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PLEMENTRMATION
Supporting information
Characterisation of “caramel-type” thermal decomposition
products of selected monosaccharides including fructose,
mannose, galactose, arabinose and ribose by advanced
electrospray ionization mass spectrometry methods
Agnieszka Golon and Nikolai Kuhnert*
School of Engineering and Science, Jacobs University Bremen,
Campus Ring 1, 28759 Bremen, Germany
To whom correspondence should be addressed. E-mail: [email protected]
Table of Contents:
Figure S1. Mass spectra of caramelised: a) fructose, b) galactose, c) mannose in the positive
ion mode using a direct infusion into an ESI-TOF-MS instrument
Table S1 High resolution mass (MS-TOF) data of caramelised: a) fructose, b) galactose, c)
ribose and d) arabinose and their parent ions (M-H) in the negative ion mode
Figure S2 Two dimensional Kendrick plots for mass increment H2O showing the distribution
of the Kendrick mass defect plotted against the nominal Kendrick mass of pseudo-molecular
ions for caramelised: a) fructose, b) galactose, c) ribose and d) arabinose in the negative ion
mode
Figure S3 Thermogravimetric curves of caramelised: a) fructose, b) galactose and c) mannose
Figure S4 Infrared spectra of caramelised: a) fructose b) galactose and c) mannose
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Figure S5 1H NMR spectra of caramelized a) fructose, b) galactose and c) mannose
Figure S6 EIC at m/z 341.0 (C12H22O11) for caramelised fructose in the negative ion mode
Figure S7 EIC at m/z 341.0 (C12H22O11) for caramelised galactose in the negative ion mode
Figure S8 MS2 spectra of fragment at m/z 341.0 (C12H22O11) for five chromatographic peaks
of caramelised fructose in the negative ion mode
Figure S9 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for ten chromatographic peaks
of caramelised fructose in the negative ion mode
Figure S10 MS2 spectra of fragment at m/z 647.0 (C24H40O20) for ten chromatographic peaks
of caramelised fructose in the negative ion mode
Figure S11 MS2 spectra of fragment at m/z 809.0 (C30H50O25) for seven chromatographic
peaks of caramelised fructose in the negative ion mode
Figure S12 MS2 spectra of fragment at m/z 341.0 (C12H22O11) for two chromatographic peaks
of caramelised galactose in the negative ion mode
Figure S13 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for four chromatographic peaks
of caramelised galactose in the negative ion mode
Figure S14 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for four chromatographic peaks
of caramelised mannose in the negative ion mode
Figure S15 MS2 spectra of fragment at m/z 647.0 (C24H40O20) for ten chromatographic peaks
of caramelised mannose in the negative ion mode
Figure S16 MS2 spectra of fragment at m/z 809.0 (C30H50O25) for seven chromatographic
peaks of caramelised mannose in the negative ion mode
Figure S17 EIC at m/z 161.0 (C6H10O5) for caramelised fructose in the negative ion mode
Figure S18 EIC at m/z 323.0 (C12H20O10) for caramelised fructose in the negative ion mode
Figure S19 EIC at m/z 161.0 (C6H10O5) for caramelised galactose in the negative ion mode
Figure S20 EIC at m/z 323.0 (C12H20O10) for caramelised galactose in the negative ion mode
Figure S21 EIC at m/z 323.0 (C12H20O10) for caramelised mannose in the negative ion mode
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Figure S22 EIC at m/z 359.0 (C12H24O12) for caramelised fructose in the negative ion mode
Figure S23 EIC at m/z 359.0 (C12H24O12) for caramelised galactose in the negative ion mode
Figure S24 EIC at m/z 149.0 (C5H10O5) for caramelised rybose in negative ion mode
Figure S25 MS2 spectra of fragment at m/z 149.0 (C5H10O5) for three chromatographic peaks
of caramelised rybose in the negative ion mode
Figure S26 EIC at m/z 149.0 (C5H10O5) for caramelised arabinose in the negative ion mode
Figure S27 MS2 spectra of fragment at m/z 149 (C5H8O4) for three chromatographic peaks of
caramelised arabinose in the negative ion mode
Figure S28 EIC at m/z 281.0 (C10H18O9) for caramelised rybose in the negative ion mode
Figure S29 MS2 spectra of fragment at m/z 281.0 (C10H18O9) for four chromatographic peaks
of caramelised rybose in the negative ion mode
Figure S30 EIC at m/z 281.0 (C10H18O9) for caramelised arabinose in the negative ion mode
Figure S31 MS2 spectra of fragment at m/z 281.0 (C10H18O9) for ten chromatographic peaks
of caramelised arabinose in the negative ion mode
Figure S32 EIC at m/z 413.0 (C15H26O13) for caramelised rybose in the negative ion mode
Figure S33 MS2 spectra of fragment at m/z 413.0 (C15H26O13) for three chromatographic
peaks of caramelised rybose in the negative ion mode
Figure S34 EIC at m/z 413.0 (C15H26O13) for caramelised arabinose in the negative ion mode
Figure S35 MS2 spectra of fragment at m/z 413.0 (C15H26O13) for six chromatographic peaks
of caramelised arabinose in the negative ion mode
Figure S36 EIC at m/z 113.0 (C5H6O3) for caramelised rybose in the negative ion mode
Figure S37 EIC at m/z 113.0 (C5H6O3) for caramelised arabinose in the negative ion mode
Figure S38 EIC at m/z 263.0 (C10H16O8) for caramelised rybose in the negative ion mode
Figure S39 MS2 spectra of fragment at m/z 263.0 (C10H16O8) for seven chromatographic
peaks of caramelised rybose in the negative ion mode
Figure S40 EIC at m/z 263.0 (C10H16O8) for caramelised arabinose in the negative ion mode
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Figure S41 MS2 spectra of fragment at m/z 263 (C10H16O8) for three chromatographic peaks
of caramelised arabinose in the negative ion mode
Figure S42 EIC at m/z 395.0 (C15H24O12) for caramelised arabinose in the negative ion mode
Figure S43 MS2 spectra of fragment at m/z 395.0 (C15H24O12) for six chromatographic peaks
of caramelised arabinose in the negative ion mode
Figure S44 EIC at m/z 527.0 (C20H32O16) for caramelised rybose in the negative ion mode
Figure S45 MS2 spectra of fragment at m/z 527.0 (C20H32O16) for six chromatographic peaks
of caramelised rybose in the negative ion mode
Figure S46 EIC at m/z 791.0 (C30H48O24) for caramelised rybose in the negative ion mode
Figure S47 MS2 spectra of fragment at m/z 791.0 (C30H48O24) for six chromatographic peaks
of caramelised rybose in the negative ion mode
TableS2 Negative ion mode ESI-MS/MS data for caramelised fructose
TableS3 Negative ion mode ESI-MS/MS data for caramelised galactose
TableS4 Negative ion mode ESI-MS/MS data for caramelised mannose
4
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a)
203.0465
100
[%]
139.0698
80
60
365.0998
40
101.0005
527.1487
20
689.1998
851.2506
0
200
400
600
800
1000
1200 m/z
800
1000
1200 m/z
b)
365.0901
Intens.
[%]
80
527.1332
60
203.0512
40
311.0636
689.1777
20
261.1095
473.1035
0
200
400
600
5
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c)
Intens.
