Supporting information for Design of NIR Chromenylium-Cyanine Fluorophore Library for Switch-ON and Ratiometric Detection of Bio-Active Species in Vivo Yanfen Wei, Dan Cheng, Tianbing Ren, Yinhui Li, Zebing Zeng, Lin Yuan* State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 4182 (PR China) * To whom correspondence should be addressed: E-mail: lyuan@hnu.edu.cn S1
Table of content 1. Supplemental Tables S1-3 S3-9 2. Supplemental Figures S9-23 S9-19 3. Synthesis and Characterization S19-26 4. Supplemental NMR Spectra S26-36 S2
DAD1 A, Sig=254,16 Ref=off (YL\BSR III 5 OH.D) DAD1 B, Sig=35,16 Ref=off (YL\BSR III 5 OH.D) DAD1 C, Sig=5,16 Ref=off (YL\BSR III 5 OH.D) DAD1 D, Sig=55,16 Ref=off (YL\BSR III 5 OH.D) 1-1 2 1 5 5 75 25 DAD1 B, Sig=35,16 Ref=off (YL\NIR33.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR33.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR33.D) DAD1 E, Sig=65,16 Ref=off (YL\NIR33.D) 1. Supplemental Tables Table S1. Representative HPLC-MS dates of CC1-36. Compd Structure HPLC MS CC1 :\CHEM32\1\DATA\SNAPSHOT.D ES-API, Pos, Scan 519.2 518.2 517.2 Max: 8.388 CC13 3 4 5 6 476.4 477.4 478.4 413.2 49.7 318.4 391.2 424.3 529.4 569. 629.5 35 4 45 5 55 6 m/z S3
25 2-1 5 5 1 5 1 5 5 25 2 1 DAD1 A, Sig=254,16 Ref=off (YL\NIR 29.D) DAD1 B, Sig=35,16 Ref=off (YL\NIR 29.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR 29.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR 29.D) DAD1 E, Sig=65,16 Ref=off (YL\NIR 29.D) 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 8 9 CC14 HO O COOH N 1 8 6 4 *MSD2 SPC, time=5.728 of D:\CHEM32\1 12.2 463. 462. 2 464. 25 5 CC15 N O COOH N 1 8 6 4 2 *MSD2 SPC, time=6.343 of D:\CHEM32\1\DATA\SNAPSHOT.D ES-API, Pos, Scan 117.1 543.2 542.2 541.3 25 5 75 S4
5 5 2 1 DAD1 A, Sig=254,16 Ref=off (YL\XIAOJI-H2O2-2.D) DAD1 B, Sig=35,16 Ref=off (YL\XIAOJI-H2O2-2.D) DAD1 C, Sig=5,16 Ref=off (YL\XIAOJI-H2O2-2.D) DAD1 D, Sig=55,16 Ref=off (YL\XIAOJI-H2O2-2.D) 1 1 5 4 2 2 CC17 *MSD2 SPC, time=5.834 of D:\CHEM32\1\DATA 1 8 6 4 2 56.2 55.2 54.2 2 4 6 CC19 573.5 575.4 46.4 558.7 595.4 385.3 631.3 685.4 432.5 515. 717.6 4 5 6 7 m/z S5
2 25-1 -1 2 2 1 5 2 DAD1 A, Sig=254,16 Ref=off (YL\NIR14.D) DAD1 B, Sig=35,16 Ref=off (YL\NIR14.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR14.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR14.D) DAD1 E, Sig=76,16 Ref=off (YL\NIR14.D) DAD1 A, Sig=254,16 Ref=off (YL\NIR15-PTLC.D) DAD1 B, Sig=35,16 Ref=off (YL\NIR15-PTLC.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR15-PTLC.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR15-PTLC.D) CC2 1 8 6 4 *MSD2 SPC, time=5.728 of D:\CHEM32\1\DATA\YL\NIR 29.D ES-API, Pos, Scan, Frag: 12.2 463. 462. 2 464. CC21 25 5 75 *MSD2 SPC, time=6.47 of D:\CHEM32\1\DATA\YL\NIR15-PTLC.D ES-API, Pos, Scan, Frag 521.2 52.2 519.2 45 5 S6
1-1 -1 5 25 1 DAD1 B, Sig=35,16 Ref=off (YL\NIR34.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR34.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR34.D) DAD1 E, Sig=65,16 Ref=off (YL\NIR34.D) 1 1 25 5 DAD1 A, Sig=254,16 Ref=off (YL\CREV3-DTT-21.D) DAD1 B, Sig=35,16 Ref=off (YL\CREV3-DTT-21.D) DAD1 C, Sig=5,16 Ref=off (YL\CREV3-DTT-21.D) DAD1 D, Sig=55,16 Ref=off (YL\CREV3-DTT-21.D) DAD1 E, Sig=65,16 Ref=off (YL\CREV3-DTT-21.D) CC33 1 8 6 4 2 *MSD2 SPC, time=5.568 of D:\CHEM32\1\DATA 492. 491. 49. 25 5 75 CC35 *MSD2 SPC, time=8.644 of D:\CHEM32\1\DATA\YL\CREV3-DTT-2.D ES-API, Pos, Scan 1 8 6 4 2 239.1 32.2 592. 591. 59. 25 5 75 S7
