Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2015
Supporting Information
Well-defined
Aqueous
Nanoassemblies
from
Amphiphilic
meta-Terphenyls and Their Guest Incorporation Yusuke Okazawa, Kei Kondo, Munetaka Akita, and Michito Yoshizawa*
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan; *e-mail:
[email protected] Contents •
Materials and methods
•
Synthesis of 4a (1H & 13C-NMR, NOESY, & HSQC spectra)
•
Synthesis of 5a (1H & 13C-NMR, NOESY, & HSQC spectra)
•
Synthesis of 1a (1H & 13C-NMR, HH-COSY, NOESY, HSQC, & HR MS spectra)
•
Self-assembly of 2a (1H & 13C-NMR, HH-COSY, NOESY, HSQC, DOSY spectra)
•
Synthesis of 4b (1H & 13C-NMR, HH-COSY, & HSQC spectra)
•
Synthesis of 5b (1H & 13C-NMR, HH-COSY, & HSQC spectra)
•
Synthesis of 1b (1H & 13C-NMR, HH-COSY, HSQC, & HR MS spectra)
•
Self-assembly of 2b (1H & 13C-NMR, HH-COSY, HSQC, DOSY spectra)
•
DLS analysis of 2a and 2b
•
AFM analysis of 2b
•
Concentration-dependent UV-vis and fluorescence spectra of 2a and 2b
•
1
•
UV-vis and fluorescence spectra of 2a+2c
•
Synthesis and DLS analysis of 2a-c⊃(3)n and 2a-c⊃(4)n
•
UV-vis and fluorescence spectra of 2c+2d and 2c+2e
•
Optimized structures of spherical assemblies (1a)n
•
1
H-NMR spectra of 2a, 2a+2c, and 2c
H-NMR spectra of 2a•(3)n and 3.
S1
Materials and methods NMR: Bruker AVANCE-400 (400 MHz) or ASCEND-500 (500 MHz), MALDI-TOF MS: Shimadzu AXIMA-CFR Plus, ESI-TOF MS: Bruker micrOTOF II, Particle Size Analysis (DLS): Wyatt Technology DynaPro NanoStar, AFM: Asylum Reseach Cypher S, FT IR: JASCO FT/IR-4200, UV-vis: JASCO V-670DS, Fluorescence: HITACHI F7000, Absolute PL quantum yield: Hamamatsu Quantaurus-QY C11347-01, Elemental analysis: LECO CHNS-932 VTF-900. Solvents and reagents: TCI Co., Ltd., Wako Pure Chemical Industries Ltd., Kanto Chemical Co., Inc., Sigma-Aldrich Co., and Cambridge Isotope Laboratories, Inc. Compounds: 1,5-dibromo-2,4-dimethoxybenzene and 1c were synthesized according to previously published procedures.[1,2] References [1]
E. Kiehlmannan, D. R. W. Lauener, Can. J. Chem., 1989, 67, 335–344.
[2]
K. Kondo, A. Suzuki, M. Akita, M. Yoshizawa, Angew. Chem. Int. Ed., 2013, 52, 2308–2312.
S2
Synthesis of 4a Br
YO-97 MeO
1) n-BuLi, THF 2) ZnCl2, THF
OMe
3) PdCl2(PhCN) 2, P(t-Bu) 3 THF OMe MeO Br
Br
1-Bromopentamethylbenzene (2.000 g, 8.805 mmol) and dry THF (50 mL) were added to a 2-necked 300 mL glass flask filled with N2. A hexane solution (2.69 M) of n-butyllithium (3.6 mL, 9.7 mmol) was added dropwise to the flask at –80 ºC under N2. After stirring at –80 ºC for 2 h, a dry THF solution (30 mL) of ZnCl2 (1.560 g, 11.44 mmol) was added to the solution. The resultant mixture was further stirred at –80 ºC for 1 h and then the solution was warmed to r.t. for 1 d to obtain pentamethylphenylzinc chloride. 1,5-Dibromo-2,4-dimethoxybenene (0.886 g, 2.99 mmol), PdCl2(PhCN)2 (80 mg, 0.2 mmol), and dry THF (30 mL) were added to a 50 mL glass flask filled with N2. A hexane solution (0.95 M) of tri-tert-butylphosphine (0.4 mL, 0.4 mmol) was added to the 50 mL flask. After stirring at r.t. for 30 min, the mixture was added to the 300 mL flask and then the resulted solution was further stirred at 85 ºC for 2 d. The precipitated crude product was extracted with CH2Cl2 and hexane (as an azeotropic solvent). The solution was concentrated under reduced pressure. The crude product was collected and washed with CH3OH to afford 4a (0.734 g, 1.70 mmol, 57% yield) as a pale gray solid. 1
H NMR (400 MHz, CDCl3, r.t.): δ 2.04 (s, 12H), 2.27 (s, 12H), 2.30 (s, 6H), 3.84 (s,
6H), 6.66 (s, 1H), 6.69 (s, 1H). 13C NMR (100 MHz, CDCl3, r.t.): δ 16.8 (CH3), 17.0 (CH3), 18.1 (CH3), 55.8 (CH3), 95.6 (CH), 123.5 (Cq), 132.1 (Cq), 132.5 (Cq), 133.8 (Cq), 133.9 (CH), 135.7 (Cq), 156.7 (Cq). FT-IR (KBr, cm–1): 3437, 2990, 2928, 2877, 2727, 1603, 1573, 1502, 1456, 1377, 1321, 1277, 1250, 1198, 1166, 1108, 1065, 1032, 997, 921, 903, 815, 785, 628. MALDI-TOF MS (dithranol): m/z Calcd. for C30H38O2: 430.29, Found 430.16 [M]+. E.A.: Calcd. for C30H38O2: C, 83.67; H, 8.89. Found: C, 83.54; H, 9.14.
