Enhancing the NMR signals of plant oil components using hyperpolarisation relayed via proton exchange.
Enhancing the NMR signals of plant oil components using hyperpolarisation relayed via proton exchange.
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DOI：
10.1039/d3sc03078d
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发表时间：
2023-09-20
期刊：
影响因子：
8.4
通讯作者：
Duckett, Simon B.
中科院分区：
文献类型：
--
作者：
Alshehri, Adel;Tickner, Ben. J.;Iali, Wissam;Duckett, Simon B.
在这项工作中，有限的灵敏度的磁共振是解决通过使用超极化方法中继信号放大可逆交换（SABRE-Relay）转移潜在的磁性从仲氢，一个容易分离的自旋异构体的氢气，主要植物油，如香茅醇，香叶醇，橙花醇的组成部分。这是通过中继极化转移来实现的，其中[Ir（H）2（IMes）（NH 2 R）3]Cl型络合物在超极化载体（NH 2 R）和含OH的植物油组分之间的不稳定质子交换之前在溶液中产生游离的超极化NH 2 R，从而为后者产生增强的NMR信号。因此，到CA。200-在几秒钟内记录这些精油的1H（0.65%1H极化）和800倍13 C NMR信号增强（0.65%13C极化）。值得注意的是，由此产生的NMR信号不仅是诊断，但证明通过一个合适的耦合网络在大自旋系统传播。的路线，以优化增强过程中通过改变载体NH 2 R的身份，其浓度被证明。为了证明实用性，这些试点测量扩展到研究更广泛的植物衍生分子，包括玫瑰醇，马鞭草烯醇，（1 R）-endo-（+）-fenchyl alcohol，（−）-carveol和芳樟醇。然后描述了进一步的测量，其证明香茅醇和香叶醇可以在现成的保健产品玫瑰香叶油中以仅几十μM的浓度在单扫描1H NMR测量中检测到，这在可比的热极化NMR实验中不可见。因此，这项工作提出了一个显着的扩展类型的分子服从超极化使用仲氢，并说明了一个现实世界中的应用，在诊断检测混合物中的低浓度分析物。超极化方法SABRE-Relay可以通过仲氢增强载体分子的中继质子交换来增强植物油组分的NMR信号。这允许更容易地检测天然油中的低浓度分析物。
In this work, the limited sensitivity of magnetic resonance is addressed by using the hyperpolarisation method relayed signal amplification by reversible exchange (SABRE-Relay) to transfer latent magnetism from para-hydrogen, a readily isolated spin isomer of hydrogen gas, to components of key plant oils such as citronellol, geraniol, and nerol. This is achieved via relayed polarisation transfer in which an [Ir(H)2(IMes)(NH2R)3]Cl type complex produces hyperpolarised NH2R free in solution, before labile proton exchange between the hyperpolarisation carrier (NH2R) and the OH-containing plant oil component generates enhanced NMR signals for the latter. Consequently, up to ca. 200-fold 1H (0.65% 1H polarisation) and 800-fold 13C NMR signal enhancements (0.65% 13C polarisation) are recorded for these essential oils in seconds. Remarkably, the resulting NMR signals are not only diagnostic, but prove to propagate over large spin systems via a suitable coupling network. A route to optimise the enhancement process by varying the identity of the carrier NH2R, and its concentration is demonstrated. In order to prove utility, these pilot measurements are extended to study a much wider range of plant-derived molecules including rhodinol, verbenol, (1R)-endo-(+)-fenchyl alcohol, (−)-carveol, and linalool. Further measurements are then described which demonstrate citronellol and geraniol can be detected in an off-the-shelf healthcare product rose geranium oil at concentrations of just a few tens of μM in single scan 1H NMR measurements, which are not visible in comparable thermally polarised NMR experiments. This work therefore presents a significant expansion of the types of molecules amenable to hyperpolarisation using para-hydrogen and illustrates a real-world application in the diagnostic detection of low concentration analytes in mixtures. The hyperpolarisation method SABRE-Relay can boost NMR signals of plant oil components by relayed proton exchange from a para-hydrogen enhanced carrier molecule. This allows low concentration analytes in natural oils to be detected more easily.
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