[%]
365.0878
80
60
203.0500
527.1296
40
20
689.1732
311.0612
635.1440
0
200
400
600
800
1000
1200
m/z
Figure S1. Mass spectra of caramelised: a) fructose, b) galactose and c) mannose in the
positive ion mode using a direct infusion into an ESI-TOF-MS instrument
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Table S1 High resolution mass (MS-TOF) data of caramelised: a) fructose, b) galactose, c) ribose, d) arabinose and their parent ions (M-H) in
the negative ion mode
a)
Peak numbering
Assignment
1
Mol. Formula
Experimental m/z [M-H]
Theoretical m/z [M-H]
Relative Error [ppm]
C9H18O2
157.1236
157.1234
1.5
2
Fru - H2O
C6H10O5
161.0457
161.0455
0.7
3
Fru
C6H12O6
179.0561
179.0561
0.0
4
C7H14O8
225.0608
225.0616
3.7
5
C14H28O2
227.2018
227.2017
0.7
6
C15H30O2
241.2181
241.2173
3.3
7
C16H32O2
255.2341
255.2330
4.6
8
C18H36O2
283.2653
283.2643
3.8
9
C12H16O8
287.0765
287.0772
2.8
10
C17H26O4
293.1760
293.1758
0.7
11
(Fru)2 - 2×H2O
C12H18O9
305.0891
305.0878
4.3
12
(Fru)2 - H2O
C12H20O10
323.0977
323.0984
2.0
13
(Fru)2
C12H22O11
341.1083
341.1089
1.9
14
(Fru)2 + H2O
C12H24O12
359.1189
359.1195
1.7
15
C13H24O13
387.1150
387.1144
1.5
16
C22H44O8
435.2970
435.2963
1.5
17
(Fru)3 - 3×H2O
C18H26O13
449.1305
449.1301
0.9
18
(Fru)3 - 2×H2O
C18H28O14
467.1408
467.1406
0.4
19
(Fru)3 - H2O
C18H30O15
485.1518
485.1512
1.3
7
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(Fru)3
C18H32O16
503.1628
503.1618
2.0
21
(Fru)3 + H2O
C18H34O17
521.1710
521.1723
2.5
22
(Fru)4 - 3×H2O
C24H36O18
611.1846
611.1829
2.9
23
(Fru)4 - 2×H2O
C24H38O19
629.1920
629.1935
1.4
24
(Fru)4 - H2O
C24H40O20
647.2027
647.2040
2.0
25
(Fru)4
C24H42O21
665.2134
665.2146
1.8
26
(Fru)4 + H2O
C24H44O22
683.2268
683.2251
2.4
27
(Fru)5 - 3×H2O
C30H46O23
773.2334
773.2357
2.9
28
(Fru)5 - 2×H2O
C30H48O24
791.2431
791.2463
4.0
29
(Fru)5 - H2O
C30H50O25
809.2545
809.2568
2.9
30
(Fru)5
C30H52O26
827.2701
827.2674
3.2
31
(Fru)5 + H2O
C30H54O27
845.2815
845.2780
4.2
32
(Fru)6 - H2O
C36H60O30
971.3119
971.3097
2.3
33
(Fru)6
C36H62O31
989.3173
989.3202
2.9
8
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b)
Peak numbering
Assignment
Mol. Formula
Experimental m/z [M-H]
Theoretical m/z [M-H]
Relative Error [ppm]
1
C6H12O2
115.0767
115.0765
2.1
2
C7H6O2
121.0294
121.0295
0.7
3
C4H8O4
119.0349
119.0350
0.7
4
C7H14O2
129.0925
129.0921
3.0
5
C8H16O2
143.1084
143.1078
4.9
6
C9H18O2
157.1236
157.1234
1.0
7
Gal - H2O
C6H10O5
161.0461
161.0455
3.7
8
Galactose
C6H12O6
179.0564
179.0561
1.4
9
C7H14O8
225.0608
225.0616
3.6
10
C16H32O2
255.2324
255.2330
2.0
11
C15H22O4
265.1452
265.1445
2.5
12
C9H18O9
269.0869
269.0878
3.5
13
C18H36O2
283.2629
283.2643
4.6
C12H16O8
287.0769
287.0772
1.2
C17H26O4
293.1758
293.1758
0.1
14
(Gal)2 - 3×H2O
15
16
(Gal)2 - 2×H2O
C12H18O9
305.0863
305.0878
4.9
17
(Gal)2 - H2O
C12H20O10
323.0985
323.0984
0.3
18
(Gal)2
C12H22O11
341.1094
341.1089
1.3
19
(Gal)2 + H2O
C12H24O12
359.1183
359.1195
3.2
20
(Gal)3 - 4×H2O
C18H24O12
431.1211
431.1195
3.8
21
(Gal)3- 3×H2O
C18H26O13
449.1281
449.1301
4.4
22
(Gal)3- 2×H2O
C18H28O14
467.1401
467.1406
1.2
9
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23
(Gal)3 - H2O
C18H30O15
485.1500
485.1512
2.4
24
(Gal)3
C18H32O16
503.1606
503.1618
2.3
25
(Gal)3 + H2O
C18H34O17
521.1729
521.1723
1.1
26
(Gal)4 - 3×H2O
C24H36O18
611.1805
611.1829
3.9
27
(Gal)4 - 2×H2O
C24H38O19
629.1907
629.1935
4.4
28
(Gal)4 - H2O
C24H40O20
647.2021
647.2040
3.0
29
(Gal)4
C24H42O21
665.2135
665.2146
1.6
30
(Gal)4 + H2O
C24H44O22
683.2222
683.2251
4.3
31
(Gal)5 - 5×H2O
C30H42O21
737.2156
737.2146
1.4
32
(Gal)5 - 4×H2O
C30H44O22
755.2227
755.2251
3.2
33
(Gal)5 - 3×H2O
C30H46O23
773.2324
773.2357
4.2
34
(Gal)5 - 2×H2O
C30H48O24
791.2425
791.2463
4.7
35
(Gal)5 - H2O
C30H50O25
809.2538
809.2568
3.4
36
(Gal)5
C30H52O26
827.2671
827.2674
0.3
37
(Gal)5 + H2O
C30H54O27
845.2752
845.2780
3.0
38
(Gal)6 - 3×H2O
C36H56O28
935.2877
935.2885
0.9
39
(Gal)6 - 2×H2O
C36H58O29
953.3013
953.2991
2.3
40
(Gal)6- H2O
C36H60O30
971.3096
971.3097
0.0
41
(Gal)6
C36H62O31
989.3187
989.3202
1.5
42
(Gal)6 + H2O
C36H64O32
1007.3352
1007.3308
4.3
10
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c)
Peak numbering
Assignment
Mol. Formula
Theoretical m/z [M-H]-
Experimental m/z [M-H]-
Relative Error [ppm]
1
Rib - 2×H2O
C5H6O3
113.0244
113.0246
1.7
2
Rib - H2O
C5H8O4
131.0350
131.0344
4.4
3
Ribose
C5H10O5
149.0455
149.0456
0.5
4
Rib + HCOOH
C6H12O7
195.0510
195.0516
3.0
6
(Rib)2 - 3×H2O
C10H12O6
227.0561
227.0572
4.7
7
(Rib)2 - 2×H2O
C10H14O7
245.0667
245.0666
0.5
8
(Rib)2 - H2O
C10H16O8
263.0772
267.0779
2.4
9
(Rib)2
C10H18O9
281.0878
281.0864
5.0
C11H16O9
291.0722
291.0714
2.4
10
11
(Rib)2 + HCOOH
C11H20O11
327.0933
327.0923
2.9
12
(Rib)3 - 3×H2O
C15H20O10
359.0984
359.0994
3.0
13
(Rib)3 - 2×H2O
C15H22O11
377.1089
377.1090
0.1
14
(Rib)3 - H2O
C15H24O12
395.1195
395.1199
1.0
15
(Rib)3
C15H26O13
413.1301
413.1293
1.8
16
(Rib)3 + HCOOH
C16H28O15
459.1355
459.1355
0.1
17
(Rib)4 - 3×H2O
C20H28O14
491.1406
491.1378
2.8
18
(Ryb)4 - 2×H2O
C20H30O15
509.1512
509.1487
4.9
19
(Ryb)4 - H2O
C20H32O16
527.1618
527.1609
1.7
20
(Ryb)4
C20H34O17
545.1723
545.1739
2.8
21
(Ryb)4 + H2O
C20H36O18
563.1829
563.1829
0.0
22
(Ryb)4 + HCOOH
C21H36O19
591.1778
591.1793
2.5
23
(Rib)5 - 3×H2O
C25H36O18
623.1829
623.1751
7.8
11
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24
(Rib)5 - 2×H2O
C25H38O19
641.1935
641.1904
4.7
25