S3
d
c
f
O
a
f O
e
c d
b e
b a
Figure S1. 1H NMR spectrum (400 MHz, CDCl3, r.t.) of 4a.
a
O
f O
c d
b e c
f
Cq Cq Cq
Cq
d
e
b
Cq
Cq
a
Figure S2. 13C NMR spectrum (100 MHz, CDCl3, r.t.) of 4a.
S4
b
c
O
a
f O
c d
b e
Figure S3a. NOESY spectrum (400 MHz, CDCl3, r.t.) of 4a. d
c
O
a
f O
c d
b e
Figure S3b. NOESY spectrum (400 MHz, CDCl3, r.t.) of 4a.
S5
a
b
a
b
f
a
O
O
c d
b e
Figure S4a. HSQC spectrum (400 MHz, CDCl3, r.t.) of 4a. c
d f e
e d c
O
a
f O
c d
f b
e
Figure S4b. HSQC spectrum (400 MHz, CDCl3, r.t.) of 4a.
S6
Synthesis of 5a MeO
OMe
YO-101 HO
OH
BBr 3 CH2Cl2
Pentamethylbenzene dimer 4a (0.500 g, 1.16 mmol) and dry CH2Cl2 (50 mL) were added to a 200 mL glass flask. A CH2Cl2 solution (1.0 M) of BBr3 (4.6 mL, 4.6 mmol) was added dropwise to this flask at 0 ºC under N2. The reaction mixture was stirred and allowed to warm to r.t. overnight. The reaction was quenched with H2O (50 mL). The two layers were separated and the aqueous layer was extracted with CH2Cl2 (3 × 100 mL). The combined organic layers were dried over MgSO4, filtrated, and concentrated under reduced pressure. The crude product was washed with acetone and hexane to afford 5a (0.453 g, 1.13 mmol, 97% yield) as a white solid.[2] 1
H NMR (400 MHz, CDCl3, r.t.): δ 2.05 (s, 12H), 2.26 (s, 12H), 2.29 (s, 6H), 4.62 (s,
6H), 6.60 (s, 1H), 6.67 (s, 1H). 13C NMR (100 MHz, CDCl3, r.t.): δ 16.9 (CH3), 16.9 (CH3), 17.9 (CH3), 101.6 (CH), 121.1 (Cq), 131.5 (Cq), 132.1 (Cq), 133.2 (Cq), 133.8 (CH), 135.3 (Cq), 153.0 (Cq). FT-IR (KBr, cm–1): 3518, 2986, 2925, 2872, 1630, 1595, 1494, 1453, 1418, 1376, 1336, 1258, 1213, 1131, 1099, 1066, 1019, 902, 851, 783, 604. MALDI-TOF MS (dithranol): m/z Calcd. for C28H34O2: 402.26, Found 402.16 [M]+. E.A.: Calcd. for C28H34O2•0.6CH3COCH3: C, 81.83; H, 8.66. Found: C, 81.67; H, 8.52.
S7
d
HO
c
f
a
OH
c
e
d b e
f a b
Figure S5. 1H NMR spectrum (400 MHz, CDCl3, r.t.) of 5a.
HO
a
OH
c d
b e
c d
Cq
Cq Cq
Cq
Cq Cq
e a
b
Figure S6. 13C NMR spectrum (100 MHz, CDCl3, r.t.) of 5a.
