Supporting Information
Discrimination of large maltooligosaccharides from isobaric dextran and
pullulan using ion mobility mass spectrometry
Short title: Ion mobility mass spectrometry of large isobaric alpha-oligoglucans
Abdul M. Rashid, Gerhard Saalbach and Stephen Bornemann*
Department of Biological Chemistry, John Innes Centre, Norwich Research Park, Norwich NR4
7UH, United Kingdom
* Correspondence to: S. Bornemann
E-mail: stephen.bornemann@jic.ac.uk
Tel: +44 (0)1603 450741
Fax: +44 (0)1603 450018
1
Table S1. Negative ion mobility of α,ω-dicarboxy-terminated polystyrene for the calibration of
collisional cross section (Ω)
z
1
Ω (Å2)
m/z drift time (ms) Literature value
401.20
4.19
132
1
505.25
5.36
163
1
609.33
6.68
196
1
713.40
7.99
210
1
817.47
9.09
236
1
921.54
10.34
262
1 1025.60
11.58
276
2
304.17
2.60
211
2
356.20
3.02
235
2
408.24
3.43
239
2
460.27
3.92
265
2
512.30
4.25
291
2
564.34
4.67
317
2
616.37
5.02
335
2
668.40
5.36
375
2
720.44
5.71
388
J.V. Hamilton, J.B. Renaud, P.M. Mayer. Experiment and theory combine to produce a practical
negative ion calibration set for collision cross-section determinations by travelling-wave ionmobility mass spectrometry. Rapid Commun. Mass Spectrom. 2012, 26, 1591.
2
Table S2. Negative ion mobility and collision cross section (Ω) of oxidised insulin chain A from
bovine pancreas (most abundant theoretical mass, 2,530.9 Da)
z
m/z drift time (ms)
Ω (Å2)
This work Literature value
2 1264.5
6.80
387
388
3
842.6
3.62
391
390
4
631.7
3.28
474
470
5
505.0
2.94
562
Not reported
Note that the Driftscope software extrapolated CCS calibration curves for ions with z ≥3 from the
calibration curves obtained with z = 1 and z = 2.
A.E. Counterman, S.J. Valentine, C.A. Srebalus, S.C. Henderson, C.S. Hoaglund, D.E. Clemmer.
High-order structure and dissociation of gaseous peptide aggregates that are hidden in mass spectra.
J. Am. Soc. Mass Spectrom. 1998, 9, 743.
3
Table S3. Negative ion mobility and collision cross section (Ω) of decadeoxythymidine
(monoisotopic theoretical mass, 2978.5 Da)
z
m/z drift time (ms)
Ω (Å2)
This work Literature value
2 1488.3
7.77
421
447
3
991.9
4.38
440
446
4
743.7
4.05
537
537
5
594.7
3.42
618
627
6
495.4
2.73
650
641
The triply charged ion was the most abundant. Note that the Driftscope software extrapolated CCS
calibration curves for ions with z ≥3 from the calibration curves obtained with z = 1 and z = 2.
C.S. Hoaglund, Y.S. Liu, A.D. Ellington, M. Pagel, D.E. Clemmer. Gas-phase DNA:
oligothymidine ion conformers. J. Am. Chem. Soc. 1997, 119, 9051.
4
Figure S1. Proposed assignment of fragment ions (each with loss of 1H+) associated with
compounds 3 and 3n (parent ion m/z 503) as shown in Figure 4. Not all potential means of arriving
at each ion are shown. Ions that are specific to an isomer are underlined and ions that have
significantly different abundances are in italics. The nomenclature of Domon and Costello has been
used.
B. Domon, C.E. Costello. A systematic nomenclature for carbohydrate fragmentations in FABMS/MS spectra of glycoconjugates. Glycoconjugate J. 1988, 5, 397.
5
161
100
a
341
4
%
545
425
383
443
normalised intensity
179
101
587
503
281
221 263
143
665
605
0
m/z
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
341
100
b
4n
%
503
161
179
545
383 425
587
101
665
221 251 281 323
143
443
0
m/z
60
80
100
100
120
140
160
180
200
200
220
240
260
280
300
300
320
340
360
380
400
420
400
m/z
440
460
480
500
500
520
540
560
580
600
600
620
640
660
680
700
720
740
700
Figure S2. Fragmentation of 4 (a) and 4n (b) oligosaccharides with DP4 after separation by IMMS.
Ions that are specific to an isomer are underlined.
6
Figure S3. Proposed assignment of fragment ions (each with loss of 1H+) associated with
compounds 4 and 4n (parent ion m/z 665) as shown in Figure S2. Ions that are specific to an isomer
are underlined. Not all potential means of arriving at each ion are shown.
7
827
100
7
a
989
normalised intensity
%
665
161
0
100
869
911
929
707
749
767
503
341
1031
1151
1073
m/z
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
900
950
1000
1050
1100
1150
1200
1250
767
100
b
7n
827
%
707
665
989
737
809
869911
503
545
0
100
100
10311073
1151
929
m/z
150
200
250
300
300
350
400
450
500
500
550
600
650
700
700
m/z
750
800
850
900
900
950
1000
1050
1100
1100
1150
1200
1250
1300
Figure S4. Fragmentation of 7 (a) and 7n (b) oligosaccharides with DP7 after separation by IMMS.
8
Figure S5. Proposed assignment of fragment ions (each with loss of 1H+) associated with
compounds 7 and 7n (parent ion m/z 1151) as shown in Figure S4. Not all potential means of
arriving at each ion are shown.
9