(Rib)5 - H2O
C25H40O20
659.2040
659.2033
1.1
26
(Rib)5
C25H42O21
677.2146
677.2162
2.3
27
(Rib)5 + H2O
C25H44O22
695.2251
695.2266
2.1
28
(Rib)5 + HCOOH
C26H44O23
723.2201
723.2236
4.9
30
(Rib)6 - 3×H2O
C30H44O22
755.2252
755.2272
2.0
31
(Rib)6 - 2×H2O
C30H46O23
773.2357
773.2327
3.1
32
(Rib)6 - H2O
C30H48O24
791.2463
791.2450
1.6
33
(Rib)6
C30H50O25
809.2568
809.2604
4.4
34
(Rib)6 + H2O
C30H52O26
827.2674
827.2709
4.2
Peak numbering
Assignment
Mol. Formula
Experimental m/z [M-H]-
Theoretical m/z [M-H -
Relative Error [ppm]
1
Ara - H2O
C5H8O4
131.0350
131.0350
0.1
2
Arabinose
C5H10O5
149.0454
149.0455
1.0
3
(Ara)2 - 3×H2O
C10H12O6
227.0550
227.0561
5.0
4
(Ara)2 - 2×H2O
C10H14O7
245.0673
245.0667
2.5
5
(Ara)2 - H2O
C10H16O8
263.0761
263.0772
1.8
6
(Ara)2
C10H18O9
281.0867
281.0878
2.0
7
(Ara)2 + H2O
C10H20O10
299.0972
299.0984
7.6
d)
12
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8
(Ara)2 + HCOOH
C11H20O11
327.0922
327.0933
2.3
9
(Ara)3 - 2×H2O
C15H22O11
377.1078
377.1089
4.0
10
(Ara)3 - H2O
C15H24O12
395.1184
395.1195
0.3
11
(Ara)3
C15H26O13
413.1290
413.1301
2.2
12
(Ara)3 + H2O
C15H28O14
431.1395
431.1406
1.4
13
(Ara)3 + HCOOH
C16H28O15
459.1344
459.1355
2.8
14
(Ara)4 - 2×H2O
C20H30O15
509.1501
509.1512
4.3
15
(Ara)4 - H2O
C20H32O16
527.1607
527.1618
1.7
16
(Ara)4
C20H34O17
545.1712
545.1723
1.0
17
(Ara)4 + H2O
C20H36O18
563.1818
563.1829
0.0
18
(Ara)4 + HCOOH
C21H36O19
591.1767
591.1778
0.4
19
(Ara)5 - 2×H2O
C25H38O19
641.1924
641.1935
0.3
20
(Ara)5 - H2O
C25H40O20
659.2029
659.2040
0.8
21
(Ara)5
C25H42O21
677.2135
677.2146
0.5
22
(Ara)5 + H2O
C25H44O22
695.2241
695.2251
0.6
23
(Ara)5 + HCOOH
C26H44O23
723.2190
723.2201
1.9
24
(Ara)6 - 2×H2O
C30H46O23
773.2346
773.2357
1.2
25
(Ara)6 - H2O
C30H48O24
791.2452
791.2463
4.0
26
(Ara)6
C30H50O25
809.2557
809.2568
2.2
27
(Ara)6 + H2O
C30H52O26
827.2663
827.2674
2.1
28
(Ara)6 + HCOOH
C31H52O27
855.2612
855.2623
0.9
13
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a)
b)
c)
14
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KMD (Kendrick mass defect) for water
1,4
1,3
1,2
1,1
1,0
0,9
0,8
0,7
0,6
0
200
400
600
800
1000
1200
Nominal Kendrick mass for water
d)
1,4
KMD (Kendrick mass) for water
1,3
1,2
1,1
1,0
0,9
0,8
0,7
0,6
0
200
400
600
800
1000
1200
Nominal Kendrick mass for water
Figure S2 Two dimensional Kendrick plots for mass increment H2O showing the distribution
of the Kendrick mass defect plotted against the nominal Kendrick mass of pseudo-molecular
ions for caramelised: a) fructose, b) galactose, c) ribose and d) arabinose in the negative ion
mode. The colours indicate the homologous series of monomers, dimers, trimers, tetramers,
pentamers, hexamers
15
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5Å-5ÅÅ10Å
a)
b)
c)
Figure S3 Thermogravimetric curves of caramelised: a) fructose, b) galactose and c)
mannose. The temperature was ramped from 25 to 180 °C (140 °C, fructose) and kept at final
temperature for 2 h
16
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This journal is © The Royal Society of Chemistry 2013
Figure S4 Infrared spectra of caramelized: a) fructose, b) galactose and c) mannose
a) IR: 3318.9, 2933.6, 2888.3, 1648.6, 1415.7, 1340.2, 1252.1, 1024.5, 978.9, 924.0, 866.4,
817.4, 778.6 cm-1
b) IR: 3308.6, 2926.3, 2360.1, 2340.7, 1645.5, 1416.8, 1320.6, 1243.4, 1024.1, 773.7 cm-1
c) IR: 3332.0, 2927.1, 2360.4, 1645.2, 1337.2, 995.8, 842.6, 783.14 cm-1
17
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a)
18
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b)
19
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
c)
20
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This journal is © The Royal Society of Chemistry 2013
Figure S5 1H NMR spectra of caramelized: a) fructose, b) galactose and c) mannose
a) 1H NMR (400 MHz, D2O): δ 9.33 (CHO, m), 7.40 (m, Ar-H), 6.54 (m, Ar-H), 3.44-3.91
(m, >CHOH), 1.98 (m, -CH3).
b) 1H NMR (400 MHz, D2O): δ 9.35 (CHO, m), 7.40 (m, Ar-H), 6.41 (m, Ar-H), 4.44-5.19
(m, >C=C-H), 3.35-4.13 (m, >CHOH).
c) 1H NMR (400 MHz, D2O): δ 9.31 (CHO, m), 7.39 (m, Ar-H), 6.52 (m, Ar-H), 4.92-5.25
(m, >C=C-H), 3.22-4.37 (m, >CHOH).
a) 1H NMR
b) 1H NMR
21
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c) 1H NMR
22
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Oligomers of hexose:
Intens.
Intens.
x105
2.0
1.5
1.0
0.5
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S6 EIC at m/z 341.0 (C12H22O11) for caramelised fructose in the negative ion mode
Intens.
x105
1.0
0.8
0.6
0.4
0.2
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S7 EIC at m/z 341.0 (C12H22O11) for caramelised galactose in the negative ion mode
23
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
-MS2(341.0), 3.6min #191
178.7
100
50
160.7
100.9
118.8 130.7
0
[%]
190.7
271.7
220.7 232.7
322.8
-MS2(341.0), 3.9min #206
150
178.7
100
220.7
50
100.9
160.7
118.7
142.7
0
[%]
280.8
250.8
310.9
322.9
-MS2(341.0), 4.1min #216
150
178.7
100
220.7
50
142.7
100.9 112.7
0
[%]
160.7
271.7
250.7
190.6
322.9
-MS2(341.0), 4.6min #246
150
178.7
100
220.7
50
160.7
142.7
118.7
0
[%]
322.9
271.6
248.6
-MS2(341.0), 5.9min #314
150
160.7
100
178.7
50
271.7
100.9 112.8
0
50
220.7
100
150
322.7
260.5
200
250
423.4
300
350
400
450 m/z
Figure S8 MS2 spectra of fragment at m/z 341.0 (C12H22O11) for five chromatographic peaks
of caramelised fructose in the negative ion mode
Intens.
