Supporting Information for Controlling Supramolecular Chiral Nanostructures by Self-Assembly of a Biomimetic b-sheet-rich Amyloidogenic Peptide Antoni Sánchez-Ferrer 1, Jozef Adamcik 1, Stephan Handschin 1, Shu Hui Hiew 2, Ali Miserez 2,3, * and Raffaele Mezzenga 1,4, * 1 Department of Health Sciences & Technology, ETH Zurich, Switzerland CH-8092 2 School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 3 School of Biological Sciences, Nanyang Technological University, Singapore 637551 4 Department of Materials Science, ETH Zurich, Switzerland CH-8093 Table of Contents Figure SI-1 page 2 Figure SI-2 page 3 Figure SI-3 page 4 Figure SI-4 page 5 Figure SI-5 page 6 Figure SI-6 page 7 Figure SI-7 page 8 Figure SI-8 page 9 Figure SI-9 page 10 Figure SI-10 page 11 Figure SI-11 page 12 Figure SI-12 page 13 Figure SI-13 page 14 Figure SI-14 page 15 Figure SI-15 page 16 Figure SI-16 page 17 Form factors P(q) page 18 1
2.47 nm 4.45 nm Figure SI-1. The chemical structure of A1H1, and the dimensions of the fully extended peptide sequence and the hydrophilic domain. 2
A) A1H1 (annealed) q = 13.4 nm-1 d = 4.69 Å x = 9 nm q = 6.42 nm-1 d = 0.98 nm x = 3.6 nm 5 10 15 q (nm-1) B) A1H1 (from dispersion) q = 13.4 nm-1 d = 4.67 Å x = 11 nm q = 6.07 nm-1 d = 1.04 nm x = 2.5 nm 5 10 15 q (nm-1) Figure SI-2. 2D and 1D WAXS intensity profile for (A) the annealed A1H1 sample at 1 C under nitrogen atmosphere, and (B) the dried A1H1 sample from the 2 wt-% A1H1 dispersion. 3
residue residue A (a.u.) d 2 A/dn ~ 2 A (a.u.) d 2 A/dn ~ 2 A) B) A1H1 (annealed) A1H1 (from dispersion) b = 62.4% a = 0.5% r = 37.1% c 2 = 2.86 10-5 b = 72.9% a = 0.6% r = 26.5% c 2 = 7.84 10-5 0.005 0.005 0.000 0.000-0.005 17401717001680166016401616001580 ~ n (cm -1 ) -0.005 17401717001680166016401616001580 ~ n (cm -1 ) Figure SI-3. FTIR spectrum and peptide secondary structure population analysis for (A) the annealed A1H1 sample at 1 C under nitrogen atmosphere, and (B) the dried A1H1 sample from the 2 wt-% dispersion. Note: b: b-sheets; a: a-helices; r: random coils. 4
A) 10-1 A1H1 (0.5 wt-%) 10-2 10-3 0.1 1 q (nm-1) B) 100 A1H1 (1 wt-%) rcore = 2.42 nm pcore = 0.33 tin = 1.81 nm tout = 2.47 nm 10-1 10-2 10-3 0.1 1 q (nm-1) C) 101 A1H1 (2 wt-%) rcore = 2.25 nm pcore = 0.26 tin = 1.98 nm tout = 2.47 nm 100 10-1 10-2 10-3 0.1 1-1 q (nm ) Figure SI-4. 2D and 1D SAXS intensity profile for A1H1 dispersions in acetonitrile/water at (A) 0.5 wt%, (B) 1 wt-%, and (C) 2 wt-%. Notes: capillaries were placed horizontally; the green fitting curve correspond to the form factor P(q). 5
A) A1H1 (0.5 wt-%) 5 10 15 15 15 q (nm-1) B) A1H1 (1 wt-%) 5 10 q (nm-1) C) A1H1 (2 wt-%) 5 10 q (nm-1) Figure SI-5. 2D and 1D WAXS intensity profile for A1H1 dispersions in acetonitrile/water at (A) 0.5 wt%, (B) 1 wt-%, and (C) 2 wt-%. 6
A) B) Figure SI-6. (A) Test-tube-inversion method for the 2 wt-% A1H1 dispersion in acetonitrile/water showing the gel-like characteristic of such sample. (B) Polarized light experiment for the 0.5 wt-%, 1 wt-%, and 2 wt-% A1H1 dispersions in acetonitrile/water. Note: the edged of the capillaries are highlighted for a better visualization. 7
S(q) 1.3 1.2 A1H1 (2 wt-%) A1H1 (1 wt-%) q = 0.137 nm -1 d = 45.7 nm 1.1 1.0 0.9 0.1 0.2 0.3 0.4 0.5 q (nm -1 ) Figure SI-7. Structure factor S(q) for the non-birefringent (1 wt-%, black curve) and the birefringent (2 wt-%, blue curve) A1H1 sample in acetonitrile/water dispersion. 8
A) B) C) Figure SI-8. AFM height (left) and amplitude (right) profile image of the deposited (A) 1 wt-%, (B) 2 wt%, and (C) 4 wt-% A1H1 dispersion in acetonitrile/water. Note: scale bar is 300 nm. 9
