Magic angle spinning dynamic nuclear polarization solid-state NMR spectroscopy of γ-irradiated molecular organic solids

IF 1.8 3区 化学 Q4 CHEMISTRY, PHYSICAL Solid state nuclear magnetic resonance Pub Date : 2022-06-01 DOI:10.1016/j.ssnmr.2022.101785
Scott L. Carnahan , Yunhua Chen , James F. Wishart , Joseph W. Lubach , Aaron J. Rossini
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引用次数: 5

Abstract

In the past 15 years, magic angle spinning (MAS) dynamic nuclear polarization (DNP) has emerged as a method to increase the sensitivity of high-resolution solid-state NMR spectroscopy experiments. Recently, γ-irradiation has been used to generate significant concentrations of homogeneously distributed free radicals in a variety of solids, including quartz, glucose, and cellulose. Both γ-irradiated quartz and glucose previously showed significant MAS DNP enhancements. Here, γ-irradiation is applied to twelve small organic molecules to test the applicability of γ-irradiation as a general method of creating stable free radicals for MAS DNP experiments on organic solids and pharmaceuticals. Radical concentrations in the range of 0.25 ​mM–10 ​mM were observed in irradiated glucose, histidine, malic acid, and malonic acid, and significant 1H DNP enhancements of 32, 130, 19, and 11 were obtained, respectively, as measured by 1H→13C CPMAS experiments. However, concentrations of free radicals below 0.05 ​mM were generally observed in organic molecules containing aromatic rings, preventing sizeable DNP enhancements. DNP sensitivity gains for several of the irradiated compounds exceed that which can be obtained with the relayed DNP approach that uses exogeneous polarizing agent solutions and impregnation procedures. In several cases, significant 1H DNP enhancements were realized at room temperature. This study demonstrates that in many cases γ-irradiation is a viable alternative to addition of stable exogenous radicals for DNP experiments on organic solids.

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γ辐照有机分子固体的魔角自旋动态核极化固体核磁共振谱
在过去的15年中,魔角旋转(MAS)动态核极化(DNP)作为一种提高高分辨率固体核磁共振光谱实验灵敏度的方法出现了。最近,γ辐照已被用于在各种固体中产生显著浓度的均匀分布的自由基,包括石英、葡萄糖和纤维素。γ辐照石英和葡萄糖先前都显示出显著的MAS DNP增强。本研究将γ-辐照应用于12个小有机分子,以测试γ-辐照作为产生稳定自由基的一般方法在有机固体和药物的MAS DNP实验中的适用性。辐照葡萄糖、组氨酸、苹果酸和丙二酸的自由基浓度在0.25 mM - 10 mM范围内,1H→13C CPMAS实验测得1H DNP分别显著增强32、130、19和11。然而,在含有芳香环的有机分子中,自由基浓度通常低于0.05 mM,这阻碍了DNP的显著增强。几种辐照化合物的DNP灵敏度增益超过了使用外相极化剂溶液和浸渍程序的中继DNP方法所能获得的灵敏度增益。在一些情况下,在室温下实现了显著的1H DNP增强。本研究表明,在许多情况下,在有机固体上进行DNP实验时,γ辐照是一种可行的选择,而不是添加稳定的外源自由基。
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来源期刊
CiteScore
5.30
自引率
9.40%
发文量
42
审稿时长
72 days
期刊介绍: The journal Solid State Nuclear Magnetic Resonance publishes original manuscripts of high scientific quality dealing with all experimental and theoretical aspects of solid state NMR. This includes advances in instrumentation, development of new experimental techniques and methodology, new theoretical insights, new data processing and simulation methods, and original applications of established or novel methods to scientific problems.
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