Mass-Remainder Analysis (MARA): An Improved Method for Elemental Composition Assignment in Petroleomics

Abstract

Data processing and visualization methods have an important role in the mass spectrometric study of crude oils and other natural samples. The recently invented data mining procedure: the Mass-remainder analysis (MARA), was further developed for the use in petroleomics. MARA is based on the calculation of the remainder after dividing by the exact mass of a base unit, in petroleomics by the mass of the CH 2 group. The two key steps in the MARA algorithm are the separation of the monoisotopic peaks from the other isotopic peaks and the subsequent intensity correction. The effectiveness of our MARA method was demonstrated on the analysis of lubricating mineral oil and crude oil samples by ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) experiments. MARA is able to handle a huge portion of the overlapped peaks even in a moderate resolution mass spectrum. Using MARA, effective chemical composition assignment and visual representation were achieved for complex mass spectra recorded by a TOF analyzer with a limited resolution of 40 000 at m/z 400. In the absence of an ultra-high resolution mass analyzer, MARA can provide a closer look on the mass spectral peaks, like a digital zoom in a simple camera.

Mass Spectral Filtering by Mass-Remainder Analysis (MARA) at High Resolution and Its Application to Metabolite Profiling of Flavonoids

“…As it was detailed in our previous works [23][24][25][26], mass-remainder analysis (MARA) and its multistep extension (M-MARA) are able to produce simplified graphical representations of the mass spectra, facilitating thereby the recognition, filtering, and grouping of the detected compounds. M-MARA simply performs sequential modulo operations on the measured m/z values in order to eliminate the homologous connections present in a complex system.…”

“…Recently, we have developed a data mining algorithm, called mass-remainder analysis (MARA) and its improved variant, multi-step mass-remainder analysis (M-MARA) for the processing and assessment of complex mass spectra [23][24][25][26][27]. In this paper, we propose a novel method for the comprehensive filtering and screening of flavonoids in the DIMS spectra of natural extracts.…”

A Short-Cut Data Mining Method for the Mass Spectrometric Characterization of Block Copolymers

“…Recently, we developed the Mass-remainder analysis (MARA), which is capable of handling the mass spectra of copolymers, even those obtained by low-resolution mass spectrometer. The capability of our method was proved by analyzing copolymers [15], epoxidized vegetable oils [16], crude oil [17], copolymer blends [18] and even for the analysis of flavonoids [19]. The further development of such a filtering method is of paramount importance for the processing of complex mass spectra.…”

An arsenal of tools based on Kendrick mass defects to process congested electrospray ionization high‐resolution mass spectra of polymers with multiple charging

“…More refined techniques are proposed to process the 4+ ion series, relying on a three-dimensional plot and using the latest notion of "pseudocontinuous" enhancement of resolution. to the KMD and KMR plots being the projections of the 3D plot on two planes (Figure 6), the third projection of the 3D plot to the third plane is the "remainder of KMs" plot, noted RKM plot (KMRs vs m/z) 54 (also reported as the "mass remainder analysis", noted MARA, [55][56][57] ) used for low-accuracy measurements such as TOF/TOF analyses or high mass range.…”