Consequently, isolated-like spin pair evolution of the detected (1)H-(13)C coherence dominates to the resulting dipolar profile, while the influence of other interacting spins is suppressed. However, this suppression is not quite complete and analysis of the selective dipolar spectra based on isolated-like spin-pair approach cannot be used generally. Especially evolution of long-range (1)H-(13)C coherence is still significantly affected by spin states of other coupled hydrogen atoms.
authors.affiliation: Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Pracovnici Oddeleni Strukturni Analyzy, Heyrovsky sq. 2, 162 06 Prague 6, Czech Republic.
authors.forename: Jiri
authors.initials: J
authors.lastname: Brus
authors.forename: Jaromír
authors.initials: J
authors.lastname: Jakes
mesh_terms: D000465:Algorithms; D003198:Computer Simulation; D003903:Deuterium / Q000032:analysis / Q000737:chemistry; D005998:Glycine / Q000032:analysis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008956:Models, Chemical; D008958:Models, Molecular; D011522:Protons; D019821:Simvastatin / Q000032:analysis* / Q000737:chemistry*; D013113:Spin Labels
chemical_list: D011522:Protons; D013113:Spin Labels; D019821:Simvastatin; D003903:Deuterium; D005998:Glycine