1 DAD1 A, Sig=254,16 Ref=off (YL\NIR-S-XIA-HG.D) DAD1 B, Sig=35,16 Ref=off (YL\NIR-S-XIA-HG.D) DAD1 C, Sig=5,16 Ref=off (YL\NIR-S-XIA-HG.D) DAD1 D, Sig=55,16 Ref=off (YL\NIR-S-XIA-HG.D) DAD1 E, Sig=65,16 Ref=off (YL\NIR-S-XIA-HG.D) CC36 1 8 6 4 2 *MSD2 SPC, time=5.969 of D:\CHEM32\1\D 558. 557. 556. 4 6 8 Table S2. Photo-physical properties of CC19-29 in EtOH. Compd n λ abs λ em Stokes Φ shift CC19 2 688 724 36.21 CC1 1.5 698 729 31.41 CC2 1 75 739 34.27 CC21 674 74 3.1 CC1 1.5 627 677 5.32 CC22 1 64 685 45.41 CC23 62 66 4.56 CC2 1.5 621 671 5.24 CC24 1 637 684 47.44 CC25 615 658 43.58 CC4 1.5 615 678 63.2 CC26 1 641 696 55.2 CC27 637 675 38.46 CC6 1.5 618 676 58.3 CC28 1 646 69 44.6 CC29 625 668 43.48 S8
Table S3. Representative NIR fluorescent probes for Hg 2+ fluorophore platforms for fluorescence imaging. Probe λ ab /λ em (nm) R1 63/69 5 B2 37/65 SiR-H g IR-89 7 5 664/68 672 /69 Em: 78/83 CC35 67/7 2 Medium Tris HCl/CH 3 CN (1 mm, ph 7.4, 1 : 1, v/v) CH 3 CN HEPE S buffer solution (1 mm, ph 7.4, 1 : 1, v/v) HEPES buffer solution at ph 7.4 MeCN H 2 O (4:1, v/v; ph = 7.2) Methanol/water (8:2) PBS buffer (5 mm, ph 7.4, containing 2% CH 3 OH) Ratiometri c 3-fold fluorescen ce enhancem ent Fluorescen ce enhancem ent Detection limit 28 nm (S/N = 3) 15 nm (S/N = 3) Imaging application based on organic Ref. HeLa cells Analyst, 213, HeLa cells -- SH-SY5Y cells Quenching 5 µm SMMC-772 Ratiometri c (I 78 nm/i 83 nm ) 15-fold fluorescen ce enhancem ent --( nanomol ar level) 1 cells 1 nm Mouse 138, 2654. J. Mater. Chem., 212, 22, 11475. Chem. Commun., 212, 48, 8781. Chem. Lett. 215, doi:1.1246/cl.1 524 -- Chem. Eur. J. model 21, 16, 14424 This Work S9
2. Supplemental Figures Figure S1. (A) Absorption spectra of compound 1 in water (ph 1) for -12 hours. (B) HPLC chromatograms of dye 1 in water (ph 1) for (a), 2 hours (b) and 12 hours (c). The samples were analyzed by HPLC with linear gradient elution (eluent A (H 2 O)/B(CH 3 CN)) 5/5, 1, /1; flow rate 1. ml/). The monitored wavelength was 55 nm. (C) The proposed fade mechanism of dye 1 in water and the mass spectra of 1-OH adduct. (D) Absorption spectra of compound CC17 in water (ph 1) for and 12 hours. (E) HPLC chromatograms of dye CC17 in water (ph 1) for (top), and 12 hours (bottom). S1
Normalized absorbance CC2 CC1 a) Normalized intensity CC2 CC1 b) 3 4 5 6 7 8 7 8 Figure S2. Normalized absorption (a) and emission (b) spectra of CC1 ( ) and CC2 ( ). 12 a).2 b) 8 4 Absorbance.1 64 66 68 7 72 74. 4 45 5 55 6 65 7 75 Figure S3. Emission (a) and absorption (b) spectra of CC2 in ph 4 to 1 in water (5% DMF as co-solvent). Figure S4. DFT optimized structure and molecular orbital plots (LUMO and HOMO) of CC 2. S11
1 8 6 4 2 CC2 CC3 65 7 75 8 Figure S5. Emission spectra of CC3 ( ) and CC2 ( ). a) Normalized absorbance CC16 CC17 CC1 CC18 b) Normalized intensity CC16 CC17 CC1 CC18 4 5 6 7 8 7 8 Figure S6. Normalized absorption (a) and emission (b) spectra of CC16-18 and CC1. Figure S7. DFT optimized structure (including dihedral angle between chromenylium and indole moieties), molecular orbital plots (LUMO and HOMO) and HOMO/ LUMO energy gaps of CC19-21 and CC1. S12
COOH HO O CC14 N 35 3 25 2 15 1 5 3 225 15 75 1 ph 62 64 66 68 7 72 74 Figure S8. Fluorescence emission spectra of CC14 in buffer solution with ph changing from 1. to 9.. Inset: ph plot of normalized emission intensities at 655 nm for CC14. Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent. 8 8 6 4 2 6 4 2 1 64 68 72 76 Figure S9. Fluorescence emission spectra of CC3 in buffer solution with ph changing from 1. to 1.. Inset: ph plot of normalized emission intensities at 65 nm for CC3. Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent. S13
