Assisted baseline subtraction in complex chromatograms using the BEADS algorithm

- Tools for the assistance in the configuration of BEADS are developed.
- Monitoring the autocorrelation allowed the correct selection of the optimal working parameters.
- A logarithmic transformation of the signal attenuated artifacts under main peaks.
- The process is simplified, shortened and the baseline subtraction made more reliable.
- The assisted BEADS processed successfully highly complex chromatograms in gradient elution.

The data processing step of complex signals in high-performance liquid chromatography may constitute a bottleneck to obtain significant information from chromatograms. Data pre‐processing should be preferably done with little (or no) user supervision, for a maximal benefit and highest speed. In this work, a tool for the configuration of a state-of-the-art baseline subtraction algorithm, called BEADS (Baseline Estimation And Denoising using Sparsity) is developed and verified. A quality criterion based on the measurement of the autocorrelation level was designed to select the most suitable working parameters to obtain the best baseline. The use of a log transformation of the signal attenuated artifacts associated to a large disparity in signal size between sample constituents. Conventional BEADS makes use of trial-and-error strategies to set up the working parameters, which makes the process slow and inconsistent. This constitutes a major drawback in its successful application. In contrast, the assisted BEADS simplifies the setup, shortens the processing time and makes the baseline subtraction more reliable. The assisted algorithm was tested on several complex chromatograms corresponding to extracts of medicinal herbs analysed with acetonitrile-water gradients, and a mixture of sulphonamides eluted with acetonitrile gradients in the presence of the non-ionic surfactant Brij-35 under micellar conditions.