Complementary π-π Interactions Induce MultiComponent Co-Assembly into Functional Fibrils Derek M. Ryan, Todd M. Doran, Bradley L. Nilsson* Department of Chemistry, University of Rochester, Rochester, NY 14627-0216, USA.
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Contents: Figure S1. Digital images of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture……………………………...…..Page 2 Figure S2. TEM images of 2.45 and 4.94 mM Fmoc-F5-Phe self-assembly…………………………………….Page 3 Table S1. Tabulation of CD spectra for each Fmoc-Phe : Fmoc-n-X-Phe co-assembly mixture.........................Page 4 Figure S3. Digital images of Fmoc-D-Phe : Fmoc-L-F5-Phe co-assembly mixture…………………………….Page 5 Figure S4. CD spectra of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe mixture…………………..….....................................Page 5 Figure S5. Comparative Rheology of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixtures……………………….Page 6 Figure S6. Comparative 19F NMR of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture…………………………Page 7 Figure S7. Comparative 1H NMR of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture…………………………Page 8 Figure S8. Comparative 19F NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture…………………...Page 9 Figure S9. Comparative 1H NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture…………………..Page 10 Figure S10. 1H NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in d6-DMSO/H2O mixtures….Page 11 Figure S11. 1H NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in d6-DMSO/H2O mixtures ….Page 12 Figure S12. Digital images of monofluorinated Fmoc-Phe : Fmoc-Phe co-assembly mixtures……………….Page 13 Figure S13. TEM images of Fmoc-Phe : Fmoc-n-F-Phe co-assembly mixtures……….……………………..Page 14 Figure S14. TEM image of Fmoc-Phe : Fmoc-3-X-Phe co-assembly mixtures………………………………Page 15 Figure S15. CD spectra of Fmoc-3-Cl-Phe and Fmoc-3-Br-Phe co-assembly mixtures………………………Page 16 Figure S16. Representative curve fit of Fmoc-Phe : Fmoc-3-F-Phe co-assembly kinetics…………………...Page 16 Figure S17. Representative curve fit of Fmoc-Phe : Fmoc-3-Cl-Phe co-assembly kinetics.…..….….............Page 17 Figure S18. Representative curve fit of Fmoc-Phe : Fmoc-3-Br-Phe co-assembly kinetics……………….....Page 17 Figure S19. Representative curve fit of Fmoc-Phe : Fmoc-F5-Phe co-assembly kinetics…….……..………..Page 18 Figure S20. Rheological frequency sweeps of Fmoc-Phe : Fmoc-3-X-Phe co-assembly mixtures………….Page 18 Figure S21. Electrostatic charge density maps of halogenated toluene derivatives…….................................Page 19
S1
Figure S1. (A) Digital image of 2.45 mM Fmoc-Phe (1), 4.9 mM Fmoc-Phe (2), 2.45 mM FmocF5-Phe (3), 4.9 mM Fmoc-F5-Phe (4), and 4.9 mM Fmoc-Phe : Fmoc-F5-Phe (5) mixture upon dilution from DMSO into water (2% DMSO/H2O v/v). (B) Digital image of 2.45 mM Fmoc-Phe (1), 4.9 mM Fmoc-Phe (2), 2.45 mM Fmoc-F5-Phe (3), 4.9 mM Fmoc-F5-Phe (4), and 4.9 mM Fmoc-Phe : Fmoc-F5-Phe (5) mixture 10 minutes after dilution. (C) Digital image of 2.45 mM Fmoc-Phe (1), 4.9 mM Fmoc-Phe (2), 2.45 mM Fmoc-F5-Phe (3), 4.9 mM Fmoc-F5-Phe (4), and 4.9 mM Fmoc-Phe : Fmoc-F5-Phe (5) mixture one hour after dilution.
S2
Figure S2. (A) TEM image of fibrils formed by Fmoc-F5-Phe self-assembly at 4.9 mM. (B) TEM image of fibrils formed by mM Fmoc-F5-Phe self-assembly at 2.45 mM.
S3
Table S1. Tabulation of CD spectra for investigated self and co-assemblies. Mixture Fmoc-F5-Phe 2.45 mM Fmoc-Phe : Fmoc-F5-Phe (1 : 1; 4.9 mM total) Fmoc-Phe : Fmoc-2-F-Phe (1:1; 4.9 mM total) Fmoc-Phe : Fmoc-3-F-Phe (1:1; 4.9 mM total) Fmoc-Phe : Fmoc-4-F-Phe (1:1; 4.9 mM total) Fmoc-Phe : Fmoc-3-Cl-Phe (1:1; 4.9 mM total) Fmoc-Phe : Fmoc-3-Br-Phe (1:1; 4.9 mM total)
CD signal (nm) 205 (min), 223 (max), 278 (max), 290(max), 300(max), 310(max) 205 (min), 217 (max), 223 (max), 276 (max), 284 (max), 299 (max), 310 (max) 226(max), 282(max), 289(max), 298(max), 310 (max) 225 (max), 278 (max), 288(max), 298(max), 310(max) 228 (min), 283 (min), 290 (min), 300 (min), 310 (min) 222 (max), 283 (max), 289 (max), 298 (max), 310 (max) 227 (max), 278 (max), 288 (max), 297 (max), 310 (max)
S4
Figure S3. (A) Digital image of Fmoc-D-Phe : Fmoc-L-F5-Phe co-assembly mixture (1), FmocLeu (2), and Fmoc-Phe : Fmoc-Leu co-assembly mixture (3) immediately upon dilution from DMSO into water. (B) Digital image of Fmoc-D-Phe : Fmoc-L-F5-Phe mixture (1), 4.9 mM Fmoc-Leu (2), and Fmoc-Phe : Fmoc-Leu mixture (3) one hour after dilution.