5 4 3 2 1 a) 5 4 3 2 1 2 3 4 5 ph 8 6 4 2 b) 7 6 5 4 4 5 6 7 8 9 1 ph 625 65 675 7 725 75 65 7 75 Figure S1. Fluorescence emission spectra of CC31 in buffer solution with ph changing from 1. to 5. (a) and 4. to 1. (b). Inset: ph plot of normalized emission intensities at 645 nm (a) or 656 nm (b). Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent. 3 25 2 15 1 5 a) 3 25 2 15 1 2 3 4 5 ph 4 3 2 1 b) 4 35 3 25 4 5 6 7 8 9 1 65 7 75 65 7 75 Figure S11. Fluorescence emission spectra of CC32 in buffer solution with ph changing from 1. to 5. (a) and 4. to 1. (b). Inset: ph plot of normalized emission intensities at 637 nm (a) or 648 nm (b). Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent. S14
COOH COO COO HO O -H H + HO O -H H + O O N N N Figure S12. Estimated chemical equilibrium of CC31 in different ph. COOH HO O CC17 N.5 a) 25 b).4 2 Absorbance.3.2.1 15 1 5. 5 55 6 65 7 75 7 72 74 76 78 Figure S13. Absorption (a) and fluorescence emission (b) spectra of CC17 (λ ex = 67 nm) in buffer solution with ph changing from 4. to 9.. Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent..36 a) 4 b) Absorbance.27.18.9 3 2 1. 4 5 6 7 8 72 74 76 78 Figure S14. Absorption (a) and fluorescence emission (b) spectra of CC33 (λ ex = 68 nm) in buffer solution with ph changing from 4. to 9.. Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent. S15
.15 a) 6 b) Absorbance.1.5 5 4 3 2 1. 5 55 6 65 7 75 7 72 74 76 78 Figure S15. Absorption (a) and fluorescence emission (b) spectra of CC34 (λ ex = 67 nm) in buffer solution with ph changing from 4. to 9.. Measurements were made in 5 mm sodium phosphate buffer at various ph values in the presence of 5% DMF as a cosolvent..4.3 Absorbance.2.1. 3 4 5 6 7 8 Figure S16. Absorption spectra of compound CC33 (5µM) in presence of intracellular nucleophilic reagent H 2 S (5 equiv.) in water (ph 1) for to 3 hours. Figure S17. Representative fluorescence images of mice injected with CC33 in vivo. (a-b) PBS (ph 5) was injected in the peritoneal cavity of mouse, followed by injection of CC33 (6 µm). (c-d) PBS (ph 8) was injected into the peritoneal cavity of the mouse, followed by injection of CC33 (6 µm). The mice were imaged with two emission channels of Channel 1 (65 nm, a, c) and Channel 2 (72 nm, b, d). S16
.12 Absorbance.8.4. 4 45 5 55 6 65 7 75 8 Figure S18. Absorption spectra of NIR fluorescent probe CC35 in the presence of various concentrations of Hg 2+ ( 1 µm) in PBS buffer (5 mm, ph 7.4, containing 2% DMF). a) 1 DAD1 A, Sig=254,16 Ref=off (YL\CREV3-DTT-21.D) DAD1 B, Sig=35,16 Ref=off (YL\CREV3-DTT-21.D) 1 DAD1 C, Sig=5,16 Ref=off (YL\CREV3-DTT-21.D) 25 DAD1 D, Sig=55,16 Ref=off (YL\CREV3-DTT-21.D) 8.4 b) DAD1 E, Sig=65,16 Ref=off (YL\CREV3-DTT-21.D) 5 MSD1 TIC, MS File (D:\CHEM32\1\DATA\YL\CREV3-DTT-21.D) ES-API, Neg, Scan, Frag: 7 DAD1 A, Sig=254,16 Ref=off (YL\NIR-S-XIA-HG.D) 75 5 25 MSD2 TIC, MS File (D:\CHEM32\1\DATA\YL\CREV3-DTT-21.D) ES-API, Pos, Scan, Frag: 7 DAD1 B, Sig=35,16 Ref=off (YL\NIR-S-XIA-HG.D) 4 1 2 DAD1 C, Sig=5,16 Ref=off (YL\NIR-S-XIA-HG.D) 5.9 DAD1 D, Sig=55,16 Ref=off (YL\NIR-S-XIA-HG.D) DAD1 E, Sig=65,16 Ref=off (YL\NIR-S-XIA-HG.D) Figure S19. Reversed-phase HPLC with absorption (254, 35, 5, 55 and 65 nm) detection. a) Reversed-phase HPLC of 5 µm CC35. b) Reversed-phase HPLC of 5 µm CC35 in the presence of 1 µm Hg 2+ for 1. The ring-opened fluorescent dye CC36 was confirmed by Liquid chromatography mass spectrometry (LC-MS) (Figure S2). S17