S8
b
c
f
a
HO
OH
c d
b e
Figure S7a. NOESY spectrum (400 MHz, CDCl3, r.t.) of 5a.
d
c
HO
a
f OH
c d
b e
Figure S7b. NOESY spectrum (400 MHz, CDCl3, r.t.) of 5a.
S9
d
ab
e
c
e,d c
a HO
a
f OH
c d
b
b
e
Figure S8. HSQC spectrum (400 MHz, CDCl3, r.t.) of 5a.
Synthesis of 1a
YO-164 –O
O HO
OH
O S
SO3–
3S
O
O
O
NaOH THF
2 Na +
Pentamethylbenzene dimer 5a (100 mg, 0.248 mmol), NaOH (60 mg, 1.5 mmol), and THF (30 mL) were added to a 50 mL glass flask. 1,3-Propanesultone (91 mg, 0.74 mmol) was added dropwise to this flask. The resultant mixture was stirred at r.t. overnight. The solvent was filtrated and then CH2Cl2 and hexane was added to the filtrate. The resultant solution was concentrated under reduced pressure. The crude product was washed with water and 1-propanol to afford 1a (0.108 g, 0.156 mmol, 63% yield) as a white solid. 1
H NMR (400 MHz, CD3OD, r.t.): δ 1.96 (s, 12H), 2.06 (dt, J = 6.8, 6.0 Hz, 4H), 2.22 (s,
12H), 2.25 (s, 6H), 2.70 (t, J = 6.8 Hz, 4H), 4.06 (t, J = 6.0 Hz, 4H), 6.42 (s, 1H), 6.81
S10
(s, 1H). 13C NMR (125 MHz, CDCl3, r.t.): δ 16.8 (CH3), 18.4 (CH3), 26.4 (CH2), 49.0 (CH2), 68.6 (CH2), 100.3 (CH), 126.0 (Cq), 132.7 (Cq), 133.0 (Cq), 134.1 (CH), 134.2 (Cq), 137.0 (Cq), 157.1 (Cq). FT-IR (KBr, cm–1): 3446, 2925, 1630, 1604, 1577, 1502, 1452, 1385, 1323, 1274, 1186, 1108, 1049, 797, 739, 610. HR MS (ESI): Calcd. for C34H44O8S2
322.1233,
Found
[M–2Na+]2–.
322.1223
E.A.:
C34H44Na2O8S2•2.5CH2Cl2: C, 48.54; H, 5.47. Found: C, 48.40; H, 5.55.
g –O
3S
O
a
d c
SO3–
f O
h c d
b e
e
2 Na +
a b
f h
g
Figure S9. 1H NMR spectrum (400 MHz, CD3OD, r.t.) of 1a.
S11
Calcd.
for
g –O
3S
O
a
SO3–
f O
h c d d,e
b
c
e 2 Na +
Cq Cq
h
Cq b Cq
Cq
g
f Cq
a
Figure S10. 13C NMR spectrum (125 MHz, CD3OD, r.t.) of 1a. b
c
g –O
3S
O
a
SO3–
f O
h c d
b e 2 Na +
Figure S11a. NOESY spectrum (500 MHz, CD3OD, r.t.) of 1a.
S12
d
c
g –O
3S
O
a
SO3–
f O
h c d
b e 2 Na +
Figure S11b. NOESY spectrum (500 MHz, CD3OD, r.t.) of 1a.
f h
g
g –O
3S
O
a
SO3–
f O
h c d
b e 2 Na +
Figure S12. 1H-1H COSY spectrum (400 MHz, CD3OD, r.t.) of 1a.
S13
e
f
c
d
h
g
d,e c g
h g –O
3S
a
O
f
SO3–
f
h c d
O
b e 2 Na +
Figure S13a. HSQC spectrum (400 MHz, CD3OD, r.t.) of 1a.
a
b
a
g –O
3S
O
a
SO3–
f O
h c d
b e
b
2 Na +
Figure S13b. HSQC spectrum (400 MHz, CD3OD, r.t.) of 1a.
S14
Found
Calcd.
Figure S14. HR MS spectrum (ESI) of 1a.
