Supporting Information

Transcription

1 Supporting Information Evaluating self-buffering ionic liquids for biotechnological applications Sze Ying Lee a, Filipa A. Vicente b, Francisca A. e Silva b, Tânia E. Sintra b, Mohamed Taha b, Ianatul Khoiroh a, João A. P. Coutinho b, Pau Loke Show a, Sónia P. M. Ventura b * a Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia Campus, Jalan Broga, Semenyih 43500, Selangor Darul Ehsan, Malaysia. b CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, Portugal. *Corresponding author: spventura@ua.pt; Fax: ; Tel: S1

2 Section S1. Experimental methods Synthesis of GB-ILs Hydroxide solution of tetrabutylammonium, tetrabutylphosphonium and cholinium, respectively, were added slowly to an aqueous solution slightly in excess of GBs equimolar. After gentle stirring for 12 hours at room temperature, the water content in the reaction mixture was evaporated under sufficient pressure reduction and heat from evaporator bath at 60 ºC using a rotary evaporator (Heidolph, model Laborota 4003 c/w rotavac vario vacuum pump), until a highly viscous liquid was obtained. The crude product was mixed with equal volume of solvent: a mixture of acetonitrile and methanol in 1:1 volume ratio was used for tetrabutyl-ammonium and -phosphonium-based GB- ILs, whereas pure methanol was used for cholinium-based GB-ILs. Then it was stirred vigorously for 2 hours at room temperature. The mixture was filtered at least twice to remove any free acid content. Afterwards, the filtrate was evaporated for the solvent removal and processed under high vacuum with constant stirring for a minimum period of 48 hours at 60 ºC or at molten state if the product was obtained as a solid salt at room temperature. The water mass fraction content in the synthesized GB-ILs was determined by coulometric Karl Fischer titration (Metrohm, model 831) and was less than 0.1 % by mass in all samples. The chemical structure of GB-ILs was confirmed by 1 H and 13 C NMR spectroscopy (Bruker, model AMX 300) operating at 300 and 75 MHz, respectively. S2

3 Table S1. 1 H and 13 C NMR analysis of GB-ILs. [N 4,4,4,4 ][MOPSO] 1 H NMR (300 MHz, D 2 O) δ 0.93 (t, J = 7.3 Hz, 12H, 5, 9, 13, 17), 1.34 (h, J = 7.3 Hz, 8H, 4, 8, 12, 16), 1.63 (p, J = 7.1 Hz, 8H, 3, 7, 11, 15), (m, 6H, 20, 24, 26), (m, 2H, 18), 3.18 (t, J = 7.1 Hz, 8H, 2, 6, 10, 14), 3.74 (t, J = 4.8 Hz, 4H, 23, 27), (m, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (4, 8, 12, 16), (3, 7, 11, 15), (24, 26), (18), (2, 6, 10, 14), (20), (19), (23, 27). [P 4,4,4,4 ][MOPSO] 1 H NMR (300 MHz, D 2 O) δ 0.92 (t, J = 7.1 Hz, 12H, 5, 9, 13, 17), (m, 16H, 3, 4, 7, 8, 11, 12, 15, 16), (m, 8H, 2, 6, 10, 14), (m, 6H, 20, 24, 26), (m, 2H, 18), 3.75 (t, J = 4.8 Hz, 4H, 23, 27), (m, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (2, 6, 10, 14), (3, 4, 7, 8, 11, 12, 15, 16), (24, 26), (18), (20), (19), (23, 27). [Ch][MOPSO] 1 H NMR (300 MHz, D 2 O) δ (m, 6H, 10, 14, 16), (m, 2H, 8), 3.18 (s, 9H, 5, 6, 7), (m, 2H, 3), 3.75 (t, J = 4.8 Hz, 4H, 13, 17), (m, 2H, 2), (m, 1H, 9). 13 C NMR (75 MHz, D 2 O) δ (5, 6, 7), (14, 16), (8), (2), (10), (9), (13, 17), (3). S3

