CELS-D-13-00474-Second Revision
Electronic Supplementary Material Electronic Supplementary Material for
Mixed solvents for cellulose derivatization under homogeneous conditions: Kinetic, spectroscopic, and theoretical studies on the acetylation of the biopolymer in binary mixtures of an ionic liquid and molecular solvents.
Haq Nawaz; Paulo A. R. Pires; Thaís A. Bioni, Elizabeth P. G. Arêas, Omar A. El Seoud,*
Institute of Chemistry, University of São Paulo, P. O. B. 26077,
05513-970 São Paulo, S. P., Brazil;
E-mail <>; Phone/Fax: 55-11-3091-3874
Figure ESM-1 Plots for calculation of the pseudo first-order rate constant (kobs) for the reaction in mixtures IL-DAS. The symbols () and (t) refer to the conductivity at “infinity”- and any time (t), respectively. Part (A) is for AlMeImCl-DMAC at [IL] = 1.887 mol/L, and T (from bottom up) = 30, 40, 50, and 60 C, respectively. Part (B) is for AlMeImCl-MeCN at [IL] = 3.025 mol/L, and T (from bottom up) = 30, 40, 50, and 60 C, respectively.
Table ESM-1Observed rate constants of the reaction, kobs in s-1, and k3,L2 mol-2s-1, at different temperatures and [AlMeImCl]for the acetylation of MCC in binary mixtures of AlMeImCl with DMAC.
Ac2O (1.057mol/L) / Temperature,C / kobs,
s-1 / k3 = kobs/[Ac2O] [IL];
L2mol-2 s-1
AlMeImCl
1.887 mol/L;
30 v % L / 30 / 5.776× 10-4 / 2.897× 10-4
40 / 7.670× 10-4 / 3.847× 10-4
50 / 1.001× 10-3 / 5.024× 10-4
60 / 1.274× 10-3 / 6.392× 10-4
2.269 mol/L;
36 v % / 30 / 9.052× 10-4 / 3.775× 10-4
40 / 1.172× 10-3 / 4.891× 10-4
50 / 1.506× 10-3 / 6.283× 10-4
60 / 1.910× 10-3 / 7.968× 10-4
2.647 mol/L;
42 v % / 30 / 1.240× 10-3 / 4.436× 10-4
40 / 1.593× 10-3 / 5.696× 10-4
50 / 2.009× 10-3 / 7.185× 10-4
60 / 2.509× 10-3 / 8.973× 10-4
3.025 mol/L;
48 v % / 30 / 1.599× 10-3 / 5.286× 10-4
40 / 2.145× 10-3 / 6.712× 10-4
50 / 2.665× 10-3 / 8.337× 10-4
60 / 3.121× 10-3 / 1.032× 10-3
3.404 mol/L;
54 v % / 30 / 2.273× 10-3 / 6.320× 10-4
40 / 2.835× 10-3 / 7.882× 10-4
50 / 3.488× 10-3 / 9.695× 10-4
60 / 4.263× 10-3 / 1.185× 10-3
3.782 mol/L;
60 v % / 30 / 2.758× 10-3 / 7.293× 10-4
40 / 3.642× 10-3 / 9.114× 10-4
50 / 4.456× 10-3 / 1.115× 10-3
60 / 5.351× 10-3 / 1.339× 10-3
CHM / 60 / 1.410× 10-3 / 7.071× 10-4
CHD / 60 / 8.425× 10-4 / 4.225× 10-4
Table ESM-2Observed rate constants of the reaction, kobs in s-1, and k3,L2mol-2 s-1, at different temperatures and [AlMeImCl] for the acetylation of MCC in binary mixtures of AlMeImClwith MeCN.
Ac2O (1.057mol/L) / Temperature,C / kobs,
s-1 / k3 = kobs/[Ac2O] [IL];
L2mol-2 s-1
AlMeImCl
2.647 mol/L;
42 v % / 30 / 2.316× 10-4 / 0.828× 10-4
40 / 3.219× 10-4 / 1.151× 10-4
50 / 4.388× 10-4 / 1.569× 10-4
60 / 5.842× 10-4 / 2.088× 10-4
3.025 mol/L;
48 v % / 30 / 3.218× 10-4 / 1.006× 10-4
40 / 4.354× 10-4 / 1.362× 10-4
50 / 5.824× 10-4 / 1.822× 10-4
60 / 7.592× 10-4 / 2.375× 10-4
3.404 mol/L;
54 v % / 30 / 4.332× 10-4 / 1.204× 10-4
40 / 5.778× 10-4 / 1.606× 10-4
50 / 7.559× 10-4 / 2.101× 10-4
60 / 9.685× 10-4 / 2.692× 10-4
3.782 mol/L;
60 v % / 30 / 5.710× 10-4 / 1.428× 10-4
40 / 7.454× 10-4 / 1.865× 10-4
50 / 9.532× 10-4 / 2.385× 10-4
60 / 1.201× 10-3 / 3.004× 10-4
Figure ESM- 2Relationship between k3 and molar concentration of ionic liquid for the acetylation of CHM in binary mixtures of AlMeImCl with DMAC at 60 C.
