Good’s Buffer Ionic Liquids as Relevant Phase-Forming Components of Self-Buffered

Aqueous Biphasic Systems

Mohamed Taha, Maria V. Quental, Francisca A. e Silva, Emanuel V. Capela, Mara G. Freire, Sónia P. M. Ventura,

and João A. P. Coutinho*

CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal;

Fax: +351 234 370 084; E-mail: jcoutinho@ua.pt (J.A.P. Coutinho)

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Table S1. Characterization of Good’s buffer ionic liquids (GB-ILs).

[P4444][Tricine]: 1H NMR (300 MHz, D2O/TSP); δ [P4444], 0.77 (12H, t,

C4C8C12C16’s H), 1.27-1.44 (16H, m, C2C3 C6C7 C10C11C14C15’s H),

2.00 (8H, m, C1C5C9C13’s H); δ [Tricine], 3.37 (6H, s, C1-C3’s H), 3.12

(2H, s, C5’s H). 13C NMR (75.47 MHz, D2O/TSP); δ [P4444], 15.42

(C4C8C12C16), 20.15 (C3C7C11C15), 20.79 (C2C6C10C14), 26.28

(C1C5C9C13); δ [Tricine], 62.97 (C4), 63.12 (C1-C3), 182.71 (C6), 47.68

(C5); melting point = 116°C.

[P4444][Tricine]

[P4444][TES]: 1H NMR (300 MHz, D2O/TSP); δ [P4444], 0.79 (12H, t,

C4C8C12C16’s H), 1.29-1.49 (16H, m, C2C3C6C7 C10C11C14C15’s H),

2.10 (8H, m, C1C5C9C13’s H); δ [TES], 3.31 (6H, s, C1-C3’s H), 2.82

(2H, t, C6’s H), 2.57 (2H, t, C5’s H). 13C NMR (75.47 MHz, D2O/TSP); δ

[P4444], 15.46 (C4C8C12C16), 20.17 (C3C7C11C15), 20.83

(C2C6C10C14), 26.28 (C1C5C9C13); δ [TES], 60.65 (C4), 57.63 (C1-C3),

51.58 (C6), 37.69 (C5); viscous liquid.

[P4444][TES]

[P4444][MES]: 1H NMR (300 MHz, D2O/TSP); δ [P4444], 0.78 (12H, t,

C4C8C12C16’s H), 1.27-1.42 (16H, m, C2C3C6C7 C10C11C14C15’s H),

2.02 (8H, m, C1C5C9C13’s H); δ [MES], 2.50 (4H, t, C4C6’s H), 2.72

(2H, t, C2’s H), 2.99 (2H, t, C1’s H), 3.63 (4H, t, C3C5’s H). 13C NMR

(75.47 MHz, D2O/TSP); δ [P4444], 15.44 (C4C8C12C16), 20.16

(C3C7C11C15), 20.80 (C2C6C10C14), 26.28 (C1C5C9C13); δ [MES],

50.02 (C4C6), 55.11 (C2), 55.44 (C1), 68.80 (C3C5); melting point = 92

°C.

[P4444][MES]

[P4444][HEPES]: 1H NMR (300 MHz, D2O/TSP); δ [P4444], 0.79 (12H, t,

C4C8C12C16’s H), 1.28-1.45 (16H, m, C2C3C6C7 C10C11C14C15’s H),

2.03 (8H, m, C1C5C9C13’s H); [HEPES], 2.46 (8H, t, C3C4C5C6’s H),

2.67 (2H, t, C8’s H), 2.94 (2H, t, C1’s H), 2.97 (2H, t, C7’s H), 3.59 (4H, t,

C2’s H). 13C NMR (75.47 MHz, D2O/TSP); δ [P4444], 15.44

(C4C8C12C16), 20.16 (C3C7C11C15), 20.80 (C2C6C10C14), 26.29

(C1C5C9C13); δ [HEPES], 50.39 (C8), 54.19 (C4C5), 54.78 (C3C6),

[P4444][HEPES]

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55.02 (C1), 60.87 (C7), 61.59 (C2); melting point = 64 °C.

Table S1. Continued.

