1 SUPPORTING INFORMATION MALDI-TOF/TOF CID Study of Poly(Butylene Adipate) Fragmentation Reactions Anthony P. Gies 1†* , Sparkle T. Ellison 2†† , Amit K. Chakraborty 1 , Nicholas W. Kwiecien 1 , and David M. Hercules 1 1 Department of Chemistry, Vanderbilt University, Nashville, TN 37235 † Present address is at the Department of Core R&D Analytical Sciences, The Dow Chemical Company, 2301 N. Brazosport Blvd., B-1219, Freeport, TX 77541 2 Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208 †† Present address is at the School of Law, University of Kansas, Lawrence, KS 66045 Polymer Chemistry: December 16, 2011 TITLE RUNNING HEAD: MALDI-TOF/TOF CID Study of PBA. CORRESPONDING AUTHOR FOOTNOTE: Address reprint requests to Anthony P. Gies, Department of Core R&D Analytical Sciences, The Dow Chemical Company, 2301 N. Brazosport Blvd., B-1219, Freeport, TX 77541. Telephone: (979) 238-1778. E-mail: [email protected] Electronic Supplementary Material (ESI) for RSC Advances This journal is © The Royal Society of Chemistry 2012
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1
SUPPORTING INFORMATION
MALDI-TOF/TOF CID Study of Poly(Butylene
Adipate) Fragmentation Reactions
Anthony P. Gies1†*
, Sparkle T. Ellison2††
, Amit K. Chakraborty1, Nicholas W. Kwiecien
1,
and David M. Hercules1
1Department of Chemistry, Vanderbilt University, Nashville, TN 37235
†Present address is at the Department of Core R&D Analytical Sciences, The Dow
Chemical Company, 2301 N. Brazosport Blvd., B-1219, Freeport, TX 77541
2Department of Chemistry and Biochemistry, University of South Carolina, Columbia,
SC 29208
††Present address is at the School of Law, University of Kansas, Lawrence, KS 66045
Polymer Chemistry: December 16, 2011
TITLE RUNNING HEAD: MALDI-TOF/TOF CID Study of PBA.
CORRESPONDING AUTHOR FOOTNOTE: Address reprint requests to Anthony P.
Gies, Department of Core R&D Analytical Sciences, The Dow Chemical Company, 2301
N. Brazosport Blvd., B-1219, Freeport, TX 77541. Telephone: (979) 238-1778. E-mail:
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
2
FIGURE CAPTIONS:
Figure S1. Medium effective kinetic energy (collision gas pressure: 1.5 × 10-6
Torr)
MALDI-TOF/TOF mass spectrum of dibutanol terminated poly(butylene adipate) (Str. 1-
E1 Li+, 1497.8 Da); covering the monomeric (A: 70–390 Da), dimeric through trimeric
(B: 390–790 Da), and tetrameric through pentameric (C: 790–1190 Da) mass regions.
Figure S2. MALDI-TOF/TOF mass spectrum for cyclic PBA structure 1-CyE at a low
collision gas pressure of 1.5 × 10-6
Torr. Precursor ion (1023.5 Da) is through Na+
cationization.
Figure S3. MALDI-TOF/TOF mass spectrum for linear butanol-carboxyl terminated
PBA structure 1-E2 at a low collision gas pressure of 1.5 × 10-6
Torr. Precursor ion
(1041.5 Da) is through Na+ cationization.
Figure S4. MALDI-TOF/TOF mass spectrum for linear butanol-carboxyl terminated
PBA structure, with an extra sodium atom (Str. 1-E2Na), at a low collision gas pressure
of 1.5 × 10-6
Torr. Precursor ion (1063.5 Da) is through Na+ cationization.
Figure S5. MALDI-TOF/TOF mass spectrum for linear butanol-carboxyl terminated
PBA structure, with and extra lithium atom (Str. 1-E2Li), at a low collision gas pressure
of 1.5 × 10-6
Torr. Precursor ion (1031.5 Da) is through Li+ cationization.
