Inherently Chiral Azonia[6]helicene-Modified -Cyclodextrin: Synthesis, Characterization and Chirality Sensing of Underivatized Amino Acids in Water

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1 Supporting Information Inherently Chiral Azonia[6]helicene-Modified -Cyclodextrin: Synthesis, Characterization and Chirality Sensing of Underivatized Amino Acids in Water Qinfei Huang, Liangwei Jiang, Wenting Liang, Jianchang Gui, Dingguo Xu, Wanhua Wu, Yoshito Nakai, Masaki Nishijima, Gaku Fukuhara, Tadashi Mori, Yoshihisa Inoue, *, and Cheng Yang*, Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu , China Chongqing Municipal & Environmental Sanitation Monitoring Department, Yubei District, Chongqing, China Institute of Environmental Sciences, Shanxi University, Taiyuan , China Department of Applied Chemistry, Osaka University, 2-1Yamada-oka, Suita , Japan Office for University-Industry Collaboration, Osaka University, 2-8 Yamada-oka, Suita , Japan Table of Contents Synthesis of (P)- and (M) H NMR spectra of (P)- and (M)-2 2 ITC, DSC and fluorescence spectra of (P)- and (M)-2 3 UV-vis spectra in water and ethanol 5 HR-MS of (P)- and (M)-2 6 2D NMR spectra of (P)- and (M)-2 8 Job plots 20 Association constants at ph Scheme S1. Syntheses of (P)- and (M)-6-deoxy-6-(3-azonia[6]helicenyl)- -cyclodextrins (2) 1

2 Figure S1. 1 H NMR spectrum (600 MHz) of (M)-2 in D 2 O at 25 C. Figure S2. 1 H NMR spectrum (600 MHz) of (P)-2 in D 2 O at 25 C. 2

3 DP (ucal / sec) a kcal / mole of injectant b Time (min) Conc. / u Figure S3. (a) Isothermal titration calorimetry thermogram obtained upon injection (18 L/injection) of (M)-2 (1.0 mm) into pure water (1.43 ml) at 25 ºC. (b) A plot of the heat released upon each injection. 0.4 DP (ucal / sec) a kcal / mole of injectant b Time (min) Conc. / u Figure S4. (a) Isothermal titration calorimetry thermogram obtained upon injection (18 L/injection) of (P)-2 (1.0 mm) into pure water (1.43 ml) at 25 ºC. (b) A plot of the heat released upon each injection. 3

4 Cp (cal / o C) Temperature ( o C) Figure S5. Differential scanning calorimetry chart for aqueous solutions of (P)-2 (black) and (M)-2 (red) at 0.35 mm; heating rate = 5 C min -1. I / a.u Normalized intensity Wavelength / nm Wavelength / nm Figure S6. Fluorescence spectra of aqueous solutions (ph 7.0) of (M)-2 at 0.67 (black), 6.7 (red), 19.5 (green), 49.6 (blue), 100 (cyan), 200 (magenta), and 300 M (dark yellow) measured at 25 C; ex = 390 nm. Insert: normalized.spectra. 4

5 / M -1 cm Wavelength / nm Figure S7. UV-vis spectra of (M)-2 in H 2 O (black) and EtOH (red) / M -1 cm Wavlength / nm Figure S8. UV-vis spectra of (P)-2 in H 2 O (black) and EtOH (red). 5

6 Figure S9. High-resolution FAB mass spectrum of (M)-2. 6

7 Figure S10. High resolution FAB mass spectrum of (P)-2. 7

8 Figure S11. 1 H- 1 H COSY spectrum of (M)-2 in D 2 O at 25 C. 8

9 F1 E1 F2 E2 G1 A1 B1 D1 C1 C2 A2 B2 D2 G2 Figure S12. Partial 1 H- 1 H COSY spectrum of (M)-2 ( ) in D 2 O at 25 C. 9

10 Figure S13. TOCSY spectrum of (M)-2 in D 2 O at 25 C. 10

11 Figure S14. Partial TOCSY spectrum of (M)-2 ( ) in D 2 O at 25 C. 11

12 F1 F3 F2 E1 E3 E2 G1 G3 G4 G2 A3 A2 A4 A1 D1 B3 D3 D2 D4 B1 B2 B4 C1 C3 C2 Figure S15. Partial TOCSY spectrum of (M)-2 ( ) in D 2 O at 25 C. 12

13 Figure S16. HMBC spectrum of (M)-2 in D 2 O at 25 C. 13

14 Figure S17. Partial HMBC spectra of (M)-2 ( ) in D 2 O at 25 C. 14

15 Figure S18. Partial HMBC spectra of (M)-2 ( ) in D 2 O at 25 C. 15

16 Figure S19. HSQC of (M)-2 in D 2 O at 25 C. 16

17 Figure S20. Partial HSQC of (M)-2 ( ) in D 2 O at 25 C. 17

18 Figure S21. Partial HSQC of (M)-2 ( ) in D 2 O at 25 C. 18

19 Figure S22. ROESY spectrum of (M)-2 in D 2 O at 25 C. 19

20 Abs [D-Trp] / mm Abs [(P)-2]/([D-Trp] +[(P)-2]) Wavelength / nm Figure S23. UV-vis spectra of mixtures of (P)-2 and D-Trp at different fractions in aqueous solution (ph 7.0) at 25 C (measured in a 1 mm quartz cell), where the total concentration was kept constant at 0.4 mm. Inset: Job plot based on the net changes of absorbance at 350 nm. 20

21 Figure S24. UV-vis spectra of mixtures of (M)-2 and L-Trp at different fractions in aqueous solution (ph 7.0) at 25 C (measured in a 1 mm quartz cell), where the total concentration was kept constant at 0.4 mm. Inset: Job plot based on the net changes of absorbance at 350 nm. 21

22 Table S1. Association Constants (K) for 1:1 Complexation of D- and L-Amino Acids with (P)- and (M)-2 at ph 9.0 and 25 C Host Guest Configuration K/M -1 a K P /K M b K D /K L c (P)-2 Ala L D Thr L D Ser L D Trp L D Pro L D Met L D Leu L D (M)-2 Ala L D 4200 Thr L D 3200 Ser L D 1200 Trp L D 2300 Pro L D 3700 Met L D 120 Leu L D a Association constant determined by the fluorimetric titration in aqueous buffer solution at ph 9.0; error in K <15%. b Relative association constant for (P)- versus (M)-2. c Relative association constant for D- versus L-amino acid. 22