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PO-CON1533E
Structural analysis of isomeric chemicalsby using high resolution MS/MS onCurved Field Re�ectron incorporatedwith a novel focusing technology
ASMS 2015 ThP 273
Shuuichi Nakaya1; Keisuke Shima1; Yuzo Yamazaki1
1Shimadzu Corporation, Kyoto, JAPAN.
2
Structural analysis of isomeric chemicals by using highresolution MS/MS on Curved Field Re�ectron incorporated with a novel focusing technology
Overview
IntroductionWhile resolution of MS has been greatly improved recently, no matter how high resolution of MS is achieved, MS/MS is essential to conduct analysis of isomeric chemicals, and the analysis is thought to be still signi�cant task given to mass spectrometry. To date, we applied PSD and high energy CID in curved �eld re�ectron to the analysis, since intensities of
fragment ions in the re�ectron were susceptible to isomeric forms. Recently, we incorporated a new focusing technology into the curved �eld re�ectron, which enabled to obtain 10,000 resolution of MS/MS. We will apply the new curved �eld re�ectron toward ambiguous assignment and differentiation of isomeric chemicals.
Isomeric oligosaccharides : Lacto-N-neotetraose(LNnT) Galβ1-3GlcNAcβ1-3Galβ1-4Glc
Lacto-N-tetraose(LNT) Galβ1-4GlcNAcβ1-3Galβ1-4Glc
Isomeric prostaglandin : Prostaglandin E2(PGE2) and prostaglandin D2(PGD2)
Matrix : 10 mg/mL of DHB in methanol.
Cation : Li, Na, Cs, Ba.
Instrument : MALDI-7090 (Shimadzu/Kratos)
Measurement : High-energy CID-MS/MS in positive ion mode.
Collision gas : helium
Collision energy : 20 keV (laboratory frame of reference).
• Precise assignment of isomeric chemicals is conducted with a new MALDI-TOF/TOF MS.• Isomeric carbohydrates and prostaglandins are differentiated successfully.• Choice of cation is signi�cant to obtain informative MS/MS spectrum.
Materials
MALDI-tandem TOFMS
Methods
3
Structural analysis of isomeric chemicals by using highresolution MS/MS on Curved Field Re�ectron incorporated with a novel focusing technology
Fig.1 Inside view of MALDI-7090
MS/MS resolution is improved with correcting the spatial distribution of ions in ASDF cell. This is achieved by applying a pulsed electrostatic �eld at the point, at which the precursor and fragments are velocity focussed but are spatially resolved.
Principle of Axial Spatial Distribution Focusing (ASDF)
Vacuum MALDIion source
Lineardetector
Curved �eldre�ectron
Re�ectrondetector
ASDF cellIon gate
CID cell
Fig.2 Axial Spatial Distribution Focusing
4
Structural analysis of isomeric chemicals by using highresolution MS/MS on Curved Field Re�ectron incorporated with a novel focusing technology
Fig.3 MS/MS of LNT and LNnT
Fig.4 fragment ions of LNT and LNnT
Fig.5 Effect of metal cations in MS/MS (PGE2)
Results
LNnT
LNT
[M+Na]+
[M+Na]+
O
O
O
O
O
O
O
OH
NHAc
OH OH
OH
HOH2C
HO
HO
HO
HOH2C HO
HOH2C HOH2C
HO
O
HO
O
O
O
O
O
OH NHAc
OH OH
OHHOH 2C
HO
HO
O
HOH2C HO
HOH2C HOH2C
HO
LNnT LNT
185.0420
B1
568.1488 Y3
388.1214
B2
365.1054 Y2
550.1742
B3
203.0526 Y1
568.1848 C3
406.1320 C2
203.0526 C1
208.0580 BZ
185.0420
B1
568.1488 Y3
388.1214
B2
365.1054 Y2
550.1742
B3
203.0526 Y1
568.1848 C3
406.1320 C2
203.0526 C1
0,2 X3
305.0843 0,2 A2
448.1425
3,5 A1 1,4 X2
331.1000
3,5 A1 Y2
259.0788
[M+Cs]+ [M+Li]+ [M+Ba-H]+
5
Structural analysis of isomeric chemicals by using highresolution MS/MS on Curved Field Re�ectron incorporated with a novel focusing technology
Fig.6 MS/MS of PGD2 and PGE2
PGE2
PGD2
[M+Ba-H]+
[M+Ba-H]+
PGE2
PGD2
318.9923
Structural analysis of isomeric chemicals by using highresolution MS/MS on Curved Field Re�ectron incorporated with a novel focusing technology
For Research Use Only. Not for use in diagnostic procedures.The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice.
© Shimadzu Corporation, 2015
First Edition: May, 2015
www.shimadzu.com/an/
Fig.7 Conceivable pathways for fragmentations of PGD2 and PGE2, including reported one in ref(1).
Conclusions• High MS/MS resolution achieved by ASDF enables to perform precise assignment in the analysis of isomeric chemicals. • Differentiation of linkage formations between Gal and GlcNAc was conducted successfully by MS/MS of sodium
adducted carbohydrates.• Charge remote fragmentation of bariated PGD2/PGE2 was applied to a differentiation of the isomeric chemicals.• Choice of cation was signi�cant to obtain interpretable fragmentation as well as FAB-tandem MS analysis.
References(1) Zirrolli, J.A., et al; J Am Soc Mass Spectrom., 1990, 1(4), 325-35.(2) Yamagaki, T., et al; J Mass Spectrom., 2006, 41(4),454-62.
342.9906 318.9906
208.9174
154.9069
363.0168
345.0063
PGD2 [M+Ba-H]+ C20H31BaO5 Exact Mass: 489.1218
PGE2 [M+Ba-H]+ C20H31BaO5 Exact Mass: 489.1218
+H
-H
262.9644 -H
+H
-H2O
417.0274
399.0168
-H
-H2O
Or,
304.9761
401.0325
389.0325 +H
Common fragment ions
401.0325
389.0325 +H