A New Anion Sensor Zinc(II) Pyridylcyclen Based on Zinc(II) Chelation Control of Twisted

Supplementary Information for

Efficient Cycloreversion of cis,syn-Thymine Photodimer by a Zn2+–Cyclen Complex Bearing a Lumiflavin and Tryptophan by Chemical Reduction and Photoreduction of a Lumiflavin Unit (Cyclen = 1,4,7,10-Tetraazacyclododecane).

Yasuyuki Yamada and Shin Aoki

Faculty of Pharmaceutical Sciences, Tokyo University of Science

2641Yamazaki, Noda 278-8510, Japan

Page 4: Figure S1. Typical potentiometric pH titration curves for a solution of (a) 0.5 mM 11ox ((ZnL4)ox(H2O)), (b) 0.5 mM T[c,s]T (3), and (c) 0.5 mM 11ox ((ZnL4)ox(H2O)) + 0.5 mM T[c,s]T (3) in 10% MeCN aqueous solution with I = 0.1 (NaNO3) at 25˚C.

Page 5: Figure S2. Distribution diagram for a mixture of 100 mM 11ox ((ZnL4)ox) and 400 mM T[c,s]T (3) in 10% MeCN aqueous solution with I = 0.1 (NaNO3) at 25˚C.

Page 6: Figure S3. Cyclic voltammogram of (a) 0.3 mM 10ox (solid line) and (b) 0.3 mM 11ox (dashed line) on a glassy carbon disk in 0.1 M nBu4NClO4–CH3CN at a scan rate of 10 mV·s–1.

Page 7: Figure S4. Change in UV-Vis absorption spectra (A) and fluorescence emission spectra (B) of 3-carboxymethyllumiflavin 16 during photoirradiation in the presence of 35 mM Et3N in an aqueous solution (pH 11) at 25°C: (a) spectra before UV irradiation, (b) after UV irradiation for 30 min, and (c) after reoxidation in air. Change in UV-Vis absorption spectra (C) and fluorescence emission spectra (D) of 16 during the photoirradiation in the presence of 35 mM DABCO in an aqueous solution (pH 11) at 25°C: (d) spectra before UV irradiation, (e) after UV irradiation for 30 min, and (f) after reoxidation in air. [16] = 50 mM. Irradiation wavelength was 365 nm.

Page 8: Figure S5. Change in UV-Vis absorption spectra (A) and fluorescence emission spectra (B) of 3-carboxymethyllumiflavin 16 during photoirradiation in the presence of 35 mM potassium oxalate in an aqueous solution (pH 11) at 25°C: (a) spectra before UV irradiation, (b) after UV irradiation for 30 min, and (c) after reoxidation in air. Change in UV-Vis absorption spectra (C) and fluorescence emission spectra (D) of 16 during the photoirradiation in the presence of 35 mM EDTA in an aqueous solution (pH 11) at 25°C: (d) spectra before UV irradiation, (e) after UV irradiation for 30 min, and (f) after reoxidation in air. [16] = 50 mM. Irradiation wavelength was 365 nm.

Page 9: Figure S6. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 3-carboxymethyllumiflavin 16 in an aqueous solution with 35 mM Et3N (closed circles), or 35 mM potassium oxalate (open circles), or 35 mM EDTA (open triangles), or 35 mM DABCO (open squares) in an aqueous solution at pH 11 (pH was adjusted with aqueous NaOH). [T[c,s]T] = 400 mM, [16] = 100 mM.

Page 10: Figure S7. UV spectra of 10ox (a) before and (b) after UV irradiation for 10 min at pH 11 in the absence of Et3N at 25°C and UV spectra of 11ox (c) before and (d) after irradiation for 10 min and (e) after reoxidation in air. [10ox] = [11ox] = 50 mM.

Page 11: Figure S8. Change in UV-Vis absorption spectra of 10ox upon addition of 1 mM EDTA in an aqueous solution (pH 11) at 25°C: spectra of (a) 10ox and (b) 10ox with 1 mM EDTA. [10ox] = 50 mM.

Page 12: Figure S9. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 (open squares) and 11 (closed squares) in an aqueous solution (pH 11) with 35 mM DABCO in comparison with that by 10 + Et3N (closed circle).

Page 13: Figure S10. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 in an aqueous solution with 35 mM EDTA at pH 7.6 (closed circles), or 35 mM EDTA at pH 11 (open circles), or 1 mM EDTA at pH 11 (open triangles), or 35 mM Et3N at pH 11 (open squares).

