符合性调整提高了螺旋环亚氧化物稳定性,具有较长的偏磁放松时间
Mateusz P Sowiński1, Sahil Gahlawat1,2, Bjarte A Lund1
1Department of Chemistry, UiT The Arctic University of Norway, 9037, Tromsø, Norway.
Communications chemistry
|June 5, 2023
概括
研究人员通过调整形态来增强光谱和成像中的氧化物稳定性. 新的封闭型螺旋环基氧化物显示出更好的抗减少能力,同时保持长时间的放松时间.
科学领域:
- 有机化学 有机化学
- 生物物理化学 生物物理化学
- 材料科学 材料科学 材料科学
背景情况:
- 氧化物作为探针和偏振剂在光谱和成像中至关重要.
- 现有的螺旋环氧化物具有良好的放松特性,但缺乏减少生物环境的稳定性.
- 增强的稳定性对于氧化物基剂的体内应用至关重要.
研究的目的:
- 在降低条件下开发具有增强稳定的氧化物支架.
- 为了研究构造调整对氧化物稳定性和性能的影响.
- 设计改进的氧化旋标签和成像剂.
主要方法:
- 合成了新的氧化物化合物与额外的替代剂.
- 利用X射线晶体学来确定分子构造.
- 运用密度函数理论 (DFT) 计算来分析形状偏好.
- 评估稳定性对抗阿斯酸盐的减少.
- 使用电子磁共振 (EPR) 光谱测量放松时间.
主要成果:
- 结合替代剂诱导了向稳定,封闭的螺旋环形状的转变.
- 封闭的螺旋环基亚氧化物表现出显著增强的稳定性,以减少ascorbate.
- 这些改性氧化物保持了长时间的放松时间,这对于EPR应用至关重要.
- X射线结晶学和DFT计算证实了形状变化.
结论:
- 符合性调整是提高氧化物稳定性的有效策略.
- 封闭的螺旋环基氧化物代表了一个有前途的稳定旋转探针类别.
- 这些发现为设计生物应用的先进氧化物基剂铺平了道路.
相关概念视频
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution
888
At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
888
¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR
1.1K
The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
1.1K
Nuclear Overhauser Enhancement (NOE)
757
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...
757
Double Resonance Techniques: Overview
248
Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
Spin decoupling is usually achieved by...
Spin decoupling is usually achieved by...
248
NMR Spectrometers: Resolution and Error Correction
740
When magnetic nuclei in a sample achieve resonance and undergo relaxation, the signal detected in NMR is an approximately exponential free induction decay. Fourier transform of an exponential decay yields a Lorentzian peak in the frequency domain. Lorentzian peaks in an NMR spectrum are defined by their amplitude, full width at half maximum, and position, where the peak width is governed by the spin-spin relaxation time alone. In real experiments, however, the applied magnetic field is rendered...
740
Other Nuclides: 31P, 19F, 15N NMR
420
Many organic, inorganic, and biological molecules contain spin-half nuclei such as nitrogen-15, fluorine-19, and phosphorus-31. As a result, NMR studies of these nuclei have found extensive applications in chemical and biological research.
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a...
While fluorine-19 and phosphorous-31 have high natural abundances (100%) and positive gyromagnetic ratios, nitrogen-15 has a low natural abundance and a negative gyromagnetic ratio. However, nitrogen-15 is still preferred over nitrogen-14 (which has a...
420


![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)