Observation of a Low-Temperature, Dynamically Driven Structural Transition in a Polypeptide by Solid-State NMR Spectroscopy

被引:82
作者
Bajaj, Vikram S.
van der Wel, Patrick C. A.
Griffin, Robert G. [1 ]
机构
[1] MIT, Francis Bitter Natl Magnet Lab, Cambridge, MA 02139 USA
基金
加拿大自然科学与工程研究理事会;
关键词
ANGLE-SPINNING NMR; SHIFT CORRELATION SPECTROSCOPY; METHYL-GROUP DYNAMICS; MOLECULAR TORSIONAL ANGLE; CHEMICAL-SHIFT; GLASS-TRANSITION; ROTATING SOLIDS; NEUTRON-SCATTERING; NUCLEAR-POLARIZATION; PROTEIN DYNAMICS;
D O I
10.1021/ja8045926
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
At reduced temperatures, proteins and other biomolecules are generally found to exhibit dynamic as well as structural transitions. This includes a so-called protein glass transition that is universally observed in systems cooled between 200 and 230 K, and which is generally attributed to interactions between hydrating solvent molecules and protein side chains. However, there is also experimental and theoretical evidence for a low-temperature transition in the intrinsic dynamics of the protein itself, absent any solvent. Here, we use low-temperature solid-state NMR to examine site-specific fluctuations in atomic structure and dynamics in the absence of solvents. In particular, we employ magic angle spinning NMR to examine a structural phase transition associated with dynamic processes in a solvent-free polypeptide, N-f-MLF-OH, lattice at temperatures as low as 90 K. This transition is characterized by the appearance of an extra set of lines in 1D N-15 spectra as well as additional cross peaks in 2D C-13-C-13 and C-13-N-15 spectra. Interestingly, the gradual, temperature-dependent appearance of the new spectral component is not accompanied by the line broadening typical of dynamic transitions. A direct comparison between the spectra of N-f-MLF-OH and the analog N-f-MLF-OMe, which does not display this transition, indicates a correlation of the structural transition to the temperature dependent motion of the aromatic phenylalanine side chain. Several quantitative solid state NMR experiments were employed to provide site-specific measurements of structural and motional features of the observed transition.
引用
收藏
页码:118 / 128
页数:11
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