[%]
-MS2(503.0), 4.0min #208
434.7
376.8
178.6
484.9
0
[%]
-MS2(502.9), 4.1min #217
436.7
100
292.6
383.0396.8
341.0
456.9
0
[%]
-MS2(503.0), 4.4min #229
383.0
100
178.7
250.9
0
[%]
434.6
340.9
295.0
-MS2(503.1), 4.8min #255
434.7
100
178.7
298.6
0
[%]
383.0
322.9 340.9 358.9
456.8
492.1
-MS2(502.9), 5.1min #270
484.9
100
178.6
251.8
0
[%]
306.8 322.7
434.7
376.7
466.9
-MS2(502.9), 5.5min #291
176.6
100
444.6
341.0
0
[%]
374.6
467.0 484.9
402.7
-MS2(503.0), 6.2min #327
100
160.7
0
[%]
383.0
340.9
178.7
298.7
367.0
434.7
411.1
457.0
485.0
-MS2(503.1), 6.7min #355
434.6
100
320.7 340.9
0
[%]
376.6
446.7
485.0
-MS2(503.1), 6.8min #362
100
178.7
341.0
351.9366.0 382.9
214.6
0
[%]
434.6
444.7
-MS2(503.0), 8.1min #428
176.6
100
434.6
341.0
484.8
380.7
0
100
200
300
400
500
600 m/z
Figure S9 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for ten chromatographic peaks
of caramelised fructose in the negative ion mode
24
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
-MS2(646.7), 3.0min #182
638.6
615.7
560.6
0
[%]
-MS2(646.6), 3.5min #215
578.5
100
600.6
0
[%]
-MS2(646.7), 3.6min #221
576.5
100
598.7
507.9
0
[%]
-MS2(647.2), 4.0min #248
578.7
100
495.6
0
[%]
-MS2(646.8), 4.5min #279
100
576.6
508.6
482.7
0
[%]
-MS2(646.7), 4.6min #285
580.7
100
509.6
320.8
0
[%]
-MS2(646.6), 5.2min #319
578.5
100
483.0
555.0
516.0
588.9600.5
0
[%]
-MS2(646.8), 5.6min #344
100
578.6
460.7
0
[%]
-MS2(646.8), 6.4min #392
578.6
100
482.8
0
[%]
-MS2(646.6), 7.4min #453
362.9
100
576.7
466.1
0
250
300
350
400
450
500
550
600
m/z
Figure S10 MS2 spectra of fragment at m/z 647.0 (C24H40O20) for ten chromatographic peaks
of caramelised fructose in the negative ion mode
Intens.
[%]
-MS2(808.7), 3.6min #223
100
50
0
[%]
-MS2(808.7), 5.0min #311
686.6
100
50
0
[%]
-MS2(809.2), 7.4min #462
670.0
100
788.6
50
0
[%]
-MS2(808.7), 7.9min #488
609.5
100
50
0
[%]
-MS2(808.6), 8.4min #520
746.4
100
50
0
[%]
-MS2(808.7), 8.7min #543
688.6
100
50
0
[%]
-MS2(808.6), 9.7min #601
750.5
100
686.8
50
0
100
200
300
400
500
600
700
800
m/z
Figure S11 MS2 spectra of fragment at m/z 809.0 (C30H50O25) for seven chromatographic
peaks of caramelised fructose in the negative ion mode
25
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
-MS2(341.0), 3.4min #182
178.7
100
75
250.8
50
25
100.9
0
[%]
220.8
160.7
142.7
112.8
260.6
232.6
271.6
322.8
280.9
340.7
-MS2(341.0), 4.1min #220
271.6
100
75
322.9
50
220.7
25
178.7
158.7
113.0
232.8
295.7
245.0
339.8
0
100
150
200
250
300
m/z
Figure S12 MS2 spectra of fragment at m/z 341.0 (C12H22O11) for two chromatographic peaks
of caramelised galactose in the negative ion mode
Intens.
[%]
-MS2(503.1), 3.4min #177
436.7
100
342.0
50
178.8
366.8
322.9
250.4
383.1
444.7 456.8
0
[%]
-MS2(502.6), 3.6min #185
434.6
100
50
340.9
262.8
178.7
383.0
458.6 472.8
0
[%]
-MS2(503.1), 3.8min #197
436.6
100
50
178.8
322.9
250.7
340.9
376.6
401.1
445.7
0
[%]
-MS2(503.0), 4.1min #216
434.7
100
50
220.7
250.9
322.9
340.9
364.9
380.7
0
150
200
250
300
350
400
450
500 m/z
Figure S13 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for four chromatographic peaks
of caramelised galactose in the negative ion mode
Intens.
[%]
-MS2(502.8), 2.5min #128
434.7
364.8
298.7
0
[%]
380.7
-MS2(503.1), 3.5min #182
178.7
100
322.9
160.7
220.7230.8
341.1
305.7
0
[%]
365.5
382.9
398.8
434.7
456.9
-MS2(503.1), 4.1min #219
100
178.7
220.8
0
[%]
434.6
444.7
341.0
250.8
485.2
-MS2(503.1), 4.9min #259
436.7
100
178.7
340.9
0
[%]
376.7
456.8
-MS2(503.0), 5.2min #276
434.6
100
376.7
0
150
200
250
300
350
400
450
500
m/z
Figure S14 MS2 spectra of fragment at m/z 503.0 (C18H32O16) for four chromatographic peaks
of caramelised mannose in the negative ion mode
26
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
-MS2(646.7), 4.8min #294
578.5
100
598.8
0
[%]
-MS2(646.6), 5.6min #342
578.7
100
50
0
[%]
-MS2(646.7), 6.8min #415
578.5
100
546.6
508.7
50
0
[%]
-MS2(646.8), 8.0min #491
578.5
100
50
0
[%]
-MS2(646.5), 8.5min #520
576.6
100
50
442.8
628.7
0
300
350
400
450
500
550
600
m/z
Figure S15 MS2 spectra of fragment at m/z 647.0 (C24H40O20) for ten chromatographic peaks
of caramelised mannose in the negative ion mode
Intens.
[%]
-MS2(808.7), 3.8min #235
100
50
0
[%]
-MS2(809.3), 4.5min #273
694.6
100
740.7
50
0
[%]
-MS2(808.5), 4.8min #294
642.2
100
670.6
50
0
[%]
-MS2(808.6), 7.8min #478
558.6
100
738.6
50
0
450
500
550
600
650
700
750
800
m/z
Figure S16 MS2 spectra of fragment at m/z 809.0 (C30H50O25) for seven chromatographic
peaks of caramelised mannose in the negative ion mode
27
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Dehydration products:
Intens.
x104
FRU27000000.179.161(L.6).D: EIC 161.0 -All MS
6
4
2
0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S17 EIC at m/z 161.0 (C6H10O5) for caramelised fructose in the negative ion mode
Intens.
x105
002-0301.Fru.(L1),341,323D: EIC 323.0 -All MS
4
3
2
1
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S18 EIC at m/z 323.0 (C12H20O10) for caramelised fructose in the negative ion mode
Intens.
x104
1.0
GAL280000000.179,161(L6).D: EIC 161.0 -All MS
0.8
0.6
0.4
0.2
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S19 EIC at m/z 161.0 (C6H10O5) for caramelised galactose in the negative ion mode
28
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
x105
GAL30000001341,359(L.1).D: EIC 323.0 -All MS
1.0
0.8
0.6
0.4
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S20 EIC at m/z 323.0 (C12H20O10) for caramelised galactose in the negative ion mode
Intens.