Table ESM-3 Overall third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with DMAC and MeCN.a,b
(IL), mol/L/ Temperature / 30 C / 40 C / 50 C / 60 C / H,kcal mol-1 / TS,
kcal mol-1 / G,
kcal mol-1
Acetylation in IL-DMAC
104 x (overall k3), L2mol-2 s-1
1.887 / 2.897 / 3.847 / 5.024 / 6.392 / 4.64 / -19.79 / 24.44
2.269 / 3.775 / 4.891 / 6.283 / 7.968 / 4.33 / -19.95 / 24.30
2.647 / 4.436
(5.36) / 5.696
(4.95)c / 7.185
(4.58) / 8.973
(4.30) / 4.04 / -20.16 / 24.22
3.025 / 5.286
(5.25) / 6.712
(4.93) / 8.337
(4.58) / 10.32
(4.34) / 3.80 / -20.31 / 24.12
3.404 / 6.320
(5.25) / 7.882
(4.91) / 9.695
(4.61) / 11.85
(4.40) / 3.53 / -20.48 / 24.03
3.782 / 7.293
(5.10) / 9.114
(4.89) / 11.15
(4.68) / 13.50
(4.49) / 3.45 / -20.53 / 23.94
Acetylation in IL-MeCN
104 x (overall k3), L2mol-2 s-1
(IL), M/ Temperature / 30 C / 40 C / 50 C / 60 C / H,
kcal mol-1 / TS,
kcal mol-1 / G,
kcal mol-1
2.647 / 0.828 / 1.151 / 1.569 / 2.088 / 5.53 (1.49) / -19.64 (0.52) / 25.18 (0.96)
3.025 / 1.006 / 1.362 / 1.822 / 2.375 / 5.09 (1.29) / -19.99 (0.32) / 25.09 (0.97)
3.404 / 1.204 / 1.606 / 2.101 / 2.692 / 4.72 (1.19) / -20.27 (0.21) / 25.01 (0.98)
3.782 / 1.428 / 1.865 / 2.385 / 3.004 / 4.31 (0.86) / -20.42 (0.11) / 24.94 (1.00)
a-Except for the overall k3 of MCC, the remaining rate constants refer to a single OH group. The values of k3 for the discrete (OH) groups of the AGU of MCC were calculated as indicated in the text, i.e., k3 = k3,Prim(OH) + 2 k3,Sec(OH) and k3,Prim(OH)/ k3,Sec(OH) = 5
b-All activation parameters were calculated at 60 C. The uncertainties in the activation parameters are 0.1 kcal mol-1 (H, and G) and 0.5 cal K-1 mol-1 (S).
c- The numbers within parenthesis refer to: (overall k3 IL-DMAC/overall k3 IL-MeCN); (H= HIL-MeCN - HIL-DMAC); (TS= TS IL-MeCN - TS IL-DMAC), and (G=GIL-MeCN- GIL-DMAC).
Table ESM-4Partial third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with DMAC using different (1.30, 3.15 and 5.00)split ratios.
