A Markov-chain-based regression model with random effects for the analysis of 18O-labelled mass spectra

The enzymatic ¹⁸O-labelling is a useful technique for reducing the influence of the between-spectra variability on the results of mass-spectrometry experiments. A difficulty in applying the technique lies in the quantification of the corresponding peptides due to the possibility of an incomplete labelling, which may result in biased estimates of the relative peptide abundance. To address the problem, Zhu et al. [A Markov-chain-based heteroscedastic regression model for the analysis of high-resolution enzymatically ¹⁸O-labeled mass spectra, J. Proteome Res. 9(5) (2010), pp. 2669–2677] proposed a Markov-chain-based regression model with heteroscedastic residual variance, which corrects for the possible bias. In this paper, we extend the model by allowing for the estimation of the technical and/or biological variability for the mass spectra data. To this aim, we use a mixed-effects version of the model. The performance of the model is evaluated based on results of an application to real-life mass spectra data and a simulation study.