Self-assembly of 2a –O
YO-104
SO3–
3S
O
O D 2O 2 Na +
Amphiphile 1a (5.5 mg, 8.0 µmol) and D2O (0.4 mL) were added to a glass test tube. When the mixture was stirred at r.t. for 1 min, the formation of 2a was confirmed by NMR, DLS, and AFM analyses. 1
H NMR (500 MHz, D2O, 2.0 mM based on 1a, r.t.): δ 1.97 (s, 12H), 2.00 (dt, J = 6.4,
6.0 Hz, 4H), 2.22 (s, 12H), 2.27 (s, 6H), 2.62 (m, J = 6.4 Hz, 4H), 4.09 (t, J = 6.0 Hz, 4H), 6.58 (s, 1H), 6.96 (s, 1H). 13C NMR (125 MHz, D2O, 2.0 mM based on 1a, r.t.): δ 15.7 (CH3), 15.9 (CH3), 17.4 (CH3), 24.3 (CH2), 47.6 (CH2), 68.2 (CH2), 101.9 (CH), 125.9 (Cq), 132.4 (Cq), 132.8 (Cq), 133.0 (CH), 134.5 (Cq), 135.0 (Cq), 155.0 (Cq). DOSY NMR (400 MHz, D2O, 2.0 based on 1a, 25 ºC): D = 4.16 x 10–10 m2 s–1.
S15
c
d
–O
3S
a
O
g
f
SO3–
h c d
O
b
e
e 2 Na +
f
a b
h
g
Figure S15. 1H NMR spectrum (500 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a.
–O
3S
O
g
f
a
O
b
SO3–
h c d d,e c
e 2 Na +
Cq
Cq b Cq Cq Cq
h
f Cq
g
a
Figure S16. 13C NMR spectrum (125 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a.
S16
f h
g
–O
3S
O
a
g
f O
SO3–
h c d
b
e 2 Na +
Figure S17. 1H-1H COSY spectrum (400 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a.
b
c
–O
3S
O
a b
g
f O
SO3–
h c d e 2 Na +
Figure S18a. NOESY spectrum (500 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a.
S17
d
c
–O
3S
O
a
g
f
SO3–
h c d
O
b
e 2 Na +
Figure S18b. NOESY spectrum (500 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a. f
c
ed h g
d,e c g
h
–O
3S
O
f
a b
g
f O
SO3–
h c d e 2 Na +
Figure S19a. HSQC spectrum (400 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a.
S18
a
b
a
–O
3S
O
a
b b
g
f O
SO3–
h c d e 2 Na +
Figure S19b. HSQC spectrum (400 MHz, D2O, 2.0 mM based on 1a, r.t.) of 2a. a)
b)
log D = –9.37
log D = –9.08
Figure S20. DOSY NMR spectra (400 MHz, 25 ºC) of a) 1a in CD3OD and b) 2a in D2O (2.0 mM based on 1a).
S19
Synthesis of 4b Br
YO-162 MeO
1) n-BuLi, THF 2) ZnCl2, THF
OMe
3) PdCl2(PhCN) 2, P(t-Bu) 3 THF OMe MeO Br
Br
1-Bromobenzene (2.000 g, 12.73 mmol) and dry THF (50 mL) were added to a 2-necked 300 mL glass flask filled with N2. A hexane solution (2.69 M) of n-butyllithium (5.2 mL, 14 mmol) was added dropwise to the flask at –80 ºC under N2. After stirring at –80 ºC for 2 h, a dry THF solution (30 mL) of ZnCl2 (2.250 g, 16.55 mmol) was added to the solution. The resultant mixture was further stirred at –80 ºC for 1 h and then the solution was warmed to r.t. for 1 d to obtain phenylzinc chloride. 1,5-Dibromo-2,4-dimethoxybenene (1.538 g, 5.197 mmol), PdCl2(PhCN)2 (140 mg, 0.364 mmol), and dry THF (30 mL) were added to a 50 mL glass flask filled with N2. A hexane solution (0.95 M) of tri-tert-butylphosphine (0.7 mL, 0.7 mmol) was added to the 50 mL flask. After stirring for 30 min at r.t., the mixture was added to the 300 mL flask and then the resulted solution was further stirred at 85 ºC for 2 d. The precipitated crude product was extracted with CH2Cl2 and hexane (as an azeotropic solvent). The solution was concentrated under reduced pressure. The crude product was collected and washed with CH3OH to afford 4b (0.962 g, 3.31 mmol, 64% yield) as a white solid. 1
H NMR (400 MHz, CDCl3, r.t.): δ 3.92 (s, 6H), 6.72 (s, 1H), 7.35 (t, J = 7.6 Hz, 2H),
7.45 (dd, J = 8.0, 7.6 Hz, 4H), 7.61 (d, J = 8.0 Hz, 4H). 13C NMR (100 MHz, CDCl3, r.t.): δ 56.0 (CH3), 96.6 (CH), 123.5 (Cq), 126.7 (CH), 128.1 (CH), 129.6 (CH), 133.1 (CH), 138.3 (Cq), 157.0 (Cq). FT-IR (KBr, cm–1): 3444, 3021, 3001, 2928, 2836, 1955, 1611, 1582, 122, 1483, 1467, 1433, 1388, 1311, 1284, 1261, 1240, 1203, 1181, 1165, 1075, 1052, 1031, 1011, 948, 899, 818, 765, 723, 701, 678. GC-MS (m/z): Calcd. for C20H18O2: 290, Found 290 [M]+. E.A.: Calcd. for C20H18O2•0.4CH3OH: C, 80.82; H, 6.52. Found: C, 80.99; H, 6.45.