[IL] / 30 C / 40 C / 50 C / 60 C / H,kcal mol-1 / TS,
kcal mol-1 / G,
kcal mol-1
k3,Prim(OH) / k3,Sec(OH) = 1.30
104 x k3; Prim(OH), L2mol-2 s-1
1.887 / 1.141 / 1.515 / 1.979 / 2.518 / 4.64 / -20.42 / 25.06
2.269 / 1.487 / 1.927 / 2.475 / 3.139 / 4.34 / -20.58 / 24.92
2.647 / 1.748 / 2.244 / 2.830 / 3.535 / 4.05 / -20.79 / 24.84
3.025 / 2.082 / 2.644 / 3.284 / 4.065 / 3.80 / -20.94 / 24.74
3.404 / 2.490 / 3.105 / 3.819 / 4.668 / 3.54 / -21.12 / 24.65
3.782 / 2.873 / 3.590 / 4.392 / 5.318 / 3.45 / -21.11 / 24.56
104 x k3; Sec(OH), L2mol-2 s-1
1.887 / 0.878 / 1.166 / 1.522 / 1.937 / 4.64 / -20.59 / 25.23
2.269 / 1.144 / 1.482 / 1.904 / 2.415 / 4.34 / -20.75 / 25.09
2.647 / 1.344 / 1.726 / 2.177 / 2.719 / 4.05 / -20.96 / 25.01
3.025 / 1.602 / 2.034 / 2.526 / 3.127 / 3.80 / -21.12 / 24.92
3.404 / 1.915 / 2.388 / 2.938 / 3.591 / 3.54 / -21.29 / 24.83
3.782 / 2.210 / 2.762 / 3.379 / 4.091 / 3.45 / -21.29 / 24.74
k3,Prim(OH) / k3,Sec(OH) = 3.15
104 x k3; Prim(OH), L2mol-2 s-1
1.887 / 1.772 / 2.353 / 3.073 / 3.910 / 4.64 / -20.13 / 24.77
2.269 / 2.309 / 2.992 / 3.843 / 4.874 / 4.34 / -20.29 / 24.62
2.647 / 2.713 / 3.484 / 4.395 / 5.488 / 4.04 / -20.51 / 24.55
3.025 / 3.233 / 4.105 / 5.099 / 6.312 / 3.80 / -20.65 / 24.45
3.404 / 3.866 / 4.821 / 5.930 / 7.248 / 3.54 / -20.82 / 24.36
3.782 / 4.461 / 5.575 / 6.820 / 8.257 / 3.45 / -20.82 / 24.27
104 x k3; Sec(OH), L2mol-2 s-1
1.887 / 0.563 / 0.747 / 0.976 / 1.241 / 4.64 / -20.89 / 25.53
2.269 / 0.733 / 0.950 / 1.220 / 1.547 / 4.34 / -21.05 / 25.38
2.647 / 0.861 / 1.106 / 1.395 / 1.742 / 4.05 / -21.26 / 25.30
3.025 / 1.026 / 1.303 / 1.619 / 2.004 / 3.80 / -21.41 / 25.21
3.404 / 1.227 / 1.530 / 1.883 / 2.301 / 3.54 / -21.58 / 25.12
3.782 / 1.416 / 1.770 / 2.165 / 2.621 / 3.45 / -21.58 / 25.03
k3,Prim(OH) / k3,Sec(OH) = 5.00
104 x k3; Prim(OH), L2mol-2 s-1
1.887 / 2.069 / 2.748 / 3.589 / 4.566 / 4.64 / -20.02 / 24.66
2.269 / 2.696 / 3.494 / 4.488 / 5.691 / 4.34 / -20.18 / 24.52
2.647 / 3.169 / 4.069 / 5.132 / 6.409 / 4.05 / -20.40 / 24.44
3.025 / 3.776 / 4.794 / 5.955 / 7.371 / 3.80 / -20.55 / 24.35
3.404 / 4.514 / 5.630 / 6.925 / 8.464 / 3.54 / -20.72 / 24.26
3.782 / 5.209 / 6.510 / 7.964 / 9.643 / 3.45 / -20.72 / 24.17
104 x k3; Sec(OH), L2mol-2 s-1
1.887 / 0.414 / 0.550 / 0.718 / 0.913 / 4.64 / -21.09 / 25.73
2.269 / 0.539 / 0.699 / 0.898 / 1.138 / 4.34 / -21.25 / 25.59
2.647 / 0.634 / 0.814 / 1.026 / 1.282 / 4.05 / -21.46 / 25.51
3.025 / 0.755 / 0.959 / 1.191 / 1.474 / 3.80 / -21.61 / 25.42
3.404 / 0.903 / 1.126 / 1.385 / 1.693 / 3.54 / -21.79 / 25.32
3.782 / 1.042 / 1.302 / 1.593 / 1.929 / 3.45 / -21.79 / 25.24
Table ESM-5Partial third order rate constants k3, and activation parameters calculated for the acetylation of microcrystalline cellulose in binary mixtures of AlMeImCl with MeCNusing different (1.30, 3.15 and 5.00)split ratios.