*MSD2 SPC, time=5.969 of D:\CHEM32\1\DATA\YL\NIR-S-XIA-HG.D ES-API, Pos, Scan, Frag: 7 1 8 6 4 2 558. 557. 556. Max: 2.93376e+6 4 6 8 1 12 Figure S2. The mass spectrometry of 5 µm CC35 in the presence of 1 µm Hg 2+ for 1. m/z 6 45 3 15 Y = -11.773 + 15.61 * X r =.998 1 2 3 4 [Hg 2+ ], µμ Figure S21. The fluorescence response of CC35 (5 µm) to Hg 2+ (.1 µm - 4 µm) in PBS buffer (5 mm, ph 7.4, containing 2% DMF) with excitation at 67 nm. S18
2 1 2 4 6 8 1 [Hg 2+ ], nm Figure S22. The fluorescence response of CC35 (1 µm) to Hg 2+ (5 nm - 95 nm) in PBS buffer (5 mm, ph 7.4, containing 2% DMF) with excitation at 67 nm. 1 Cell Viability (%) 8 6 4 2 a b c d e f g Concentration, µm Figure S23. Cytotoxic effect of CC35. MCF-7 cells were incubated with each concentration (a: ; b: 1 µm; c: 3 µm; d: 5 µm; e: 7 µm; f: 1 µm; g: 15 µm) of probes for 24 h. Cell viability was assayed with MTT test. Results are expressed as mean ± standard deviation of three independent experiments. 3. Synthesis and Characterization Synthesis of CC1-34: CC8, CC1, CC12, and CC18 were synthesized according to reported procedure (J. Am. Chem. Soc. 212, 134, 12; Biomaterials 215, 56, 1-9). Other compounds (CC1-34) were synthesized according to following procedure: A mixture of 4-(2-carboxyphenyl)-chromenylium derivatives (.22 mmol) and aldehyde (.24 mmol) was dissolved in ethanoyl ethanoate and then heated to 5 o C for 3 to 5 hours until starting materials disappearing. After cooling, water (2 S19
ml) was added to the mixture and the solvent was removed under reduced pressure. The resulting residue was purified by column chromatography on silica gel (CH 2 Cl 2 to CH 2 Cl 2 /acetone = 1: 1) to afford the compound CC1-CC34 as a solid. CC1: Yield: 63%. 1 H NMR (4 MHz, d 6 -DMSO) δ 8.37 (s, 1H), 8.21 8.8 (m, 3H), 7.85 (t, J = 7.4 Hz, 1H), 7.74 (t, J = 7.6 Hz, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.42 7.31 (m, 3H), 7.25 (s, 1H), 6.99 (s, 1H), 6.78 (d, J = 9. Hz, 1H), 3.95 (s, 3H), 3.59 (q, J = 6.9 Hz, 4H), 2.83 (2H), 2.19 (2H), 1.79 (2H), 1.21 (t, J = 6.9 Hz, 6H). 13 C NMR (1 MHz, d 6 -DMSO) δ 167.75, 159.86, 15.54, 137.5, 133.99, 13.46, 128.52, 123.54, 121.51, 119.66, 112.88, 111.1, 1.12, 99.85, 96.6, 45.14, 33.85, 28.3, 25.4, 21.11, 13.1. HRMS (m/z): [M] + calcd for [C 34 H 33 N 2 O 3 ] + 517.2486, found 517.2478. CC2: Yield: 57%. 1 H NMR (4 MHz, MeOD) δ 8.61 (s, 1H), 8.19 (d, J = 7.2 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 7.95 (s, 1H), 7.71 7.66 (2H), 7.47 (d, J = 6.5 Hz, 1H), 7.31 7.27 (2H), 7.23 (d, J = 4.3 Hz, 2H), 7.9 (s, 2H), 3.68 (q, J = 6.9 Hz, 4H), 2.92 (2H), 2.3 (2H), 1.92 (2H), 1.32 (t, J = 6.9 Hz, 6H). HRMS (m/z): [M] + calcd for [C 33 H 31 N 2 O 3 ] + 53.2329, found 53.2318. CC3: Yield: 53%. 1 H NMR (4 MHz, CDCl 3 ) δ 8.45 (d, J = 7.3 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 7.8 (d, J = 7.4 Hz, 1H), 7.65 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.46 (s, 2H), 7.44 7.38 (m, 2H), 7.24 (d, J = 7.7 Hz, 1H), 6.52 (d, J = 8.9 Hz, 1H), 6.47 (s, 1H), 6.38 (d, J = 8.7 Hz, 1H), 3.38 (q, J = 7. Hz, 4H), 2.69 (s, 3H), 2.9 (t, J = 6.4 Hz, 2H), 1.73 1.68 (2H), 1.43 (2H), 1.19 (t, J = 7. Hz, 6H). HRMS (m/z): [M] + calcd for [C 35 H 33 N 2 O 4 ] + 545.2435, found 545.2419. CC4: Yield: 49%. 1 H NMR (4 MHz, MeOD) δ 8.38 (s, 1H), 8.26 (d, J = 7.7 Hz, 1H), 7.77 (t, J = 7.4 Hz, 1H), 7.73 7.66 (m, 4H), 7.56 7.46 (m, 4H), 7.3 7.24 (m, 2H), 7.21 (d, J = 7.5 Hz, 1H), 7.14 (d, J = 9.6 Hz, 1H), 7.7 (d, J = 9.5 Hz, 1H), 7.1 (s, 1H), 3.62 (q, J = 6.9 Hz, 4H), 2.63 (t, J = 5.6 Hz, 2H), 2.41 (t, J = 5.6 Hz, 2H), 1.73-1.69 (2H), 1.26 (t, J = 6.9 Hz, 6H). 13 C NMR (1 MHz, MeOD) δ 163.2, 162.82, 158.3, 155.6, 142.1, 137.5, 134.84, 133.38, 132.29, 132.16, 13.83, 129.66, 129.56, 128.73, 128.63, 128.46, 127.31, 125.84, 122.94, 122.58, 121.48, 12.71, 12.26, 116.66, 116.49, 113.29, 111.64, 11.53, 95.9, 45.34, 29.35, 26.12, 22.33, 21.51, 11.38. HRMS (m/z): [M] + calcd for [C 39 H 35 N 2 O 3 ] + 579.2642, found S2
