Supplementary Materials: Development of Amyloseand β-cyclodextrin-based Chiral Fluorescent Sensors Bearing Terthienyl Pendants

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1 S1 of S12 Supplementary Materials: Development of Amyloseand β-cyclodextrin-based Chiral Fluorescent Sensors Bearing Terthienyl Pendants Tomoyuki Ikai, Changsik Yun, Yutaka Kojima, Daisuke Suzuki, Katsuhiro Maeda and Shigeyoshi Kanoh 1. Supporting Data Figure S1. Histogram analysis of the DLS measurements of Am-1b in THF (a) and hexane/thf (90/10, v/v) (b) at 30 C after filtration through a membrane filter with a pore size of 0.45 μm. [Glucose unit] = M. Figure S2. CD and absorption spectra of Am-1b and Ce-1b in hexane/thf (90/10, v/v) at 25 C. [Glucose unit] = M. (Reproduced with permission from Reference [1]. Copyright 2016 The Royal Society of Chemistry).

S2 of S12 Figure S3. CD and absorption spectra of CyD-1b in THF (blue line) and hexane/thf (90/10, v/v) (red line) at 25 C. [Glucose unit] = 1.0 10 5 M. Figure S4.

2 S2 of S12 Figure S3. CD and absorption spectra of CyD-1b in THF (blue line) and hexane/thf (90/10, v/v) (red line) at 25 C. [Glucose unit] = M. Figure S4. Fluorescence spectra of Am-1b (a,b) and CyD-1b (c,d) upon the addition of various amounts of 5 (0 70 mm) in THF (a,c) and hexane/thf (90/10, v/v) (b,d) at room temperature. [Glucose unit] = M, λex = 450 nm. Insets: Photographs of the corresponding solutions in the absence (left) and presence (right) of nitrobenzene (70 mm) under irradiation at 365 nm.

3 S3 of S12 Figure S5. Stern Volmer plots for the fluorescence quenching of Ce-1b (λex = 450 nm) by the (R)- (red) and (S)- (blue) isomers of 6 (a) and 10 (b) in hexane/thf (90/10, v/v) at room temperature. [Glucose unit] = M. The results of the fluorescence quenching using 7a, 8, 9 and 11a as guest quenchers were reported in Reference [1]. Figure S6. Fluorescence spectra of Am-1b (a,b) and CyD-1b (c,d) in the absence (red line) and presence (blue line) of rac-7c (a,c) and rac-11c (b,d) in hexane/thf (90/10, v/v) at room temperature. [Glucose unit] = M, λex = 450 nm.

4 S4 of S12 (R )-11a (S )-11a Elution time (min) Figure S7. Chromatogram for the resolution of 11a on Am-1b-based CSP (column: 25 cm 0.20 cm (i.d.); eluent: ethanol; flow rate: 0.05 ml min 1 ).

5 S5 of S12 2. NMR Spectral Data = Am-1a-5.jdf Sample_Id = S# = PYRIDINE-D5 Creation_Time = 1-MAY :05:10 Revision_Time = 27-AUG :46:45 Current_Time = 27-AUG :46:51 Dim_Units = [] Site = ECS 400 Spectrometer = JNM-ECS400 Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] = [MHz] = 5[] X_Resolution = [Hz] = [kHz] = [MHz] Irr_Offset = 5[] = [MHz] Tri_Offset = 5[] Scans = 300 Total_Scans = 300 Recvr_Gain = 52 = 80[dC] X_90_Width = 9.4[us] X_Acq_Time = [s] = 0.7[dB] = 4.7[us] Dante_Presat Repetition_Time = [s] Figure S8. 1 H-NMR (pyridine-d5, 400 MHz, 80 C) spectrum of Am-1a = Am-1b-3.jdf Sample_Id = S# = CHLOROFORM-D Creation_Time = 21-AUG :30:01 Revision_Time = 27-AUG :02:24 Current_Time = 27-AUG :02:45 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 350 Total_Scans = 350 Recvr_Gain = 50 = 55[dC] Dante_Presat Figure S9. 1 H-NMR (CDCl3, 500 MHz, 55 C) spectrum of Am-1b.

