Random swapping, an effective and efficient way to boost the intensities of cross peaks in a 2D asynchronous spectrum

Analysis of mixture via chromatographic-spectroscopic and analogous experiments is a common task in analytical chemistry. A 2D/nD asynchronous spectrum is effective in retrieving spectra of pure substances even if different components cannot be separated. However, noise in the 2D/nD asynchronous spectrum becomes a bottleneck in the analysis. Finding a suitable sequence of the 1D spectra used in constructing the 2D/nD asynchronous spectrum is helpful to improve the signal-to-noise level. A 2D/nD asynchronous spectrum is often produced via a large number of 1D spectra. The resultant colossal number of the possible sequences makes stochastic search the only possible way to find a suitable sequence. Random changing (RC) and random swapping (RS) are two ways to obtain a new sequence. We found that the possibility of finding a better sequence via an RS is significantly higher than that via an RC in the advanced stage of stochastic searching. This is the reason why the performance of RS is superior to that of RC in two model systems where 2D asynchronous spectra are used. We applied the RS approach on the analysis of water/isopropanol mixtures, and satisfactory sequences are acquired with affordable computational cost. Thus, the RS approach brings about an opportunity increase the signal-to-noise level of a 2D asynchronous spectrum in the analysis of the bilinear data from complex mixed samples.