4 Table S1. Continued. [N 4,4,4,4 ][BES] 1 H NMR (300 MHz, D 2 O) δ 0.93 (t, J = 7.4 Hz, 12H, 5, 9, 13, 17), 1.35 (h, J = 7.3 Hz, 8H, 4, 8, 12, 16), 1.61 (p, J = 7.2 Hz, 8H, 3, 7, 11, 15), 2.70 (t, J = 6.1 Hz, 4H, 21, 24), (m, 4H, 18, 19), 3.17 (t, J = 7.2 Hz, 8H, 2, 6, 10, 14), 3.66 (t, J = 6.1 Hz, 4H, 22, 25). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (4, 8, 12, 16), (3, 7, 11, 15), (18), (19), 54.91(21, 24), (2, 6, 10, 14), (22, 25). [P 4,4,4,4 ][BES] 1 H NMR (300 MHz, D 2 O) δ 0.90 (t, J = 7.0 Hz, 12H, 5, 9, 13, 17), (m, 16H, 3, 4, 7, 8, 11, 12, 15, 16), (m, 8H, 2, 6, 10, 14), 2.70 (t, J = 6.1 Hz, 4H, 21, 24), (m, 4H, 18, 19), 3.66 (t, J = 6.1 Hz, 4H, 22, 25). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (2, 6, 10, 14), (3, 4, 7, 8, 11, 12, 15, 16), (18), (19), (21, 24), (22, 25). [Ch][BES] 1 H NMR (300 MHz, D 2 O) δ 2.74 (t, J = 6.0 Hz, 4H, 11, 14), (m, 4H, 8, 9), 3.17 (s, 9H, 5, 6, 7), (m, 2H, 3), 3.68 (t, J = 6.0 Hz, 4H, 12, 15), (m, 2H, 2). 13 C NMR (75 MHz, D 2 O) δ (8), (9), (5, 6, 7), 54.85(11, 14), (2), (12, 15), (3). S4

5 Table S1. Continued. [N 4,4,4,4 ][TAPSO] 1 H NMR (300 MHz, D 2 O) δ 0.92 (t, J = 7.3 Hz, 12H, 5, 9, 13, 17), 1.33 (h, J = 7.4 Hz, 8H, 4, 8, 12, 16), 1.62 (p, J = 7.5 Hz, 8H, 3, 7, 11, 15), 2.68 (dd, J = 12.1, 8.7 Hz, 1H, 20'), 2.83 (dd, J = 12.1, 3.5 Hz, 1H, 20"), 3.05 (dd, J = 5.9, 2.7 Hz, 2H, 18), 3.17 (t, J = 7.5 Hz, 8H, 2, 6, 10, 14), 3.54 (d, J = 1.8 Hz, 6H, 24, 26, 28), 4.11 (dddd, J = 8.7, 6.6, 5.3, 3.5 Hz, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (4, 8, 12, 16), (3, 7, 11, 15), (20), (18), (2, 6, 10, 14), (24, 26, 28), (23), (19). [P 4,4,4,4 ][TAPSO] 1 H NMR (300 MHz, D 2 O) δ 0.89 (t, J = 7.1 Hz, 12H, 5, 9, 13, 17), (m, 16H, 3, 4, 7, 8, 11, 12, 15, 16), (m, 8H, 2, 6, 10, 14), 2.67 (dd, J = 12.1, 8.7 Hz, 1H, 20'), 2.83 (dd, J = 12.0, 3.5 Hz, 1H, 20"), 3.05 (dd, J = 5.8, 2.7 Hz, 2H, 18), 3.54 (d, J = 1.8 Hz, 6H, 24, 26, 28), 4.11 (dddd, J = 8.6, 6.5, 5.2, 3.5 Hz, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (2, 6, 10, 14), (3, 4, 7, 8, 11, 12, 15, 16), (20), (18), (24, 26, 28), (23), (19). [Ch][TAPSO] 1 H NMR (300 MHz, D 2 O) δ 2.74 (dd, J = 12.1, 8.8 Hz, 1H, 10'), 2.90 (dd, J = 12.2, 3.5 Hz, 1H, 10"), 3.08 (dd, J = 5.9, 2.6 Hz, 2H, 8), 3.18 (s, 9H, 5, 6, 7), 3.49 (m, 2H, 3), 3.57 (d, J = 1.7 Hz, 6H, 14, 16, 18), (m, 2H, 2), 4.14 (dddd, J = 8.7, 6.6, 5.2, 3.4 Hz, 1H, 9). 13 C NMR (75 MHz, D 2 O) δ (10), (5, 6, 7), (8), (2), (14, 16, 18), (13), (9), (3). S5