6 S6 of S = CyD-1a-4.jdf Sample_Id = S# Creation_Time = 8-OCT :13:27 Revision_Time = 27-AUG :14:34 Current_Time = 27-AUG :14:46 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 69 Total_Scans = 69 Recvr_Gain = 60 = 80[dC] Dante_Presat Figure S10. 1 H-NMR (DMSO-d6, 500 MHz, 80 C) spectrum of CyD-1a = CyD-1b-4.jdf Sample_Id = S# = CHLOROFORM-D Creation_Time = 10-OCT :27:26 Revision_Time = 27-AUG :33:47 Current_Time = 27-AUG :33:57 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 250 Total_Scans = 250 = 55[dC] Dante_Presat Figure S11. 1 H-NMR (CDCl3, 500 MHz, 55 C) spectrum of CyD-1b.

7 S7 of S = (R)-g12 DMSO -4.jdf Sample_Id = S# Creation_Time = 1-JUL :19:47 Revision_Time = 27-AUG :28:57 Current_Time = 27-AUG :29:07 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 16 Total_Scans = 16 Recvr_Gain = 46 = 20.7[dC] Dante_Presat Figure S12. 1 H-NMR (DMSO-d6, 500 MHz, rt) spectrum of (R) sexp( 2.0[Hz], 0.0[s] ) = (R)D-g12 C NMR -4.jdf Experiment = single_pulse_dec Sample_Id = 111 Creation_Time = 23-JUN :11:24 Revision_Time = 27-AUG :50:48 Current_Time = 27-AUG :53:56 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 411 Total_Scans = 411 = 19.8[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (DMSO-d6, 125 MHz, rt) spectrum of (R)-6.

8 S8 of S = (S)-g12 DMSO-2.jdf Sample_Id = S# Creation_Time = 30-JUN :27:21 Revision_Time = 27-AUG :22:53 Current_Time = 27-AUG :23:37 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 16 Total_Scans = 16 Recvr_Gain = 50 = 20[dC] Dante_Presat Figure S14. 1 H-NMR (DMSO-d6, 500 MHz, rt) spectrum of (S) sexp( 2.0[Hz], 0.0[s] ) = (S)L-g12 C NMR-4.jdf Experiment = single_pulse_dec Sample_Id = 111 Creation_Time = 23-JUN :38:00 Revision_Time = 27-AUG :56:28 Current_Time = 27-AUG :56:46 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 455 Total_Scans = 455 = 19.7[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (DMSO-d6, 125 MHz, rt) spectrum of (S)-6.

9 S9 of S = (D)-g15 DMSO-3.jdf Sample_Id = S# Creation_Time = 8-FEB :52:52 Revision_Time = 27-AUG :38:40 Current_Time = 27-AUG :38:45 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 16 Total_Scans = 16 Recvr_Gain = 60 = 80[dC] Dante_Presat Figure S16. 1 H-NMR (DMSO-d6, 500 MHz, 80 C) spectrum of (R) sexp( 2.0[Hz], 0.0[s] ) = (D)-g15 C NMR -4.jdf Experiment = single_pulse_dec Sample_Id = 111 Creation_Time = 23-JUN :13:19 Revision_Time = 27-AUG :02:46 Current_Time = 27-AUG :03:03 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 473 Total_Scans = 473 = 20.5[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (DMSO-d6, 125 MHz, rt) spectrum of (R)-10.

