Supporting Information. for. Self-assembly of chiral fluorescent nanoparticles. based on water-soluble L-tryptophan derivatives of p-

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1 Supporting Information for Self-assembly of chiral fluorescent nanoparticles based on water-soluble L-tryptophan derivatives of p- tert-butylthiacalix[4]arene Pavel L. Padnya 1,2, Irina A. Khripunova 1, Olga A. Mostovaya 1, Timur A. Mukhametzyanov 1, Vladimir G. Evtugyn 1, Vyacheslav V. Vorobev 1, Yuri N. Osin 1 and Ivan I. Stoikov *1 Address: 1 Kazan Federal University, Kremlevskaya, 18, Kazan, Russian Federation and 2 Peoples Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow, Russian Federation Ivan I. Stoikov - Ivan.Stoikov@mail.ru * Corresponding author Additional experimental parameters and results S1

2 Figure S1: 1 H NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-8), DMSO-d 6, 298 K, 400 MHz S2

3 Figure S2: 1 H NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-9), DMSO-d 6, 298 K, 400 MHz. S3

4 Figure S3: 1 H NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-10), DMSO-d 6, 298 K, 400 MHz. S4

5 Figure S4: 1 H NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-11), DMSO-d 6, 298 K, 400 MHz. S5

6 Figure S5: 13 C NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-8), DMSO-d 6, 298 K, 100 MHz. S6

7 Figure S6: 13 C NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-9), DMSO-d 6, 298 K, 100 MHz. S7

8 Figure S7: 13 C NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-10), DMSO-d 6, 298 K, 100 MHz. S8

9 Figure S8: 13 C NMR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-11), DMSO-d 6, 298 K, 100 MHz. S9

10 Figure S9: Mass spectrum (ESI) of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-8). S10

11 Figure S10: Mass spectrum (ESI) of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-9). S11

12 Figure S11: Mass spectrum (ESI) of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-10). S12

13 Figure S12: Mass spectrum (ESI) of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-11). S13

14 A 1,3 1670,30cm-1; 1,25A 1,2 1,1 1,0 0,9 2959,03cm-1; 0,88A 0,8 0,7 3199,13cm-1; 0,78A 2867,1 1735,70cm-1; 0,65A 1542,38cm-1; 0,75A 1440,51cm-1; 0,72A 1457,65cm-1; 0,70A 1213,90cm-1; 0,62A 0,6 3046,67cm-1; 0,57A 1268,84cm-1; 0,55A 0,5 1095,10cm-1; 0,50A 0,4 1342,84cm-1; 0,39A 1363,39cm-1; 0,38A 1394,54cm-1; 0,36A 1022,66cm-1; 0,42A 740,55cm-1; 0,40A 0,3 0,2 0,1 2166,24cm-1; 0,11A 895,26cm-1; 0,11A 876,50cm-1; 0,12A 558,56cm-1; 0,11A -0,0-0, cm-1 Имя HR-9_1_1_1 Описание Sample 018 By Administrator Date среда, марта Figure S13: IR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-8). S14

15 A 1,3 1675,47cm-1; 1,26A 1,2 1,1 1,0 0,9 2960,36cm-1; 0,90A 0,8 3206,58cm-1; 0,83A 1535,75cm-1; 0,80A 0, ,82cm-1; 0,71A 1425,26cm-1; 0,69A 1442,25cm-1; 0,69A 1458,12cm-1; 0,67A 0,6 3043,27cm-1; 0,62A 1215,68cm-1; 0,61A ,77cm-1; 0,55A 0,5 0,4 1342,68cm-1; 0,42A 1377,23cm-1; 0,41A 1023,59cm-1; 0,44A 1094,96cm-1; 0,39A 744,01cm-1; 0,37A 0,3 0,2 0,1 881,58cm-1; 0,11A 831,28cm-1; 0,06A -0,0-0, cm-1 Имя HR-14_1_1_1 Описание Sample 019 By Administrator Date среда, марта Figure S14: IR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(3,3 -dimethyl-3 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumpropyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-9). S15

16 A 1,3 1675,64cm-1; 1,26A 1,2 1,1 1,0 0,9 2960,48cm-1; 0,88A 0,8 3186,81cm-1; 0,75A 1535,10cm-1; 0,68A 0,7 3310,8 1735,04cm-1; 0,66A 1442,77cm-1; 0,72A 0,6 3043,34cm-1; 0,56A ,09cm-1; 0,59A 1267,82cm-1; 0,52A 0,5 0,4 1361,50cm-1; 0,39A 1394,80cm-1; 0,42A 1342,59cm-1; 0,40A 1094,45cm-1; 0,46A 1023,06cm-1; 0,43A 741,59cm-1; 0,36A 0,3 0,2 0,1 876,46cm-1; 0,09A 811,50cm-1; 0,06A -0,0-0, cm-1 Имя HR-17_1_1_1 Описание Sample 001 By Administrator Date среда, марта Figure S15: IR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (cone-10). S16