Figure S6. MALDI-TOF/TOF mass spectrum for linear carboxyl-carboxyl terminated
PBA structure 1-E3 at a low collision gas pressure of 1.5 × 10-6
Torr. Precursor ion
(753.4 Da) is through Li+ cationization.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
3
Figure S7. MALDI-TOF/TOF mass spectrum for linear butanol-ethanol terminated PBA
structure 1-E4 at a low collision gas pressure of 1.5 × 10-6
Torr. Precursor ion (1085.6
Da) is through Na+ cationization.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
4
Figure S1.
A. B.
C.
Medium KE: Monomeric Region
Base Peak (129.1 Da) = 100 % Peak Intensity
Medium KE: Dimeric/Trimer Region
Peak Intensity (625.3 Da) = 50 % of Base Peak
Medium KE: Tetrameric Through Pentameric Region
Peak Intensity (825.4 Da) = 64 % of Base Peak
100 200 300
100
83
.1 *
2-C
(O)C
(-C
OO
H)
II0
97
.1 2
-OO
0
Li+
10
1.1
*
2-C
C(-
CO
OH
) 0
15
1.1
2
-OE
II 0
L
i+
13
5.1
2
-CC
(O)
II0
Li+
73
.1 *
2-O
B0
11
1.1
*
2-C
(O)C
(O)
II0
12
9.1
*
2-C
C(O
) 0
15
3.1
2
-CC
0
Li+
18
3.1
*
2-B
C(O
) II
0
20
1.1
2
-OC
(O)
II0
H+
+
2
-CB
II 0
H
+
26
1.1
2
-BB
II 1
L
i+
32
1.2
2
-BO
(+C
OC
H2)
II1
Li+
36
5.2
2
-OC
(-C
H2C
OO
H)
II1
Li+
35
3.2
2
-CC
1
Li+
23
5.1
2
-BC
(+E
) II
1
Li+
33
5.1
2
-CC
(O)
II1
Li+
29
5.1
2
-OO
II 1
L
i+
22
5.1
2
-OC
1
Li+
27
9.2
2
-OB
II 1
L
i+
35
1.2
2
-OE
II 1
L
i+20
7.1
2
-OC
(O)
II0
Li+
+
C
B I
I 0
Li+
Peak I
nte
nsity (
%)
Mass (m/z)
400 500 600 700
50
59
3.3
2
-CP
II 2
L
i+
57
9.3
2
-OC
(-C
OO
H)
II2
Li+
65
1.4
2
-OC
(+E
) II
3
Li+
62
1.3
2
-BC
(+M
) II
3
Li+
42
1.2
2
-BC
(+M
) II
2
Li+
66
1.3
2
-BB
II 3
L
i+
46
1.2
2
-BB
II 2
L
i+
76
5.4
2
-OC
(-C
H2C
OO
H)
II3
Li+
75
3.4
2
-CC
3
Li+
75
1.4
2
-OE
II 3
L
i+
73
5.3
2
-CC
(O)
II3
Li+
56
5.3
2
-OC
(-C
H2C
OO
H)
II2
Li+
55
3.3
2
-CC
2
Li+
63
5.3
2
-BC
(+E
) II
3
Li+
43
5.2
2
-BC
(+E
) II
2
Li+
53
5.2
2
-CC
(O)
II2
Li+
69
5.3
2
-OO
II 3
L
i+
62
5.3
2
-OC
3
Li+
49
5.2
2
-OO
II 2
L
i+
42
5.2
2
-OC
2
Li+
67
9.4
2
-OB
II 3
L
i+
47
9.3
2
-OB
II 2
L
i+
55
1.3
2
-OE
II 2
L
i+
60
7.3
2
-OC
(O)
II2
Li+
+
2
-CB
II 3
L
i+
40
7.2
2
-OC
(O)
II1
Li+
+
2
-CB
II 2
L
i+
Pe
ak I
nte
nsity (
%)
Mass (m/z)
800 900 1000 1100
64
10
51
.6
2-O
C(+
E)
II5 L
i+
11
65
.6
2-O
C(-
CH
2C
OO
H)
II5 L
i+
11
53
.6
2-C