x105
MAN30000003.341,323(L1)D: EIC 323.0 -All MS
2.0
1.5
1.0
0.5
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S21 EIC at m/z 323.0 (C12H20O10) for caramelised mannose in the negative ion mode
29
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Hydration products:
Intens.
x106
002-0301.Fru.(L1),341,323D: EIC 359.0 -All MS
0.8
0.6
0.4
0.2
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S22 EIC at m/z 359.0 (C12H24O12) for caramelised fructose in the negative ion mode
Intens.
x105
GAL30000001341,359(L.1).D: EIC 359.0 -All MS
1.25
1.00
0.75
0.50
0.25
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S23 EIC at m/z 359.0 (C12H24O12) for caramelised galactose in the negative ion mode
30
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Monomer and oligomers of pentose:
Intens.
x106
RYB000007.D: EIC 149.0 -All MS
1.0
0.8
0.6
0.4
0.2
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S24 EIC at m/z 149.0 (C5H10O5) for caramelised rybose in the negative ion mode
Intens.
[%]
-MS2(148.7), 2.9min #163
130.7
100
88.9
50
59.4
0
[%]
71.3
112.7
100.9
85.0
118.7
-MS2(148.7), 3.1min #171
130.7
100
88.9
50
59.4
0
[%]
71.2
112.8
100.9
85.1
118.7
-MS2(148.7), 3.6min #200
88.9
130.7
100
50
59.3
0
50
60
112.7
71.2
70
100.9
85.0
80
90
100
110
118.7
120
130
140
150 m/z
Figure S25 MS2 spectra of fragment at m/z 149.0 (C5H10O5) for three chromatographic peaks
of caramelised rybose in the negative ion mode
Intens.
x105
ARA000002.D: EIC 149.0 -All MS
5
4
3
2
1
0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S26 EIC at m/z 149.0 (C5H10O5) for caramelised arabinose in the negative ion mode
31
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
-MS2(148.7), 3.3min #187
130.7
100
88.9
112.8
50
71.3
0
[%]
100.8
84.9
118.7
-MS2(148.7), 4.1min #229
88.9
100
50
62.5
130.7
112.8
118.7
71.3
128.7
0
[%]
-MS2(148.7), 12.7min #719
62.3
100
50
0
50
60
70
80
90
100
110
120
130
140
150
m/z
Figure S27 MS2 spectra of fragment at m/z 149 (C5H8O4) for three chromatographic peaks of
caramelised arabinose in the negative ion mode
Intens.
x106
RYB000008.D: EIC 281.0 -All MS
4
3
2
1
0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S28 EIC at m/z 281.0 (C10H18O9) for caramelised rybose in the negative ion mode
Intens.
[%]
100
-MS2(280.8), 2.9min #159
148.6
112.8
88.9
100.8
130.7
142.6
118.8124.7
0
[%]
154.6 160.6
184.6190.6
172.6
202.6 210.5
220.7
-MS2(280.8), 3.4min #187
130.7
148.6
100
89.0
0
[%]
100.9
190.6
112.8
202.6
220.7
262.7
232.7
-MS2(280.8), 3.8min #214
148.6
100
89.0
0
[%]
100.9
130.7
112.8
190.6
262.7
232.7
-MS2(280.8), 6.1min #344
148.7
100
88.9
0
80
100.8
100
130.7
112.7
120
190.6
140
160
180
200
220
240
260
280
m/z
Figure S29 MS2 spectra of fragment at m/z 281.0 (C10H18O9) for four chromatographic peaks
of caramelised rybose in the negative ion mode
32
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
x105
4
ARA000003.D: EIC 281.0 -All MS
3
2
1
0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S30 EIC at m/z 281.0 (C10H18O9) for caramelised arabinose in the negative ion mode
Intens.
[%]
100
-MS2(280.8), 3.6min #193
190.7
50
100.9
0
[%]
130.7
112.8
232.7
212.5
262.7
-MS2(280.8), 3.8min #203
148.7
190.7
130.7
100
262.7
50
89.0
100.9
112.8
184.5
0
[%]
212.5 220.7
232.7
250.8
279.5
-MS2(280.8), 4.1min #218
190.7
100
50
130.7
89.0
0
[%]
100.9
148.7
112.8
210.5
184.5
262.6
232.6
-MS2(280.8), 4.3min #228
190.6
100
130.7
50
100.8
0
[%]
148.7
112.7
184.5
160.7
202.6 210.5
232.6
220.6
244.7
262.6
-MS2(280.8), 4.6min #247
148.7
100
130.7
50
89.0
100.9
0
[%]
112.8
118.8
210.4
184.5190.6
262.6
220.6
-MS2(280.8), 5.0min #268
130.7
100
100.8
50
85.1
0
[%]
190.6
148.7
112.7
154.5
104.9
210.5
186.6
168.6
220.7
232.6
250.7
262.6
-MS2(280.7), 6.3min #338
130.7
100
50
85.0
0
[%]
92.8 100.9
210.5
148.6
112.7
262.5
184.5190.6
280.7
236.7
-MS2(280.8), 7.4min #394
148.6
100
130.7
50
89.0
100.8
0
[%]
112.8
118.7
212.4
262.6
184.5190.6
137.6
220.6
234.5
-MS2(280.8), 8.9min #472
262.6
100
212.4
130.7
50
148.7
89.0 94.8
0
[%]
184.6
190.6
112.7
280.6
219.9
-MS2(280.8), 10.4min #556
148.6
100
130.7
50
84.0 88.9
0
75
100.9
100
184.5
190.6
112.7118.7
125
150
175
212.4 220.6
200
225
262.5
235.6
250
275
m/z
Figure S31 MS2 spectra of fragment at m/z 281.0 (C10H18O9) for ten chromatographic peaks
of caramelised arabinose in the negative ion mode
33
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
x106
RYB000009.D: EIC 413.0 -All MS
1.5
1.0
0.5
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S32 EIC at m/z 413.0 (C15H26O13) for caramelised rybose in the negative ion mode
Intens.
[%]
-MS2(412.9), 3.4min #180
280.8
308.8
100
50
130.7
0
[%]
148.6
155.6
262.7
172.6
190.6
202.6
220.7
232.7
250.7
292.8
318.5
342.6 352.7
382.8 394.9
-MS2(413.0), 4.1min #224
280.7
100
50
130.7
0
[%]
262.7
190.6
148.7
142.7
322.8
172.6
220.7
232.7
244.7
334.8
352.9
394.9
-MS2(412.9), 5.2min #284
280.8
100
50
130.7
148.7
0
190.6
172.7
150
322.9
262.7
352.8
244.7
202.7
200
250
300
394.9
350
400
m/z
Figure S33 MS2 spectra of fragment at m/z 413.0 (C15H26O13) for three chromatographic
peaks of caramelised rybose in the negative ion mode
Intens.
x104
ARA000007.D: EIC 413.0 -All MS
2.5
2.0
1.5
1.0
0.5
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S34 EIC at m/z 413.0 (C15H26O13) for caramelised arabinose in the negative ion mode
34
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
[%]
100
-MS2(413.3), 3.3min #175
345.6
278.5
354.5
288.7
366.9
0
[%]
-MS2(412.9), 5.9min #316
130.7
100
148.7
0
[%]
280.7
232.8
172.8
190.6
294.5
286.4
262.7
210.4
322.9
345.5 354.6
368.7
-MS2(412.9), 6.7min #357
280.8
100
190.6
148.6
0
[%]
260.5
208.4
322.8
294.6
352.5
394.9
375.5
345.6
-MS2(412.9), 7.0min #378
280.8
100
0
[%]
130.7
262.7
148.7
130.7
100
296.5
190.7
323.0
280.7
184.6
354.4
376.5
394.9
-MS2(412.9), 7.7min #415
352.6
262.7
311.7 322.7
0
[%]
-MS2(412.9), 8.5min #454
100
262.7
276.5
294.6
322.9
328.5
345.6353.8
0
150
200
250
300
350
400
m/z
Figure S35 MS2 spectra of fragment at m/z 413.0 (C15H26O13) for six chromatographic peaks
of caramelised arabinose in the negative ion mode
Dehydrated pentoses:
Intens.