S20
d
c
b
f e
O
a
f O
c d
b d c
b e
e
a
Figure S21. 1H NMR spectrum (400 MHz, CDCl3, r.t.) of 4b.
c
O
a
d
c b
Cq b
Cq
d e
f
e Cq
f O
a
Figure S22. 13C NMR spectrum (100 MHz, CDCl3, r.t.) of 4b.
S21
c
d
e
d
f
a
O
O
c d
b
e
Figure S23. 1H-1H COSY spectrum (400 MHz, CDCl3, r.t.) of 4b.
f a
f
a
O
a
f O
c b
d e
Figure S24a. HSQC spectrum (400 MHz, CDCl3, r.t.) of 4b.
S22
c
d
b e
e d c
b O
a
f O
c b
d e
Figure S24b. HSQC spectrum (400 MHz, CDCl3, r.t.) of 4b.
Synthesis of 5b MeO
OMe
YO-12 BBr 3
HO
OH
CH2Cl2
Benzene dimer 4b (1.000 g, 3.444 mmol) and dry CH2Cl2 (100 mL) were added to a 200 mL glass flask. A CH2Cl2 solution (1.0 M) of BBr3 (13.8 mL, 13.8 mmol) was added dropwise to the flask at 0 ºC under N2. The reaction mixture was stirred and allowed to warm to r.t. overnight. The reaction was quenched with H2O (50 mL). The two layers were separated and then the aqueous layer was extracted with CH2Cl2 (3 × 100 mL). The combined organic layers were dried over MgSO4, filtrated, and concentrated under reduced pressure. The crude product was washed with acetone and hexane to afford 5b (0.850 g, 3.24 mmol, 94% yield) as a white solid.[2] 1
H NMR (400 MHz, CDCl3, r.t.): δ 5.34 (s, 2H), 6.65 (s, 1H), 7.16 (s, 1H), 7.37-7.40 (m,
2H), 7.45 (d, J = 4.4 Hz, 4H), 7.45 (d, J = 4.4 Hz, 4H). 13C NMR (100 MHz, CDCl3, S23
r.t.): δ 103.3 (CH), 121.5 (Cq), 127.7 (CH), 129.3 (CH), 129.4 (CH), 131.7 (CH), 136.9 (Cq), 153.3 (Cq). FT-IR (KBr, cm–1): 3471, 3064, 3025, 2925, 1615, 1532, 1513, 1484, 1445, 1397, 1346, 1313, 1257, 1160, 1075, 1031, 985, 898, 841, 804, 787, 759, 700, 637, 619. GC-MS (m/z): Calcd. for C20H14O2: 262, Found 262 [M]+. E.A.: Calcd. for C20H14O2•0.2CH3COCH3: C, 81.56; H, 5.59. Found: C, 81.56; H, 5.56.
c
HO
d
a
c b
b e
f OH
d e
a f
Figure S25. 1H NMR spectrum (400 MHz, CDCl3, r.t.) of 5b.
S24
cd
a
HO
OH
c e Cq
Cq b
d
b
e
a
Cq
Figure S26. 13C NMR spectrum (100 MHz, CDCl3, r.t.) of 5b. d
e HO
a
f OH
c b
d e
Figure S27. 1H-1H COSY spectrum (400 MHz, CDCl3, r.t.) of 5b.
S25
c,d a
b e
a
e HO
c,d
a
f OH
c
b b
d e
Figure S28. HSQC spectrum (400 MHz, CDCl3, r.t.) of 5b.
