对于固定蛋白质矩阵中的兰坦化离子序列的磁感应张量异构
I Bertini1, M B Janik, Y M Lee
1Department of Chemistry, University of Florence, Via Gino Capponi 9, 50121, Florence, Italy.
Journal of the American Chemical Society
|July 18, 2001
概括
兰他尼德离子被纳入了calbindin D ((9k),显示出一致的协调环境. 这项研究验证了Bleaney关于溶液中兰化物复合物的理论,为磁性特性提供了洞察力.
科学领域:
- 生物物理化学 生物物理化学
- 结构生物学 结构生物学
- 兰化物化学 兰化物化学
背景情况:
- 兰化物离子在生物系统中充当探针,但它们的协调环境和蛋白质中的磁性属性尚未完全理解.
- 卡尔宾丁D ((9k) 是一种结合的蛋白质,可以在其结合部位容纳各种类离子.
研究的目的:
- 调查结蛋白calbindin D ((9k)) 中的一系列兰化离子的协调环境和磁性特性.
- 用一个一致的蛋白质环境来实验评估Bleaney在溶液中的兰坦化物复合物的理论.
主要方法:
- 在calbindin D ((9k)) 的C端结合部位中加入化离子 (不包括Pm和Gd).
- 核磁共振 (NMR) 光谱学,特别是异核单量子相干 (HSQC) 实验,用于测量化学变化.
- 通过减去La (III) 和Lu (III) 衍生物的二磁性贡献来估计伪接触移位 (PCS).
- 同时确定结构,使用来自Ce (III) 衍生物的核过量效应 (NOE) 数据和来自所有兰坦化物的PCS数据.
主要成果:
- 在calbindin D ((9k)) 内的兰化物系列中保持了一致的协调环境.
- 大量的NMR信号允许对PCS进行超精细转移的专属分配.
- 对于每个兰坦化物,确定了磁感应张量异位素,与布莱尼的理论有很好的一致性.
- 这项研究证实了所有纳入的兰坦化的协调环境的相似性.
结论:
- 兰化物离子可以可靠地用于探测像calbindin D ((9k)) 等蛋白质的结构和动态.
- 这些结果为布莱尼的理论提供了强有力的实验支持,特别是关于溶液中兰他化物复合物的磁性.
- 这项工作为在复杂的生物系统中使用胺离子作为磁性探针奠定了基础.
相关概念视频
Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Crystal Field Theory - Octahedral Complexes
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Crystal Field Theory - Tetrahedral and Square Planar Complexes
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Colors and Magnetism
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
Diamagnetism
Materials consisting of paired electrons have zero net magnetic moments. However, when these materials are placed under an external magnetic field, the moments opposite to the field are induced. Such materials are called diamagnets. Diamagnetism is the response of the diamagnets when placed in an external magnetic field.
Diamagnetism was discovered by Anton Brugmans in 1778 when he observed that bismuth gets repelled by magnetic fields, thus theorizing that diamagnets get repelled by magnets.
Diamagnetism was discovered by Anton Brugmans in 1778 when he observed that bismuth gets repelled by magnetic fields, thus theorizing that diamagnets get repelled by magnets.
Magnetic Susceptibility and Permeability
In linear magnetic materials, like paramagnets and diamagnets, magnetization is proportional to the magnetic field intensity. The constant of proportionality, a dimensionless number, is called magnetic susceptibility. The value of the susceptibility depends on the type of material.
When diamagnetic materials are placed under an external magnetic field, the moments opposite to the field are induced. Hence, the susceptibility for diamagnets has a minimal negative value of 10-5–10-6. Since...
When diamagnetic materials are placed under an external magnetic field, the moments opposite to the field are induced. Hence, the susceptibility for diamagnets has a minimal negative value of 10-5–10-6. Since...


