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Hyperpolarization of Neat Liquidsby NMR Signal Amplification by Reversible Exchange

机译:纯净液体的超极化通过NMR信号通过可逆交换放大

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摘要

We report NMR Signal Amplification by Reversible Exchange (SABRE) hyperpolarization of the rare isotopes in “neat” liquids, each composed only of an otherwise pure target compound with isotopic natural abundance (n.a.) and millimolar concentrations of dissolved catalyst. Pyridine (Py) or Py derivatives are studied at 0.4% isotopic natural abundance 15N, deuterated, 15N enriched, and in various combinations using the SABRE-SHEATH variant (microTesla magnetic fields to permit direct 15N polarization from parahydrogen via reversible binding and exchange with an Ir catalyst). We find that the dilute n.a. 15N spin bath in Py still channels spin order from parahydrogen to dilute 15N spins, without polarization losses due to the presence of 14N or 2H. We demonstrate P15N ≈ 1% (a gain of 2900 fold relative to thermal polarization at 9.4 T) at high substrate concentrations. This fundamental finding has a significant practical benefit for screening potentially hyperpolarizable contrastagents without labeling. The capability of screening at n.a. levelof 15N is demonstrated on examples of mono- and dimethyl-substitutedPy (picolines and lutidines previously identified as promising pHsensors), showing that the presence of a methyl group in the orthoposition significantly decreases SABRE hyperpolarization.
机译:我们报告了“纯”液体中稀有同位素的可逆交换(SABRE)超极化的NMR信号放大,每种液体仅由具有同位素天然丰度(n.a.)和毫摩尔浓度的溶解催化剂的纯净目标化合物组成。使用SABRE-SHEATH变体(microTesla)以0.4%同位素自然丰度 15 N,氘化, 15 N富集的吡啶(Py)或Py衍生物进行了研究磁场通过可逆结合和与Ir催化剂的交换而允许对氢直接产生 15 极化)。我们发现稀释n.a. Py中的 15 N自旋浴仍然将自氢的自旋顺序传递到稀薄的 15 N自旋,没有由于 14 N或 2 H。我们证明了在高底物浓度下P15N≈1%(相对于9.4 T时的热极化,增加2900倍)。这一基本发现对于筛选潜在的超极化对比度具有重大的实际益处。代理商没有标签。筛选能力水平在单和二甲基取代的例子中证明了 15 NPy(甲基吡啶和二甲基吡啶以前被确定为有希望的pH传感器),表明邻位甲基的存在位置显着降低SABER超极化。

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