Synthesis of 1b
YO-13 O
O S
HO
OH
O
–O
SO3–
3S
O
O
NaOH THF
2 Na +
Benzene dimer 5b (500 mg, 1.91 mmol), NaOH (458 mg, 11.4 mmol), and THF (50 mL) were added to a 50 mL glass flask. 1,3-Propanesultone (755 mg, 5.72 mmol) was added dropwise to the flask. The resultant mixture was stirred at r.t. overnight. The suspended solution was filtrated and then CH2Cl2 (5 mL) and hexane (50 mL) was added to the filtrate. The resultant solution was concentrated under reduced pressure. The crude product was washed with water (2 mL) and 1-propanol (20 mL) to afford 1b (0.500 g, 0.908 mmol, 48% yield) as a white solid. 1
H NMR (400 MHz, CD3OD, r.t.): δ 2.21 (dt, J = 6.8, 6.0 Hz, 4H), 2.93 (t, J = 6.8 Hz,
S26
4H), 4.19 (t, J = 6.0 Hz, 4H), 6.83 (s, 1H), 7.21 (s, 1H), 7.24 (t, J = 7.2 Hz, 2H), 7.37 (dd, J = 8.0, 7.2 Hz, 4H), 7.50 (d, J = 8.0 Hz, 4H). 13C NMR (100 MHz, CD3OD, r.t.): δ 26.4 (CH2), 49.6 (CH2), 68.7 (CH2), 100.4 (CH), 125.2 (Cq), 127.7 (CH), 128.9 (CH), 130.5 (CH), 133.4 (CH), 139.8 (Cq), 157.4 (Cq). FT-IR (KBr, cm–1): 3525, 2940, 2883, 1630, 1610, 1582, 1520, 1484, 1469, 1442, 1409, 1386, 1315, 1277, 1237, 1185, 1044, 890, 816, 798, 769, 699, 656, 623. HR MS (ESI): m/z Calcd. for C24H24NaO8S2 527.0805, Found 527.0807 [M–Na+]–. E.A.: Calcd. for C24H24Na2O8S2•1.9H2O: C, 49.29; H, 4.79. Found: C, 49.14; H, 4.61.
c
d
b
e g O 3S O
a
f
SO3
h
O
c b
d e
2Na
f h
a
g
Figure S29. 1H NMR spectrum (400 MHz, CD3OD, r.t.) of 1b.
S27
g O 3S
c
a
O
d
e Cq b
Cq
SO3
h
O
c b
Cq
f
h
f
d e
2Na
g
a
Figure S30. 13C NMR spectrum (100 MHz, CD3OD, r.t.) of 1b.
f h
g
g O 3S O
a
SO3
f h
O
c b
d e
2Na
Figure S31a. 1H-1H COSY spectrum (400 MHz, CD3OD, r.t.) of 1b.
S28
d
c
e d g O 3S O
a
SO3
f h
O
c d
b
e
2Na
Figure S31b. 1H-1H COSY spectrum (400 MHz, CD3OD, r.t.) of 1b.
f h
a
g
g
h f
a
O 3S O
a
g
f
SO3
h
O
c b
d e
2Na
Figure S32a. HSQC spectrum (400 MHz, CD3OD, r.t.) of 1b.
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c
d
b e
e d c
b g O 3S O
a
SO3
f h
O
c b
d e
2Na
Figure S32b. HSQC spectrum (400 MHz, CD3OD, r.t.) of 1b.
Found
Calcd.
Figure S33. HR MS spectrum (ESI) of 1b.
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Self-assembly of 2b
–O
YO-20
SO3–
3S
O
O D 2O 2 Na +
Amphiphile 1b (0.4 mg, 0.8 µmol) and D2O (0.4 mL) were added to a glass test tube. When the mixture was stirred at r.t. for 1 min, the formation of 2b was confirmed by NMR, DLS, and AFM analyses. 1
H NMR (400 MHz, D2O, 2.0 mM based on 1b, r.t.): δ 2.18 (dt, J = 7.6, 6.4 Hz, 4H),
3.00 (t, J = 7.6 Hz, 4H), 4.26 (t, J = 6.4 Hz, 4H), 6.97 (s, 1H), 7.36 (s, 1H), 7.45 (t, J = 7.4 Hz, 2H), 7.54 (dd, J = 8.0, 7.4 Hz, 4H), 7.58 (d, J = 8.0 Hz, 4H). 13C NMR (125 MHz, D2O, 2.0 mM based on 1b, r.t.): δ 26.2 (CH2), 48.0 (CH2), 67.7 (CH2), 100.6 (CH), 124.4 (Cq), 127.3 (CH), 128.4 (CH), 129.5 (CH), 132.2 (CH), 137.4 (Cq), 155.5 (Cq). DOSY NMR (400 MHz, D2O, 2.0 mM based on 1b, 25 ºC): D = 5.01 x 10–10 m2 s–1.
c d b
a
e
g O 3S O
a
SO3
f h
O
c b
d e
2Na
f h
a
g
Figure S34. 1H NMR spectrum (400 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b.