Figure SI-9. AFM height profile image of the deposited 1 wt-% A1H1 dispersion in acetonitrile/water showing the local alignment due to deposition. 10
A) 2.0 <d> = 28 nm <w> = nm h (nm) 1.5 1.0 0.5 0.0 0 40 60 80 100 1 140 160 d (nm) B) 1.5 <d> = 15 nm <w> = 10 nm h (nm) 1.0 0.5 0.0 0 40 60 80 d (nm) C) 2.0 <d> = 15 nm <w> = 11 nm h (nm) 1.5 1.0 0.5 0.0 0 40 60 d (nm) Figure SI-10. AFM height profile image (left) and cross section height profile (right) of the deposited (A) 1 wt-%, (B) 2 wt-%, and (C) 4 wt-% A1H1 dispersion in acetonitrile/water. Note: scale bar is 60 nm. 11
10 1 A1H1 (dry gel) A) 10 2 10 1 10 0 A1H1 (gel) r core = 1.65 nm p core = 0.33 t in = 1.98 nm t out = 2.47 nm 10-1 10-2 0.1 1 B) q (nm -1 ) 10 0 q -3.4 10-1 10-2 0.1 1 q (nm -1 ) Figure SI-11. 2D and 1D SAXS intensity profiles for (A) the A1H1 gel in acetonitrile/water from the 2 wt-% A1H1 dispersion, and (B) the corresponding dry gel. Note: the green fitting curve correspond to the form factor P(q). 12
0.99937 Adj. R-Square Value y0 A) Peak1(C) A1H1 (gel) Peak2(C) 8.8990 xc 0.0605 A 2112.2916 w 0.0676 mu 0.95 y0 8.8990 xc 0.283 A 5.4271 w 0.0346 mu y0 Peak3(C) q = 13.4 nm-1 d = 4.70 nm x = 10 nm Peak4(C) 8.8990 xc 0.3407 A 10.9064 w 0.0432 mu 0.0167 y0 8.8990 xc 0.40 A 8.8101 w 0.0417 mu Peak5(C) y0 8.8990 xc 0.4608 A 6.2400 w 0.0479 mu Peak6(C) Peak7(C) y0 8.8990 xc 0.5216 A 3.481 w 0.0549 mu 0.6724 y0 8.8990 xc 1.3367 A 7.4872 w 0.0642 mu y0 5 10 15 Peak8(C) -1 q (nm ) B) A1H1 (dry gel) q = 13.3 nm-1 d = 4.71 Å x = 11 nm q = 6.21 nm-1 d = 1.01 nm x = 3.5 nm 5 10 1.7229 A 1714.7868 w 0.8321 mu 0.7280 y0 8.8990 xc Peak9(C) 15 q (nm-1) Figure SI-12. 2D and 1D WAXS intensity profiles for (A) the A1H1 gel in acetonitrile/water from the 2 wt-% A1H1 dispersion, and (B) the corresponding dry gel. 13 8.8990 xc A
A) B) C) Figure SI-13. AFM height (left) and amplitude (right) profile images of dry gel showing the different type of fibers upon solvent removal. Note: scale bar is 1 µm. 14
Figure SI-14. Polarized light optical microscope image of the dry gel. Note: scale bar is 500 µm 15
h (nm) h (nm) 10 8 <d> = 55 nm <w> = nm 6 4 2 0 0 40 80 1 160 0 d (nm) 6 <d> = 45 nm <w> = 15 nm 4 2 0 0 40 80 1 160 d (nm) Figure SI-15. AFM height profile images (left) and cross section height profiles (right) of the dry gel. Note: scale bar is 100 nm. 16
Figure SI-16. CryoSEM images of the deposited 2 wt-% A1H1 dispersion in acetonitrile/water. 17
Form factor for a hollow poly-core two-shell cylinder object The scattering intensity for a colloidal system can be described as = NP(q)S(q), where N is proportional to the concentration and scattering volume, P(q) is the form factor, and S(q) is the structure factor. The form factor for a hollow poly-core two-shell cylinder is described by the following expression: EG F 2J 7 (qr -./0 sin α) sin @q L P(q) = k * +(ρ -./0 ρ 23 )V 2 cosαd -./0 qr -./0 sin α q L 2 cosα H 2J 7 (qr 23 sin α) sin @q L + (ρ 23 ρ.jk )V 2 cosαd 23 qr 23 sin α q L 2 cosα + (ρ.jk ρ H )V.JK 2J 7 (qr.jk sin α) qr.jk sin α sin @q L 2 cosαd q L L 2 cosα F sinα dα Where k is the scaling factor, r core, r in, r out and r 0 is the scattering length density for the core, inner shell, outer shell and solvent, respectively; V core, V in and V out is the volume of the core, inner shell, and outer shell, respectively; r core, r in and r out is the radius of the core, inner shell and outer shell, respectively; t in and t out is the thickness of the inner shell and outer shell, respectively; and L the length of the cylindrical object. The relationship between the radii and thicknesses are: r 23 = r -./0 + t 23 r.jk = r -./0 + t 23 + t.jk The corresponding volumes are: F V -./0 = πr -./0 L V 23 = π(r -./0 + t 23 ) F L V.JK = π(r -./0 + t 23 + t.jk ) F L 18