[IL] / 30 C / 40 C / 50 C / 60 C / H,kcal mol-1 / TS,
kcal mol-1 / G,
kcal mol-1
k3,Prim(OH) / k3,Sec(OH) = 1.30
104 x k3; Prim(OH), L2mol-2 s-1
2.647 / 0.326 / 0.453 / 0.618 / 0.823 / 5.53 / -20.27 / 25.80
3.025 / 0.396 / 0.537 / 0.718 / 0.936 / 5.10 / -20.62 / 25.72
3.404 / 0.474 / 0.633 / 0.828 / 1.060 / 4.72 / -20.91 / 25.63
3.782 / 0.563 / 0.735 / 0.940 / 1.183 / 4.31 / -21.25 / 25.56
104 x k3; Sec(OH), L2mol-2 s-1
2.647 / 0.251 / 0.349 / 0.475 / 0.633 / 5.53 / -20.44 / 25.97
3.025 / 0.305 / 0.413 / 0.552 / 0.720 / 5.10 / -20.79 / 25.89
3.404 / 0.365 / 0.487 / 0.637 / 0.816 / 4.72 / -21.08 / 25.81
3.782 / 0.433 / 0.565 / 0.723 / 0.910 / 4.31 / -21.42 / 25.73
k3,Prim(OH) / k3,Sec(OH) = 3.15
104 x k3; Prim(OH), L2mol-2 s-1
2.647 / 0.506 / 0.704 / 0.960 / 1.277 / 5.53 / -19.98 / 25.51
3.025 / 0.615 / 0.833 / 1.114 / 1.453 / 5.10 / -20.33 / 25.42
3.404 / 0.736 / 0.982 / 1.285 / 1.647 / 4.72 / -20.62 / 25.34
3.782 / 0.873 / 1.141 / 1.459 / 1.837 / 4.31 / -20.96 / 25.27
104 x k3; Sec(OH), L2mol-2 s-1
2.647 / 0.161 / 0.223 / 0.305 / 0.405 / 5.53 / -20.74 / 26.27
3.025 / 0.195 / 0.264 / 0.354 / 0.461 / 5.10 / -21.09 / 26.18
3.404 / 0.234 / 0.312 / 0.408 / 0.523 / 4.72 / -21.38 / 26.10
3.782 / 0.277 / 0.362 / 0.463 / 0.583 / 4.31 / -21.72 / 26.03
k3,Prim(OH) / k3,Sec(OH) = 5.00
104 x k3; Prim(OH), L2mol-2 s-1
2.647 / 0.591 / 0.822 / 1.121 / 1.491 / 5.53 / -19.88 / 25.41
3.025 / 0.719 / 0.973 / 1.301 / 1.696 / 5.09 / -20.23 / 25.32
3.404 / 0.860 / 1.147 / 1.501 / 1.923 / 4.72 / -20.51 / 25.24
3.782 / 1.020 / 1.332 / 1.704 / 2.146 / 4.31 / -20.86 / 25.17
104 x k3; Sec(OH), L2mol-2 s-1
2.647 / 0.118 / 0.164 / 0.224 / 0.298 / 5.53 / -20.94 / 26.47
3.025 / 0.144 / 0.195 / 0.260 / 0.339 / 5.10 / -21.29 / 26.39
3.404 / 0.172 / 0.229 / 0.300 / 0.385 / 4.72 / -21.58 / 26.30
3.782 / 0.204 / 0.266 / 0.341 / 0.429 / 4.31 / -21.92 / 26.23
Table ESM-6Solvatochromic parameters for IL/DMAC and MCC-IL/DMAC, and their pure components.a
IL/DMAC; 40 oCSolvent; Molarity of IL (mol/L) in DAS / ET(33), kcal mol-1 / SA / SB
Pure DMACb / 51.50 / 0.024 / 0.804
1.887 / 58.80 / 0.120 / 0.829
2.520 / 59.02 / 0.133 / 0.798
3.150 / 59.18 / 0.148 / 0.777
3.782 / 59.39 / 0.166 / 0.753
Pure IL / 59.85 / 0.131 / 0.651
MCC-IL/DMAC; 40 oC
1.887 / 58.65 / 0.144 / 0.841
2.520 / 58.81 / 0.161 / 0.809
3.150 / 58.99 / 0.180 / 0.785
3.782 / 59.14 / 0.201 / 0.763
a- ET33, SA, SB refer to the empirical polarity, acidity, and basicity, respectively, of the solvent or binary solvent mixture (Reichardt et al. 2011).
b- Solvatochromic parameters for pure DMAC were taken from literature(Antonious et al. 2002; Catalán 2009).The corresponding values for pure MeCN are: 55.4, 0.044, and 0.356, for ET(33), SA, and SB, respectively (Antonious et al. 2002; Catalán 2009). All other solvatochromic parameters were determined in the present work.
References
Antonious MS, Tada EB, El Seoud OA (2002) Thermo-solvatochromism in Aqueous Alcohols: Effects of the Molecular Structures of the Alcohol and the Solvatochromic Probe. J Phys Org Chem 15:403-412
Catalán J (2009) Toward a Generalized Treatment of the Solvent Effect Based on Four Empirical Scales: Dipolarity (SdP, a New Scale), Polarizability (SP), Acidity (SA), and Basicity (SB) of the Medium. J Phys Chem B 113:5951–5960
Reichardt C, Welton T (2011) Solvents and Solvent Effects in Organic Chemistry. 4 ed. Weinheim: Wiley: VCH