title: Comprehensive solid-state NMR analysis reveals the effects of N-methylation on the molecular dynamics of glycine.
abstract: Molecular dynamics of metabolites are important for their interactions and functions. To understand the structural dependence of molecular dynamics for N-methylated glycines, we comprehensively measured the (13)C and (1)H spin-lattice relaxation times for sarcosine, N,N-dimethylglycine, betaine, and betaine hydrochloride over a temperature range of 178-460 K. We found that the reorientations of methyl groups were observed for all these molecules, whereas reorientations of whole trimethylamine groups were detected in betaines. While similar rotational properties were observed for methyl groups in N,N-dimethylglycine and those in betaine, three methyl groups in betaine hydrochloride had different motional properties (E(a) ≈ 20.5 kJ/mol, τ(0) ≈ 1.85 × 10(-13) s; E(a) ≈ 13.9 kJ/mol, τ(0) ≈ 2.1 × 10(-12) s; E(a) ≈ 15.8 kJ/mol, τ(0) ≈ 1.1 × 10(-12) s). N,N-Dimethylglycine showed a phase transition at 348.5 K with changed relaxation behavior for methyl groups showing distinct E(a) and τ(0) values. The DIPSHIFT experiments showed that CH(3) and CH(2) moieties in these molecules had dipolar-dephasing curves similar to these moieties in alanine and glycine. The activation energies for CH(3) rotations positively correlated with the number of substituted methyl groups. These findings provided useful information for the structural dependence of molecular dynamics for N-methylated glycines and demonstrated solid-state NMR as a useful tool for probing the structure-dynamics relationships.
authors.affiliation: State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Wuhan, PR China.
authors.forename: Jing
authors.initials: J
authors.lastname: Huang
authors.forename: Limiao
authors.initials: L
authors.lastname: Jiang
authors.forename: Pingping
authors.initials: P
authors.lastname: Ren
authors.forename: Limin
authors.initials: L
authors.lastname: Zhang
authors.forename: Huiru
authors.initials: H
authors.lastname: Tang
mesh_terms: D001622:Betaine / Q000737:chemistry; D002152:Calorimetry, Differential Scanning; D002247:Carbon Isotopes / Q000737:chemistry; D005998:Glycine / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008745:Methylation; D056004:Molecular Dynamics Simulation; D011522:Protons; D012521:Sarcosine / Q000031:analogs & derivatives / Q000737:chemistry; D013696:Temperature
chemical_list: D002247:Carbon Isotopes; D011522:Protons; D001622:Betaine; C025138:dimethylglycine; D005998:Glycine; D012521:Sarcosine