Srivastava Madhur, Georgieva Elka R, Freed Jack H
National Biomedical Center for Advanced ESR Technology, ‡Meinig School of Biomedical Engineering, and §Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
J Phys Chem A. 2017 Mar 30;121(12):2452-2465. doi: 10.1021/acs.jpca.7b00183. Epub 2017 Mar 17.
We adapt a new wavelet-transform-based method of denoising experimental signals to pulse-dipolar electron-spin resonance spectroscopy (PDS). We show that signal averaging times of the time-domain signals can be reduced by as much as 2 orders of magnitude, while retaining the fidelity of the underlying signals, in comparison with noiseless reference signals. We have achieved excellent signal recovery when the initial noisy signal has an SNR ≳ 3. This approach is robust and is expected to be applicable to other time-domain spectroscopies. In PDS, these time-domain signals representing the dipolar interaction between two electron spin labels are converted into their distance distribution functions P(r), usually by regularization methods such as Tikhonov regularization. The significant improvements achieved by using denoised signals for this regularization are described. We show that they yield P(r)'s with more accurate detail and yield clearer separations of respective distances, which is especially important when the P(r)'s are complex. Also, longer distance P(r)'s, requiring longer dipolar evolution times, become accessible after denoising. In comparison to standard wavelet denoising approaches, it is clearly shown that the new method (WavPDS) is superior.
我们采用了一种基于小波变换的新方法,用于对脉冲双极电子自旋共振光谱(PDS)的实验信号进行去噪。我们表明,与无噪声参考信号相比,时域信号的信号平均时间可减少多达2个数量级,同时保持底层信号的保真度。当初始噪声信号的信噪比≳3时,我们实现了出色的信号恢复。这种方法很稳健,有望应用于其他时域光谱学。在PDS中,这些表示两个电子自旋标记之间偶极相互作用的时域信号通常通过诸如蒂霍诺夫正则化等正则化方法转换为它们的距离分布函数P(r)。描述了使用去噪信号进行这种正则化所取得的显著改进。我们表明,它们产生的P(r)具有更准确的细节,并且能更清晰地分离各个距离,当P(r)很复杂时这一点尤为重要。此外,经过去噪后,可以获取需要更长偶极演化时间的更长距离的P(r)。与标准小波去噪方法相比,清楚地表明新方法(WavPDS)更优越。