Supporting Information Thermo- and Solvent-Responsive Polymer ...
Supporting Information
Thermo- and Solvent-Responsive Polymer Complex Created from Supramolecular Complexation between a Helix-Forming Polysaccharide and a Cationic Polythiophene Tomohiro Shiraki, †Arnab Dawn, § Youichi Tsuchiya, † Seiji Shinkai†,§,‡ * † Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 203-1 Moto-oka, Nishi-ku, Fukuoka 819-0385 Japan. TEL: +81-92-805-3810 FAX: +81-92805-3814 § Institute for Advanced Study, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan. ‡Department of Nanoscience, Faculty of Engineering, Sojo University, 4-22-1 Ikeda, Kumamoto 8600082, Japan. E-mail: [email protected]
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Experimental Materials Curdlan and 3-bromo-1-propyne were purchased from Wako Pure Chemical Ltd. Triethylene glycol monomethyl ether and potassium tert-butoxide were obtained from Tokyo Chemical Industry Co. Schizophyllan was kindly supplied by Mitsui Sugar Co. Other reagents were purchased from suppliers such as Wako Pure Chemical Ltd., Tokyo Chemical Industry Co., and Sigma-Aldrich Co. All reagents were used without further purification.
Synthesis 2,5,8,11-Tetraoxatetradec-13-yne (1) In 3 mL of THF, triethylene glycol monomethyl ether (2.0 g, 12.2 mmol) was dissolved under an argon atmosphere. After cooling with an ice bath, 25 mL of THF suspension of potassium tert-butoxide (1.56 g, 13.9 mmol) was added. To the solution, 1.82 mL of 3-bromo-1-propyne (24.2 mmol) in 50 mL THF was added dropwise. The reaction mixture was stirred for 1 h at 0 °C and allowed to room temperature. After stirring for 24 h, 200 mL of ether acetate was added and washed with 75 mL of saturated NaCl aqueous solution three times. The separated organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated to dryness and 1 was obtained as pale yellow oil (1.84g, 76%). 1H NMR (400MHz, CDCl3, TMS): δ = 4.21 (d, 2H), 3.63-3.73 (m. 10H), 3.56 (m, 2H), 3.38 (s, 3H), 2.43 ppm (t, 1H).
Cur-oeg Cur-N3 (200mg, 1.07 mmol (monomer unit)) was dissolved in 10 mL of DMSO. To the solution, CuBr2 (11.95 mg), ascorbic acid (47.11 mg), propylamine (0.5 mL), and water (0.5 mL) were added. After adding 541 mg of 1 (2.67 mmol), the reaction mixture was stirred at room temperature for 3 days and subjected to dialysis with distilled water (MWCO 8000). Freeze-dry treatment afforded a pale yellow solid of Cur-oeg (368 mg, 76%). 1H NMR (400 MHz, 60 °C, [D6]DMSO, TMS): δ = 8.13 (s, 1H), 5.08 (s, 1H), 4.92 (s, 1H), 4.79 (d, 1H), 4.53 (s, 2H), 4.45(br, 2H), 3.59-3.40 (m, 16H), 3.23 ppm (s, 3H).; 13C NMR (100 MHz, 25 °C, [D6]DMSO) : δ =144.39, 126.15, 103.23, 84.45, 74.65, 73.84, 71.77, 70.27, 70.19, 70.07, 69.48, 63.97, 58.55, 50.98 ppm ; FT-IR (powder, ATR-Ge): 3380, 3142, 2876, 1642, 1462, 1352, 1306, 1246, 1082, 850 cm-1; elemental analysis: C16H27N3: cal C 19.35, H 6.99, M 10.79: found C 48.41, H 6.80, N 10.45.; SEC (Shodex OHpak SE-806M HQ, DMSO containg 5 mM LiBr, 40 °C, pullulan standards) Mw = 7.1×104. (Mw/Mn = 1.9, degree of polymerization (DP) = ca. 182). S2
Sample Preparation A stock solution of PT1 was prepared with a concentration of 4 mM in pure water. Cur-oeg and SPG were dissolved in DMSO with the concentration of 12 mM and 8 mM, respectively. These concentrations were calculated with respect to their monomer units. The PT1 solution was mixed with the Cur-oeg or the SPG solution and the mixtures were diluted with water, where the final composition of the solvent became water : DMSO = 95 : 5 (v/v). The mixed solutions were used for measurements after leaving overnight at 25 °C, except the dynamic complexation experiments. The TEM samples were prepared by the following methods. On a carbon-coated copper mesh grid, one drop of a sample solution was placed. After 5 minutes standing, the solution was removed with filter paper. The grid was dried in vacuo once. A staining solution of 1 wt% phosphotungstic acid aqueous solution was adjusted to pH 7 with NaOH. One drop of the staining solution was placed on the grid and removed with filter paper quickly. The resulted grid was dried under an ambient atmosphere before drying in vacuo for more than 6 hours. For investigation of heated samples, all solutions including sample solutions and a staining solution and TEM grids were heated at 55 °C. The drying process was also performed at 55 °C. AFM samples placed on mica substrates were prepared by the similar procedure to TEM samples.