6 Table S1. Continued. [N 4,4,4,4 ][CAPSO] 1 H NMR (300 MHz, D 2 O) δ 0.93 (t, J = 7.3 Hz, 12H, 5, 9, 13, 17), (m, 6H, 29, 30, 31), 1.35 (h, J = 7.3 Hz, 8H, 4, 8, 12, 16), 1.61 (p, J = 7.9 Hz, 8H, 3, 7, 11, 15), (m, 4H, 28, 32), (m, 1H, 27), 2.61 (dd, J = 12.6, 8.7 Hz, 1H, 20), 2.84 (dd, J = 12.6, 3.6 Hz, 1H, 20), (m, 2H, 18), 3.17 (t, J = 7.9 Hz, 8H, 2, 6, 10, 14), (m, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (4, 8, 12, 16), 23.11(3, 7, 11, 15), (29, 31), (30), (28, 32), (20), (18), (27), (2, 6, 10, 14), (19). [P 4,4,4,4 ][CAPSO] 1 H NMR (300 MHz, D 2 O) δ 0.90 (t, J = 7.1 Hz, 12H, 5, 9, 13, 17), (m, 6H, 29, 30, 31), (m, 16H, 3, 4, 7, 8, 11, 12, 15, 16), (m, 4H, 28, 32), (m, 8H, 2, 6, 10, 14), (m, 1H, 27), 2.62 (dd, J = 12.7, 8.8 Hz, 1H, 20), 2.84 (dd, J = 12.7, 3.6 Hz, 1H, 20), (m, 2H, 18), (m, 1H, 19). 13 C NMR (75 MHz, D 2 O) δ (5, 9, 13, 17), (2, 6, 10, 14), (3, 4, 7, 8, 11, 12, 15, 16), (29, 30, 31), (28, 32), (20), (18), (27), (19). [Ch][CAPSO] 1 H NMR (300 MHz, D 2 O) δ (m, 5H, 19, 20, 21'), (m, 1H, 21"), (m, 4H, 18, 22), (m, 1H, 17), 2.64 (dd, J = 12.7, 8.8 Hz, 1H, 10), 2.85 (dd, J = 12.7, 3.6 Hz, 1H, 10), (m, 2H, 8), 3.17 (s, 9H, 5, 6, 7), (m, 2H, 3), (m, 2H, 2), (m, 1H, 9). 13 C NMR (75 MHz, D 2 O) δ (19, 21), (20), (18, 22), (10), (5, 6, 7), (8), (17), (2), (9), (3). S6

7 Table S2. Buffering properties of GBs and GB-ILs (0.05 M) at (25 and 37) ºC. 25 ºC 37 ºC GBs/ GB-ILs Buffer Buffer mid-point buffer mid-point buffer capacity, capacity, ph region ph region β* β* MOPSO [N 4,4,4,4 ][MOPSO] [P 4,4,4,4 ][MOPSO] [Ch][MOPSO] BES [N 4,4,4,4 ][BES] [P 4,4,4,4 ][BES] [Ch][BES] TAPSO [N 4,4,4,4 ][TAPSO] [P 4,4,4,4 ][TAPSO] [Ch][TAPSO] CAPSO [N 4,4,4,4 ][CAPSO] [P 4,4,4,4 ][CAPSO] [Ch][CAPSO] *Buffer capacity, β, is expressed as the relationship between the increment of strong base or acid added and the final ph increment, as described in the below eq.: β = dc b d (ph) = dc a d (ph) where C b and C a, are the number of moles per liter of monoprotic strong base or acid added. S7

8 Table S3. EC 50 values (mg L -1 ) estimated following 5, 15, 30 min of exposure of the luminescent marine bacteria Vibrio fischeri to GB-ILs, with the respective 95% confidence lower and upper limits. GBs/GB- ILs EC 50 (mg L -1 ) 5 min (lower limit; upper limit) MOPSO (497.99; ) [N 4,4,4,4 ][MOPSO] (574.39; ) [P 4,4,4,4 ][MOPSO] (232.58; ) [Ch][MOPSO] ( ; ) BES ( ; ) [N 4,4,4,4 ][BES] (489.84; ) [P 4,4,4,4 ][BES] (265.84; ) [Ch][BES] ( ; ) TAPSO (670.89; ) [N 4,4,4,4 ][TAPSO] (391.95; ) [P 4,4,4,4 ][TAPSO] (232.69; ) [Ch][TAPSO] ( ; ) CAPSO ( ; ) [N 4,4,4,4 ][CAPSO] (125.06; ) [P 4,4,4,4 ][CAPSO] (161.56; ) [Ch][CAPSO] ( ; ) EC 50 (mg L -1 ) 15 min (lower limit; upper limit) (431.30; ) (280.11; ) (185.93; ) ( ; ) ( ; ) (316.28; ) (144.62; ) ( ; ) (534.50; ) (213.28; ) (145.86; ) ( ; ) ( ; ) (98.18; ) (122.68; ) ( ; ) EC 50 (mg L -1 ) 30 min (lower limit; upper limit) (597.79; ) (198.99; ) (152.98; ) ( ; ) ( ; ) (241.68; ) (117.47; ) ( ; ) (675.02; ) (165.27; ) (101.41; ) ( ; ) (494.40; ) (102.16; ) (103.02; ) ( ; ) S8

