Yamasaki et al_Supporting Information_JOC_revised

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1 Supporting Information Structure-Reactivity Relationship of Piperidine Nitroxide: Electrochemical, ESR and Computational Studies Toshihide Yamasaki a, Fumiya Mito a, Yuko Ito a, Sokkar Pandian b, Yuichi Kinoshita a, Koji Nakano c, Ramachandran Murugesan b,d, Kiyoshi Sakai e, Hideo Utsumi e, Ken-ichi Yamada a, * a Department of Bio-functional Science, Faculty of Pharmaceutical Sciences, Kyushu University, Higashi-ku, Maidashi, Fukuoka , Japan b School of Chemistry, Madurai Kamaraj University, Madurai , India c Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka , Japan d Networking Resource Center in Biological Sciences, Madurai Kamaraj University, Madurai , India e Innovation Center for Medical Redox Navigation, Kyushu University, Higashi-ku, Maidashi, Fukuoka , Japan toshihide@pch.phar.kyushu-u.ac.jp *Corresponding author: Ken-ichi Yamada Department of Bio-functional Science, Faculty of Pharmaceutical Sciences, Kyushu University, Higashi-ku, Maidashi, Fukuoka , Japan Phone: ; Fax: yamada@pch.phar.kyushu-u.ac.jp S1

2 Table of contents Figure S1. Figure S2. Figure S3. Figure S4. Figure S5. Figure S6. Figure S7. Figure S8. Figure S9. Figure S10. Figure S11. Figure S12. Figure S13. Figure S14. Figure S15. 1 H NMR spectrum of 10 S3 13 C NMR spectrum of 10 S4 1 H NMR spectrum of 11 S5 13 C NMR spectrum of 11 S6 1 H NMR spectrum of 12 S7 13 C NMR spectrum of 12 S8 1 H NMR spectrum of 13 S9 13 C NMR spectrum of 13 S10 1 H NMR spectrum of 14 S11 13 C NMR spectrum of 14 S12 1 H NMR spectrum of 15 S13 13 C NMR spectrum of 15 S14 1 H NMR spectrum of 17 S15 13 C NMR spectrum of 17 S16 Correlation between nitroxide SM-ascorbate HM energy gap and reduction rate of nitroxide radicals S17 TABLE S1. ESR parameters of nitroxides S18 TABLE S2. Calculated descriptors of the nitroxide radicals S19 quantum chemical coordinates and total energy of nitroxide S20~S33 S2

3 Figure S1. 1 H NMR spectrum of 10 (400 MHz, CDCl 3 ) N H S S3

4 Figure S2. 13 C NMR spectrum of 10 (75 MHz, CDCl 3 ) N H S S4

5 Figure S3. 1 H NMR spectrum of 11 (400 MHz, CDCl 3 ) N H S S5

6 Figure S4. 13 C NMR spectrum of 11 (75 MHz, CDCl 3 ) N H S S6

7 Figure S5. 1 H NMR spectrum of 12 (400 MHz, CDCl 3 ) N H S7

8 Figure S6. 13 C NMR spectrum of 12 (75 MHz, CDCl 3 ) N H S8

9 Figure S7. 1 H NMR spectrum of 13 (400 MHz, CDCl 3 ) N H S9

10 Figure S8. 13 C NMR spectrum of 13 (75 MHz, CDCl 3 ) N H S10

11 Figure S9. 1 H NMR spectrum of 14 (400 MHz, CDCl 3 ) N H N Ac S11

12 Figure S C NMR spectrum of 14 (75 MHz, CDCl 3 ) N H N Ac S12

13 Figure S11. 1 H NMR spectrum of 15 (300 MHz, CDCl 3 ) N H S 2 S13

14 Figure S C NMR spectrum of 15 (75 MHz, CDCl 3 ) N H S 2 S14

15 Figure S13. 1 H NMR spectrum of 17 (300 MHz, CDCl 3 ) N H S S15

16 Figure S C NMR spectrum of 17 (75 MHz, CDCl 3 ) N H S S16

17 Figure S15. Correlation between nitroxide SM-ascorbate HM energy gap and reduction rate of nitroxide radicals S17

18 TABLE S1. ESR parameters of nitroxides Nitroxide g-value ± ± ± ± ± ± a ± b ± a ± b ± c ± hfc (mt) ± ± ± ± ± ± ± ± ± ± ± Line width (µt) ± ± ± ± ± ± ± ± ± ± ±2.24 S18

19 TABLE S2. Calculated descriptors of the nitroxide radicals Nitroxide SM energy (au) SM- HM A Energy (au) Signal decay rate (min -1 ) Accessible surface area (Å 2 ) a b a b c *HM A is corresponding energy values for ascorbate. S19

20 nitroxide 1 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H H H C C H H H C H H C C C C C H H H N H C H H H TTAL ENERGY = nitroxide 2 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z S20

21 H C C H H H N H C C H H C H C H H C C H C C H H C H H H H H H H TTAL ENERGY = nitroxide 3 CRDINATES F ALL ATMS ARE (ANGS) S21

22 ATM CHARGE X Y Z H H H H H C H C H C C C N C H C H H C C H H C H C H H C H H C H H H H S22

23 H H H TTAL ENERGY = nitroxide 4 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H H H C C H H H C N C H C C H H C C C H H C H H H C C S23

24 H H C C C H H H H H H H TTAL ENERGY = nitroxide 5 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H H C C H H H H C H N C C C C S24

25 C H C H C C H H C H H H C H H C C C C H C C H H H H H H TTAL ENERGY = nitroxide 6 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H S25

26 H C H C H H H H C C H H N C C H C C H C H C H C H H H H C H C H H TTAL ENERGY = S26

27 nitroxide 7a CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H H H H C C H H H C H H N C C N C C C H C C H C H C C H N C C S27

28 H H C C H H H H H H H H H H TTAL ENERGY = nitroxide 7b CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H H H C C H H C H H C C H C C S28

29 C C H N H N H H C C C C H H H H H H H H TTAL ENERGY = nitroxide 8a CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H S H C H C H H S29

30 C H H C H C H C H N H C H C C C H C H H H H C H S C H H TTAL ENERGY = nitroxide 8b CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z S30

31 H S H C H C C H H H H C C C H C H H H C N H C C H H C H H H H TTAL ENERGY = nitroxide 8c S31

32 CRDINATES F ALL ATMS ARE (ANGS) ATM CHARGE X Y Z H H C H H H H C H C H H H H C H H C C C C N H C C H H S H C H H C S32

33 C H H H TTAL ENERGY = S33

Microsoft Word - molecules supple.docx

Microsoft Word - molecules supple.docx Supporting Information Secondary Metabolites from the Marine-Derived Fungus Dichotomomyces sp. L-8 and Their Cytotoxic Activity Li-Hong Huang 1,2, Yan-Xiu Chen 1,2, Jian-Chen Yu 3, Jie Yuan 3, Hou-Jin