Instruments & Measurements 1
H NMR spectra were obtained on a JEOL JNM-ECS400. UV-vis absorption was recorded on a
JASCO V-670 spectrophotometer with a Peltier type thermostatic cell holder. CD spectra were recorded on a JASCO J-720WI spectropolarimeter with a thermostatic bath. The path length of the quartz cells was 1 cm.
Fluorescence spectroscopy was conducted on a Perkin Elmer LS55 luminescence
spectrometer with a 1-mm quartz cell. The temperature was controlled by a thermostatic bath. FT-IR spectra were collected on a JASCO FT/IR-4200 with an ATR PRO450-S (Ge). For transmission electron microscopy (TEM) and atomic force microscopy (AFM), a JEOL JEM-2010(acceleration voltage 120 kV) and Veeco Nanoscope IIIa (Tapping mode) were used.
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Figure S1. 13C NMR spectrum of PT1 in the aromatic region. CD3OD, TMS.
Figure S2. TEM images of (A) PT1 itself and (B) Cur-oeg itself; negative stain with 1 wt.% phosphotungstic acid aqueous solution adjusted to pH 7 with NaOH. S4
Figure S3. (A) UV/vis absorption, (B) CD, and (C) fluorescence spectra of PT1/SPG complex for the temperature change from 5 °C to 85 ° C; in water containing 5 vol.% DMSO, [PT1]unit = 0.2 mM, [SPG]unit = 0.4 mM, λex = 409 nm. (D) Temperature dependence of peak wavelengths of the UV/vis absorption (dot), the first Cotton effect of CD (square), and the fluorescence (triangle).
Figure S4. (A) UV/vis absorption, (B) fluorescence spectra of PT1 itself for the temperature change from 5 °C to 85 ° C; in water containing 5 vol.% DMSO, [PT1]unit = 0.2 mM, λex = 409 nm. (C) Temperature dependence of peak wavelengths of the UV/vis absorption (dot) and the fluorescence (triangle). S5
Figure S5. (A) Peak intensity change at 481 nm (θ481nm) for ICD of PT1/Cur-oeg complex at 55 °C as a function of molar ratio for [Cur-oeg]unit to [PT1]unit. (B) Spectral changes of the PT1 absorption at 55 °C upon adding Cur-oeg; [PT1]unit = 0.2 mM, [Cur-oeg]unit = 0 ~ 0.9 mM, in water containing 5 vol.% DMSO.
Figure S6. TEM images of PT1/Cur-oeg complex prepared (A) at 55 °C and (B) at 25 ° C; negative stain with 1 wt.% phosphotungstic acid aqueous solution adjusted to pH 7 with NaOH.
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Figure S7. (A) UV/vis absorption and (B) CD spectra of PT1/Cur-oeg complex in 90 vol.% organic solvents (blue line: dioxane, red line: acetone); 25 °C.
Figure S8. Normalized UV/vis absorption spectra of (A) PT1 film and (B) PT1/SPG film. The asprepared film was subjected to the humid air and methanol vapor and then dried in vacuo again.