C5 L
i+1
15
1.6
2
-OE
II 5
L
i+
95
3.5
2
-CC
4 L
i+
93
5.4
2
-CC
(O)
II4 L
i+
10
95
.5
2-O
O II 5
L
i+
10
25
.5
2-O
C5 L
i+
89
5.4
2
-OO
II 4
L
i+
82
5.4
2
-OC
4 L
i+
10
79
.6
2-O
B II 5
L
i+
87
9.5
2
-OB
II 4
L
i+
95
1.5
2
-OE
II 4
L
i+
10
07
.5
2-O
C(O
) II
4 L
i+
80
7.4
2
-OC
(O)
II3 L
i+
Pea
k I
nte
nsity (
%)
Mass (m/z)
CH2HO O C
O
CH2 C
O
O CH2 O4 4 4
H
Li+
71-E1 Li+
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5
Figure S2. 223.1 169.1
223.1
369.2 423.2 569.3
Na+
477.2 277.1 * 55.1
769.4 623.3
677.3 623.3 423.2
C
O
OCHCH2CH2 CH2 C
O
O CH2 O C
O
CH2 C
4 4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
OH
4 4 4 4
877.4 823.4
823.4 969.5
CH2
200 400 600 800 1000
223.1
2
-CB
II 1
N
a+
73.1
*
2-O
B0
509.2
2
-OO
2II
2
Na
+
1005.5
2
-BC
(O)
II5
Na
+ (
M -
18 D
a)
441.2
2
-OC
2
Na
+
841.4
2
-OC
4
Na
+
641.3
2
-OC
3
Na
+
129.1
*
2-C
C(O
) 0
951.5
2
-CC
(O)
II4
Na
+
751.4
2
-CC
(O)
II3
Na
+
551.2
2
-CC
(O)
II2
Na
+
349.2
2
-BE
II 1
N
a+
895.5
2
-OB
II 4
N
a+
695.4
2
-OB
II 3
N
a+
495.2
2
-OB
II 2
N
a+
877.4
2
-BB
II 4
N
a+
677.3
2
-BB
II 3
N
a+
477.2
2
-BB
II 2
N
a+
969.5
2
-CC
4
Na
+
769.4
2
-CC
3
Na
+
569.3
2
-CC
2
Na
+
369.2
2
-CC
1
Na
+
911.5
2
-OO
4
Na
+
111.1
*
2-C
(O)C
(O)
II0
823.4
2
-CB
II 4
N
a+
623.3
2
-CB
II 3
N
a+Precursor Ion: 6,115 Counts
Cropped Spectrum: 550 Counts
102
3.5
1
-CyE
Na+
423.2
2
-CB
II 2
N
a+
Pe
ak I
nte
nsity
Mass (m/z)
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
6
Figure S3. 223.1 169.1
241.1
369.2 423.2 569.3
Na+
495.3 295.2 * 73.1
769.4 623.3
695.4 641.3 441.2
C
O
OCH2HO CH2 C
O
O CH2 O C
O
CH2 C
4 4 4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
OH
4 4 4 4
895.5 841.4
823.4 969.5
200 400 600 800 1000
73.1
*
2-O
B0
511.2
2
-OO
II 2
N
a+
239.1
2
-OC
II 1
N
a+
1023.5
2
-CB
II 5
N
a+
(M
- 1
8 D
a)
311.1
2
-OO
II 1
N
a+
841.4
2
-OC
4
Na
+
711.4
2
-OO
II 3
N
a+
641.3
2
-OC
3
Na
+
441.2
2
-OC
2
Na
+
295.2
2
-OB
II 1
N
a+
129.1
*
2-C
C(O
) 0
895.5
2
-OB
II 5
N
a+
695.4
2
-OB
II 4
N
a+
495.3
2
-OB
II 3
N
a+
969.5
2
-CC
5
Na
+
769.4
2
-CC
4
Na
+
569.3
2
-CC
3
Na
+
367.2
2
-OE
II 1
N
a+
913.5
2
-OO
4
Na
+
111.1
*
2-C
(O)C
(O)
II0
823.4
2
-CB
II 3
N
a+
+
2
-OC
(O)
II3
Na
+
623.3
2
-CB
II 2
N
a+
+
2
-OC
(O)
II2
Na
+