x105
RYB000007.D: EIC 113.0 -All MS
1.25
1.00
0.75
0.50
0.25
0.00
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S36 EIC at m/z 113.0 (C5H6O3) for caramelised rybose in the negative ion mode
Intens.
x104
ARA000002.D: EIC 113.0 -All MS
8
6
4
2
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S37 EIC at m/z 113.0 (C5H6O3) for caramelised arabinose in the negative ion mode
35
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
Intens.
x106
1.0
RYB000008.D: EIC 263.0 -All MS
0.8
0.6
0.4
0.2
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S38 EIC at m/z 263.0 (C10H16O8) for caramelised rybose in the negative ion mode
Intens.
[%]
-MS2(262.7), 3.5min #196
260.5
130.8
84.9
0
[%]
160.6
-MS2(262.8), 4.9min #280
202.6
100
87.0
0
[%]
100.9
110.7
130.7
172.6
190.7
-MS2(262.8), 6.3min #355
260.5
86.9
100
100.9
0
[%]
260.5
218.6
130.7
112.8
202.7
184.6 190.7
142.7 148.6
232.7
-MS2(262.8), 6.7min #379
87.0
100
260.5
130.7
112.7
0
[%]
190.6
142.6 148.6 154.6
202.6
232.6
-MS2(262.8), 8.4min #468
260.5
100
130.7
0
[%]
-MS2(262.8), 9.4min #524
202.6
100
87.0
0
[%]
112.7
260.5
142.7
-MS2(262.8), 12.5min #690
260.5
100
130.7
0
80
100
120
190.6
140
160
180
202.6
200
220
240
260
m/z
Figure S39 MS2 spectra of fragment at m/z 263.0 (C10H16O8) for seven chromatographic
peaks of caramelised rybose in the negative ion mode
Intens.
x105
ARA000006.D: EIC 263.0 -All MS
0.8
0.6
0.4
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S40 EIC at m/z 263.0 (C10H16O8) for caramelised arabinose in the negative ion mode
36
Electronic Supplementary Material (ESI) for Food & Function
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Intens.
[%]
-MS2(262.7),
260.5 3.7min #199
50
232.7
130.7
0
[%]
-MS2(262.6), 5.7min #301
260.5
100
50
118.6
0
[%]
-MS2(262.6), 11.7min #626
260.5
100
50
118.7
0
120
140
160
180
200
220
240
260
m/z
Figure S41 MS2 spectra of fragment at m/z 263 (C10H16O8) for three chromatographic peaks
of caramelised arabinose in the negative ion mode
Intens.
x104
ARA000007.D: EIC 395.0 -All MS
3
2
1
0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S42 EIC at m/z 395.0 (C15H24O12) for caramelised arabinose in the negative ion mode
Intens.
[%]
100
-MS2(394.8), 3.6min #194
112.7
252.8
216.5
324.7
271.6
0
[%]
348.9 358.9
374.7
392.9
-MS2(394.9), 4.0min #214
328.6
100
0
[%]
100
260.5
112.7
-MS2(394.9), 4.3min #228
112.7
348.8
140.6
198.6
242.6
322.8
260.6
0
[%]
100
-MS2(394.9), 4.4min #236
324.7
112.8
258.7
302.7
348.8
0
[%]
100
-MS2(394.9), 4.9min #262
280.8
112.7
236.7
130.6
324.7
262.8
351.1
0
[%]
100
376.6
-MS2(394.9), 5.5min #294
112.7
254.5
325.6
280.6
0
150
200
250
300
350
m/z
Figure S43 MS2 spectra of fragment at m/z 395.0 (C15H24O12) for six chromatographic peaks
of caramelised arabinose in the negative ion mode
37
Electronic Supplementary Material (ESI) for Food & Function
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Intens.
x105
RYB000010.D: EIC 527.0 -All MS
2.0
1.5
1.0
0.5
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S44 EIC at m/z 527.0 (C20H32O16) for caramelised rybose in the negative ion mode
Intens.
[%]
100
-MS2(526.8), 3.4min #177
244.5
390.7
0
[%]
176.5
260.5
330.5
408.4 420.7 434.7
480.7
456.6 468.5
496.4
-MS2(526.9), 3.9min #202
480.8
100
390.7
244.5
0
[%]
260.5270.5
176.5 190.5
288.8
312.7
332.6
348.7
458.6
410.5420.7
506.7
-MS2(527.0), 4.9min #257
262.8
100
0
[%]
202.7
330.8
348.8
460.5
390.7
480.9
-MS2(526.9), 5.2min #272
480.9
100
330.8
262.8
0
[%]
394.9
348.8
412.9
456.6
508.9
-MS2(526.9), 5.8min #302
460.6
100
0
[%]
262.7
198.5
330.7
348.9
365.4 377.8
394.9404.7
480.9
473.0
420.8
506.5
-MS2(527.0), 11.4min #593
460.5
100
232.7 244.7
0
200
262.8
250
322.8 334.8
280.8
300
352.8
376.8
350
394.9
402.6412.9
400
468.1 480.9490.9
450
508.9
500
m/z
Figure S45 MS2 spectra of fragment at m/z 527.0 (C20H32O16) for six chromatographic peaks
of caramelised rybose in the negative ion mode
Intens.
x104
RYB000012.D: EIC 791.0 -All MS
1.5
1.0
0.5
0.0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
Time [min]
Figure S46 EIC at m/z 791.0 (C30H48O24) for caramelised rybose in the negative ion mode
38
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Intens.
