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A novel method for compound identification in liquid chromatography-high resolution mass spectrometry (LC-HRMS) is proposed. The method, based on Bayesian statistics, accommodates all possible uncertainties involved, from instrumentation up to data analysis into a single model yielding the probability of the compound of interest being present/absent in the sample. This approach differs from the classical methods in two ways. First, it is probabilistic (instead of deterministic); hence, it computes the probability that the compound is (or is not) present in a sample. Second, it answers the hypothesis "the compound is present", opposed to answering the question "the compound feature is present". This second difference implies a shift in the way data analysis is tackled, since the probability of interfering compounds (i.e., isomers and isobaric compounds) is also taken into account. [ABSTRACT FROM AUTHOR]

A new method for comparison of GCxGC-MS is proposed. The method is aimed at spotting the differences between two GCxGC-MS injections, in order to highlight the differences between two samples, in order to flag differences in composition, or to spot compounds only present in one of the samples. The method is based on application of the Jensen-Shannon divergence (JS) analysis combined with Bayesian hypothesis testing. In order to make the method robust against misalignment in both time dimensions, a moving-window approach is proposed. Using a Bayesian framework, we provide a probabilistic visual map (i.e., log likelihood ratio map) of the significant differences between two data sets consequently excluding the deterministic (i.e., "yes" or "no") decision. We proved this approach to be a versatile tool in GCxGC-MS data analysis, especially when the differences are embedded inside a complex matrix. We tested the approach to spot contamination of diesel samples. [ABSTRACT FROM AUTHOR]

We introduce a novel Bayesian probabilistic peak detection algorithm for liquid chromatography-mass spectroscopy (LC-MS). The final probabilistic result allows the user to make a final decision about which points in a chromatogram are affected by a chromatographic peak and which ones are only affected by noise. The use of probabilities contrasts with the traditional method in which a binary answer is given, relying on a threshold. By contrast, with the Bayesian peak detection presented here, the values of probability can be further propagated into other preprocessing steps, which will increase (or decrease) the importance of chromatographic regions into the final results. The present work is based on the use of the statistical overlap theory of component overlap from Davis and Giddings (Davis, J. M.; Giddings, J. Anal. Chem. 1983, 55, 418-424) as prior probability in the Bayesian formulation. The algorithm was tested on LC-MS Orbitrap data and was able to successfully distinguish chemical noise from actual peaks without any data preprocessing. [ABSTRACT FROM AUTHOR]

A new method for peak detection in two-dimensional chromatography is presented. In a first step, the method starts with a conventional one-dimensional peak detection algorithm to detect modulated peaks. In a second step, a sophisticated algorithm is constructed to decide which of the individual one-dimensional peaks have been originated from the same compound and should then be arranged in a two-dimensional peak. The merging algorithm is based on Bayesian inference. The user sets prior information about certain parameters (e.g., second-dimension retention time variability, first-dimension band broadening, chromatographic noise). On the basis of these priors, the algorithm calculates the probability of myriads of peak arrangements (i.e., ways of merging one-dimensional peaks), finding which of them holds the highest value. Uncertainty in each parameter can be accounted by adapting conveniently its probability distribution function, which in turn may change the final decision of the most probable peak arrangement. It has been demonstrated that the Bayesian approach presented in this paper follows the chromatographers' intuition. The algorithm has been applied and tested with LCxLC and GCxGC data and takes around 1 min to process chromatograms with several thousands of peaks. [ABSTRACT FROM AUTHOR]

A method to select the optimal window size of the Savitzky-Golay (SG) algorithm is presented. The approach is based on a comparison of the fitting residuals (i.e., the differences between the input signal and the smoothed signal) with the noise of the instrument. The window size that yields an autocorrelation of the residuals closest to the autocorrelation of the noise of the instrument is considered optimal. The method is applied in two steps. In a first step, the lag-one autocorrelation value of the noise of the instrument is computed through the study of a blank signal. In a second step, the SG algorithm is applied to "smooth" the signal using different window sizes. The method was applied to data from NMR, chromatography, and mass spectrometry and was shown to be robust. It finds the optimal window size for different signal features. This allows the method to be used in an unsupervised way, embedded in a more complex algorithm in which smoothing and/or differentiation of signals is required, provided that the lag-one autocorrelation value of the instrument noise does not change.