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Determination of the Gas-phase Acidities of Oligopeptides
Published on: June 24, 2013
胆固醇在不和酸乙醇胺中的分子组织:X射线衍射和固态2HNMR揭示了与酸乙醇胆的差异
Saame Raza Shaikh1, Vadim Cherezov, Martin Caffrey
1Department of Biology, Indiana University Purdue University Indianapolis, 723 West Michigan Street, Indianapolis, Indiana 46202-5132, USA.
Journal of the American Chemical Society
|April 20, 2006
概括
胆固醇与酸乙烯胺 (PE) 与酸胆 (PC) 相比,与酸乙烯胺 (PE) 相互作用的方式不同. 增加PE乙烯链中的不和度会降低胆固醇的溶解度,影响膜组织和潜在的健康益处.
科学领域:
- 膜生物物理学 膜生物物理学
- 脂质双层组织组织
- 胆固醇-脂质相互作用
背景情况:
- 主要的哺乳动物等离子体膜脂质包括类胆 (PC),类乙醇胺 (PE) 和胆固醇.
- 虽然PC-胆固醇的相互作用已经被充分理解,但PE-胆固醇的相互作用在很大程度上仍未被探索.
- 了解这些相互作用对于理解细胞膜结构和功能至关重要.
研究的目的:
- 为了研究胆固醇在酸丁乙醇胺 (PE) 中的分子组织,具有不同的乙烯链不和.
- 为了比较胆固醇在PEs中的行为与其在酸丁胆 (PCs) 中已知的行为.
主要方法:
- 使用X射线衍射来确定不同程度的乙烯链不和的PE中的胆固醇溶解度.
- 乳 (2H) 核磁共振 (NMR) 光谱法用于评估这些PE膜内的胆固醇的方向.
主要成果:
- 在sn-1和PE中胆固醇溶解度随着sn-2链中的多不和度的增加而显著降低,从一个双键的51mol%降至两个链中的六个双键的8.5mol%.
- 尽管溶解度降低,但胆固醇的方向 (倾斜角度为15±1度) 仍然不受PE中的乙烯链不和的影响.
- 这种行为与PCs形成鲜明对比,PCs始终包含大约50%的醇,这表明PE的差异性亲和力和横向分离倾向.
结论:
- 在PE中胆固醇溶解度高度依赖于乙链不和度,与PC不同.
- 多不和PE对胆固醇具有差异性亲和力,可能会在膜内驱动横向分离.
- 这些发现可能解释了饮食中的多不和脂肪酸的生物学含义,这些脂肪酸优先纳入PE,以及它们的相关健康益处.
相关概念视频
Proton (¹H) NMR: Chemical Shift
Organic molecules primarily contain carbon and hydrogen atoms. While all the hydrogen isotopes are NMR-active, protium or hydrogen-1 is the most abundant. It has a significant energy separation between its nuclear spin states due to its large gyromagnetic ratio. As per Boltzmann's distribution, an increase in the energy separation implies a greater excess population of nuclei available for excitation, resulting in a strong NMR absorption signal.
Absorption signals of all the protium nuclei in a...
Absorption signals of all the protium nuclei in a...
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 of Labile Protons: Temporal Resolution
Protons bonded to heteroatoms such as nitrogen and oxygen exhibit a range of chemical shift values. This is due to the varying degree of hydrogen bonding between the proton and the heteroatom in other molecules. The extent of hydrogen bonding affects the electron density around the proton, thereby giving different chemical shift values for the protons in the proton NMR spectrum.
The –OH proton in alcohols typically appears in the range of δ 2 to 5 ppm but can vary depending on the specific...
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Spectroscopy of Carboxylic Acid Derivatives
Infrared spectroscopy is primarily used to determine the types of bonds and functional groups. In carboxylic acid derivatives, a typical carbonyl bond absorption is observed around 1650–1850 cm−1. For esters, the absorption is recorded at around 1740 cm−1, while acid halides show the absorption at about 1800 cm−1. Another acid derivative, the acid anhydrides, exhibit two carbonyl absorption around 1760 cm−1 and 1820 cm−1, arising from the symmetrical and unsymmetrical carbonyl vibration.
In the...
In the...
NMR Spectroscopy and Mass Spectrometry of Aldehydes and Ketones
In aldehydes, the hydrogen atom connected to the carbonyl carbon helps distinguish aldehydes from other carbonyl compounds using ¹H NMR spectroscopy. The closeness of aldehydic hydrogen to the electrophilic carbonyl carbon highly deshields the hydrogen atom causing its signal to appear around 10 ppm in the ¹H NMR spectra. α hydrogens split the aldehydic proton signal, which helps identify the number of α hydrogens in the molecule. For instance, one α hydrogen creates a doublet for an aldehydic...
Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation
The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include ⍺-cleavage and McLafferty rearrangement. Fragmentation by ⍺-cleavage preferentially occurs at the carbon-carbon bond at the ⍺-position next to the carboxylic group to generate a neutral radical and a cation. Long chain compounds with hydrogen at their γ-carbon undergo McLafferty rearrangement to give a radical cation and a neutral alkene.
For example, the fragmentation of...
For example, the fragmentation of...

