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Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

机译:液态光学检测NMR光谱中的磁光对比

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摘要

We use optical Faraday rotation (OFR) to probe nuclear spins in real time at high-magnetic field in a range of diamagnetic sample fluids. Comparison of OFR-detected NMR spectra reveals a correlation between the relative signal amplitude and the fluid Verdet constant, which we interpret as a manifestation of the variable detuning between the probe beam and the sample optical transitions. The analysis of chemical-shift-resolved, optically detected spectra allows us to set constraints on the relative amplitudes of hyperfine coupling constants, both for protons at chemically distinct sites and other lower-gyromagnetic-ratio nuclei including carbon, fluorine, and phosphorous. By considering a model binary mixture we observe a complex dependence of the optical response on the relative concentration, suggesting that the present approach is sensitive to the solvent-solute dynamics in ways complementary to those known in inductive NMR. Extension of these experiments may find application in solvent suppression protocols, sensitivity-enhanced NMR of metalloproteins in solution, the investigation of solvent-solute interactions, or the characterization of molecular orbitals in diamagnetic systems.
机译:我们使用光学法拉第旋转(OFR)来在一系列反磁性样品液中的高磁场下实时探测核自旋。 OFR检测的NMR光谱的比较揭示了相对信号幅度与流体Verdet常数之间的相关性,我们将其解释为探针束与样品光学跃迁之间的变量失谐的体现。对化学位移分辨的光学检测光谱的分析使我们能够为化学上不同位置的质子和其他低旋磁比核(包括碳,氟和磷)的超精细耦合常数的相对振幅设置约束。通过考虑模型二元混合物,我们观察到光学响应对相对浓度的复杂依赖性,这表明本方法以与感应NMR中已知的互补方式对溶剂-溶质动力学敏感。这些实验的扩展可能会应用于溶剂抑制方案,溶液中金属蛋白的灵敏度增强的NMR,溶剂-溶质相互作用的研究或抗磁系统中分子轨道的表征。

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