1
Data: m0 sans repet final0001.A1[c] 23 Jan 2017 16:50 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, P.Ext. @ 2300 (bin 78)
Supplementary Materials:
%Int.
1.1 mV[sum= 225 mV] Profiles 1-200 Smooth Av 50
179.3
m0 sans repet final0001 [+/-]. A1
100
Processing Parameter Settings
90
80
70
60
50
40
30
20
195.2
10
0
113.5
179.9
100
273.8
200
339.5
300
483.7
400
500
2
3
4
600
700
800
900
10001[c].A1
m/z
Fig.m0
S1.2000001.A1[c]
MALDI-TOF
of the
original
untreated
lignin
Data:
23spectrum
Jan 2017 16:52
Cal:
red phosphorus
23 Jan
2017(sample
13:48 S0), without ion gate.
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, Blanked, P.Ext. @ 2300 (bin 78)
%Int.
0.1 mV[sum= 11 mV] Profiles 1-200 Smooth Av 50
273.9
100
90
80
201.2
70
60
50
204.3
297.8
40
214.2
30
20
271.9
202.5
298.8
255.0
225.1
239.2
275.1
300.6
320.8
329.5
418.2
353.2 374.3
395.5
442.8
474.9
10
0
200
250
5
6
300
350
m/z
400
450
5001[c].A1
Fig. S2. MALDI-TOF spectrum of the original untreated lignin (sample S0), with ion gate at 200 Da.
7
Polymers 2017, 9, x; doi: FOR PEER REVIEW
www.mdpi.com/journal/polymers
Data: m0 4000001.A2[c] 23 Jan 2017 16:53 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, Blanked, P.Ext. @ 2300 (bin 78)
Polymers 2017, 9, x FOR PEER REVIEW
2 of 14
%Int.
0.1 mV[sum= 10 mV] Profiles 1-200 Smooth Av 50
457.8
m0 4000001 [+/-]. A2
100
Processing Parameter Settings
434.0
90
441.9
80
70
429.9
60
50
411.9
451.4
40
30
495.7
475.5
529.4
20
538.3
579.0
584.9
646.6
717.7
10
886.9
778.3
0
400
500
600
700
8
9
10
800
10001[c].A2
900
m/z
Fig. S3. MALDI-TOF spectrum of the original untreated lignin (sample S0), with ion gate at 400 Da.
Data: MTRA 3 ion gate sans0001.D6[c] 30 May 2016 13:36 Cal: CAL 30 May 2016 12:20
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 80, P.Ext. @ 2300 (bin 78)
%Int.
138 mV[sum= 138275 mV] Profiles 1-1000 Smooth Gauss 2 -Baseline 6
177.4
100
205.4
90
183.5
80
70
60
137.5
50
359.1
199.4
176.4
40
331.1
221.3
30
387.1
200.4
20
198.4
10
138.5
0
100
11
12
13
192.3
200
536.9
375.1
273.3
317.3
300
550.9
381.1
441.3
400
698.7
711.7
528.9
500
600
700
873.4
800
900
10001[c].D6
m/z
Fig S4. MALDI-TOF spectrum of the catechol+TEP+NH3 reaction at 180 ° C (sample S4), without ion gate.
Data: m8 sans rept0001.D22[c] 23 Jan 2017 17:05 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, P.Ext. @ 2300 (bin 78)
Polymers 2017, 9, x FOR PEER REVIEW
%Int.
0.1 mV[sum= 15 mV] Profiles 1-200 Smooth Av 50
3 of 14
328.0
m8 sans rept0001 [+/-]. D22
100
Processing Parameter Settings
90
80
70
60
50
40
329.1
30
347.5
20
101.3
319.8
165.7
389.4
468.8
628.6
250.1
10
0
100
14
15
16
200
300
400
500
600
700
800
900
10001[c].D22
m/z
Fig S5. MALDI-TOF spectrum of the glycerol+TEP reaction at 180 ° C (sample S5), without ion gate.