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g O 3S
a
O
SO3
f h
O
c b d
d e
2Na
c Cq
e Cq b Cq
h
f
g
a
Figure S35. 13C NMR spectrum (125 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b.
f h
g
g O 3S O
a
SO3
f h
O
c b
d e
2Na
Figure S36a. 1H-1H COSY spectrum (400 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b.
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d
e g O 3S O
SO3
f
a
h
O
c d
b
e
2Na
Figure S36b. 1H-1H COSY spectrum (400 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b.
f h
a
g
g
h f
a
O 3S O
a
g
f
SO3
h
O
c b
d e
2Na
Figure S37a. HSQC spectrum (400 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b.
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c
d e
b
e d c b
g O 3S O
a
SO3
f h
O
c b
d e
2Na
Figure S37b. HSQC spectrum (400 MHz, D2O, 2.0 mM based on 1b, r.t.) of 2b. a)
b)
log D = –9.30
log D = –9.03
Figure S38. DOSY NMR spectra (400 MHz, 25 ºC) of a) 1b in CD3OD and b) 2b in D2O (2.0 mM based on 1b).
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a)
b) 90
90 d av. = 1.6 nm
60 45 30 15 0 0.1
60 45 30 15
1
10
0 0.1
100 nm
c)
1
10
100 nm
d) 90
60 d av. = 2.0 nm
75 60 45 30 15 0 0.1
d av. = 2.2 nm
50 40
% Mass
% Mass
d av. = 1.6 nm
75 % Mass
% Mass
75
30 20 10
1
10
0 0.1
100 nm
1
10
100 nm
Figure S39. Concentration-dependent particle size distribution of 2a by DLS analysis (H2O, r.t.): a) 1.0, b) 2.0, c) 5.0, and d) 10 mM based on 1a. b)
a)
90
60 d av. = 1.4 nm
40 30 20
1
10
45 30 0 0.1
100 nm
1
10
100 nm
d)
c)
90
60 dav. = 2.1 nm
50 40 30 20
60 45 30 15
10 0 0.1
d av. = 2.0 nm
75 % Mass
% Mass
60
15
10 0 0.1
d av. = 2.0 nm
75 % Mass
% Mass
50
1
10
100 nm
0 0.1
1
10
100 nm
Figure S40. Concentration-dependent particle size distribution of 2b by DLS analysis (H2O, r.t.): a) 1.0, b) 2.0, c) 5.0, and d) 10 mM based on 1b.
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a) 2 nm
b)
count (N)
20
20
0
nm
d av = 1.8 nm
15 10 5 0 0
4
2
8 nm
6
Figure S41. a) AFM image of 2b on mica. b) the size and number (N) distribution. a)
b) 3.0
1.5
1.0
Absorbance
Absorbance
2.5
2.0 mM 1.0 mM
0.5
2.0
2.0 mM
1.5 1.0
1.0 mM
0.5 0 250
0.5 mM 275
300
325
0 250
nm
0.5 mM 275
325
300
nm
Figure S42. Concentration-dependent UV-vis spectra (H2O, r.t.) of a) 2a and b) 2b. a)
b) 6.0
Fluorescence (x10 3)
Fluorescence (x10 3)
4.0
0.5 mM Φ = 0.09 1.0 mM Φ = 0.09
2.0
2.0 mM Φ = 0.08 0 290
320
350
380
410
440
0.5 mM Φ = 0.36
2.0 mM Φ = 0.37 0 300
nm
1.0 mM Φ = 0.37
3.0
330
360
390
420
450
nm
Figure S43a. Concentration-dependent fluorescence spectra (H2O, r.t.) of a) 2a and b) 2b. Excitation wavelengths: λex = 286 nm for 2a, λex = 299 nm for 2b. b) 1.0
Normalized fluorescence
Normalized fluorescence
a) 2a 1a
0.5
330
0 290
320
350
380
330
410
440
nm
0.001 mM
1.0
0.01, 0.1, 1.0 mM
0.5 330 0 290
320
350
380
410
440
nm
Figure S43b. a) Fluorescence spectra (λex = 286 nm, 1.0 mM based on 1a, r.t.) of 1a (CH3OH) and 2a (H2O). b) Concentration-dependent fluorescence spectra (λex = 286 nm, 1.0, 0.1, 0.01, and 0.001 mM based on 1a, r.t.) of 2a in H2O.