10 S10 of S = (L)-g15 DMSO-3.jdf Sample_Id = S# Creation_Time = 5-FEB :26:06 Revision_Time = 27-AUG :37:46 Current_Time = 27-AUG :37:50 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 16 Total_Scans = 16 Recvr_Gain = 62 = 80[dC] Dante_Presat Figure S18. 1 H-NMR (DMSO-d6, 500 MHz, 80 C) spectrum of (S) sexp( 2.0[Hz], 0.0[s] ) = (L)-g15 C NMR -4.jdf Experiment = single_pulse_dec Sample_Id = 111 Creation_Time = 23-JUN :45:44 Revision_Time = 27-AUG :04:00 Current_Time = 27-AUG :05:01 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 532 Total_Scans = 532 Recvr_Gain = 56 = 20.4[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (DMSO-d6, 125 MHz, rt) spectrum of (S)-10.

11 S11 of S = (R)-G4-2.jdf Sample_Id = S# = CHLOROFORM-D Creation_Time = 24-NOV :57:50 Revision_Time = 27-AUG :26:16 Current_Time = 27-AUG :26:32 Dim_Units = [] Site = ECS 400 Spectrometer = JNM-ECS400 Field_Strength = [T] (400[MHz]) X_Acq_Duration = [s] = [MHz] = 5[] X_Resolution = [Hz] = [kHz] = [MHz] Irr_Offset = 5[] = [MHz] Tri_Offset = 5[] Scans = 32 Total_Scans = 32 Recvr_Gain = 46 = 20[dC] X_90_Width = 9.4[us] X_Acq_Time = [s] = 0.7[dB] = 4.7[us] Dante_Presat Repetition_Time = [s] Figure S20. 1 H-NMR (CDCl3, 400 MHz, rt) spectrum of (R)-11c sexp( 2.0[Hz], 0.0[s] ) = (R)-G4 C NMR-4.jdf Experiment = single_pulse_dec Sample_Id = 111 = CHLOROFORM-D Creation_Time = 22-JUN :35:36 Revision_Time = 27-AUG :58:25 Current_Time = 27-AUG :59:03 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 1000 Total_Scans = 1000 = 20.4[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (CDCl3, 125 MHz, rt) spectrum of (R)-11c.

12 S12 of S = (S)-G4-4.jdf Sample_Id = S# = CHLOROFORM-D Creation_Time = 26-NOV :57:05 Revision_Time = 27-AUG :37:12 Current_Time = 27-AUG :37:27 Dim_Units = [] = 5.0[] Irr_Offset = 5.0[] Tri_Offset = 5.0[] Scans = 32 Total_Scans = 32 = 19.9[dC] Dante_Presat Figure S22. 1 H-NMR (CDCl3, 500 MHz, rt) spectrum of (S)-11c sexp( 2.0[Hz], 0.0[s] ) = (S)-G4 C NMR -4.jdf Experiment = single_pulse_dec Sample_Id = 111 = CHLOROFORM-D Creation_Time = 22-JUN :32:24 Revision_Time = 27-AUG :59:55 Current_Time = 27-AUG :00:15 Dim_Size = Dim_Title = 13C Dim_Units = [] X_Acq_Duration = [s] = 13C = [MHz] = 100[] X_Points = X_Prescans = 4 X_Resolution = [Hz] = [kHz] Irr_Offset = 5.0[] Scans = 848 Total_Scans = 848 = 21.2[dC] X_90_Width = 9[us] X_Acq_Time = [s] = 30[deg] = 6[dB] = 3[us] Irr_Atn_Dec = [dB] Irr_Atn_Noe = [dB] Irr_Noise = WALTZ Decoupling = TRUE Noe = TRUE Noe_Time = 2[s] Repetition_Time = [s] X : parts per Million : 13C Figure S C-NMR (CDCl3, 125 MHz, rt) spectrum of (S)-11c. Reference 1. Ikai, T.; Suzuki, D.; Kojima, Y.; Yun, C.; Maeda, K.; Kanoh, S. Chiral fluorescent sensors based on cellulose derivatives bearing terthienyl pendants. Polym. Chem. 2016, 7,

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