Data: m8 rept 1000001.D23[c] 23 Jan 2017 17:07 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, Blanked, P.Ext. @ 2300 (bin 78)
%Int.
0.1 mV[sum= 23 mV] Profiles 1-200 Smooth Av 50
179.3
m8 rept 1000001 [+/-]. D23
100
Processing Parameter Settings
90
80
70
60
50
40
111.7
328.0
30
20
10
180.1
127.4 187.6
268.0
339.7
417.3
0
100
17
18
19
200
300
400
500
600
700
800
900
10001[c].D23
m/z
Fig S6. MALDI-TOF spectrum of the glycerol+TEP reaction at 180 ° C (sample S5), with ion gate at 100 Da.
Data: m8 rept 3000002.D23[c] 23 Jan 2017 17:15 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 85, Blanked, P.Ext. @ 2300 (bin 78)
Polymers 2017, 9, x FOR PEER REVIEW
4 of 14
%Int.
0.3 mV[sum= 54 mV] Profiles 1-200 Smooth Av 50
328.1
m8 rept 3000002 [+/-]. D23
100
Processing Parameter Settings
90
80
70
60
50
40
30
628.7
329.0
20
302.9
382.6
449.8
10
515.8
563.6
623.4
697.1
0
20
21
766.9
818.2
904.6
955.8
300
400
500
600
700
800
900
10001[c].D23
Data: m11 repet 2000001.A16[c] 23 Jan 2017 17:20 Cal: red phosphorus 23 Jan 2017 13:48
m/z
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 80, Blanked, P.Ext. @ 2300 (bin 78)
Fig%Int.
S7. MALDI-TOF
spectrum
of the
glycerol+TEP
reaction
at 180 ° C (sample S5), with ion gate at 300 Da.
0.6 mV[sum=
114 mV]
Profiles
1-200 Smooth
Av 50
323.0
m11 repet 2000001 [+/-]. A16
100
Processing Parameter Settings
90
80
628.6
310.0
70
575.5
60
50
40
629.5
30
324.0
20
10
219.1
322.0
0
200
22
23
24
577.4
312.2
300
578.4
420.3 472.9 524.2 579.6
400
500
600
m/z
(a)
650.6
712.3
700
774.1
800
900
10001[c].A16
Data: m11 repet 4000001.A16[c] 23 Jan 2017 17:21 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 91, Blanked, P.Ext. @ 2300 (bin 78)
Polymers 2017, 9, x FOR PEER REVIEW
5 of 14
%Int.
0.2 mV[sum= 34 mV] Profiles 1-200 Smooth Av 50
628.5
m11 repet 4000001 [+/-]. A16
100
Processing Parameter Settings
90
80
70
60
50
40
629.5
30
20
10
220.4
309.7
398.9
464.9
523.1
602.6
835.8
686.7
0
200
25
26
27
28
29
30
300
400
500
600
700
800
900
10001[c].A16
m/z
(b)
Fig S8. MALDI-TOF spectrum of the lignin+TEP reaction at 90 ° C (sample S6): (a) with ion gate at 200
Data: m2 repet 2000001.C1[c] 23 Jan 2017
16:59
Cal:
phosphorus
Da; (b)
with
ionred
gate
at 400 Da.23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, Blanked, P.Ext. @ 2300 (bin 78)
%Int.
3.5 mV[sum= 704 mV] Profiles 1-200 Smooth Av 50
201.3
m2 repet 2000001 [+/-]. C1
100
Processing Parameter Settings
90
80
70
60
50
40
30
339.5
20
10
341.5
207.2
0
200
31
32
33
311.7 367.4
268.9
300
400
442.0
498.6
500
600
m/z
(a)
700
800
900
10001[c].C1
Data: m2 repet 4000001.C2[c] 23 Jan 2017 17:01 Cal: red phosphorus 23 Jan 2017 13:48
Shimadzu Biotech Axima Performance 2.9.3.20110624: Mode Linear, Power: 70, Blanked, P.Ext. @ 2300 (bin 78)
Polymers 2017, 9, x FOR PEER REVIEW
6 of 14
%Int.
