Tandem Mass-Remainder Analysis of Industrially Important Polyether Polyols

Abstract

The characteristics of the polyalkylene oxide polyether polyols highly influence the properties of final polyurethane products. As a novel approach, in order to gain structural information, the recently invented data mining procedures, namely the Mass-remainder analysis (MARA) and the Multistep Mass-remainder analysis (M-MARA) are successfully applied for the processing of tandem mass spectrometry (MS/MS) data of various industrially important polyether polyols. M-MARA yields an ultra-simplified graphical representation of the MS/MS spectra and sorts the product ions based on their double bond equivalent (DBE) values. The maximum DBE values unambiguously differentiate among the various polyether polyols. Accordingly, the characteristic DBE values were 0, 1 for the linear diol polyethers, 0, 1, 2 for the three-arm, and 0, 1 2, 3, 4 for the six-arm polyether polyols. In addition, it was also found that the characteristic collision energy necessary for the optimum fragmentation yield depended linearly on the molecular weight of the polyols. This relationship offers an easy way for instrument tuning to gain structural information.

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.…”

“…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. Equation (1) reveals the general formula for the three-step M-MARA [ 26 ]: MR 3 = [( m/z MOD R 1 ) MOD R 2 ] MOD R 3 where the modulo (MOD) operation finds the mass remainder (MR n ) after the division by R n ( n = 1, 2, 3). It can easily be seen, that MARA is highly effective for data mining of mass spectra containing numerous peaks with periodicities generated by e.g., a repeat unit (polymers) or the CH 2 group (hydrocarbons).…”

“…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. Equation (1) reveals the general formula for the three-step M-MARA [26]:…”

“…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.…”