Supporting Information
Self-Assembly of Peptide-Thiophene Conjugates: Peptide Zipping Regulated
Packing of Thiophene and Supramolecular Chirality
Zongxia Guo, Yubao Song, Ruiying Gong, Youbing Mu, Yi Jiang, Ming Li and Xiaobo Wan
Table of Contents
Synthesis of PTP and TPT ......................................................................................... S1
Solubility and gel formation ...................................................................................... S2
Gel pictures ................................................................................................................ S3
SEM images of PTP and TPT gels .......................................................................... S4
FT-IR of PTP in powder and gels ............................................................................ S5
FT-IR of TPT in powder and gels ............................................................................ S6
FL spectra in solution and gels ................................................................................ S7
XRD of PTP and TPT xerogels ............................................................................... S8
CD spectra of PTP gels ............................................................................................ S9
CD spectra of TPT gels .......................................................................................... S10
Sequential variable-temperature CD spectra of PTP gel in ethanol ........................ S11
H-bonds formed between PTPs and TPTs in -sheets............................................. S12
S1. Synthesis:
O
O
N
H
O
O
H
N
O
1
N
H
S
S
H
N
S
S
N3
O
2
CuSO4
Ascorbic acid
DMF
O
O
O
H
N
O
N
H
O
H
N
N
H
O
N
NN
S
S
S
S
NN
N
H
N
O
N
H
H O
N
O
O
N
H
O
O
PTP
Synthesis
of
dimethyl
16,16'-(4,4'-(3,3'''-dioctyl-[2,2':5',2'':5'',2'''-quaterthiophene]-5,5'''-diyl)bis(1H-1,2,3-triazole-4,1-diyl))bis(2,
8-diisopropyl-4,7,10,13-tetraoxo-3,6,9,12-tetraazahexadecan-1-oate) (PTP) The mixture of compound 1 (91 mg,
0.2 mmol) and 2 (60.2 mg, 0.1 mmol) in 5mL DMF was stirred in the presence of a catalytic amount of
CuSO4·5H2O (2.5 mg, 0.01 mmol) and ascorbic acid (7 mg, 0.04 mmol) at room temperature overnight. Et2O (30
mL) was added to the mixture, and the precipitate was filtered and washed with Et2O to afford PTP in 92% yield.
Brown solid. 1H NMR (600 MHz, d6-DMSO) δ = 0.85(m, 30H), 1.26 (m, 16H), 1.36 (m, 4H), 1.64 (m, J = 7.2 Hz,
4H), 1.99(m, 4H), 2.09 (m, 4H), 2.17 (t, J = 7.2 Hz, 4H), 2.77 (t, J = 7.4 Hz, 4H), 3.62 (s, 3H), 3.76(m, 8H), 4.17 (t,
J = 7.4Hz, 4H) , 4.42 (t, J = 6.6 Hz, 4H) , 7.21(d, J = 3.6 Hz, 4H, Ar); 7.36 (s, 2H, Ar), 7.38(d, J = 3.6 Hz, 2H,
NHCO), 7.85 (d, J = 8.6 Hz, 2H, NHCO) , 8.12 (t, J = 5.6 Hz, 2H, NHCO) , 8.26(t, J = 5.6 Hz, 2H, NHCO), 8.55 (s,
2H, Ar, triazole); 13C NMR (150 MHz, d6-DMSO) δ = 13.9, 18.1, 18.2, 18.9, 19.2, 22.1, 25.7, 28.6, 28.7, 28.7, 28.8,
29.77, 30.0, 30.5, 31.3, 31.6, 41.6, 41.9, 49.1, 51.7, 57.4, 57.8, 121.1, 124.9, 127.0, 127.1, 128.3, 131.4, 134.3,
135.6, 140.1, 141.2, 168.95, 169.04, 171.2, 171.4, 171.9. HRMS (EI): calcd for [M+Na]+ C74H108N14O12S4:
1535.7046, found: 1535.7206.
