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Solid-state determination of hop bitter acids in beer by UV–MALDI–Orbitrap mass spectrometry

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Abstract

Despite of the fact that the manufacturing of beer dated from many centuries, and nevertheless, of enormous analytical instrumental elaborations, developments and implementations for highly precise and accurate protocols for determination of foodstuffs, the quantitation of beer ingredients still represent significant challenge. It is caused by: (A) high complexity of the beer as foodstuffs matrix with significant proteins and maltooligosaccharide content as well as diversity of more than 57 low-molecular weight hop bitter acidic analytes and their oxidation products; (B) higher instability and variety of chemical oxidation processes typical for these ingredients; (C) easy isometrization and rearrangements, tautomerism and large number of different conformations of hop bitter acids; (D) structural similarity of the analytes; (E) photo-instability of the ingredients; and (F) still unavailable commercial standards for all hop acids, which difficult the analysis of major and minor components in crude hop extracts, during brewing process and storage of final food product. The diverse number of chemical and photochemical processes may be conducted at each these stages of beer manufacturing, which caused need of methodological elaborations and implementations of accurate analytical protocols for on-line analysis of beer components. For this reason the paper content encompasses quantitative solid-state analysis of hop bitter acids in different brands beer beverages employing UV–MALDI–Orbitrap MS method. Despite of its powerful instrumental capability, this mass spectrometric method has been scarce utilized in analysing of beer foodstuffs, limiting the scientific efforts and reports to mainly qualitative analysis and fingerprinting of proteins and maltooligosaccharides. In this respect the study provided novelty in the field of the quantitative analytical chemistry of low molecular weight analytes in beer demonstrating its capability for accurate determination of closely structural ingredients such as the large number of naturally occurring hop bitter acids.

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Scheme 1
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Abbreviations

CHCA:

α-Cyano-4-hydroxycinnamic acid

ANOVA:

Analysis of variance

APCI:

Atmospheric pressure chemical ionization (mass spectrometric method)

ATT:

6-Aza-2-thiothymine

DHA:

2,4-Dihydroxy benzoic acid

DHB:

2,5-Dihydroxy benzoic acid

ECD:

Electron capture detection

ESI:

Electrospray ionization (mass spectrometric method)

Fs:

Fluorescence (detection)

GC:

Gas-chromatography

HPLC:

High performance liquid chromatography

LODs:

Concentration limit of detection (analyte)

LOQs:

Concentration limit of quantitation (analyte)

LC:

Liquid chromatography

LMW:

Low molecular weight (analytes)

MLODs:

Concentration method detection limit (instrumental)

MLOQs:

Concentration method quantitation limit (instrumental)

MALDI:

Matrix/assisted laser desorption ionization (mass spectrometric method)

MS:

Mass spectrometry

MS/MS:

Mass spectrometry in a tandem mode of operation

MVA:

Multi-variative analysis

NMR:

Nuclear magnetic resonance

PO:

Polynomial order

RA:

Relative abundance

RTs:

Retention times

TOF:

Time-of-flight (mass spectrometric method)

THAP:

2,4,6-Trihydroxyacetophenone

UV:

Ultraviolet (irradiation or detection)

UHPLC:

Ultra-high pressure liquid chromatography

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Acknowledgments

The authors thank Deutscher Akademischer Austausch Dienst, Deutsche Forschungsgemeinschaft. Authors also thank the central instrumental laboratories for structural analysis at Dortmund University of Technology (Nordrhein-Westfalen, Germany) and the analytical and computational laboratories at the Institute of Environmental Research at the same University. Michael Spiteller has received grants (Deutsche Forschungsgemeinschaft 255/21-1 and 255/22-1; NRW–EU–Ziel2–Programms); Bojidarka Ivanova has received grant (Deutsche Forschungsgemeinschaft 255/22-1). This article does not contain any studies with human or animal subjects.

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  1. Lehrstuhl für Analytische Chemie, Institut für Umweltforschung, Fakultät für Chemie, Universität Dortmund, Otto-Hahn-Straße 6, 44227, Dortmund, Nordrhein-Westfalen, Germany

    Bojidarka Ivanova & Michael Spiteller

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  1. Bojidarka Ivanova
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Correspondence to Bojidarka Ivanova.

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11694_2014_9195_MOESM1_ESM.doc

Crystallographic data for structural analysis have been deposited to Cambridge Crystallographic Data Centre, CCDC 782344, 782345 and 782347. Copies of this information may be obtained from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk); ORTEP diagrams (Fig. S1); UV–Vis–NIR and IR-data (Fig. S2; Tables S2, S3); Experimental crystallographic data refinements (Table S1); Chemical diagrams (Scheme S1); Thermodynamics (Table S4). Supplementary material 1 (DOC 1147 kb)

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Ivanova, B., Spiteller, M. Solid-state determination of hop bitter acids in beer by UV–MALDI–Orbitrap mass spectrometry. Food Measure 8, 343–355 (2014). https://doi.org/10.1007/s11694-014-9195-2

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