Mathematical chromatography deciphers the molecular fingerprints of dissolved organic matter

Wünsch, Urban; Hawkes, Jeffrey A.

doi:10.1039/c9an02176k

Cited by 9 publications

(7 citation statements)

References 62 publications

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“…Also, one should note that the molecular composition of different fractions could be different. The low-size fraction of DOM is known to exhibit higher H/C and lower O/C ratios in comparison with the large-size fraction . Thus, the lower EET efficiency observed in the low-size fraction could be caused by the differences in the chemical composition.…”

Section: Resultssupporting

confidence: 62%

“…The lowsize fraction of DOM is known to exhibit higher H/C and lower O/C ratios in comparison with the large-size fraction. 63 Thus, the lower EET efficiency observed in the low-size fraction could be caused by the differences in the chemical composition. Overall, the observed decrease in the ultrafast component for the fractions with lower sizes may originate from the lower number of donor−acceptor interactions of chromophores within them.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances

Yakimov

Rubekina

Budylin

et al. 2021

Environ. Sci. Technol.

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Humification is a ubiquitous natural process of biomass degradation that creates multicomponent systems of nonliving organic matter, including dissolved organic matter (DOM) and humic substances (HS) in water environments, soils, and organic rocks. Despite significant differences in molecular composition, the optical properties of DOM and HS are remarkably similar, and the reason for this remains largely unknown. Here, we employed fluorescence spectroscopy with (sub)picosecond resolution to elucidate the role of electronic interactions within DOM and HS. We revealed an ultrafast decay component with a characteristic decay lifetime of 0.5–1.5 ps and spectral diffusion originating from excitation energy transfer (EET) in the system. The rate of EET was positively correlated to the fraction of aromatic species and tightness of aromatic species packing. Diminishing the number of EET donor–acceptor pairs by reduction with NaBH4 (decrease of the acceptor number), decrease of pH (decrease of the electron-donating ability), or decrease of the average particle size by filtration (less donor–acceptor pairs within a particle) resulted in a lower impact of the ultrafast component on fluorescence decay. Our results uncover the role of electronic coupling among fluorophores in the formation of DOM and HS optical properties and provide a framework for studying photophysical processes in heterogeneous systems of natural fluorophores.

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Section: Resultssupporting

confidence: 62%

Section: ■ Materials and Methodsmentioning

confidence: 99%

Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances

Yakimov

Rubekina

Budylin

et al. 2021

Environ. Sci. Technol.

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“… 13 , 55 , 58 Fluorescence or NMR spectroscopy could add valuable information if DOM would be fractionated before MS 2 data acquisition, i.e., to assess indirect (statistical) links of MS 2 features with complementary forms of structural insight. 21 , 92 − 94 Our findings must however be taken with caution for four reasons: SIRIUS Δ m features (list c) were not obtained on the same instrument and thus may include features that, although correlated with certain compound classes, may not appear in DOM under the same instrumental settings. SIRIUS Δ m features may be biased toward certain classes of compounds ( Figure S-3 ), as our set of 14 aromatic compounds.…”

Section: Resultsmentioning

confidence: 83%

Mass Difference Matching Unfolds Hidden Molecular Structures of Dissolved Organic Matter

Simon

Dührkop

Petras

et al. 2022

Environ. Sci. Technol.

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Ultrahigh-resolution Fourier transform mass spectrometry (FTMS) has revealed unprecedented details of natural complex mixtures such as dissolved organic matter (DOM) on a molecular formula level, but we lack approaches to access the underlying structural complexity. We here explore the hypothesis that every DOM precursor ion is potentially linked with all emerging product ions in FTMS 2 experiments. The resulting mass difference (Δ m ) matrix is deconvoluted to isolate individual precursor ion Δ m profiles and matched with structural information, which was derived from 42 Δ m features from 14 in-house reference compounds and a global set of 11 477 Δ m features with assigned structure specificities, using a dataset of ∼18 000 unique structures. We show that Δ m matching is highly sensitive in predicting potential precursor ion identities in terms of molecular and structural composition. Additionally, the approach identified unresolved precursor ions and missing elements in molecular formula annotation (P, Cl, F). Our study provides first results on how Δ m matching refines structural annotations in van Krevelen space but simultaneously demonstrates the wide overlap between potential structural classes. We show that this effect is likely driven by chemodiversity and offers an explanation for the observed ubiquitous presence of molecules in the center of the van Krevelen space. Our promising first results suggest that Δ m matching can both unfold the structural information encrypted in DOM and assess the quality of FTMS-derived molecular formulas of complex mixtures in general.

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Section: Figure 2ementioning

confidence: 81%

Mass difference matching unfolds hidden molecular structures of dissolved organic matter

Simon

Dührkop

Petras

et al. 2022

Preprint

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Ultrahigh-resolution Fourier transform mass spectrometry (FTMS) has revealed unprecedented detail of natural complex mixtures such as dissolved organic matter (DOM) on a molecular formula level, but we lack approaches to access the underlying structural complexity. We here explore the hypothesis that every DOM precursor ion is potentially linked with all emerging product ions in FTMS2 experiments. The resulting mass difference (Δm) matrix is deconvoluted to isolate individual precursor ion Δm profiles and matched with structural information, which was derived from 42 Δm features from 14 in-house reference compounds and a global set of 11477 Δm features with assigned structure specificities, using a dataset of ~18000 unique structures. We show that Δm matching is highly sensitive in predicting potential precursor ion identities in terms of molecular and structural composition. Additionally, the approach identified unresolved precursor ions and missing elements in molecular formula annotation (P, Cl, F). Our study provides first results how Δm matching refines structural annotations in Van Krevelen space, but simultaneously demonstrates the wide overlap between potential structural classes. We show that this effect is likely driven by chemodiversity and offers an explanation for the observed ubiquitous presence of molecules in the center of the Van Krevelen space. Our promising first results suggest that Δm matching can both unfold the structural information encrypted in DOM and assess the quality of FTMS-derived molecular formulas of complex mixtures in general.

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Mathematical chromatography deciphers the molecular fingerprints of dissolved organic matter

Abstract: Mathematical chromatography offers information reduction and feature extraction in complex liquid chromatography—mass spectrometry datasets.

Cited by 9 publications

References 62 publications

Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances

Ultrafast Energy Transfer Determines the Formation of Fluorescence in DOM and Humic Substances

Mass Difference Matching Unfolds Hidden Molecular Structures of Dissolved Organic Matter

Mass difference matching unfolds hidden molecular structures of dissolved organic matter

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