S
S
H
N
S
S
N3
O
N
H
O
H
N
O
H
N
N
H
O
N3
O
4
3
CuSO4
Ascorbic acid
DMF
S
H
N
S
S
S
N
NN
O
O
N
H
H
N
O
O
N
H
H
N
O
N
N N
S
S
S
S
TPT
Synthesis
of
2-(2-(4-(4-(3,3'''-dioctyl-[2,2':5',2'':5'',2'''-quaterthiophen]-5-yl)-1H-1,2,3-triazol-1-yl)butanamido)acetamido
)-N-(2-((1-((4-(4-(3,3'''-dioctyl-[2,2':5',2'':5'',2'''-quaterthiophen]-5-yl)-1H-1,2,3-triazol-1-yl)butyl)amino)-3methyl-1-oxobutan-2-yl)amino)-2-oxoethyl)-3-methylbutanamide (TPT) The mixture of compound 3 (116 mg,
0.2 mmol) and 4 (54 mg, 0.1 mmol) in 5mL DMF was stirred in the presence of a catalytic amount of CuSO4·5H2O
(2.5 mg, 0.01 mmol) and ascorbic acid (7 mg, 0.04 mmol) at room temperature overnight. Et2O (30 mL) was added
to the mixture, and the precipitate was filtered and washed with Et2O to afford PTP in 94% yield.
Brown solid. 1H NMR (600 MHz, d6-DMSO) δ = 0.81(m, 24H), 1.23 (m, 42H), 1.60 (m, 8H), 1.84 (t, J = 7.4 Hz,
2H), 1.93(m, 2H), 2.09 (m, 2H), 2.17 (t, J = 7.4 Hz, 2H), 2.74 (t, J = 7.4 Hz, 8H), 3.10 (m, 2H), 3.76(m, 4H), 4.10
(m, 2H) , 4.39 (m,4H) , 7.03(d, J = 5.1 Hz, 2H, Ar), 7.12(d, J = 3.7 Hz, 2H, Ar); 7.17 (d, J = 3.8 Hz, 2H, Ar), 7.33(s,
6H, Ar), 7.47 (d, J = 5.2 Hz, 2H, Ar) , 7.70 (d, J = 8.7 Hz, 1H, NHCO) , 7.87(d, J = 8.4 Hz, 1H, NHCO), 7.99 (t, J
= 5.2 Hz,1H, NHCO), 8.13(t, J = 5.2 Hz, 1H, NHCO), 8.27 (t, J = 5.2 Hz, 1H, NHCO) , 8.49 (s,1H, Ar, triazole) ,
8.53(s, 1H, Ar, triazole); 13C NMR (150 MHz, d6-DMSO) δ = 14.4, 18.5, 18.6, 19.6, 19.7, 22.6, 26.2, 26.4, 27.5,
29.0, 29.11, 29.14, 29.2, 30.2, 30.4, 30.84, 30.87, 31.75, 31.76, 32.1, 38.2, 42.38, 42.41, 49.6, 49.7, 58.3, 121.3,
121.5, 125.2, 125.5, 127.36, 127.38, 127.44, 127.48, 128.8, 129.7, 131.0, 131.8, 134.7, 135.1, 136.0, 136.1, 140.2,
140.5, 141.6, 169.0, 170.0, 171.1, 171.8, 171.9. HRMS (EI): calcd for [M+Na]+ C90H123N11O5S8]: 1716.7367,
found: 1716.7341.
S2. Solubility and gel formation
The solubility and gel formation experiments were performed in various solvents and the results were summarized.
The gel formation was confirmed by vial inversion method. The minimum gelation concentration (MGC) in this
report was defined as the concentration at which the samples could form stable gels within 24 hours after cooling
down to room temperature (250C).