Page 14: Figure S11. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 in an aqueous solution with 35 mM potassium oxalate at pH 7.6 (closed circles), or 35 mM potassium oxalate at pH 11 (open circles), or 35 mM Et3N at pH 11 (open squares).

Figure S1. Typical potentiometric pH titration curves for a solution of (a) 0.5 mM 11ox ((ZnL4)ox(H2O)), (b) 0.5 mM T[c,s]T (3), and (c) 0.5 mM 11ox ((ZnL4)ox(H2O)) + 0.5 mM T[c,s]T (3) in 10% MeCN aqueous solution with I = 0.1 (NaNO3) at 25˚C.

Figure S2. Distribution diagram for a mixture of 100 mM 11ox ((ZnL4)ox) and 400 mM T[c,s]T (3) in 10% MeCN aqueous solution with I = 0.1 (NaNO3) at 25˚C.

Figure S3. Cyclic voltammogram of (a) 0.3 mM 10ox (solid line) and (b) 0.3 mM 11ox (dashed line) on a glassy carbon disk in 0.1 M nBu4NClO4–CH3CN at a scan rate of 10 mV·s–1.

Figure S4. Change in UV-Vis absorption spectra (A) and fluorescence emission spectra (B) of 3-carboxymethyllumiflavin 16 during photoirradiation in the presence of 35 mM Et3N in an aqueous solution (pH 11) at 25°C: (a) spectra before UV irradiation, (b) after UV irradiation for 30 min, and (c) after reoxidation in air. Change in UV-Vis absorption spectra (C) and fluorescence emission spectra (D) of 16 during the photoirradiation in the presence of 35 mM DABCO in an aqueous solution (pH 11) at 25°C: (d) spectra before UV irradiation, (e) after UV irradiation for 30 min, and (f) after reoxidation in air. [16] = 50 mM. Irradiation wavelength was 365 nm.

Figure S5. Change in UV-Vis absorption spectra (A) and fluorescence emission spectra (B) of 3-carboxymethyllumiflavin 16 during photoirradiation in the presence of 35 mM potassium oxalate in an aqueous solution (pH 11) at 25°C: (a) spectra before UV irradiation, (b) after UV irradiation for 30 min, and (c) after reoxidation in air. Change in UV-Vis absorption spectra (C) and fluorescence emission spectra (D) of 16 during the photoirradiation in the presence of 35 mM EDTA in an aqueous solution (pH 11) at 25°C: (d) spectra before UV irradiation, (e) after UV irradiation for 30 min, and (f) after reoxidation in air. [16] = 50 mM. Irradiation wavelength was 365 nm.

Figure S6. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 3-carboxymethyllumiflavin 16 in an aqueous solution with 35 mM Et3N (closed circles), or 35 mM potassium oxalate (open circles), or 35 mM EDTA (open triangles), or 35 mM DABCO (open squares) in an aqueous solution at pH 11 (pH was adjusted with aqueous NaOH). [T[c,s]T] = 400 mM, [16] = 100 mM.

Figure S7. UV spectra of 10ox (a) before and (b) after UV irradiation for 10 min at pH 11 in the absence of Et3N at 25°C and UV spectra of 11ox (c) before and (d) after irradiation for 10 min and (e) after reoxidation in air. [10ox] = [11ox] = 50 mM.

Figure S8. Change in UV-Vis absorption spectra of 10ox upon addition of 1 mM EDTA in an aqueous solution (pH 11) at 25°C: spectra of (a) 10ox and (b) 10ox with 1 mM EDTA. [10ox] = 50 mM.

Figure S9. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 (open squares) and 11 (closed squares) in an aqueous solution (pH 11) with 35 mM DABCO in comparison with that by 10 + Et3N (closed circle).

Figure S10. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 in an aqueous solution with 35 mM EDTA at pH 7.6 (closed circles), or 35 mM EDTA at pH 11 (open circles), or 1 mM EDTA at pH 11 (open triangles), or 35 mM Et3N at pH 11 (open squares).

Figure S11. Reaction rates for photoreversion of T[c,s]T (3) at 20°C by 10 in an aqueous solution with 35 mM potassium oxalate at pH 7.6 (closed circles), or 35 mM potassium oxalate at pH 11 (open circles), or 35 mM Et3N at pH 11 (open squares).