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dc.contributor.author
Boulos, Samy
dc.contributor.author
Nyström, Laura
dc.date.accessioned
2017-11-02T09:05:37Z
dc.date.available
2017-11-02T08:58:59Z
dc.date.available
2017-11-02T09:05:37Z
dc.date.issued
2017-11-02
dc.identifier.issn
2296-2646
dc.identifier.other
10.3389/fchem.2017.00090
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/203424
dc.identifier.doi
10.3929/ethz-b-000203424
dc.description.abstract
The oxidation of cereal (1→3,1→4)-β-D-glucan can influence the health promoting and technological properties of this linear, soluble homopolysaccharide by introduction of new functional groups or chain scission. Apart from deliberate oxidative modifications, oxidation of β-glucan can already occur during processing and storage, which is mediated by hydroxyl radicals (HO•) formed by the Fenton reaction. We present four complementary sample preparation strategies to investigate oat and barley β-glucan oxidation products by hydrophilic interaction ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), employing selective enzymatic digestion, graphitized carbon solid phase extraction (SPE), and functional group labeling techniques. The combination of these methods allows for detection of both lytic (C1, C3/4, C5) and non-lytic (C2, C4/3, C6) oxidation products resulting from HO•-attack at different glucose-carbons. By treating oxidized β-glucan with lichenase and β-glucosidase, only oxidized parts of the polymer remained in oligomeric form, which could be separated by SPE from the vast majority of non-oxidized glucose units. This allowed for the detection of oligomers with mid-chain glucuronic acids (C6) and carbonyls, as well as carbonyls at the non-reducing end from lytic C3/C4 oxidation. Neutral reducing ends were detected by reductive amination with anthranilic acid/amide as labeled glucose and cross-ring cleaved units (arabinose, erythrose) after enzyme treatment and SPE. New acidic chain termini were observed by carbodiimide-mediated amidation of carboxylic acids as anilides of gluconic, arabinonic, and erythronic acids. Hence, a full characterization of all types of oxidation products was possible by combining complementary sample preparation strategies. Differences in fine structure depending on source (oat vs. barley) translates to the ratio of observed oxidized oligomers, with in-depth analysis corroborating a random HO•-attack on glucose units irrespective of glycosidic linkage and neighborhood. The method was demonstrated to be 1) sufficiently sensitive to allow for the analysis of oxidation products also from a mild ascorbate-driven Fenton reaction, and 2) to be specific for cereal β-glucan even in the presence of other co-oxidized polysaccharides. This opens doors to applications in food processing to assess potential oxidations and provides the detailed structural basis to understand the effect oxidized functional groups have on β-glucan’s health promoting and technological properties.
en_US
dc.format
application/pdf
dc.language.iso
en
en_US
dc.publisher
Frontiers
en_US
dc.rights.uri
http://rightsstatements.org/page/InC-NC/1.0/
dc.subject
β-glucan oxidation
en_US
dc.subject
Fenton-reaction
en_US
dc.subject
hydrophilic interaction liquid chromatography
en_US
dc.subject
lichenase
en_US
dc.subject
β-glucosidase
en_US
dc.subject
labeling
en_US
dc.subject
UPLC-MS/MS
en_US
dc.title
Complementary Sample Preparation Strategies for Analysis of Cereal β-Glucan Oxidation Products by UPLC-MS/MS
en_US
dc.type
Journal Article
dc.rights.license
In Copyright - Non-Commercial Use Permitted
ethz.journal.title
Frontiers in Chemistry
ethz.journal.volume
5
en_US
ethz.pages.start
90
en_US
ethz.size
24 p.
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Lausanne
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02070 - Dep. Gesundheitswiss. und Technologie / Dep. of Health Sciences and Technology::02701 - Inst.f. Lebensmittelwiss.,Ernährung,Ges. / Institute of Food, Nutrition, and Health::03858 - Nyström, Laura M. / Nyström, Laura M.
en_US
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02070 - Dep. Gesundheitswiss. und Technologie / Dep. of Health Sciences and Technology::02701 - Inst.f. Lebensmittelwiss.,Ernährung,Ges. / Institute of Food, Nutrition, and Health::03858 - Nyström, Laura M. / Nyström, Laura M.
en_US
ethz.date.deposited
2017-11-02T08:59:03Z
ethz.source
FORM
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2017-11-02T09:05:45Z
ethz.rosetta.lastUpdated
2021-02-14T19:54:41Z
ethz.rosetta.versionExported
true
ethz.COinS
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