579.2633. CC5: Yield: 51%. 1 H NMR (4 MHz, CDCl 3 ) δ 8.4 (s, 1H), 8.22 (d, J = 5.9 Hz, 1H), 7.78 (s, 1H), 7.65 (t, J = 7. Hz, 1H), 7.53 (2H), 7.11 (d, J = 8.6 Hz, 1H), 7.6 (2H), 6.93 (d, J = 8.6 Hz, 1H), 6.8 (d, J = 8.9 Hz, 1H), 6.74 (d, J = 8.5 Hz, 1H), 4.2 (s, 3H), 3.59 (7H), 2.78 (2H), 2.37 2.14 (2H), 1.75 (2H), 1.29 (t, J = 6.9 Hz, 6H). HRMS (m/z): [M] + calcd for [C 35 H 35 N 2 O 4 ] + 547.2591, found 547.2578. CC6: Yield: 55%. 1 H NMR (4 MHz, MeOD) δ 8.42 (s, 1H), 8.28 (d, J = 7.8 Hz, 1H), 7.8 (t, J = 7.4 Hz, 1H), 7.71 (t, J = 7.5 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 7.35 (d, J = 7.3 Hz, 1H), 7.3 (d, J = 7.5 Hz, 1H), 7.15 (q, J = 7.3 Hz, 3H), 7.12 7.8 (m, 1H), 7.3 (d, J = 9.5 Hz, 1H), 3.65 (q, J = 6.9 Hz, 4H), 2.82 (t, J = 5.5 Hz, 2H), 2.61 (s, 3H), 2.44 (t, J = 6.4 Hz, 2H), 1.8 1.7 (m, 2H), 1.28 (t, J = 6.9 Hz, 6H). HRMS (m/z): [M] + calcd for [C 34 H 33 N 2 O 3 ] + 517.2486, found 517.2469. CC7: Yield: 48%. 1 H NMR (4 MHz, MeOD) δ 8.22 (d, J = 7.6 Hz, 1H), 8.17 (s, 1H), 7.7 7.76 (2H), 7.66 (d, J = 8.9 Hz, 2H), 7.24 (d, J = 7.4 Hz, 1H), 7.14 (s, 1H), 7.4 7.11 (2H), 6.84 (d, J = 8.7 Hz, 2H), 3.66 (q, J = 7. Hz, 4H), 3.1 (s, 6H), 2.99 (t, J = 6.8 Hz, 2H), 2.42(t, J = 4.4 Hz, 2H), 1.88 1.8 (m, 2H), 1.29 (t, J = 7. Hz, 6H). MS (ESI): m/z = 57.3 [M]+. HRMS (m/z): [M] + calcd for [C 33 H 35 N 2 O 3 ] + 57.2642, found 57.2629. CC9: Yield: 47%. 1 H NMR (4 MHz, CDCl 3 ) δ 8.23 (d, J = 7.8 Hz, 1H), 7.99 (s, 1H), 7.66 (t, J = 7.4 Hz, 1H), 7.58 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 7.4 Hz, 1H), 7.1 (d, J = 1.9 Hz, 1H), 6.97 (s, 1H), 6.86 (d, J = 9.4 Hz, 1H), 6.75 (dd, J = 9.4, 2. Hz, 1H), 6.7 (d, J = 3.9 Hz, 1H), 6.34 6.29 (m, 1H), 3.96 (s, 3H), 3.58 (q, J = 7.1 Hz, 4H), 2.78 (t, J = 4.9 Hz, 2H), 2.2 (t, J = 7.6 Hz, 2H), 1.85 1.71 (m, 2H), 1.27 (t, J = 7.1 Hz, 6H). MS (ESI): m/z = 467.2 [M]+. HRMS (m/z): [M] + calcd for [C 3 H 31 N 2 O 3 ] + 467.2329, found 467.2335. CC11: Yield: 5%. 1 H NMR (4 MHz, MeOD) δ 8.69 (s, 1H), 8.3 (d, J = 7.7 Hz, 1H), 8.19 (d, J = 7.5 Hz, 1H), 8.12 (s, 1H), 7.82 (t, J = 7.2 Hz, 1H), 7.77 7.71 (1H), 7.47 (d, J = 7.5 Hz, 1H), 7.38 7.21 (m, 9H), 7.12 (d, J = 9.4 Hz, 1H), 7.3 (d, J = 9.4 Hz, 1H), 5.56 (s, 2H), 3.7 (q, J = 13.8, 6.9 Hz, 4H), 2.94 (t, J = 5.7 Hz, 2H), 2.44 (t, J = 4.8 Hz, 2H), 2.6 2.2 (m, 2H), 1.33 (t, J = 6.9 Hz, 6H). HRMS (m/z): [M] + S21
calcd for [C 4 H 37 N 2 O 3 ] + 593.2799, found 593.2783. CC13: Yield: 63%. 1 H NMR (4 MHz, CDCl 3 ) δ 7.97 (d, J = 7.3 Hz, 1H), 7.89 (d, J = 7.6 Hz, 1H), 7.72 (1H), 7.7 (d, J = 7.6 Hz, 1H), 7.62 (s, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.53 (1H), 7.37 (t, J = 7.5 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.22 (1H), 6.82 (s, 1H), 6.61 (s, 2H), 3.87 (s, 3H), 3.85 (s, 3H), 2.85 (t, 2H), 2.68 (t, 2H), 2.25 2.17 (m, 2H). HRMS (m/z): [M] + calcd for [C 31 H 26 NO 4 ] + 476.1856, found 476.1848. CC14: Yield: 32%. 1 H NMR (4 MHz, MeOD) δ 8.47 (s, 1H), 8.15 (d, J = 6.5 Hz, 1H), 7.9 (d, J = 7.1 Hz, 1H), 7.83 (s, 1H), 7.59 (d, J = 7. Hz, 1H), 7.54 (d, J = 7.5 Hz, 1H), 7.4 (d, J = 7.6 Hz, 1H), 7.33 7.27 (2H), 7.6 (2H), 6.94 (d, J = 8.8 Hz, 1H), 6.77 (d, J = 8.9 Hz, 1H), 3.87 (s, 3H), 2.81 (s, 2H), 2.44 2.36 (m, 2H), 1.84 (s, 2H). HRMS (m/z): [M] + calcd for [C 3 H 24 NO 4 ] + 472. 17, found 462. 