9 Table S4. EC 50 values (mmol L -1 ) estimated following 5, 15, 30 min of exposure of the luminescent marine bacteria Vibrio fischeri to GB-ILs, with the respective 95% confidence lower and upper limits. GBs/GB- ILs EC 50 (mmol L -1 ) 5 min (lower limit; upper limit) MOPSO 4.87 (2.21; 7.53) [N 4,4,4,4 ][MOPSO] 1.55 (1.23; 1.87) [P 4,4,4,4 ][MOPSO] 0.57 (0.48; 0.66) [Ch][MOPSO] (17.23; 21.53) BES 7.60 (4.86; 10.35) [N 4,4,4,4 ][BES] 1.39 (1.08; 1.70) [P 4,4,4,4 ][BES] 0.61 (0.56; 0.67) [Ch][BES] (28.21; 32.89) TAPSO 3.23 (2.59; 3.87) [N 4,4,4,4 ][TAPSO] 0.98 (0.78; 1.19) [P 4,4,4,4 ][TAPSO] 0.49 (0.45; 0.54) [Ch][TAPSO] (7.43; 16.55) CAPSO 6.41 (4.22; 8.61) [N 4,4,4,4 ][CAPSO] 0.28 (0.26; 0.30) [P 4,4,4,4 ][CAPSO] 0.36 (0.33; 0.39) [Ch][CAPSO] (58.15; 61.83) EC 50 (mmol L -1 ) 15 min (lower limit; upper limit) 5.04 (1.91; 7.95) 0.78 (0.60; 0.95) 0.41 (0.38; 0.44) (15.85; 18.55) 8.07 (4.98; 11.17) 0.76 (0.70; 0.82) 0.35 (0.31; 0.40) (16.72; 29.21) 2.77 (2.06; 3.48) 0.50 (0.43; 0.57) 0.30 (0.28; 0.33) 7.16 (4.82; 9.49) 7.55 (4.75; 10.35) 0.24 (0.21; 0.27) 0.28 (0.25; 0.32) (52.57; 58.92) EC 50 (mmol L -1 ) 30 min (lower limit; upper limit) 5.53 (2.65; 8.41) 0.52 (0.43; 0.62) 0.33 (0.32; 0.35) (15.70; 21.65) (7.69; 13.17) 0.54 (0.53; 0.54) 0.27 (0.25; 0.29) (15.62; 30.70) 3.72 (2.60; 4.84) 0.35 (0.33; 0.37) 0.22 (0.20; 0.25) 9.49 (6.58; 12.40) (2.08; 19.57) 0.22 (0.21; 0.22) 0.23 (0.21; 0.25) (51.26; 63.31) S9

10 Table S5. Experimental weight fraction data for the system composed of GB-ILs (1) + C 6 H 5 K 3 O 7 (2) +H 2 O at (25 ± 1) C. [N 4,4,4,4 ][MOPSO] [P 4,4,4,4 ][MOPSO] [N 4,4,4,4 ][BES] 100 w1 100 w2 100 w1 100 w2 100 w1 100 w2 100 w1 100 w2 100 w1 100 w S10

11 Table S5. Continued. [P 4,4,4,4 ][BES] [N 4,4,4,4 ][TAPSO] [P 4,4,4,4 ][TAPSO] [N 4,4,4,4 ][CAPSO] [P 4,4,4,4 ][CAPSO] 100 w1 100 w2 100 w1 100 w2 100 w1 100 w2 100 w1 100 w2 100 w1 100 w S11