[P4444][CHES]: 1H NMR (300 MHz, D2O/TSP); 1H NMR (300 MHz,

D2O/TSP); δ [P4444], 0.78 (12H, t, C4C8C12C16’s H), 1.28-1.45 (16H, m,

C2C3C6C7 C10C11C14C15’s H), 2.02 (8H, m, C1C5C9C13’s H ); δ

[CHES], 0.94 (10H, m, C2-C6’s H), 2.38-2.47 (H, m, C1’s H), 2.95 (2H,

m, C8’s H), 2.95 (2H, t, C7’s H). 13C NMR (75.47 MHz, D2O/TSP); δ

[P4444], 15.43 (C4C8C12C16), 20.15 (C3C7C11C15), 20.79

(C2C6C10C14), 25.60 (C1C5C9C13); δ [CHES], 26.08 (C3C5), 26.28

(C4), 39.56 (C2C6), 53.42 (C8), 63.09 (C7), 63.37 (C1); melting point = 55

°C.

[P4444][CHES]

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Table S2. Experimental weight fraction data for the binodal curve of the systems composed of [P4444][GB]

(1) + K3C6H5O7 (2) at (25 ± 1) °C.

[P4444][TES]Mw = 453.66 g.mol-1

[P4444][MES]Mw = 453.66 g.mol-1

[P4444][HEPES]Mw = 496.72 g.mol-1

100w1 100 w2 100w1 100 w2 100 w1 100 w2 100 w1 100 w2

61.87 4.37 62.37 1.95 14.47 21.49 60.68 1.7847.02 8.97 55.07 3.07 14.02 21.86 48.71 4.7825.52 19.15 46.15 5.21 13.60 22.21 44.95 6.0823.75 20.22 38.99 7.55 13.35 22.44 39.04 8.3022.00 21.44 35.53 9.45 13.12 22.55 25.28 15.2520.31 22.47 32.17 10.43 12.86 22.75 22.19 18.3519.24 23.17 29.24 12.18 12.62 22.89 19.02 20.8518.35 23.72 25.01 14.22 12.33 23.10 18.80 21.0617.37 24.41 24.37 14.94 12.13 23.25 18.23 21.3816.52 24.96 23.45 15.59 11.94 23.41 17.95 21.6315.50 25.68 22.73 15.99 11.64 23.79 17.67 21.8714.54 26.39 22.10 16.27 11.41 23.87 17.20 22.1513.98 26.79 21.05 17.21 11.19 24.14 16.91 22.2612.66 28.22 20.19 17.49 10.81 24.41 16.52 22.5411.98 28.75 19.88 17.71 10.64 24.5711.48 29.15 19.30 18.08 10.26 25.3211.02 29.45 18.82 18.32 10.05 25.339.73 30.41 18.48 18.78 9.90 25.449.31 30.82 17.96 19.05 9.76 25.589.07 30.88 17.56 19.34 9.49 25.928.73 31.18 17.16 19.518.00 31.88 16.73 19.907.64 32.21 16.30 20.017.15 32.68 15.93 20.216.80 33.07 15.77 20.586.26 33.70 15.05 21.165.85 34.17 14.78 21.345.30 34.72 14.47 21.49

14.02 21.8613.60 22.2113.35 22.4413.12 22.5512.86 22.75

    12.62 22.89        

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Table S2. Continued.[P4444][CHES]Mw = 465.71 g.mol-1

[P4444][Tricine]Mw = 437.59 g.mol-1

100w1 100w2 100w1 100w2 100w1 100w2

56.03 2.15 16.45 13.89 49.06 8.7049.84 3.00 15.99 14.29 43.97 10.2144.57 4.00 15.59 14.18 47.70 9.1532.64 7.78 15.34 14.33 32.05 15.8431.63 8.05 15.07 14.48 27.35 19.3327.81 9.15 14.68 14.61 19.56 25.3626.97 9.60 14.39 14.75 16.67 27.8126.32 9.76 14.08 14.88 15.34 28.9525.90 9.93 13.79 15.04 13.32 30.5625.13 10.40 13.47 15.17 11.27 32.4824.61 10.45 13.13 15.40 10.38 33.1823.90 10.97 12.83 15.45 9.04 34.2323.18 11.16 12.54 15.62 8.45 34.7222.35 11.41 12.22 15.80 7.75 35.2821.72 11.67 11.96 15.91 7.30 35.5421.10 11.98 11.81 16.06 6.93 35.8920.65 12.16 11.51 16.21 6.54 36.1220.24 12.27 6.21 36.4319.61 12.48 5.81 36.3619.40 12.66 5.54 36.6219.13 12.77 5.31 36.7318.83 13.02 5.02 36.8618.49 13.1017.95 13.4117.50 13.5517.05 13.6616.60 13.86        

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Table S3. Correlation parameters used to describe the experimental binodal data by Eq. (S1)a, and

respective standard deviations (σ) and correlation coefficients.