Solvents
PTP
TPT
State
MGC (mg/mL)
State
MGC (mg/mL)
THF
G
10 (1.11wt%)
G
5 (0.56wt%)
1,4-Dioxane
G
8 (0.77wt%)
G
2 (0.19wt%)
MeOH
G
2 (0.25wt%)
I
EtOH
G
0.60 (0.08wt%)
I
Acetone
G
5 (0.62wt%)
I
CHCl3
I
G
DMF
S
S
DMSO
S
S
Toluene
I
I
Benzene
I
I
Et2O
I
I
EtOAc
I
P
Acetonitrile
I
P
Hexane
I
I
H2O
I
I
8 (0.53wt%)
Table S1. Solubility and gel formation ability of PTP and TPT. S: soluble; P: precipitate; I: insoluble; G: gel.
S3. Gel pictures:
Figure S1. Gel pictures of PTP in THF (a), 1,4-Dioxane (b), Methanol (c), Acetone (d) and Ethanol (e); and TPT in
THF (f), 1,4-Dioxane (g) and CHCl3 (h).
S4 SEM images of PTP and TPT gels.
Figure S2. SEM images of gel fibers. Yellow arrows indicate the left-handed twists. The scale bar in the images is
400 nm.
S5 FT-IR of PTP in powder and gels
The FT-IR of PTP xerogels was recorded to detect the formation of peptide secondary structures. The formation of
anti parallel -sheets were confirmed, which are indicated by green oval circles.1
Figure S3. FI-IR of PTP in powders and xerogels prepared from different solvents. The red lines are the second
derivatives for clearly showing the peptide secondary structures.
S6. FT-IR of TPT in powder and gels
The FT-IR of TPT xerogels was recorded to detect the formation of peptide secondary structures. The formation of
parallel -sheets were confirmed, which are indicated by green oval circles.2
Figure S4. FI-IR of TPT in powders and xerogels prepared from different solvents. The red lines are the second
derivatives for clearly showing the peptide secondary structures.
S7. FL spectra in solution and gels
Figure S5. Normalized FL spectra of PTP (a) and TPT (b) in solution (DMF, 1.010-6 M) and in gels.
S8. XRD of PTP and TPT xerogels
All PTP and TPT gels showed weak peaks with d spacing of 0.44 nm which is in agreement with the distance of
-sheet interstrand and weak peaks with d spacing of 0.38 nm in accordance with the distance of - stacking.3
Figure S6. XRD of PTP and TPT xerogels. PTP gels prepared from THF (a), 1,4-Dioxane (b), Methanol (c),
Ethanol (d) and Acetone (e); and TPT gels prepared from THF (f), 1,4-Dioxane (g) and CHCl3 (h).
S9. CD spectra of PTP gel in acetone
For all CD measurement, 10 times of measurements were performed both for PTP and TPT in each solvent. For
PTP in MeOH, EtOH, THF and 1,4-dioxane, the same direction of CD signals were always obtained for each
solvent. However, for PTP in acetone, 4 times of positive and 6 times of negative CD signals were observed.
Figure S7. CD spectra of PTP gels prepared in acetone in different batches.
S10 Sequential variable-temperature CD spectra of PTP in ethanol
Figure S8. The variable-temperature CD spectra of PTP gel in ethanol at different temperatures. The noise of CD
spectra at 400 nm started to appear from 50C at which the gel started to disassemble based on the CD
intensity-temperature plot.
S11 H-bonds formed between PTPs and TPTs in  -sheets
Figure S9. Proposed hydrogen bonding formed between PTPs (a) and TPTs (b) in -sheet structures.
Yellow arrows indicate the hydrogen bonding.
References:
1. N. Yamada, K. Ariga, M. Naito, K. Matsubara and E. Koyama, J. Am. Chem. Soc., 1998, 120, 12192.
2. S. R. Diegelmann, J. M. Gorham and J. D. Tovar, J. Am. Chem. Soc., 2008, 130, 13840.
3. (a) E.-K. Schillinger, E. Mena-Osteritz, J. Hentschel, H. G. Börner and P. Bäuerle, Adv.Mater., 2009, 21, 1562;
(b) A. K. Shaytan, E.-K. Schillinger, P. G. Khalatur, E. Mena-Osteritz, J. Hentschel, H. G. Börner, P. Bäuerle, and
A. R. Khokhlov, ACS Nano, 2011, 5, 6894.