Université de Lyon, Centre de RMN à Très Hauts Champs de Lyon, UMR5082 - CNRS/UCBL/ENS de Lyon, Villeurbanne, France.
Université de Lyon, CPE Lyon, CNRS, Catalyse, Chimie, Polymères et Procédés, UMR 5265, Lyon, France.
Nat Commun. 2021 Aug 4;12(1):4695. doi: 10.1038/s41467-021-24279-2.
Hyperpolarization by dissolution dynamic nuclear polarization (dDNP) has enabled promising applications in spectroscopy and imaging, but remains poorly widespread due to experimental complexity. Broad democratization of dDNP could be realized by remote preparation and distribution of hyperpolarized samples from dedicated facilities. Here we show the synthesis of hyperpolarizing polymers (HYPOPs) that can generate radical- and contaminant-free hyperpolarized samples within minutes with lifetimes exceeding hours in the solid state. HYPOPs feature tunable macroporous porosity, with porous volumes up to 80% and concentration of nitroxide radicals grafted in the bulk matrix up to 285 μmol g. Analytes can be efficiently impregnated as aqueous/alcoholic solutions and hyperpolarized up to P(C) = 25% within 8 min, through the combination of H spin diffusion and H → C cross polarization. Solutions of C-analytes of biological interest hyperpolarized in HYPOPs display a very long solid-state C relaxation times of 5.7 h at 3.8 K, thus prefiguring transportation over long distances.
通过溶解动态核极化(dDNP)实现的超极化,在光谱学和成像方面具有很有前景的应用,但由于实验复杂性,仍未得到广泛应用。通过从专用设备远程制备和分配超极化样品,可以实现 dDNP 的广泛普及。在这里,我们展示了超极化聚合物(HYPOPs)的合成,它可以在几分钟内生成自由基和无污染的超极化样品,在固态中的寿命超过数小时。HYPOPs 具有可调节的大孔孔隙率,多孔体积高达 80%,并且在体基质中接枝的氮氧自由基的浓度高达 285μmol/g。分析物可以作为水溶液/醇溶液高效浸渍,并通过 H 自旋扩散和 H→C 交叉极化在 8 分钟内将超极化至 P(C)=25%。在 HYPOPs 中超极化的具有生物意义的 C 分析物的溶液在 3.8 K 时显示出非常长的固态 C 弛豫时间为 5.7 小时,因此预示着可以远距离运输。
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