GB-ILs A ± σ B ± σ 105 (C ± σ) R2

[P4444][TES] 113.0 ± 1.2 -0.287 ± 0.003 3.1 ± 0.0 0.9997

[P4444][Tricine] 110.1 ± 8.5 -0.373 ± 0.002 2.4 ± 0.2 0.9963

[P4444][MES] 98.3 ± 0.5 -0.328 ± 0.002 4.0 ± 0.1 0.9996

[P4444][HEPES] 89.9 ± 1.65 -0.280 ± 0.008 3.05 ± 0.3 0.9987

[P4444][CHES] 93.2 ± 1.0 -0.355 ± 0.005 15.4 ± 0.3 0.9991a[IL ]=A × exp( B [ salt ]0.5− [ salt ]3 )(S1); where [IL] and [salt] are the IL and salt weight percentages,

respectively. The coefficients A, B, and C are adjustable parameters obtained by the regression.

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Table S4. Data for the tie-lines (TLs) and tie-line lengths (TLLs). Initial mixture compositions are

represented as [Salt]M and [IL]M whereas [Salt]Salt and [IL]Salt are the composition of IL and salt at the IL-rich

phase, respectively, and vice-versa.

ILWeight fraction composition / wt %

[IL]IL [Salt]IL [IL]M [Salt]M [IL]Salt [Salt]Salt TLL

[P4444][TES]79.51 1.51 39.46 19.77 5.09 35.43 78.4055.66 5.99 39.52 14.42 10.64 29.50 50.80

[P4444][Tricine] 81.47 1.26 39.74 18.77 13.20 29.91 89.85 55.81 6.19 38.91 15.48 14.31 28.98 67.52

[P4444][HEPES]79.66 0.187 40.40 18.22 5.02 34.44 82.12 71.07 0.706 40.59 15.00 8.46 30.08 69.16

[P4444][CHES]81.30 0.149 39.87 19.18 0.0003 37.49 89.46 77.40 0.275 42.94 16.12 0.001 35.85 41.41

[P4444][MES]3.60 33.01 40.23 17.77 82.22 0.297 85.15 30.08 5.55 38.98 16.30 77.21 0.543 77.51

[P4444]Cl76.76 2.70 38.31 22.61 2.43 41.19 83.7156.50 5.17 38.91 13.99 8.12 29.43 54.1357.71 4.97 39.22 14.89 7.32 30.61 56.54

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Fig. S1. The synthetic pathway for the synthesis of [P4444][GB] ILs.

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Fig. S2. GLEE output showing measured electrode potentials and residuals as a function of the calculated –

log[H+].

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Fig. S3 pH titration curves of 1·10-3 mol·dm-3 of GB/[P4444][GB] at 25 °C and I = 0.1 mol·dm-3 of NaNO3.

The dashed lines are the calculated pH from the refinement operations. (b) Species-distribution diagrams of

1·10-3 mol·dm-3 of GB/[P4444][GB] at 25 °C and I = 0.1 mol·dm-3 of NaNO3.

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Fig. S4 Evaluation of the cation nature in the ternary phase diagrams (in mol.kg -1) composed of GB-IL +

K3C6H5O7 + water at 25 °C and atmospheric pressure: () [P4444][Tricine], () [P4444][MES], () [P4444]

[HEPES], () [P4444][TES], () [P4444][CHES], (▲) [N4444][Tricine], (▲) [N4444][MES], (▲) [N4444]

[HEPES], (▲) [N4444][TES], (▲) [N4444][CHES]. The [N4444][GBs] data from were taken from Ref. (Taha et

al., 2014).

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Fig. S5 Size exclusion chromatograms of a BSA solution in PBS (0.5 g L–1) (—), Bovine serum solution

(—), top phase of the system composed of [P4444][Tricine] + C6H5K3O7 (—), top phase of the system

composed of [P4444][TES] + C6H5K3O7 (—), top phase of the system composed of [P4444][HEPES] +

C6H5K3O7 (—), top phase of [P4444][MES] + K3C6H5O7 (—), top phase of the system composed of [P4444]

[CHES] + C6H5K3O7 (—).

References

Taha, M., e Silva, F., Quental, M.V., Ventura, S.P.M., Freire, M.G., Coutinho, J.A.P., (2014) Good's buffers as a basis for developing self-buffering and biocompatible ionic liquids for biological research. Green Chem., 3149–3159.

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