12 Table S6. Correlation constants obtained by the regression of the experimental binodal data through the application of eq. 2 and respective standard deviation, σ, and correlation, R 2, for the studied systems. GB-ILs A ± σ B ± σ 10 5 (C ± σ) R 2 [N 4,4,4,4 ][MOPSO] ± ± ± [P 4,4,4,4 ][MOPSO] ± ± ± [N 4,4,4,4 ][BES] ± ± ± [P 4,4,4,4 ][BES] ± ± ± [N 4,4,4,4 ][TAPSO] ± ± ± [P 4,4,4,4 ][TAPSO] ± ± ± [N 4,4,4,4 ][CAPSO] ± ± ± [P 4,4,4,4 ][CAPSO] ± ± ± S12

13 Table S7. H-bond formation tendency of various anions of GB-ILs. Anions No. of H-bond No. of H-bond acceptor donor [MOPSO] [BES] [TAPSO] [CAPSO] S13

14 Tetrabutylammonium 2-hydroxy-3-morpholinopropanesulfonate [N 4,4,4,4][MOPSO] Tetrabutylphosphonium 2-hydroxy-3-morpholinopropanesulfonate [P 4,4,4,4][MOPSO] Cholinium 2-hydroxy-3-morpholinopropanesulfonate [Ch][MOPSO] Tetrabutylammonium 2-(bis(2-hydroxyethyl)amino)ethanesulfonate [N 4,4,4,4][BES] Tetrabutylphosphonium 2-(bis(2-hydroxyethyl)amino)ethanesulfonate [P 4,4,4,4][BES] Cholinium 2-(bis(2-hydroxyethyl)amino)ethanesulfonate [Ch][BES] Tetrabutylammonium N-[Tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonate [N 4,4,4,4][TAPSO] Tetrabutylphosphonium N-[Tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonate [P 4,4,4,4][TAPSO] Cholinium N-[Tris(hydroxymethyl)methyl]-3-amino-2- hydroxypropanesulfonate [Ch][TAPSO] Tetrabutylammonium 3-(cyclohexylamino)-2-hydroxypropanesulfonate [N 4,4,4,4][CAPSO] Tetrabutylphosphonium 3-(cyclohexylamino)-2-hydroxypropanesulfonate [P 4,4,4,4][CAPSO] Figure S1. Chemical structures, full names and acronyms of the synthesized GB-ILs. Cholinium 3-(cyclohexylamino)-2-hydroxypropanesulfonate [Ch][CAPSO] S14

15 [[N 4,4,4,4 ][BES]]/ (wt%) [[P 4,4,4,4 ][MOPSO]]/ (wt%) [[N 4,4,4,4 ][MOPSO]]/ (wt%) (a) [C 6 H 5 K 3 O 7 ] / (wt%) (b) [C 6 H 5 K 3 O 7 ] / (wt%) (c) [C 6 H 5 K 3 O 7 ] / (wt%) S15

16 [[N4444][MOPSO]]/ (wt%) [[N4444][MOPSO [[P 4,4,4,4 ][TAPSO]]/ (wt%) [[N 4,4,4,4 ][TAPSO]]/ (wt%) [[P 4,4,4,4 ][BES]]/ (wt%) (d) (e) [C 6 H 5 K 3 O 7 ] / (wt%) [C 6 H 5 K 3 O 7 ] / (wt%) Chart Title (f) [C 6 H 5 K 3 O 7 ] / (wt%) Figure S2. Ternary phase diagrams of systems consisting of (a) [N 4,4,4,4 ][MOPSO], (b) Merchuk [P 4,4,4,4 ][MOPSO], (c) [N 4,4,4,4 ][BES], (d) 30.00[P 4,4,4,4 ][BES], (e) [N 4,4,4,4 ][TAPSO], TLL5 (f) [N4444][MOPSO] [P 4,4,4,4 ][TAPSO], [N4444][MOPSO] K 3 C 6 H 5 O 7 + water at 25 ± 1 (ºC): Merchuk ( ) binodal [N4444][MOPSO] curve data, ( ) TLL data, ( ) Merchuk adjusted binodal data through Eq.(2), 0.00 ( ) TLL5 mixture Merchuk compositions for lipase Extraction point partition. TLL TLL TLL TLL1 [C H K O ] / TLL1 (wt%) 444][MOPSO]]/ (wt%) S16

17 S P kda Lipase Figure S3. Sodium dodecyl sulphate-polyacrylamide gel (SDS-PAGE) patterns of commercial lipase from P. cepacia: Lane P: molecular mass standard (6-202 kda), Lane S: commercial lipase from P. cepacia; 12% acrylamide gel with silver staining. S17