Total mass difference statistics algorithm: a new approach to identification of high-mass building blocks in electrospray ionization Fourier transform ion cyclotron mass spectrometry data of natural organic matter.
The ultrahigh-resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrum of natural organic matter (NOM) contains several thousand peaks with dozens of molecules matching the same nominal mass. Such a complexity poses a significant challenge for automatic data interpretation, in which the most difficult task is molecular formula assignment, especially in the case of heavy and/or multielement ions. In this study, a new universal algorithm for automatic treatment of FTICR mass spectra of NOM and humic substances based on total mass difference statistics (TMDS) has been developed and implemented. The algorithm enables a blind search for unknown building blocks (instead of a priori known ones) by revealing repetitive patterns present in spectra. In this respect, it differs from all previously developed approaches. This algorithm was implemented in designing FIRAN-software for fully automated analysis of mass data with high peak density. The specific feature of FIRAN is its ability to assign formulas to heavy and/or multielement molecules using "virtual elements" approach. To verify the approach, it was used for processing mass spectra of sodium polystyrene sulfonate (PSS, M(w) = 2200 Da) and polymethacrylate (PMA, M(w) = 3290 Da) which produce heavy multielement and multiply-charged ions. Application of TMDS identified unambiguously monomers present in the polymers consistent with their structure: C(8)H(7)SO(3)Na for PSS and C(4)H(6)O(2) for PMA. It also allowed unambiguous formula assignment to all multiply-charged peaks including the heaviest peak in PMA spectrum at mass 4025.6625 with charge state 6- (mass bias -0.33 ppm). Application of the TMDS-algorithm to processing data on the Suwannee River FA has proven its unique capacities in analysis of spectra with high peak density: it has not only identified the known small building blocks in the structure of FA such as CH(2), H(2), C(2)H(2)O, O but the heavier unit at 154.027 amu. The latter was identified for the first time and assigned a formula C(7)H(6)O(4) consistent with the structure of dihydroxyl-benzoic acids. The presence of these compounds in the structure of FA has so far been numerically suggested but never proven directly. It was concluded that application of the TMDS-algorithm opens new horizons in unfolding molecular complexity of NOM and other natural products.
Kunenkov
Erast V
EV
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia.
Kononikhin
Alexey S
AS
Perminova
Irina V
IV
Hertkorn
Norbert
N
Gaspar
Andras
A
Schmitt-Kopplin
Philippe
P
Popov
Igor A
IA
Garmash
Andrew V
AV
Nikolaev
Evgeniy N
EN
D000465:Algorithms; D001578:Benzopyrans / Q000737:chemistry*; D015233:Models, Statistical; D011109:Polymethacrylic Acids / Q000737:chemistry*; D011137:Polystyrenes / Q000737:chemistry*; D012984:Software; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods / Q000706:statistics & numerical data*
D001578:Benzopyrans; D011109:Polymethacrylic Acids; D011137:Polystyrenes; C030613:polymethacrylic acid; C003321:polystyrene sulfonic acid; C005023:fulvic acid