Precursor Ion: 1,350 Counts
Cropped Spectrum: 250 Counts
104
1.5
1
-E2
Na
+
423.2
2
-CB
II 1
N
a+
+
2
-OC
(O)
II1
Na
+
Pe
ak I
nte
nsity
Mass (m/z)
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Figure S4. 245.1 191.1
241.1
391.2 445.2 591.3
Na+
495.3 295.2 * 73.1
791.4 645.3
695.4 641.3 441.2
C
O
OCH2HO CH2 C
O
O CH2 O C
O
CH2 C
4 4 4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
ONa
4 4 4 4
895.5 841.4
845.4 991.5
200 400 600 800 1000
713.3
2
-OO
3
Na
+
1045.5
2
-OC
(O)
II5
Na
Na
+ (
M -
18 D
a)
973.5
2
-CC
(O)
II5 N
aN
a+
991.5
2
-CC
5
Na
Na
+
791.4
2
-CC
4
Na
Na
+773.4
2
-CC
(O)
II4
Na
Na
+
591.3
2
-CC
3
Na
Na
+573.3
2
-CC
(O)
II3
Na
Na
+
517.3
2
-OB
II 3
N
aN
a+
845.4
2
-CB
II 4
N
aN
a+
863.4
2
-OC
4
Na
Na
+
645.3
2
-CB
II 3
N
aN
a+
663.3
2
-OC
3
Na
Na
+
191.1
2
-CC
0
NaN
a+
263.1
2
-OC
1
Na
Na
+245.1
2
-CB
II 1
N
aN
a+
+
2
-OC
(O)
II1
Na
Na
+
373.2
2
-CC
(O)
II2
Na
Na
+
533.2
2
-OO
II 2
N
aN
a+
1023.5
2
-OC
(O)
II5
Na
+
463.2
2
-OC
2
Na
Na
+
317.2
2
-OB
II 2
N
aN
a+
129.1
*
2-C
C(O
) 0
895.5
2
-OB
II 5
N
a+
695.4
2
-OB
II 4
N
a+
391.2
2
-CC
2
Na
Na
+
911.5
2
-OO
II 4
N
a+
111.1
*
2-C
(O)C
(O)
II0
823.4
2
-CB
II 4
N
a+
623.3
2
-CB
II 3
N
a+
Precursor Ion: 440 Counts
Cropped Spectrum: 230 Counts
10
63
.5
1-E
2 N
aN
a+
445.2
2
-CB
II 2
N
aN
a+
Pea
k I
nte
nsity
Mass (m/z)
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
8
Figure S5. 213.1 159.1
225.1
359.2 413.2 559.3
Li+
479.3 279.2 * 73.1
759.4 613.3
679.4 625.3 425.2
C
O
OCH2HO CH2 C
O
O CH2 O C
O
CH2 C
4 4 4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
OLi
4 4 4 4
879.5 825.4
813.4 959.5
200 400 600 800 1000
95
3.5
2
-CC
4
Li+
15
9.1
2
-CC
0
LiL
i+
73
5.4
2
-CC
(O)
II3
Li+
53
5.2
2
-CC
(O)
II2
Li+
33
5.1
2
-CC
(O)
II1
Li+
23
1.1
2
-OC
1
LiL
i+
18
3.1
*
2-B
C(O
) II
0
73
.1
* 2
-OB
0
15
3.1
2
-CC
0
Li+
10
07
.5
2-O
C(O
) II
4
Li+
(M
- 1
8 D
a)
83
1.4
2
-OC
4
LiL
i+
63
1.3
2
-OC
3
LiL
i+
43
1.2
2
-OC
2
LiL
i+
30
3.1
2
-OO
1
LiL
i+2
85
.2
2-O
B I
I 1
LiL
i+
21
3.1
2
-CB
II 0
L
iLi+
+
2
-OC
(O)
II0
LiL
i+12
9.1
*
2-C
C(O
) 0
87
9.5
2
-OB
II 4
L
i+
67
9.4
2
-OB
II 3
L
i+
47
9.3
2
-OB
II 2
L
i+
95
9.5
2
-CC
4
LiL
i+
75
3.4
2
-CC
3
Li+
55
9.3
2
-CC
2
LiL
i+
35
9.2
2
-CC
1
LiL
i+
89
7.4
2
-OO
4
Li+