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Thermo- and Solvent-Responsive Polymer Complex Created from Supramolecular Complexation between a Helix-Forming Polysaccharide and a Cationic Polythiophene Tomohiro Shiraki, †Arnab Dawn, § Youichi Tsuchiya, † Seiji Shinkai†,§,‡ * † Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 203-1 Moto-oka, Nishi-ku, Fukuoka 819-0385 Japan. TEL: +81-92-805-3810 FAX: +81-92805-3814 § Institute for Advanced Study, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan. ‡Department of Nanoscience, Faculty of Engineering, Sojo University, 4-22-1 Ikeda, Kumamoto 8600082, Japan. E-mail: [email protected]
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Experimental Materials Curdlan and 3-bromo-1-propyne were purchased from Wako Pure Chemical Ltd. Triethylene glycol monomethyl ether and potassium tert-butoxide were obtained from Tokyo Chemical Industry Co. Schizophyllan was kindly supplied by Mitsui Sugar Co. Other reagents were purchased from suppliers such as Wako Pure Chemical Ltd., Tokyo Chemical Industry Co., and Sigma-Aldrich Co. All reagents were used without further purification.
Synthesis 2,5,8,11-Tetraoxatetradec-13-yne (1) In 3 mL of THF, triethylene glycol monomethyl ether (2.0 g, 12.2 mmol) was dissolved under an argon atmosphere. After cooling with an ice bath, 25 mL of THF suspension of potassium tert-butoxide (1.56 g, 13.9 mmol) was added. To the solution, 1.82 mL of 3-bromo-1-propyne (24.2 mmol) in 50 mL THF was added dropwise. The reaction mixture was stirred for 1 h at 0 °C and allowed to room temperature. After stirring for 24 h, 200 mL of ether acetate was added and washed with 75 mL of saturated NaCl aqueous solution three times. The separated organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated to dryness and 1 was obtained as pale yellow oil (1.84g, 76%). 1H NMR (400MHz, CDCl3, TMS): δ = 4.21 (d, 2H), 3.63-3.73 (m. 10H), 3.56 (m, 2H), 3.38 (s, 3H), 2.43 ppm (t, 1H).
Cur-oeg Cur-N3 (200mg, 1.07 mmol (monomer unit)) was dissolved in 10 mL of DMSO. To the solution, CuBr2 (11.95 mg), ascorbic acid (47.11 mg), propylamine (0.5 mL), and water (0.5 mL) were added. After adding 541 mg of 1 (2.67 mmol), the reaction mixture was stirred at room temperature for 3 days and subjected to dialysis with distilled water (MWCO 8000). Freeze-dry treatment afforded a pale yellow solid of Cur-oeg (368 mg, 76%). 1H NMR (400 MHz, 60 °C, [D6]DMSO, TMS): δ = 8.13 (s, 1H), 5.08 (s, 1H), 4.92 (s, 1H), 4.79 (d, 1H), 4.53 (s, 2H), 4.45(br, 2H), 3.59-3.40 (m, 16H), 3.23 ppm (s, 3H).; 13C NMR (100 MHz, 25 °C, [D6]DMSO) : δ =144.39, 126.15, 103.23, 84.45, 74.65, 73.84, 71.77, 70.27, 70.19, 70.07, 69.48, 63.97, 58.55, 50.98 ppm ; FT-IR (powder, ATR-Ge): 3380, 3142, 2876, 1642, 1462, 1352, 1306, 1246, 1082, 850 cm-1; elemental analysis: C16H27N3: cal C 19.35, H 6.99, M 10.79: found C 48.41, H 6.80, N 10.45.; SEC (Shodex OHpak SE-806M HQ, DMSO containg 5 mM LiBr, 40 °C, pullulan standards) Mw = 7.1×104. (Mw/Mn = 1.9, degree of polymerization (DP) = ca. 182). S2
Sample Preparation A stock solution of PT1 was prepared with a concentration of 4 mM in pure water. Cur-oeg and SPG were dissolved in DMSO with the concentration of 12 mM and 8 mM, respectively. These concentrations were calculated with respect to their monomer units. The PT1 solution was mixed with the Cur-oeg or the SPG solution and the mixtures were diluted with water, where the final composition of the solvent became water : DMSO = 95 : 5 (v/v). The mixed solutions were used for measurements after leaving overnight at 25 °C, except the dynamic complexation experiments. The TEM samples were prepared by the following methods. On a carbon-coated copper mesh grid, one drop of a sample solution was placed. After 5 minutes standing, the solution was removed with filter paper. The grid was dried in vacuo once. A staining solution of 1 wt% phosphotungstic acid aqueous solution was adjusted to pH 7 with NaOH. One drop of the staining solution was placed on the grid and removed with filter paper quickly. The resulted grid was dried under an ambient atmosphere before drying in vacuo for more than 6 hours. For investigation of heated samples, all solutions including sample solutions and a staining solution and TEM grids were heated at 55 °C. The drying process was also performed at 55 °C. AFM samples placed on mica substrates were prepared by the similar procedure to TEM samples.
