title: Analysis of local molecular motions of aromatic sidechains in proteins by 2D and 3D fast MAS NMR spectroscopy and quantum mechanical calculations.
abstract: We report a new multidimensional magic angle spinning NMR methodology, which provides an accurate and detailed probe of molecular motions occurring on timescales of nano- to microseconds, in sidechains of proteins. The approach is based on a 3D CPVC-RFDR correlation experiment recorded under fast MAS conditions (ν(R) = 62 kHz), where (13)C-(1)H CPVC dipolar lineshapes are recorded in a chemical shift resolved manner. The power of the technique is demonstrated in model tripeptide Tyr-(d)Ala-Phe and two nanocrystalline proteins, GB1 and LC8. We demonstrate that, through numerical simulations of dipolar lineshapes of aromatic sidechains, their detailed dynamic profile, i.e., the motional modes, is obtained. In GB1 and LC8 the results unequivocally indicate that a number of aromatic residues are dynamic, and using quantum mechanical calculations, we correlate the molecular motions of aromatic groups to their local environment in the crystal lattice. The approach presented here is general and can be readily extended to other biological systems.
authors.affiliation: Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, PL-90-363 Łodz, Poland. marekpot@cbmm.lodz.pl.
authors.forename: Piotr
authors.initials: P
authors.lastname: Paluch
authors.affiliation: Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, PL-90-363 Łodz, Poland. marekpot@cbmm.lodz.pl.
authors.forename: Tomasz
authors.initials: T
authors.lastname: Pawlak
authors.affiliation: Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, PL-90-363 Łodz, Poland. marekpot@cbmm.lodz.pl.
authors.forename: Agata
authors.initials: A
authors.lastname: Jeziorna
authors.affiliation: Unit of Catalysis and Chemistry of Solids (UCCS), CNRS-8181, University Lille North of France, 59652 Villeneuve d'Ascq, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Trébosc
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, USA. tpolenov@udel.edu.
authors.forename: Guangjin
authors.initials: G
authors.lastname: Hou
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, USA. tpolenov@udel.edu.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Vega
authors.affiliation: Unit of Catalysis and Chemistry of Solids (UCCS), CNRS-8181, University Lille North of France, 59652 Villeneuve d'Ascq, France and Physics Department & Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Amoureux
authors.affiliation: Institute of Organic Chemistry and Biochemistry, AS CR, Flemingovo nam. 2, Prague, Czech Republic. dracinsky@uochb.cas.cz.
authors.forename: Martin
authors.initials: M
authors.lastname: Dracinsky
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, USA. tpolenov@udel.edu.
authors.forename: Tatyana
authors.initials: T
authors.lastname: Polenova
authors.affiliation: Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, PL-90-363 Łodz, Poland. marekpot@cbmm.lodz.pl.
authors.forename: Marek J
authors.initials: MJ
authors.lastname: Potrzebowski
mesh_terms: D002247:Carbon Isotopes / Q000737:chemistry; D056445:Cytoplasmic Dyneins / Q000737:chemistry*; D008958:Models, Molecular; D019906:Nuclear Magnetic Resonance, Biomolecular; D010455:Peptides / Q000737:chemistry; D011789:Quantum Theory; D018080:Receptors, GABA-B / Q000737:chemistry*
chemical_list: D002247:Carbon Isotopes; D010455:Peptides; D018080:Receptors, GABA-B; D056445:Cytoplasmic Dyneins