1716. CC15: Yield: 5%. 1 H NMR (4 MHz, CDCl 3 ) δ 8.26 (d, J = 4.4 Hz, 1H), 8.13 (s, 1H), 7.78 (d, J = 7.1 Hz, 1H), 7.62 (s, 1H), 7.52 (2H), 7.35 (3H), 6.97 (d, J = 6.7 Hz, 1H), 6.5 (s, 1H), 3.9 (s, 3H), 3.44 (d, J = 23.5 Hz, 4H), 3.7 (2H), 2.8 (2H), 2.6 (2H), 2.13 (8H). HRMS (m/z): [M] + calcd for [C 36 H 33 N 2 O 3 ] + 541.2486, found 541.2468. CC16: Yield: 56%. 1 H NMR (4 MHz, MeOD) δ 8.72 (d, J = 14.6 Hz, 1H), 7.99 (d, J = 7.3 Hz, 1H), 7.54 7.47 (m, 3H), 7.41 7.34 (m, 2H), 7.3 (d, J = 7.1 Hz, 1H), 7.7 (d, J = 7. Hz, 1H), 6.99 (s, 1H), 6.81 (d, J = 8.9 Hz, 1H), 6.75 (d, J = 8.9 Hz, 1H), 6.29 (d, J = 14.7 Hz, 1H), 3.84 (s, 3H), 3.68 (s, 3H), 2.6 (t, J = 5.6 Hz, 2H), 2.34 (t, J =6.7 Hz, 2H), 1.78 1.73 (8H). MS (ESI): m/z = 518.2[M] +. HRMS (m/z): [M] + calcd for [C 34 H 32 NO 4 ] + 518.2326, found 518.2319. CC17: Yield: 44%. 1 H NMR (4 MHz, d 6 -DMSO) δ1.65-1.75 (m, 2H), 1.78 (m, 6H), 2.18-2.22 (m, 1H), 2.29-2.34 (m, 1H), 2.66 (1H), 3.85 (s, 1H), 6.5 (d, J = 14.2 Hz, 1H), 6.1 (d, J = 8.4 Hz, 1H), 6.76 (dd, J = 8.6, 2.2 Hz, 1H), 7. (d, J = 2. Hz, 1H), 7.32 (d, J = 7.2 Hz, 1H), 7.44 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.63 (d, J = 8. Hz, 1H), 7.68 (t, J = 7.4 Hz, 1H), 7.75 (d, J = 7.2 Hz, 1H), 7.8 (t, J = 7.2 Hz, 1H), 8.14 (d, J = 7.6 Hz, 1H), 8.66 (d, J = 14. Hz, 1H), 1.79 (s, 1H, -OH), 12.97(s, 1H, -COOH). 13 C NMR (1 MHz, d 6 -DMSO) 2.9, 23.63, 26.83, 27.68, 32.53, 5.23, 12.16, 13.81, 112.96, 114.22, 114.78, 115.48, 122.59, 126.81, 127.64, 128.94, S22
129.54, 129.87, 13.6, 13.96, 133.12, 135.46, 141.93, 142.63, 144.54, 147.37, 153.73, 16.86, 161.65, 166.91, 177.8. MS (ESI) 54.2. HRMS (m/z): [M] + calcd for [C 33 H 3 NO 4 ] + 54.2169, found 54.2156. CC19: Yield: 31%. 1 H NMR (4 MHz, CDCl 3 ) δ 8.35 (d, J = 13.7 Hz, 1H), 8.26 (d, J = 7.6 Hz, 1H), 7.61 (t, J = 7.3 Hz, 1H), 7.53 (t, J = 7.4 Hz, 1H), 7.33 (2H), 7.14 (t, J = 7.3 Hz, 1H), 7.8 (d, J = 7.4 Hz, 1H), 7.1 (d, J = 7.7 Hz, 1H), 6.77 (d, J = 9.2 Hz, 1H), 6.65 (d, J = 9.2 Hz, 1H), 6.55 (s, 1H), 5.92 (d, J = 13.4 Hz, 1H), 3.58 3.45 (7H), 2.72 (s, 2H), 2.53 2.36 (2H), 2.4 (2H), 1.89 (2H), 1.75 (s, 6H), 1.26 (t, J = 6.6 Hz, 6H). MS (ESI): m/z = 573.5 [M]+. CC2: Yield: 53%. 1 H NMR (4 MHz, MeOD) δ 8.24 (t, J = 1.2 Hz, 2H), 7.78 (t, J = 7.5 Hz, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.53 (d, J = 7.4 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.28 (2H), 6.89 6.83 (2H), 6.78 (d, J = 9.1 Hz, 1H), 5.97 (d, J = 14. Hz, 1H), 3.48 (s, 3H), 3.43 (q, J = 7. Hz,4H), 2.89 2.86 (t, J = 6.2 Hz, 2H), 2.73 2.63 (2H), 1.84 (s, 3H), 1.76 (s, 3H), 1.21 (t, J = 7. Hz, 6H). 13 C NMR (1 MHz, CDCl 3 ) δ 172.73, 168.2, 167.73, 156.11, 151.34, 149.19, 148.6, 142.78, 14.88, 137.95, 135.43, 133.17, 131.76, 131.7, 129.45, 129.41, 128.66, 127.58, 125.18, 122.44, 122.25, 113.65, 111.82, 11.56, 1.6, 97.23, 49.2, 45., 29.69, 28.46, 28.11, 12.59. MS (ESI): m/z = 545.2 [M] +. CC21: Yield: 29%. 1 H NMR (4 MHz, MeOD) δ 8.49 (d, J = 14.1 Hz, 1H), 8.16 (d, J = 7.8 Hz, 1H), 7.76 7.7 (1H), 7.65 (d, J = 8.6, 1H), 7.5 (d, J = 7.2 Hz, 1H), 7.44 7.37 (2H), 7.28 (2H), 6.98 (d, J = 9.1, 1H), 6.83 (, 2H), 6.31 (1H), 6.23 (d, J = 1. Hz, 1H), 3.63 3.48 (7H), 1.75 (s, 6H), 1.28 (t, 6H). MS (ESI): m/z = 519.2[M] +. HRMS (m/z): [M] + calcd for [C 34 H 35 N 2 O 3 ] + 519.2642, found 519.2633. CC22: Yield: 7%. 1 H NMR (4 MHz, MeOD) δ 8.31 (s, 1H), 8.26 (d, J = 8.1 Hz, 1H), 8.3 (d, J = 7.9 Hz, 1H), 7.92 (s, 1H), 7.78 (t, J = 7.6 Hz, 1H), 7.72 (t, J = 7.8 Hz, 2H), 7.54 (d, J = 8.3 Hz, 1H), 7.39 7.34 (2H), 7.21 7.14 (m, 2H), 7.8 (d, J = 9.3 Hz, 1H), 3.95 (s, 3H), 3.65 (q, J = 6.9 Hz, 4H), 3.7(t, J = 6.4 Hz, 2H), 2.88 (t, J = 6.4 Hz,2H), 1.3 (t, J = 6.9 Hz, 6H). MS (ESI): m/z = 53.2[M] +. HRMS (m/z): [M] + calcd for [C 33 H 31 N 2 O 3 ] + 53.2329, found 53.2316. CC23: Yield: 36%. 1 H NMR (4 MHz, MeOD) δ 8.44 (d, J = 15.4 Hz, 1H), 8.12 (d, S23