Instruments & Measurements 1
H NMR spectra were obtained on a JEOL JNM-ECS400. UV-vis absorption was recorded on a
JASCO V-670 spectrophotometer with a Peltier type thermostatic cell holder. CD spectra were recorded on a JASCO J-720WI spectropolarimeter with a thermostatic bath. The path length of the quartz cells was 1 cm.
Fluorescence spectroscopy was conducted on a Perkin Elmer LS55 luminescence
spectrometer with a 1-mm quartz cell. The temperature was controlled by a thermostatic bath. FT-IR spectra were collected on a JASCO FT/IR-4200 with an ATR PRO450-S (Ge). For transmission electron microscopy (TEM) and atomic force microscopy (AFM), a JEOL JEM-2010(acceleration voltage 120 kV) and Veeco Nanoscope IIIa (Tapping mode) were used.
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Figure S1. 13C NMR spectrum of PT1 in the aromatic region. CD3OD, TMS.
Figure S2. TEM images of (A) PT1 itself and (B) Cur-oeg itself; negative stain with 1 wt.% phosphotungstic acid aqueous solution adjusted to pH 7 with NaOH. S4
Figure S3. (A) UV/vis absorption, (B) CD, and (C) fluorescence spectra of PT1/SPG complex for the temperature change from 5 °C to 85 ° C; in water containing 5 vol.% DMSO, [PT1]unit = 0.2 mM, [SPG]unit = 0.4 mM, λex = 409 nm. (D) Temperature dependence of peak wavelengths of the UV/vis absorption (dot), the first Cotton effect of CD (square), and the fluorescence (triangle).
Figure S4. (A) UV/vis absorption, (B) fluorescence spectra of PT1 itself for the temperature change from 5 °C to 85 ° C; in water containing 5 vol.% DMSO, [PT1]unit = 0.2 mM, λex = 409 nm. (C) Temperature dependence of peak wavelengths of the UV/vis absorption (dot) and the fluorescence (triangle). S5
Figure S5. (A) Peak intensity change at 481 nm (θ481nm) for ICD of PT1/Cur-oeg complex at 55 °C as a function of molar ratio for [Cur-oeg]unit to [PT1]unit. (B) Spectral changes of the PT1 absorption at 55 °C upon adding Cur-oeg; [PT1]unit = 0.2 mM, [Cur-oeg]unit = 0 ~ 0.9 mM, in water containing 5 vol.% DMSO.
Figure S6. TEM images of PT1/Cur-oeg complex prepared (A) at 55 °C and (B) at 25 ° C; negative stain with 1 wt.% phosphotungstic acid aqueous solution adjusted to pH 7 with NaOH.
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Figure S7. (A) UV/vis absorption and (B) CD spectra of PT1/Cur-oeg complex in 90 vol.% organic solvents (blue line: dioxane, red line: acetone); 25 °C.
Figure S8. Normalized UV/vis absorption spectra of (A) PT1 film and (B) PT1/SPG film. The asprepared film was subjected to the humid air and methanol vapor and then dried in vacuo again.
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