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Oxygen as a paramagnetic probe for nuclear magnetic resonance: Structure and paramagnetic profile of a lipid bilayer/membrane model system.

机译:作为核磁共振顺磁性探针的氧:脂质双层/膜模型系统的结构和顺磁性分布。

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Paramagnetic contact shifts and relaxation rate enhancements from molecular oxygen dissolved in a model membrane, were studied by nuclear magnetic resonance spectroscopy. The model membrane system was an isotropic bicelle formed using 1-myristelaidoyl-2-myristoyl-d27-sn-glycero-3-phosphocholine (MLMPC), a custom phospholipid, and 1-2-dihexanoyl-d22- sn-glycero-3-phosphocholine (DHPC). The 13C and 1H spectra of MLMPC were assigned. Molecular oxygen was delivered at external pressures of 20 and 50 atm. Paramagnetic contact shifts were found to scale with the oxygen solubility gradient in the lipid bilayer, were found to be invariant to temperature changes in the region studied (288K to 331K), and scaled linearly with changes in oxygen pressure. Relaxation rate enhancements from oxygen were low in the headgroup region and increased to a roughly constant rate in the acyl chain region. Rates were comparable to values predicted by simple thermodynamic theories which take into account the observed gradients in diffusion rates and solubility of oxygen in bilayers.
机译:通过核磁共振波谱研究了溶解在模型膜中的分子氧的顺磁接触位移和弛豫速率增强。模型膜系统是使用1-肉豆蔻酰基-2-肉豆蔻酰基-d27-sn-甘油-3-磷酸胆碱(MLMPC),定制的磷脂和1--2-二己酰基-d22-sn-甘油-3-磷酸胆碱(DHPC)。分配了MLMPC的13C和1H光谱。分子氧是在20和50 atm的外部压力下输送的。发现顺磁性接触位移与脂质双层中的氧溶解度梯度成比例,被发现对于所研究区域(288K至331K)的温度变化是不变的,并且随氧压的变化呈线性变化。氧的弛豫速率增强在头基区域较低,而在酰基链区域则增加至大致恒定的速率。速率与简单热力学理论预测的值相当,该理论考虑了观察到的扩散速率梯度和双层中氧的溶解度。

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