0.1 mV[sum= 25 mV] Profiles 1-200 Smooth Av 50
411.1
m2 repet 4000001 [+/-]. C2
100
Processing Parameter Settings
458.8
90
80
486.6
70
60
409.1
460.8
407.1
474.7
50
500.6
40
484.6
30
528.4
464.8
542.4
20
520.5
10
608.9
0
400
34
35
36
37
38
39
40
41
42
43
500
600
700
800
900
10001[c].C2
m/z
(b)
Fig S9. MALDI-TOF spectrum of the lignin+TEP reaction at 180 °C (sample S1): (a) with ion gate at 200 Da; (b)
with ion gate at 400 Da.
Polymers 2017, 9, x FOR PEER REVIEW
44
45
7 of 14
Table S1. Structures determinate for MALDI-TOF analysis of original untreated lignin.
Calculated (Da)
Structure
Comment
HO
With Na+
177
CH3
O
OH
HO
Without Na+, deprotonated
180
O
OH
HO
HO
Without Na+
198
O
OH
H3C
OH
242/ 265
Without/with Na+
H3C
OH
HO
274/ 297
Without/with Na+
HO
O
OH
Polymers 2017, 9, x FOR PEER REVIEW
8 of 14
HO
304/ 327
Without/with Na+
HO
O
O
OH
O
O
401
O
OH OH
OH
With Na+
OH
O
O
O
420/ 433
O
O
O OH
OH
O
444
O
O
OH
O
443
O
O
OH
With Na+
O
O OH
OH
With Na+
O
O OH
OH
Without/with Na+
HO
O
O
O
514/ 537
O
OH
Without/with Na+
O
O OH
OH
541/ 564
OH
O
O
O
O
OH
OH
OH
Without/with Na+
Polymers 2017, 9, x FOR PEER REVIEW
9 of 14
HO
O
O
HO
530/ 552
O
OH
O
558/ 581
OH OH
46
47
O OH
O
O
O
O
O
OH
OH
OH
Without/with Na+
OH
Without/with Na+
Polymers 2017, 9, x FOR PEER REVIEW
10 of 14
48
49
50
Table S2. Interpretation of peaks of MALDI-TOF spectrum derived from the reaction of catechol+TEP+NH3 at 180 °C
(Ph = phenyl; OEt = -OCH2CH3).
51
Peak
Assignement (with Na+)
(Da)
52
53
54
331
OH-Ph-OPO(OEt)O-Ph-OH
359
OH-Ph-OPO(OEt)O-Ph-OEt
405
(EtO)2OPO-Ph-OPO(OEt)2
387
EtO-Ph-OPO(OEt)O-Ph-OEt
535
OH-Ph-OPO(OEt)O-Ph-OPO(OEt)O-Ph-OH
873
OH-Ph-OPO(OEt)O-Ph-OPO(OEt)O-Ph-OPO(OEt)O-Ph-OPO(OEt)2
222
NH2-Ph-NH-Ph-NH2
331
NH2-Ph-OPO(OEt)O-Ph-NH2
359
NH2-Ph-NH-Ph-OPO(OEt)2
359
OH-Ph-NH-Ph-NHPO(OEt)2
360
OH-Ph-NH-Ph-OPO(OEt)2
360
EtO-Ph-OPO(OEt)O-Ph-NH2
387
EtO-Ph-NH-Ph-NHPO(OEt)2
388
EtO-Ph-NH-Ph-OPO(OEt)2
Polymers 2017, 9, x FOR PEER REVIEW
55
56
11 of 14
Polymers 2017, 9, x FOR PEER REVIEW
12 of 14
57
58
59
Table S3. Oligomer species formed during the reaction at 180° C between glycerol and TEP.