J = 7.3 Hz, 1H), 8.7 (d, J = 7.7 Hz, 1H), 7.98 (s, 1H), 7.72 7.66 (2H), 7.62 (s, 1H), 7.53 (d, J = 8. Hz, 1H), 7.42 7.36 (m, 2H), 7.32 (d, J = 7.4 Hz, 1H), 7.29 (d, J = 9.7 Hz, 1H), 7.19 (s, 1H), 7.12 (d, J = 15.7 Hz, 1H), 7.5 (s, 1H), 3.9 (s, 3H), 3.62 (q, J = 6.8 Hz, 4H), 1.29 (t, J = 6.8 Hz, 6H). HRMS (m/z): [M] + calcd for [C 31 H 29 N 2 O 3 ] + 477.2173, found 477.2162. CC24: Yield: 52%. 1 H NMR (4 MHz, MeOD) δ 8.23 (d, J = 7.6 Hz, 1H), 8.11 (s, 1H), 7.93 (d, J = 7.4 Hz, 1H), 7.82 7.66 (3H), 7.36 (d, J = 7.5 Hz, 1H), 7.32 (d, J = 7.4 Hz, 1H), 7.26 7.12 (3H), 7.4 (d, J = 9.5 Hz, 1H), 6.98 (s, 1H), 3.62 (q, J =7. Hz, 4H), 2.87 (t, J = 4.4 Hz, 2H), 2.79 (t, J = 4.4 Hz, 2H), 1.3 (t, J = 7. Hz, 6H). HRMS (m/z): [M] + calcd for [C 32 H 29 N 2 O 3 ] + 489.2173, found 489.2159. CC25: Yield: 4%. 1 H NMR (4 MHz, MeOD) δ 8.51 (d, J = 15.5 Hz, 1H), 8.17 (d, J = 7.2 Hz, 1H), 8.7 (d, J = 4.9 Hz, 1H), 8.2 (s, 1H), 7.75 7.67 (2H), 7.48 (dd, J = 7.6, 3.6 Hz, 1H), 7.42 (d, J = 7.4 Hz, 1H), 7.3 (d, J = 4.4 Hz, 1H), 7.27 (s, 1H), 7.26 (s, 1H), 7.21 (s, 1H), 7.16 (d, J = 15.6 Hz, 1H), 7.7 (d, J = 9.2 Hz, 1H), 7.5 (s, 1H), 3.62 (q, J = 7. Hz, 4H), 1.28 (t, J = 7. Hz, 6H). HRMS (m/z): [M] + calcd for [C 3 H 27 N 2 O 3 ] + 463.216, found 463.211. CC26: Yield: 57%. 1 H NMR (4 MHz, MeOD) δ 8.23 (d, J = 7.7 Hz, 1H), 8.9 (s, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.76 (t, J = 7.4 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.61 (d, J = 7.2 Hz, 2H), 7.56 7.5 (3H), 7.47 (d, J = 7.9 Hz, 1H), 7.31 (d, J = 7.5 Hz, 1H), 7.26 (d, J = 7.7 Hz, 1H), 7.21 (d, J = 7.6 Hz, 1H), 7.17 (d, J = 9.6 Hz, 1H), 7.1 (d, J = 9.7 Hz, 1H), 7.1 (s, 1H), 3.62 (q, J = 7.1 Hz, 4H), 2.73 (t, J = 7.2 Hz, 2H), 2.6(t, J = 7.2 Hz, 2H), 1.27 (t, J = 7.1 Hz, 6H). 13 C NMR (1 MHz, MeOD) δ 17.57, 169.82, 167.85, 158.51, 154.26, 144.32, 137.21, 134.29, 132.42, 131.92, 13.98, 13.6, 129.85, 129.25, 129.2, 129.11, 129.3, 128.78, 128.75, 126.94, 123.4, 121.19, 12.42, 116.1, 115.56, 111.85, 111.35, 96.37, 45.25, 29.35, 27.89, 11.4. MS (ESI): m/z = 565.2[M] +. CC27: Yield: 42%. 1 H NMR (4 MHz, MeOD) δ 8.28 (d, J = 15.4 Hz, 1H), 8.8 7.98 (2H), 7.66 (s, 2H), 7.61 (5H), 7.45 (d, J = 7. Hz, 1H), 7.33 (d, J = 9.1 Hz, 2H), 7.28 (d, J = 5.2 Hz, 2H), 7.7 (3H), 6.69 (s, 1H), 3.58 (q, J = 6.9 Hz, 4H), 1.26 (t, J = 6.9 Hz, 6H). MS (ESI): m/z = 539.2[M] +. HRMS (m/z): [M] + calcd for [C 36 H 31 N 2 O 3 ] + S24
539.2329, found 539.2314. CC28: Yield: 52%. 1 H NMR (4 MHz, MeOD) δ 8.27 (d, J = 7.7 Hz, 1H), 8.1 (s, 1H), 7.89 (d, J = 7.9 Hz, 1H), 7.81 (t, J = 7.3 Hz, 1H), 7.72 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 7.7 Hz, 2H), 7.19 (d, J = 7.2 Hz, 1H), 7.16 (s, 1H), 7.15 7.7 (m, 2H), 7.4 (d, J = 9. Hz, 1H), 3.63 (q, J = 6.9 Hz, 4H), 3.24 (t, J =9.8 Hz, 2H), 2.74 (t, J = 9.8 Hz, 2H), 2.69 (s, 3H), 1.28 (t, J = 6.9 Hz, 6H). 13 C NMR (1 MHz, MeOD) δ 171.8, 167.54, 158.8, 153.66, 147.43, 138.76, 137.1, 134.58, 132.66, 131.73, 131.9, 129.77, 129.2, 128.94, 128.49, 125.71, 124.86, 123., 121.46, 12.79, 115.35, 114.64, 113.29, 112.88, 111.55, 96.69, 45.7, 31.68, 29.35, 22.34, 13.4, 11.44. MS (ESI): m/z = 53.2[M] +. CC29: Yield: 36%. 