11
1.1
*
2-C
(O)C
(O)
II0
80
7.4
2
-CB
II 3
L
i+
60
7.3
2
-CB
II 2
L
i+
Precursor Ion: 2,490 Counts
Cropped Spectrum: 700 Counts
10
31
.5
1-E
2 L
iLi+
40
7.2
2
-CB
II 1
L
i+
Pea
k I
nte
nsity
Mass (m/z)
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
9
Figure S6. 207.1 153.1 353.2 407.2 553.3
Li+
207.1
607.3
407.2353.2153.1
HO C
O
CH2 C
4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
OH
4 4 4
607.3553.3
200 400 600
69
7.4
2
-CC
(-C
H2C
OO
H) 3
L
i+
73
5.4
2
-CC
(O)
II3
Li+
(M
- 1
8 D
a)
53
5.2
2
-CC
(O)
II2
Li+
71
.1
* 2
-OB
II 0
15
3.1
2
-CC
0
Li+
62
5.3
2
-OC
3
Li+
42
5.2
2
-OC
2
Li+
27
9.2
2
-OB
II 1
L
i+
20
7.1
2
-CB
II 0
L
i+
+
2-O
C(O
) II
0
Li+
12
9.1
*
2-C
C(O
) 0
67
9.4
2
-OB
II 3
L
i+
47
9.3
2
-OB
II 2
L
i+
55
3.3
2
-CC
2
Li+
35
3.2
2
-CC
1
Li+
60
7.3
2
-CB
II 2
L
i+
+
2-O
C(O
) II
2
Li+
Precursor Ion: 650 Counts
Cropped Spectrum: 400 Counts
75
3.4
1
-E3 L
i+
40
7.2
2
-CB
II 1
L
i+
+
2-O
C(O
) II
1
Li+
Pea
k I
nte
nsity
Mass (m/z)
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
10
Figure S7. 295.2 241.1
213.1
441.2 495.3 641.3
Na+
467.3 267.2 * 45.1
841.4 695.4
667.4
* 73.1
613.3 413.2 1013.5
C
O
OCH2HO CH2 C
O
O CH2 O C
O
CH2 C
2 4 4 4 44 4
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 O C
O
CH2 C
O
O CH2 OH
4 4 4 4
867.5 813.4
895.5 1041.5
200 400 600 800 1000
939.5
2
-O(-
28
)E II 4
N
a+
739.4
2
-O(-
28
)E II 3
N
a+
539.3
2
-O(-
28
)E II 2
N
a+
567.3
2
-OE
II 2
N
a+
413.2
2
-O(-
28
)C2 N
a+
511.2
2
-OO
II 2
N
a+
613.3
2
-O(-
28
)C3 N
a+
495.3
2
-OB
II 2
N
a+
311.1
2
-OO
II 1
N
a+
813.4
2
-O(-
28
)C4 N
a+
895.5
2
-OB
II 4
N
a+
695.4
2
-OB
II 3
N
a+
1041.5
2
-OC
5 N
a+
183.1
*
2-B
C(O
) II
0
73.1
*
2-O
B0
1013.5
2
-O(-
28
)C5 N
a+
841.4
2
-OC
4 N
a+
711.3
2
-OO
II 3
N
a+
641.3
2
-OC
3 N
a+
441.2
2
-OC
2 N
a+
273.1
2
-OB
II 1
H
+
129.1
*
2-C
C(O
) 0
867.5
2
-O(-
28
)B II 4
N
a+
667.4
2
-O(-
28
)B II 3
N
a+
467.3
2
-O(-
28
)B II 2
N
a+
767.4
2
-OE
II 3
N
a+
367.2
2
-OE
II 1
N
a+
911.4
2
-OO
II 4
N
a+
111.1
*
2-C
(O)C
(O)
II0
Precursor Ion: 510 Counts
Cropped Spectrum: 90 Counts
10
85
.6
1-E
4 N
a+
Pe
ak I
nte
nsity
Mass (m/z)
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012
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