论文标题

负强度的NMR光谱的盲源分离

Blind Source Separation for NMR Spectra with Negative Intensity

论文作者

McCarty, Ryan J., Ronghe, Nimish, Woo, Mandy, Alam, Todd M.

论文摘要

NMR光谱数据集,尤其是在样品有限的系统中,可能难以解释它们是否包含多个化学成分(相,多晶型,分子,晶体,玻璃等),并且可能重叠的谐振可能性。在本文中,我们基准了几种用于分析包含负强度的NMR光谱数据集的盲源分离技术。为了进行基准测试,我们生成了一个大型的合成数据库,该数据库的四型固态NMR样光谱,该光谱模拟了旋转晶体T1弛豫或营养尖端/翻转角度实验。我们的基准测试方法仅集中在盲源分离技术重现基础纯组件的光谱的能力上。通常,我们发现FastICA(快速独立的组件分析),简化(简单性相互作用的自我模型分析)和NNMF(非负矩阵分解)是表现最佳的技术。我们证明,盲目分离之前的数据集归一化方法并不能大大改善预后。在研究的噪声水平范围内,我们没有发现技术排名的急剧变化。如果预测过量(虚幻)纯组件(虚幻)纯粹的组件,那么FastICA和Simplisma的准确性会迅速降解。我们的结果表明SVD(单数值分解)方法的性能不佳,我们提出了用于矩阵初始化的替代技术。基准的技术也应用于真实的固态NMR数据集。通常,合成数据集的建议与实际数据分析的建议和结果一致。讨论为将盲源分离到NMR数据集以及将来的基准研究的光谱学家提供了一些其他建议。

NMR spectral datasets, especially in systems with limited samples, can be difficult to interpret if they contain multiple chemical components (phases, polymorphs, molecules, crystals, glasses, etc...) and the possibility of overlapping resonances. In this paper, we benchmark several blind source separation techniques for analysis of NMR spectral datasets containing negative intensity. For benchmarking purposes, we generated a large synthetic datasbase of quadrupolar solid-state NMR-like spectra that model spin-lattice T1 relaxation or nutation tip/flip angle experiments. Our benchmarking approach focused exclusively on the ability of blind source separation techniques to reproduce the spectra of the underlying pure components. In general, we find that FastICA (Fast Independent Component Analysis), SIMPLISMA (SIMPLe-to-use-Interactive Self-modeling Mixture Analysis), and NNMF (Non-Negative Matrix Factorization) are top-performing techniques. We demonstrate that dataset normalization approaches prior to blind source separation do not considerably improve outcomes. Within the range of noise levels studied, we did not find drastic changes to the ranking of techniques. The accuracy of FastICA and SIMPLISMA degrades quickly if excess (unreal) pure components are predicted. Our results indicate poor performance of SVD (Singular Value Decomposition) methods, and we propose alternative techniques for matrix initialization. The benchmarked techniques are also applied to real solid state NMR datasets. In general, the recommendations from the synthetic datasets agree with the recommendations and results from the real data analysis. The discussion provides some additional recommendations for spectroscopists applying blind source separation to NMR datasets, and for future benchmark studies.

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