Figure S4. CD spectra of 4.9 mM Fmoc-F5-Phe (red), 1 : 1 Fmoc-Phe : Fmoc-F5-Phe (blue), and 2 : 1 Fmoc-Phe : Fmoc-F5-Phe.
S5
Figure S5. Frequency sweep rheology of 4.9 mM Fmoc-F5-Phe (red), 2.45 mM Fmoc-F5-Phe (black), 1 : 1 Fmoc-Phe : Fmoc-F5-Phe (blue), and 2 : 1 Fmoc-Phe : Fmoc-F5-Phe (green).
S6
Figure S6. Solution phase 19F NMR of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in 100% d6-DMSO (bottom) and 2% d6-DMSO/D2O (top) with a 7.4 mM Fmoc-3-F-Phe in d6-DMSO external standard.
S7
Figure S7. Solution phase 1H NMR of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in 100% d6-DMSO (bottom) and 2% d6-DMSO/D2O (top) with a 24 mM dimethylformamide (DMF) in d6-DMSO external standard.
S8
Figure S8. Solution phase 19F NMR of 2: 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in 100% d6-DMSO (top) and 2% d6-DMSO/D2O (bottom) with a 7.4 mM Fmoc-3-F-Phe in d6DMSO external standard.
S9
Figure S9. Solution phase 1H NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture in 100% d6-DMSO (top) and 2% d6-DMSO/D2O (bottom) with a 24 mM dimethylformamide (DMF) in d6-DMSO external standard.
S10
Figure S10. 1H NMR of 1 : 1 Fmoc-Phe : Fmoc-F5-Phe in increasing ratios of d6-DMSO/H2O. A is the Fmoc-F5-Phe carbamate proton and B is the Fmoc-Phe carbamate proton. All chemical shifts were referenced to TMS standard.
S11
Figure S11. 1H NMR of 2 : 1 Fmoc-Phe : Fmoc-F5-Phe mixture in increasing ratios of d6DMSO/ H2O. A is the Fmoc-F5-Phe carbamate proton and B is the Fmoc-Phe carbamate proton. All chemical shifts were referenced to TMS standard.
S12
Figure S12. (A) Digital image of Fmoc-Phe : Fmoc-2-F-Phe co-assembly mixture (1), Fmoc-Phe : Fmoc-3-F-Phe mixture (2), Fmoc-Phe : Fmoc-4-F-Phe mixture (3), Fmoc-Phe : Fmoc-3-ClPhe co-assembly mixture (4), and Fmoc-Phe : Fmoc-3-Br-Phe co-assembly mixture (5) immediately after dilution. (B) Digital image of Fmoc-Phe : Fmoc-2-F-Phe co-assembly mixture (1), Fmoc-Phe : Fmoc-3-F-Phe co-assembly mixture (2), Fmoc-Phe : Fmoc-4-F-Phe coassembly mixture (3), Fmoc-Phe : Fmoc-3-Cl-Phe co-assembly mixture (4), and Fmoc-Phe : Fmoc-3-Br-Phe co-assembly mixture (5) one hour after dilution.
S13
Figure S13. (A) TEM image of Fmoc-Phe : Fmoc-2-F-Phe co-assembled fibrils. (B) TEM image of Fmoc-Phe : Fmoc-3-F-Phe co-assembled fibrils. (C) TEM images of Fmoc-Phe : Fmoc-4-FPhe co-assembled fibrils.
S14
Figure S14. (A) TEM image of Fmoc-Phe : Fmoc-3-Cl-Phe co-assembled fibrils. (B) TEM image of Fmoc-Phe : Fmoc-3-Br-Phe co-assembled fibrils.
S15
Figure S15. CD spectra of Fmoc-Phe : Fmoc-3-Cl-Phe (black) and Fmoc-Phe : Fmoc-3-Br-Phe (red) co-assembly mixtures.
Figure S16. Kinetic curve fit of Fmoc-Phe : Fmoc-3-F-Phe mixture.
S16
Figure S17. Kinetic curve fit of Fmoc-Phe : Fmoc-3-Cl-Phe co-assembly mixture.
Figure S18. Kinetic curve of Fmoc-Phe : Fmoc-3-Br-Phe co-assembly mixture.
S17
Figure S19. Kinetic curve of Fmoc-Phe : Fmoc-F5-Phe co-assembly mixture.
Figure S20. Rheological frequency sweep analyses of Fmoc-Phe : Fmoc-3-F-Phe (blue), FmocPhe : Fmoc-3-Cl-Phe (red), and Fmoc-Phe : Fmoc-3-Br-Phe (green) hydrogels.
S18
Figure S21. Electrostatic charge density maps of halogenated Phe derivative benzyl side chains approximated by substituted toluene.
S19