Calculated,
with Na
Structure
+
(Da)
251
CH 2OPO(OCH 2CH 3)2
CH 2O(PO)-OCH 2CHOHCH 2OH
CHOH
CHO
CH 2OH
CH 2OH
or
CH 2O(PO)-OEt
CHO
341
CH 2O(PO)(OEt) 2
CH 2OPO(OCH 2CH 3)2
CH 2OPO(OCH 2CH 3)2
CHO(PO)(OCH 2CH 3)2
CHOH
CH 2OH
or
CH 2O(PO)(OCH 2CH 3)2 or
CH 2O(PO)-(OCH 2CHOHCH 2OH)
387
CHO
CH 2O(PO)(OEt) 2
OCH2CHOHCH2OH
CH 2O(PO)-O
-
CHOH
268
CH 2OH
OCH2CHOHCH2OH
CH 2O(PO)-OCH 2CHOHCH 2O -(PO)-O
450
CHOH
CH 2OH
OEt
-
Polymers 2017, 9, x FOR PEER REVIEW
13 of 14
OCH2CHOHCH2OH
CH 2O(PO)-OCH 2CHOHCH 2O -(PO)-O
767
-
OEt
CHO(PO)-(OEt) 2
CH 2O(PO)-(OEt)
OCH2CHOHCH2OH
OCH2CHOHCH2OH
CH 2O(PO)-OCH 2CHOHCH 2O -(PO)-OCH 2CHOHCH 2OH
906
CHO(PO)-(OEt)-O
-
CH 2O(PO)-OCH 2CHOHCH 2OH
OCH2CHOHCH2OH
60
61
OCH2CHOHCH2OH
Polymers 2017, 9, x FOR PEER REVIEW
62
63
14 of 14
Table S4. Oligomer species formed during the reaction between TEP and lignin (Ph: aryl group; (PO): P=O group)
Structure
Calculated
(Da)
(with Na+)
(EtO)-(PO)-[O(CH2)3PhOH(OCH3)]2
477, 449 by
(EtO)-(PO)-[O-Ph(CH2CH2CH2OH)(OCH3)]2
demethylation
[(CH3O)(OH)Ph-(CH2)3O]-(PO)(OEt)-[OCH2-Ph(OH)(OCH3)]
449
[(CH 3O)(OHCH 2CH2CH2)Ph-O]-(PO)(OEt)-[OCH 2-Ph(OH)(OCH 3)]
[(CH3O)(OH)Ph-(CH2)3O]-(PO)(OEt)-[O-Ph(CH2OH)(OCH 3)]
[(CH3O)(OHCH2CH2CH2)Ph-O]-(PO)(OEt)-[O-Ph(CH2OH)(OCH3)]
(EtO) 2-(PO)-[O-CH2(OH)CHCH2PhOH(OCH3)]
356
(EtO) 2-(PO)-[O-(OHCH2)CHCH2PhOH(OCH3)]
(EtO) 2-(PO)-[O- Ph(OCH 3)(CH 2CH(OH)CH 2OH]
(EtO)-(PO)-[OCH 2(OH)CHCH2PhOH(OCH 3)] 2
*(EtO)-(PO)-[O- Ph(OHCH2(OH)CHCH2)(OCH3)] 2
509 (486
**
without Na)
(PO)-[O-CH2(OH)CHCH2PhOH(OCH3)]3
*(PO)-[O- Ph(OHCH 2(OH)CHCH 2)(OCH 3)] 3
**
661
[(OH)(CH3O)PhCH2CH(OH)CH2-O]-(PO)(OEt)-[O-CH2PhOH(OCH3)]
*[OHCH2(OH)CHCH2(CH3O)Ph-O]-(PO)(OEt)-[O-Ph(CH2OH)(OCH3)] **
[(CH 3O)(OH)PhCH2CH(OH)CH 2-O]-(PO)-[O-(CH 2)3PhOH(OCH 3)] 2
*
[(CH3O)OHCH 2(OH)CHCH 2Ph-O]-(PO)-[O- Ph(OCH 3)CH2CH2CH2OH] 2
64
65
66
67
68
* or introduction on the other aliphatic –OH for one or more of the monomers.
** or bond through aliphatic -OHs and aromatic –OHs.
465
**
629