gc-hrms and gc×gc-hrms: tackling the identification ... · gc-hrms and gc×gc-hrms: tackling the...
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GC-HRMS and GC×GC-HRMS: tackling the identification
challenges in complex matrices
Daniela Peroni
JSB Netherlands
JSB Group
• Agilent Technologies Value Added Reseller (VAR).
• Knowledge partner in chromatography and mass spectrometry solutions.
• Providers of custom-made systems.
• Specialist in GC×GC.
• Offices in the Netherlands/UK/Belgium/Germany.
• Demo lab (Lelystad, NL).
Outline
• GC-QTOF
• Targeted search in complex food samples analysis.
• Advantages for samples with broad concentration range.
• GC×GC-QTOF
• Targeted search in complex food samples analysis.
• Fingerprinting of complex food samples.
• Age markers in diesel oil samples.
• Visual group characterization of petrochemical samples.
Allyl isothiocyanate
Butyl isothiocyanate
PhenylethylisothiocyanateButenyl
isothiocyanate
Lynalool3-Methylthiopropylisothiocyanate
GC-QTOF applications: mustard
SPME of head-spaceSplit 1:10HR mode
EIC – Accurate mass
EIC - Nominal mass
Targeted search: benzyl isothiocyanate
GC-QTOF applications: mustard
TIC
Targeted search: benzyl isothiocyanate
142.0929± 10 ppm
142.0± 0.5 m/z
149.0299 ± 10 ppm
149.0 ± 0.5 m/z
Estragole(M+1)+,C10H12O,
149.0911 m/z
Anethole(M+1)+, C10H12O,
149.0910 m/z
149.0295 m/z
GC-QTOF applications: mustard
GC-QTOF applications: mustard
GC-QTOF applications: mustard
MS Interpreter (connected to the NIST library search).
GC-QTOF applications: mustard
trans 2-Hexenal
trans-4-Hexen-1-ol
2,4-dimethyl-hexane
2-Hexen-1-ol
2-Heptenal
trans-Decenal
Citral
From SPME fiber
Commercial olive oil (supermarket)
Artisanal olive oil (Italy) trans 2-Hexenal
2-Hexen-1-ol
GC-QTOF applications: olive oil
SPME of head-space, split 1:10HR mode
GC-QTOF applications: olive oil
GC-QTOF applications: olive oil
Fragment (nominal)
Theoreticalformula
Exact massMeasuredmass
Formulaproposed
Hit #Error (ppm)
97,0C6H9O+(loss of CH3)
97,0653 97,0648 C6H9O+ 1 <0,1
83,0C5H7O+(loss of C2H5)
83,0497 83,0497 C5H7O+ 1 0,5
69,0C4H5O+(loss of C3H7+)
69,0335 69,0340 C9H13+ 1 - 1,6
2-Heptenal
Vanillin
Piperonal
Guaiacol
p-Creosol
Vanillyl ethyl ether
Vanillyl alcohol
GC-QTOF applications: vanilla extract
Liquid injectionSplit 1:10EDR mode
GC-QTOF applications: vanilla extract
Very good spectral qualityNo spectral skewingGood library match
GC-QTOF applications: vanilla extract
S/N=392
S/N=3,7
GC×GC-QTOF - Mustard
HR mode
Allyl isothiocyanate
3-methyl isothiazole
Acetic acid
Phenylethyl isothiocyanate
EstragoleButenyl isothiocyanate
Linalool
Butenenitrile
SPME of headspace, Split 1:10HR mode
GC×GC-QTOF - Mustard
Selected Ion Chromatogram (SIC) for 163.04557±0,01 m/z
Targeted search: phenylethyl isothiocyanate
GC×GC-QTOF - Mustard
Targeted search: phenylethyl isothiocyanate
GC×GC-QTOF - Mustard
Coeluting in 1D,fully separated in 2D
Identification of unknown
GC×GC-QTOF - Tea leaves
Lemon green tea
Black tea
Strawberry tea
SPME of head-space, split 1:5HR mode
Visual comparison – qualitative fingerprinting
GC×GC-QTOF - Tea leaves
Lemon green tea vs. Strawberry tea (reference)• Green peaks: more abundant• Red peaks: less aboundant
Key differeces are vizualized in a quick, easy way.
GC×GC-QTOF - Tea drinks
Lemon green tea
Black tea
Strawberry tea
SPME of head-space, split 1:5EDR mode
GC×GC-QTOF - Tea drinks
split 1:5EDR mode
Lemon green tea
GC×GC-QTOF - Tea drink
Methyl cinnamate
2-Decanal
Citral
Caryophyllene
Decadienal
2-Undecenal
Strawberry tea
VerbenolAnethole
Citral
Aromadendrene
CaryophylleneDecadienal
Linalyl acetate2-Decanal
Lemon green tea
GC×GC-QTOF - Tea drink
Linalyl acetate:
Fragment (nominal)
Formula suggested byMS Interpreter
Exact mass
Measuredmass
Formula proposedby GC Image
Hit #Error (ppm)
196,0 C12H20O2+ (M+) 196,1458 196,1458 C12H20O2+ 10,2
154,0 C10H18O+ (loss of C2H3O) 154,1358 154,1352 C10H18O+ 1 0,2
136,0 C10H16+ (loss C2H4O4) 136,1252 136,1247 C10H16+ 1 1,6
121,0 C9H13+ (loss C2H4O4+CH3)121,1017 121,1012
C9H13+ 11,6
Structure confirmation: mass accuracy of multiple fragments.
GC×GC-QTOF - Tea drink
Targeted Template Matching
Lemon green tea
GC×GC-QTOF - Tea drink
Targeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Targeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Targeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Untargeted Template Matching: all peaks detected are in the template.
Lemon green tea
Strawberry tea
GC×GC-QTOF - Tea drink
Untargeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Untargeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Untargeted Template Matching
Strawberry tea
GC×GC-QTOF - Tea drink
Untargeted Template Matching
GC×GC-QTOF – Petrochemical samples
Age markers in diesel oil
The C17/pristane ratio gives an indication of the oil degradation.
GC×GC-QTOF – Petrochemical samples
GC×GC-QTOF – Petrochemical samples
Age markers in diesel oil
NIST
NIST
GC×GC gives cleaner spectra.Better for identification!
GC×GC-QTOF – Petrochemical samples
Colorization of groups in diesel oil (GC Image)
GC×GC-QTOF – Petrochemical samples
Extra selectivity thanks to accurate mass.
Nominal mass
Accurate mass
Colorization of groups in diesel oil (GC Image)
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