タンパク質の表面的介電定数とその温度が,遠隔の化学的シフト効果による依存性
Liaoyuan An1, Yefei Wang, Ning Zhang
1Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences , Qingdao, 266101, China.
Journal of the American Chemical Society
|September 6, 2014
まとめ
この研究は,タンパク質の電場変化を測定するための新しいNMRプロトコルを導入しています. この方法は,化学シフト乱動 (CSP) を正確に定量化し,温度に依存する介電性体を明らかにします.
科学分野:
- バイオフィジックス 生物物理学
- 構造生物学 構造生物学とは
- 核磁共振 (NMR) スペクトロスコピー
背景:
- タンパク質の突然変異は,電場を変化させ,分子相互作用に影響を与える可能性があります.
- これらの微妙な電場変化を遠隔で測定することは困難です.
- 核磁共振 (NMR) は,タンパク質の構造と動態を研究するための強力なツールです.
研究 の 目的:
- 遠隔化学シフト干渉 (CSP) を正確に測定するための核磁気共鳴 (NMR) プロトコルを開発および検証.
- 変異による電場変化とCSPとの関係を調査する.
- タンパク質の表面的介電定数 (εa) とその温度依存度を測定する.
主な方法:
- GB3タンパク質変異体 (K19AとK19E) の (1) H (N) CSPを測定するために新しいNMRプロトコルを使用しました.
- CSPを電場変化に合わせるためにバッキンガム方程式を適用した.
- 明確な溶媒で分子動力学シミュレーションを行った.
主要な成果:
- 変異によって引き起こされる電場変化によって引き起こされる微小,遠隔のCSPの正確な測定が達成されました.
- タンパク質 GB3.3 に対して 298 K で 8.6 ± 0.8 の表面的介電定数 (εa) が決定されました.
- CSPと派生したEa値は,強い温度依存を示し,Eaは278Kの7.3から313Kの10.5に増加した.
- 分子ダイナミクスシミュレーションでは,溶媒水がエーアに有意に寄与していることが示された.
結論:
- 開発されたNMRプロトコルは,タンパク質内の電場乱れを正確に定量化することを可能にします.
- この研究は,タンパク質の介電性および温度の影響についての洞察を提供します.
- 溶媒水は,タンパク質の観察された介電性行動において重要な役割を果たします.
関連する概念動画
Susceptibility, Permittivity and Dielectric Constant
3.6K
When placed in an external electric field, a dielectric material gets polarized. The charge density in the dielectric material is given by the sum of the bound and free charge densities, while the total charge density can also be written in terms of the total electric field. The bound charge density can be measured in terms of polarization, leading to the relationship between electric displacement and polarization.
3.6K
Inductive Effects on Chemical Shift: Overview
2.3K
The protons in unsubstituted alkanes are strongly shielded with chemical shifts below 1.8 ppm. Methine, methylene, and methyl protons appear at approximately 1.7, 1.2 and 0.7 ppm, while the proton signal from methane appears at 0.23 ppm. An electronegative substituent, such as chlorine, withdraws the electron density from the protons, increasing their chemical shift. Progressive substitution of the hydrogens in methane by chlorine shifts the proton signals increasingly downfield, to 3.05 ppm in...
2.3K
NMR Spectroscopy: Chemical Shift Overview
3.6K
The position of the absorption signal of a sample is reported relative to the position of the signal of tetramethylsilane (TMS), which is added as an internal reference while recording spectra. The difference between the absorption frequencies of the sample and TMS (in Hz) is divided by the spectrometer operating frequency (in MHz) to obtain a dimensionless quantity called the chemical shift. It is reported on the δ (delta) scale and expressed in parts per million.
For instance, the proton...
For instance, the proton...
3.6K
π Electron Effects on Chemical Shift: Overview
1.5K
An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
1.5K
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
1.7K
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as...
1.7K
Chemical Shift: Internal References and Solvent Effects
1.4K
In an NMR sample, precise measurement of the absolute absorption frequencies of nuclei is difficult. A standard internal reference compound is added, and the frequency difference between the reference signal and sample signals is measured.
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
1.4K


