通过双量子固态NMR检测到的罗多素染色体的蛋白质诱导的结合干扰
Marina Carravetta1, Xin Zhao, Ole G Johannessen
1Physical Chemistry Division, Stockholm University, S-106 91 Stockholm, Sweden.
Journal of the American Chemical Society
|March 25, 2004
概括
高分辨率的NMR揭示了罗多素的视网二烯染色体的键长变化. 这支持了一个水分子和充电残留物稳定光异构化的模型.
科学领域:
- 生物物理学的生物物理.
- 结构生物学 结构生物学
- 频谱学是一种光谱学.
背景情况:
- 罗多普辛是一种关键的视觉色素,负责光线检测.
- 了解视网烯染色体的结构对于阐明其功能至关重要.
- 之前的研究缺乏关于染色体键动态的原子级细节.
研究的目的:
- 为了获得高分辨率的碳-碳键长度数据,用于 rhodopsin 中的 retinylidene 染色体.
- 为了研究染色体内的局部扰动.
- 为了测试光异构化机制的模型.
主要方法:
- 双量子固态核磁共振 (NMR) 光谱学.双量子固态核磁共振 (NMR) 光谱学.
- 使用非晶体,同位素标记的牛罗多素样本.
- 实现空间分辨率为3皮科米 (分钟).
主要成果:
- 检测到网利丁染色体碳-碳键长度的局部干扰.
- 观察到从质子化希夫基向聚烯链的电荷透.
- 在谷氨酸-181和氨酸-186附近发现了水分子稳定正电荷的证据.
结论:
- 这些发现支持一个模型,其中附近的水分子和极地残留物稳定电荷.
- 这种稳定是为了促进视网二烯染色体的快速和选择性光异构化.
- 提供了对视觉信号传导机制的原子层次见解.
相关概念视频
¹H NMR: Complex Splitting
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
¹H NMR: Interpreting Distorted and Overlapping Signals
Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...
Atomic Nuclei: Magnetic Resonance
The number of nuclear spins aligned in the lower energy state is slightly greater than those in the higher energy state. In the presence of an external magnetic field, as the spins precess at the Larmor frequency, the excess population results in a net magnetization oriented along the z axis. When a pulse or a short burst of radio waves at the Larmor frequency is applied along the x axis, the coupling of frequencies causes resonance and flips the nuclear spins of the excess population from the...
NMR Spectroscopy: Spin–Spin Coupling
The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved in...
¹H NMR Signal Multiplicity: Splitting Patterns
When protons A and X are coupled, their nuclear spin energy levels are slightly modified. This is because the energy required to excite proton A to a spin state parallel to proton X is slightly different from the energy required for it to become anti-parallel to spin X. Consequently, there are two possible excitation frequencies for A (A1 and A2), depending on the spin state of X, and vice versa. The mutual nature of coupling implies that the difference between frequencies A1 and A2, indicated...
Nuclear Overhauser Enhancement (NOE)
Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the nuclear Overhauser enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring spin-active...