[%]
100
-MS2(791.1), 4.0min #225
514.9
569.0
638.5
664.8
0
[%]
-MS2(790.9), 5.3min #300
722.5
100
376.5
578.8
767.2
699.8
647.5
0
[%]
-MS2(791.0), 5.4min #309
605.8
100
744.9
660.2
376.5
260.5
0
[%]
-MS2(790.9), 5.7min #324
722.5
100
376.6
260.6
664.6
586.6
0
[%]
-MS2(790.7), 9.5min #548
722.6
100
755.0
636.4
490.6
374.6
0
[%]
732.4
-MS2(791.2), 11.0min #641
654.5
100
722.6
0
300
400
500
600
700
m/z
Figure S47 MS2 spectra of fragment at m/z 791.0 (C30H48O24) for six chromatographic peaks
of caramelised rybose in the negative ion mode
39
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Table S2 Negative ion mode ESI-MS/MS data for caramelised fructose
MS
m/z
160.8
178.9
283.1
322.9
341.0
367.0
413.2
485.2
503.2
529.2
2
m/z (Intensity)
113.1 (100.0); 101.2 (77.7); 131.0 (31.8); 71.6 (16.0); 83.4 (13.5)
89.3 (100.0); 160.9 (98.5); 143.0 (85.2); 119.1 (67.6); 113.1 (34.8); 131.1 (30.5); 101.2
(24.9); 71.6 (17.4); 148.9 (16.9); 107.1 (13.4); 87.3 (13.0); 59.8 (10.1); 125.0 (9.0); 178.9
(3.4); 99.2 (2.2)
MS
3
m/z (Intensity)
142.9: 125.0 (100.0); 87.3 (67.4); 115.1 (56.5)
89.2: 71.6 (100.0); 59.8 (70.74)
119.0: 101.2 (100.0); 89.3 (10.5)
131.0: 113.1 (100.0); 101.2 (91.2)
160.8: 113.1 (100.0); 131.0 (47.4); 142.9
(32.8); 101.1 (14.3)
264.9 (100.0); 217.9 (26.2); 114.1 (20.7); 283.1 (19.7); 246.8 (15.2); 221.9 (10.3); 186.9
264.8: 246.8 (100.0); 217.9 (57.01)
(9.8); 220.8 (9.0)
160.9 (100.0); 232.9 (80.4); 113.1 (22.4); 322.9 (21.2); 143.0 (15.2); 178.8 (12.5); 202.9
232.9: 160.9 (100.0); 113.1 (67.6); 142.9 (65.2)
(8.9); 274.9 (6.7); 101.2 (6.2); 304.9 (4.1); 131.0 (3.9); 250.9 (3.8); 220.9 (2.7); 119.1 (2.4);
292.9 (2.2); 125.1 (2.2)
160.9: 113.1 (100.0); 101.2 (50.4); 142.9
(47.7); 160.9 (25.3); 89.3 (22.1); 85.4 (16.5)
178.9 (100.0); 322.9 (90.6); 160.9 (34.5); 220.9 (18.1); 341.0 (14.9)
178.8: 160.9 (100.0); 89.3 (88.6)
160.9: 101.1 (100.0)
276.9 (100.0); 186.9 (47.0); 348.9 (47.7); 204.9 (40.1); 367.0 (17.2); 168.9 (13.8); 330.9
276.8: 186.9 (100.0); 204.9 (93.9); 168.9
(12.4); 127.0 (7.5); 156.9 (6.1); 306.9 (5.6); 192.9 (4.2); 190.9 (3.2); 336.9 (3.7); 178.9
(38.6); 156.9 (14.6); 216.9 (6.9)
(2.6); 172.9 (2.2); 113.1 (1.9); 125.1 (1.6); 258.8 (1.4); 312.9 (1.9); 216.8 (1.0)
186.9: 127.0 (100.0)
348.9: 330.9 (100.0); 186.9 (78.3); 204.9
(73.2); 276.9 (26.6); 258.9 (33.6); 168.9 (40)
204.8: 186.9 (98.7); 168.9 (100); 156.9 (44.4)
344.9 (100.0); 252.9 (48.1); 322.9 (40.0)
322.9 (100.0); 160.9 (19.3); 178.9 (9.2); 232.9 (7.9); 485.2 (7.2); 395.0 (5.6); 143.0 (3.9);
304.9 (3.7); 467.0 (2.7); 383.0 (2.6); 340.9 (1.4); 425.0 (1.1); 449.0 (1.1); 214.9 (1.0);
286.9 (0.9)
340.9 (100.0); 485.0 (58.3); 413.0 (53.7); 178.9 (50.0); 322.9 (50.0); 383.0 (43.8); 160.9
(13.8); 250.8 (7.5); 443.0 (6.8); 220.8 (6.4)
511.1 (100.0); 349.0 (60.1); 439.0 (33.6); 367.0 (20.2); 529.2 (17.0); 276.9 (16.6); 186.9
(12.8); 204.9 (11.4); 330.9 (4.9); 168.9 (3.7); 258.9 (3.3); 493.1 (3.2); 469.1 (2.2); 246.9
MS
4
m/z (Intensity)
113.0: 95.2
(100) 85.4
(47.25)
186.9: 115.1
(100.0)
204.9: 168.9
(100.0)
322.9:160.9 (100.0); 232.9 (87.2); 113.1 (27.0);
143.0 (13.9); 178.9 (10.3)
341:178.9 (100.0)
511.1: 348.9 (100.0); 439.0 (42.5); 168.8
(28.4); 276.9 (22.1); 258.9 (21.4); 168.9 (17.5)
40
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647.2
665.3
683.2
691.2
989.3
(2.0); 481.1 (2.0)
439.0: 349.0(100.0)
349.0: 186.8 (42.2); 258.9 (41.2)
485.01 (100.0); 323.0 (34.4); 467.1 (3.6); 566.1 (2.4); 232.9 (1.7); 323.9 (1.4); 304.9 (1.3);
341.0 (1.1); 629.2 (0.9); 395.0 (0.8); 178.9 (0.6)
485.1 (100.0); 503.0 (87.0); 340.9 (70.9); 545.1 (52.3); 575.2 (49.2); 322.9 (38.9); 647.2
(36.3); 383.0 (34.5); 413.0 (26.9)
647.2 (100.0); 485.1 (33.1); 503.0 (0.5)
511.1 (100.0); 673.2 (38.0); 348.9 (32.6); 439.0 (20.3); 529.1 (13.8); 601.2 (12.8); 691.2
(9.1); 367.0 (8.2)
647.2 (100.0); 899.3 (55.6); 827.3 (47.8); 869.3 (42.3); 665.2 (42.2); 545.2 (38.7); 485.1
(29.0); 503.1 (21.0); 707.3 (20.2); 340.9 (18.6); 383.1 (17.4); 809.2 (16.6); 737.3 (16.1);
971.3 (16.0); 322.9 (11.2)
485.1: 322.9 (100.0); 232.9 (9.0)
322.9: 232.8
(67.3)
647.2: 485.1 (100.0)
41
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Table S3 Negative ion mode ESI-MS/MS data for caramelised galactose
MS
m/z
2
MS
m/z (Intensity)
m/z (Intensity)
160.9 113.1(100) 101.1 0(90.7) 131.0(47.8) 142.9(33.0) 89.2(13.9) 87.3(12.9)
160.9(100) 89.3(61.5) 142.9(43.9) 119.0(35.7) 113.1(25.2) 131.0 (21.6) 101.2(21.6) 148.9(8.5) 87.3(7.6) 107.1(7.3)
178.8 125.0(6.2) 59.8(5.7) 71.5(5.5
220.9 160.9(100)
255.0 236.9(100) 224.9(63.9) 75.4(60.8) 178.9(59.5)
323.0 160.9(100) 113.1(34.9) 220.9(27.0) 232.8(26.8) 304.9(17.6) 178.9(17.2) 262.9(16.6) 142.9(15.2) 244.8 (6.4) 250.8 (6.0)
178.9(100) 322.9(69.3) 160.9(40.02) 250.9(30.2) 220.9(27.2) 142.9(22.4) 113.1(20.3) 119.0(14) 101.2 (13.3) 266.9
341.0 (11.2) 280.9(11.1) 125.0(8.5) 131.0(8.2) 311.0(7.8)