17 A 1,3 1675,70cm-1; 1,26A 1,2 1,1 1,0 0,9 2960,45cm-1; 0,83A 0,8 0,7 3186,82cm-1; 0,76A 2870,7 1532,53cm-1; 0,72A 1456,90cm-1; 0,66A 1734,99cm-1; 0,69A 1442,07cm-1; 0,68A 1425,16cm-1; 0,67A 1213,24cm-1; 0,64A 0,6 3037,26cm-1; 0,56A 1265,45cm-1; 0,54A 0,5 0,4 1376,76cm-1; 0,39A 1342,86cm-1; 0,42A 1394,56cm-1; 0,39A 1019,34cm-1; 0,44A 1092,91cm-1; 0,40A 742,77cm-1; 0,40A 0,3 0,2 0,1 2250,11cm-1; 0,13A 810,67cm-1; 0,06A 878,36cm-1; 0,07A -0,0-0, cm-1 Имя HR-18_1_1_1 Описание Sample 002 By Administrator Date среда, марта Figure S16: IR spectrum of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(N-(2,2 -diethyl-2 -{(ethoxycarbonyl[s-(1 H-indol-3 - yl)methyl]methyl)amidocarbonylmethyl}ammoniumethyl)carbamoylmethoxy]-2,8,14,20-tetra thiacalix[4]arene tetrabromide (1,3-alternate-11). S17

18 Figure S17: Size distribution by intensity of solution of the macrocycle 8 in the water ( М). S18

19 Figure S18: Size distribution by intensity of solution of the macrocycle 9 in the water ( М). S19

20 Figure S19: Size distribution by intensity of solution of the macrocycle 10 in the water ( М). S20

21 Figure S20: Size distribution by intensity of solution of the macrocycle 11 in the water ( М). S21

22 Figure S21: Zeta potential of solution of the macrocycle 8 in the water ( М). S22

23 Figure S22: Zeta potential of solution of the macrocycle 9 in the water ( М). S23

24 Figure S23: Zeta potential of solution of the macrocycle 10 in the water ( М). S24

25 Figure S24: Zeta potential of solution of the macrocycle 11 in the water ( М). S25

26 Figure S25: TEM image of self-associates based on thiacalix[4]arene cone-8 in water ( М). Scale bar 200 nm. S26

27 Figure S26: TEM image of self-associates based on thiacalix[4]arene 1,3-alternate-9 in water ( М). Scale bar 5 µm. S27

28 Figure S27: TEM image of self-associates based on thiacalix[4]arene cone-10 in water ( М). Scale bar 200 nm. S28

29 Figure S28: TEM image of self-associates based on thiacalix[4]arene 1,3-alternate-11 in water ( М). Scale bar 2 µm. S29

30 Figure S29: A) Fluorescence spectra of compound 2 in water and methanol ( М), B) UV spectrum of compound 2 in water ( М). S30

31 g-factor g-factor 0, in water 0, in water 0, in water 0, in water 0, in water 0, , ,0002-0,0003-0,0004 Wavelength (nm) 0, in methanol 0, in methanol 0, in methanol 0, in methanol 0, in methanol 0, , ,0002 Wavelength (nm) Figure S30: g-factors of compounds 2 and 8 11 in water and methanol ( М). The optical activity of chiral systems is quantified using the anisotropy factor (g-factor) [1,2]: g = Δε /ε where Δε and ε are the molar circular dichroism and molar extinction coefficient, respectively. References 1. Yan, W.; Xu, L.; Xu, C.; Ma, W.; Kuang, H.; Wang, L.; Kotov, N. A. J. Am. Chem. Soc., 2012, 134, Cheng, J.; Le Saux, G.; Gao, J.; Buffeteau, T.; Battie, Y.; Barois, P.; Ponsinet, V.; Delville, M.-H.; Ersen, O.; Pouget, E.; Oda, R. ACS Nano, 2017, 11, S31

Supporting information. Design, Synthesis, and Cancer Cell Growth Inhibitory Activity of Triphenylphosphonium Derivatives of the Triterpenoid Betulin

Supporting information. Design, Synthesis, and Cancer Cell Growth Inhibitory Activity of Triphenylphosphonium Derivatives of the Triterpenoid Betulin Supporting information Design, Synthesis, and Cancer Cell Growth Inhibitory Activity of Triphenylphosphonium Derivatives of the Triterpenoid Betulin Olga V. Tsepaeva, Andrey V. Nemtarev, Timur I. Abdullin,