1 H NMR (4 MHz, MeOD) δ 8.6 (d, J = 14.8 Hz, 1H), 7.98 (s, 1H), 7.82 (d, J = 7.2 Hz, 1H), 7.54 (s, 2H), 7.33 (d, J = 9.1 Hz, 1H), 7.26 7.16 (3H), 7.13 (d, J = 6.8 Hz, 1H), 6.92 (s, 1H), 6.87 (d, J = 9.4 Hz, 1H), 6.74 (d, J = 14.6 Hz, 1H), 6.67 (s, 1H), 3.55 (q, J = 6.3 Hz, 4H), 2.66 (s, 3H), 1.28 (t, J = 6.1 Hz, 6H). MS (ESI): m/z = 477.2 [M] +. HRMS (m/z): [M] + calcd for [C 31 H 29 N 2 O 3 ] + 477.2173, found 477.2163. CC3: Yield: 28%. 1 H NMR (4 MHz, MeOD) δ 8.78 (s, 1H, NH), 8.27 (d, J = 7.5 Hz, 1H), 8.12 (s, 1H), 8.6 (d, J = 7.2 Hz, 1H), 7.78 (t, J = 7.6 Hz, 1H), 7.72 (d, J = 7.6 Hz, 1H), 7.7 (d, J = 7.2 Hz, 1H), 7.62 (dd, J = 7.6 Hz, 1H), 7.52 (dd, J = 7.6 Hz, 1H), 7.35 (d, J = 4.8 Hz, 1H), 7.33 (s, 1H), 7.29 (d, J = 7.4 Hz, 1H), 7.6 (d, J = 9. Hz, 1H), 6.97 (d, J = 9.1 Hz, 1H), 2.93 (t, J = 3.6 Hz, 2H), 2.47 (t, J = 3.6 Hz, 2H), 2.32 (t, J = 3.6 Hz, 2H). MS (ESI): m/z = 448. [M] +. HRMS (m/z): [M] + calcd for [C 29 H 22 NO 4 ] + 448.1543, found 448.1535. CC31: Yield: 27%. 1 H NMR (4 MHz, MeOD) δ 8.3 (dd, J = 6.2, 3.6 Hz, 1H), 7.93 (d, J = 7.6 Hz, 1H), 7.87 (s, 1H), 7.67 (s, 1H), 7.58 (d, J = 3.6 Hz, 1H), 7.56 (d, J = 3.6 Hz, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 7.28 (t, J = 7.6 Hz, 1H), 7.2 (dd, J = 7.6, 3.6 Hz, 1H), 7.15 (d, J = 9.3 Hz, 1H), 6.76 (d, J = 1.8 Hz, 1H), 6.68 (dd, J = 7.4, 1.6 Hz, 1H), 3.87 (s, 3H), 2.98 2.93 (m, 2H), 2.82 2.66 (m, 2H). HRMS (m/z): [M] + calcd for [C 29 H 22 NO 4 ] + 448.1543, found 448.1534. CC32: Yield: 21%. 1 H NMR (4 MHz, DMSO) δ 7.97 (d, J = 7.7 Hz, 1H), 7.84 (d, J S25
= 7.6 Hz, 1H), 7.8 (t, J = 1. Hz, 1H), 7.75 7.65 (m, 2H), 7.51 (s, 1H), 7.45 (d, J = 8. Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.18 (t, J = 7.2 Hz, 1H), 7.14 7.1 (1H), 6.89 (s, 1H), 6.63 (d, J = 8.8 Hz, 1H), 6.58 (d, J = 8.8 Hz, 1H), 2.92 2.76 (2H), 2.44 2.3 (2H). MS (ESI): m/z = 434.[M] +. HRMS (m/z): [M] + calcd for [C 28 H 2 NO 4 ] + 434.1387, found 434.1379. CC33: Yield: 25%. 1 H NMR (4 MHz, MeOD/CDCl 3 ) δ 8.24 (d, J = 14.3 Hz, 1H), 8.8 (d, J = 7.5 Hz, 1H), 7.59 (t, J = 7.3 Hz, 1H), 7.54 (d, J = 7.4 Hz, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 1H), 7.38 (t, J = 8.8 Hz, 1H), 7.3 (t, J = 7.6 Hz, 1H), 7.21 (d, J = 7.3 Hz, 1H), 6.96 (s, 1H), 6.86 (d, J = 8.7 Hz, 1H), 6.69 (d, J = 8.3 Hz, 1H), 6.3 (d, J = 14.3 Hz, 1H), 3.67 (s, 3H), 2.83(t, J = 5.6 Hz, 2H), 2.7(t, J = 5.6 Hz, 2H), 1.72 (s, 6H). 13 C NMR (1 MHz, MeOD/CDCl 3 ) δ 175.42, 167.8, 161.59, 154.75, 147.26, 142.49, 141.3, 14.27, 134.11, 133.12, 131.2, 13.59, 129., 128.87, 128.76, 127.49, 126.15, 122.13, 12.97, 116.69, 114.83, 111.48, 12.84, 11.78, 49.81, 31.12, 27.22, 27.12, 24.23. MS (ESI): m/z = 49.[M] +. HRMS (m/z): [M] + calcd for [C 32 H 28 NO 4 ] + 49.213, found 49.225. CC34: Yield: 23%. 1 H NMR (4 MHz, MeOD) δ 8.55 (t, J = 13.2 Hz, 1H), 7.89 (dd, J = 6.8, 3.6 Hz, 1H), 7.57 7.53 (3H), 7.47 (t, J = 7.5 Hz, 1H), 7.4 (d, J = 7.9 Hz, 1H), 7.36 7.32 (2H), 7.2 (d, J = 8.8 Hz, 1H), 6.98 6.89 (m, 2H), 6.78 (dd, J = 8.8, 2. Hz, 1H), 6.48 (d, J = 13.1 Hz, 1H), 6.27 (d, J = 12.6 Hz, 1H), 3.71 (s, 3H), 1.76 (s, 6H). MS (ESI): m/z = 464.3[M]+. HRMS (m/z): [M] + calcd for [C 3 H 26 NO 4 ] + 464.1856, found 464.1849. S26
4. Supplemental Spectra 1 H NMR of CC 1 in d 6 -DMSO. 1 C NMR of CC 1 in d 6 -DMSO. S27
1 H NMR of CC 4 in MeOD. 13 C NMR of CC 4 in MeOD. S28
1 H NMR of CC 5 in CDCl 3. 1 H NMR of CC 6 in MeOD S29
1 H NMR of CC 15 in CDCl 3. 1 H NMR of CC17 in d 6 -DMSO. S3
1 C NMR of CC17 in d 6 -DMSO. 1 H NMR of CC19 in CDCl 3. S31
1 H NMR of CC2 in MeOD. 13 C NMR of CC2 in CDCl 3. S32
1 H NMR of CC26 in MeOD. 13 C NMR of CC26 in MeOD. S33
1 H NMR of CC33 in MeOD. 33 C NMR of CC33 in MeOD/CD 3 Cl. S34
1 H NMR of CC34 in MeOD. 1 H NMR of CC35 in CDCl 3. S35
13 C NMR of CC35 in CDCl 3. S36