A new approach to recognizing the correct pattern of cross-peaks from a noisy 2D asynchronous spectrum by detecting intrinsic symmetry via the Kolmogorov-Smirnov test.

Abstract

The characteristic cluster pattern of cross-peaks in a 2D asynchronous spectrum provides an effective way to reveal the specific physicochemical nature of subtle spectral changes caused by intermolecular interactions. However, the inevitable presence of noise in the 1D spectra used to construct a 2D asynchronous spectrum is significantly amplified, which poses a serious challenge in identifying the correct cluster pattern of the cross-peaks. While mirror symmetry occurs in some types of cross-peaks, it does not occur in other types. The Kolmogorov-Smirnov test provides a statistical means to check whether the mirror symmetry exists or not between a pair of cross-peaks covered by heavy noise. Thus, different types of cross-peak clusters can be distinguished by excavating intrinsic spectral features from the noisy 2D asynchronous spectrum. The effectiveness of this approach in investigating the nature of intermolecular interactions was showcased in both a simulated model system and a real artemisinin/N-methyl pyrrolidone system.