449.0 286.9(100) 431.0(65.8) 160.9(47.3) 322.9(33)
322.9(100) 160.9(15.6) 178.9(6.4) 304.9(4.6) 467.1(4.2) 220.9(4.1) 383.0(3.2) 425.0 (3.0) 340.9(2.9) 449.1(2.8)
485.2 395.0 (2.5) 142.9(2.2) 364.9(2.0) 232.9(1.8) 262.9(1.8)
340.9(100) 322.9(45) 383.0(29.5) 485.1(28) 178.9(27.2) 443.0(14.5) 220.9(13.2) 250.9(11.9) 413.0(11.9) 160.9(9.0)
503.0 280.9(6.6) 304.9 (6.0) 262.8(4.1)
519.0 483.1(100)
611.2 449.0(100) 431.0(18) 593.1 (17.9) 322.9(17.2) 286.9(15.5) 485.0 (8.8) 220.9(5.6) 521.1(4.3) 178.9(4.0)
485.1(100) 323.0(32.4) 467.1(23) 566.2(4.6) 629.2(4.4) 304.9(3.3) 383.0(2.8) 341.0(2.8) 503.1(2.3) 220.9(2.1)
527.1(1.8) 611.2(1.6) 557.2(1.6) 365.0 (1.5) 587.2(1.4) 425.1(1.3) 545.2(1.3) 449.1(0.5) 262.9(0.5) 395.0(0.5)
250.9(1.1) 615.2(0.9) 244.9(0.8) 407.0(0.8) 232.9(0.7) 286.9(0.7) 393.0(0.7) 638.2(0.7) 362.9(0.6) 575.2(0.5)
647.2 413.1(0.5)
503.1(100) 485.1(53.5) 647.2(44.5) 322.9(27.1) 383.0(26.7) 341.0(15.9) 545.2 (15) 443.1 (10.2) 220.9(7.0)
413.1(5.9) 605.2(5.6) 575.2 (4.4) 262.9(3.8) 280.9(3.8) 395.0 (3.3) 467.1(2.9) 629.2(2.8) 178.9(2.7) 664.3(2.6)
665.2 304.9(2.3) 160.9 (2 ) 425.1(1.8) 563.1(1.3)
683.2 647.2(100)
507.1(100)
687.0 272.9(20)
737.3 656.2(100)
773.3 611.2(100)
791.3 629.3(100)
3
485.1(11.4) 665.2(10.9)
525.1(68.5) 344.9(60.1) 363.0(52.1) 405.0 (46.2) 655.2 (41.1) 669.2 (28.4) 242.9(27.8) 567.1(26.1)
160.9: 113.1 (100) 131.0 (68.82) 142.9(31.59)
161.0: 113.1(100)
179.0: 89.3(100)
323.0: 160.9(100) 113.1(40.5) 232.9 (32.8)
340.9: 78.9(100)
383.0: 220.9(100)
485.1: 322.9(100) 160.9(7.4) 220.9 (7.0)
304.9 (5.1)
503.1: 340.9(100) 322.9(38.4) 383.0(29.0)
178.9(18.8)
485.1: 341.0 (70.43) 322.9(100)
383.0: 220.9(100)
545.2: 383.0(100)
647.2: 485.1(100)
525.1: 344.9(100)
575.2(83.0) 719.2(41.0) 596.2(22)
449.1(35.9) 593.2(25.6) 755.3(23.6) 323.0(11.6) 485.1(9.5) 431.0(8.3)
647.2(58.9) 773.3(4102) 467.1(30.7) 611.2 (26.8) 755.2(26.8) 322.9(25)
383.0(6.3) 491.1(6.0)
611.2: 449.1(100)
42
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
647.3(100) 485.1(33.6) 629.2(23.3) 467.1(9.4) 323.0(8.9) 791.3(3.8) 728.3 (3.7) 383.0(3.5) 503.2(2.7) 665.2(2.6)
809.3 545.2(2.5) 527.2(2.5) 689.3(2.4) 304.9(1.7) 341.0(1.4) 707.2 (1.3)
647.3: 485.1(100) 467.1(22.6) 323.0(23.6)
485.1: 322.9(100)
665.2(100) 647.2(40.1) 485.1(39.9) 503.1(39.3) 809.3(32.3) 340.9 (16.3) 383.0(16.1) 545.1(15.6) 707.3(120.6)
827.3 322.9(9.2) 767.2(5.9) 737.2(5.5) 443.1(4.3) 831.2(3.4) 262.8(3.3) 467.0(3.1)
972.3 810.3(100) 648.2(25.82)
989.3 827.3(100) 665.3(62.8) 809.3(47.5) 647.2(40.7) 503.1(21) 545.2(20.9) 971.3(18.5) 383.0(17.1) 485.0(16.8)
Table S4 Negative ion mode ESI-MS/MS data for caramelised mannose
MS
279.9
283.1
322.9
341.0
665.2
691.2
673.2(100) 511.1(7.32) 348.9(3.43)
503.1
647.2
3
m/z (Intensity)
101.1(100) 113.1(86.9) 85.3(68.0)
160.9(100) 135.0 (85.4 119.0 (79.1) 89.3(78.2) 150.9(71.8) 122.0(69.4)
114.1(100) 191.9(78.2) 113.1 (61.8)
113.1(100)
114.1(100) 113.1(58.6) 219.9(8.2) 221.9(5.7) 218.9(4.5) 262.9(3.7) 251.9(3.6) 178.8(3.3)
165.9(2.5)
114.1(100) 217.9(69.7) 264.9(66.9) 221.8(38.9) 255.9(20.9)
160.9(100) 114.1(41.4) 220.9(38.3) 276.0(15.0) 113.1(12.2) 304.9(10.8) 232.9(9.1)
322.9(100) 114.1(96.9) 279.9(82.9) 276.0(75.3) 178.9(35.9) 264.9(13.3) 294.0(11.7) 341.0 (11.0)
280.9 (10.2) 160.9(9.0) 220.9 (5.9) 119.1(4.7) 217.9(4.6) 113.1 (3.9) 250.9 (3.1) 221.9(2.8)
282.9(2.6)
322.9(100) 178.9(9.7) 220.9 (9.3) 160.9(8.5) 341.0(7.4) 467.1(7.0)
340.9(100) 443.1(73.6) 383.0(42.0) 485.1(40.1) 322.9(38.1) 178.9(36.9)
160.9(9.3) 280.9(8.1) 425.0(7.5) 304.9(7.2) 262.9(5.2) 250.9(4.7)
485.1(100) 322.9(21.0) 467.1 (15.7) 629.2 (10.0) 425.0(7.4)
503.1(100) 647.2(45.5) 341.0(43.8) 485.1(41.8) 605.2(38.4) 545.1(35.1)
323.0(19.1) 575.2(15.6) 587.2(10.0) 413.0(9.9) 467.1(4.3) 280.9(4.0)
485.1
MS
m/z (Intensity)
m/z
161.0
178.9
253.2
255.0
2
425.0(4.8) 304.9(4.5)
413.0(18.5) 220.9(12.3)
323.0: 275.9(85.05) 114.1 (100)
217.9(16.7)
275.9: 232.9 217.9
323.0: 160.9(100)
MS
4
m/z
(Intensity)
276.0:
133(100)
341.0: 178.9 (100)
485.1: 322.9(100)
383.0(32.7) 443.1(23.9)
220.9(3.8) 304.9(3.1)
673.2: 511.1(100) 613.2(65.43)
655.2(32.4) 493.1(31.79)
43
Electronic Supplementary Material (ESI) for Food & Function
This journal is © The Royal Society of Chemistry 2013
647.2(100) 629.2(27.7) 485.1(38.7) 791.3(13.4)
665.2(100) 503.1(61.1) 647.2(37.0) 545.1(29.2) 707.2(27.4) 485.1(25.6) 809.3(22.8) 605.2(18.6)
827.3 383.0(15.2) 767.3(14.8) 341.0(12.2) 737.2(12.2) 443.1(11.4) 575.2(10)
673.2(100) 775.3(83.5) 817.3(57.8) 511.1(43.1) 715.3(43.1) 493.1 (37.8) 745.3(35) 665.2(34.8)
835.4 451.1(21.3) 613.2(20.8) 553.1(16.2)
827.3(100) 665.2(65.0) 503.1(37.3) 809.2(35.6) 647.2(34.0) 929.2(25.8) 707.2(22.7) 869.3(22.3)
989.4 485.0(20.4) 971.2 (20)
1151.4 989.3(100) 827.3(62.21)
1313.4 1151.3(100)
1159.3(100) 1261.4(54.96) 1303.4(59.80) 1201.3(33.08) 1141.4(42.75) 997.3(50.64) 835.3(38.93)
1321.4 673.2(25.7)
809.3
44