S36
2a
2a + 2c =1:1
2c 10
8
9
7
6
5
4
3
2
1 ppm
Figure S44. 1H NMR spectra (400 MHz, D2O, r.t.) of 2a, 2c, and 2a + 2c (1.0 mM based on the corresponding monomer).
b)
Absorbance
2.0
2a : 2c =1: 3 2a : 2c =1:1
1.0
2a : 2c = 3: 1 0 250
300
350
400
450
6.0
Fluorescence (x10 3)
a)
nm
2a : 2c = 3: 1 3.0
2a : 2c =1: 3 2a : 2c =1:1
0 300 350 400 450 500 550 nm
Figure S45. a) UV-vis and b) fluorescence spectra (H2O, r.t., λex = 286 nm) of the 1:3, 1:1, and 3:1 mixtures of 2a and 2c (1.0 mM based on the corresponding monomer).
Synthesis of 2a-c•(3)n HO 2a-c +
O
O COOH
H 2O
2a-c•(3)n
Fluorescein (3)
Fluorescein (3; 0.33 mg, 1.0 μmol) was added to a H2O solution (2.0 mL) of 2a-c (2.0 μmol based on 1a-c) in a micro tube. The suspend mixture was stirred at r.t. for 1 h. After filtration, the resulting green solution including 2a-c•(3)n was confirmed by UV-vis and fluorescence analyses.
S37
Synthesis of 2a-c•(4)n Br HO
Br O
O
2a-c + Br
Br COOH
2a-c•(4)n
H 2O
Eosin Y (4)
Eosin Y (4; 0.65 mg, 1.0 μmol) was added to a H2O solution (2.0 mL) of 2a-c (2.0 μmol based on 1a-c) in a micro tube. The suspend mixture was stirred at r.t. for 1 h. After filtration, the resulting red solution including 2a-c•(4)n was confirmed by UV-vis and fluorescence analyses. a)
b) 60 d av. = 10.2 nm
30 20 10
30 20 10
1
10
0 0.1
100 nm
d)
1
10
% Mass
40 30 20 0 0.1
1
10
100 nm
1
10
100 nm
90 d av. = 1.6 nm
75 60 45 30 15
10
30
f)
0 0.1
d av. = 1.7 nm
75 % Mass
50
45
0 0.1
100 nm
90 d av. = 12.7 nm
60
15
e) 60
% Mass
40
d av. = 2.3 nm
75 % Mass
40
90 d av. = 1.6 nm
50 % Mass
% Mass
50
0 0.1
c) 60
60 45 30 15
1
10
100 nm
0 0.1
1
10
100 nm
Figure S46. Particle size distribution of a) 2a•(3)n, b) 2b•(3)n, c) 2c•(3)n, d) 2a•(4)n, e) 2b•(4)n, and f) 2c•(4)n by DLS analysis (H2O, 1.0 mM based on the corresponding monomers, r.t.).
S38
a)
R O
R O
R O
R O
+
H 2O
1c
H 2O
1d
(R = -CH2CH2CH2SO3–•Na +)
(1c)n•(1d)m
c) Normalized fluorescence
Normalized absorbance
b)
250
2c + 2d
2d 2d + 2c 2c
300
350
400
450 nm
2c 2d
2d + 2c
350 400 450 500 550 600 nm
Figure S47. (a) Schematic representation of the formation of a complex mixture of nanoassemblies (1c)n•(1d)m in water. (b) Normalized UV-visible and (c) fluorescence spectra (H2O, r.t., λex = 293 nm) of 2c, 2d, and 2c + 2d (1.0 mM based on 1c,d each).
a)
R O
R O
1c +
H 2O
2c + 2e
H 2O
1e (1c)n•(1e)m
(R = -CH2CH2CH2SO3–•Na +)
c)
250
Normalized fluorescence
Normalized absorbance
b) 2e 2e + 2c 2c
300
350
400
450 nm
2e
2e + 2c
2c
350 400 450 500 550 600 nm
Figure S48. (a) Schematic representation of the formation of a complex mixture of nanoassemblies (1c)n•(1e)m in water. (b) Normalized UV-visible and (c) fluorescence spectra (H2O, r.t., λex = 293 nm) of 2c, 2e, and 2c + 2e (1.0 mM based on 1c,e each).
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a)
b)
c) b) b)
b)
core diameter: ~1.0 nm outer diameter: ~2.0 nm
core diameter: ~1.2 nm outer diameter: ~2.5 nm
core diameter: ~1.5 nm outer diameter: ~3.0 nm
Figure S49. Optimized structures of spherical assemblies (a) (1a)4, (b) (1a)5, and (c) (1a)6.
2a•(3)n
330 3
8
7
6
5
1
4
3
2
ppm
Figure S50. H NMR spectra (400 MHz, D2O, r.t.) of 2a•(3)n (2.0 mM based on 1a) and 3 (saturated concentration).
S40
