1

Cholesterol-tethered AIEE Fluorogens: Formation of Self-Assembled Nanostructures.

Veerabhadraiah Palakollu and SriramKanvah*

Department of Chemistry, Indian Institute of Technology Gandhinagar, Chandkheda,

Ahmedabad 382424

e-mail: kanvah@gmail.com, sriram@iitgn.ac.in

Figure S1. Absorption spectra of a) stilbene(1), b) stilbene-choelsterol(2) and c) diene(3) in

homogeneous solvents

250 300 350 400 450 500 550

0.0

0.1

0.2

0.3

0.4

Abs

orba

nce

Wavelength (nm)

DCM THF Heptane Dioxane DMF Acetonitrile

S1a

250 300 350 400 450 500 550 600

0.0

0.1

0.2

0.3

0.4

Abs

orba

nce

Wavelength (nm)

Hepatne DCM Dioxane THF DMF Acetonitrile

S1b

250 300 350 400 450 500 550 600

0.00

0.05

0.10

0.15

0.20

0.25

0.30

Abs

orba

nce

Wavelength (nm)

Heptane DCM Dioxane THF DMF Acetonitrile

S1c

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

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Table S1.Excitation data of (1) to (4) in organic solvents. The excitation data are uncorrected.

Solvent λex(nm)

Solvent λex(nm)

Heptane 389 Heptane 384Dioxane 390 CH2Cl2 390THF 395 Dioxane 387CH3CN 392 CH3CN 385

(1)

Water 399

(2)

Water 389

Heptane 420 Heptane 411

Dioxane 417 Dioxane 419

THF 421 THF 419

CH3CN 413 CH3CN 423

(3)

Water 421

(4)

Water 422

Fig S1a: Excitation Spectra of (1), (2), (3) and (4) in homogeneous solvents.

300 350 400 4500.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

Dichloromethane Heptane Dioxane Tetrahydrofuran Acetonitrile Water

(1)

250 300 350 400 4500.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

Heptane Acetonitrile Dioxane Water Dichlloromethane

(2)

300 350 400 450 5000.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

Hepatne Dioxane Tetrahydron Acetonitrile Water

(3)

300 350 400 4500.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

Heptane Water Tetrahydrofuran Acetonitrile

(4)

3

Figure S2.Emission spectra ofa) stilbene (1), b) stilbene-cholesterol (2) in homogeneous

solvents

Figure S3. Emission spectra of diene (3) and diene-cholesterol (4) in solid state

400 450 500 550 600 650 7000.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

THF Dioxane DCM DMF Heptane Acetonitrile

S2b

450 500 550 600 650 700 7500.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

(a. u

)

Wavelength (nm)

Diene Diene-Cholesterol

400 450 500 550 600 650 700

0.0

0.2

0.4

0.6

0.8

1.0In

tens

ity (a

. u)

Wavelength (nm)

Heptane DCM Dioxane Acetonitrile DMF THF

S2a

4

Figure S4.SEM images of a) stilbene (1) and b) stilbene cholesterol (2) in dioxane

Figure S5.SEM images of a) diene and b) diene cholesterol in dioxane

Figure S6. UV spectra of stilbene (1) in sodium cholate solutions

S4a S4b

S5a S5b

300 400 500 600

0.0

0.1

0.2

0.3

0.4

Abso

rban

ce

Wavelength (nm)

Stilbene-Water 6mM 20mM

5

Figure S7. Sigmoid plots of cholate concentration vs emission intensity at ~467 nm of a) stilbene (1)[CMC is 14.6 mM], b) stilbene cholesterol (2)[CMC is 14.7 mM]and c) diene (3) [CMC is 16.5 mM] as the probes d) Colors changes of aqueous sodium-cholate solution at 8mM and 16mM respectively in presence of dyes (stilbene (1), stilbene-cholesterol (2), diene (3) under UV lighting conditions

8 10 12 14 16 18 20 22 24 26

2.0x105

4.0x105

6.0x105

8.0x105

1.0x106

1.2x106

Inte

nsity

Cholate concentration (mM)

8 10 12 14 16 18 20 22 24

2.0x105

4.0x105

6.0x105

8.0x105

1.0x106

Inte

nsity

Cholate concentration (mM)8 10 12 14 16 18 20 22

3.00x105

4.50x105

6.00x105

7.50x105

9.00x105

Inte

nsity

Cholate concentration (mM)

S7a S7b

S7cStilbene 1 Stilbene 2Diene-3

S7d

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Figure S8.SEM images of sodium cholate at a) lower (8 mM) and b) higher concentrations (16

M) in Millipore water

Figure S9.SEM images of diene (3) and diene cholesterol (4) at different concentration of

cholate. a) 8mM and at b) 16mM for (1); (c) 8mM; d) 16mM for (2). Inset shows the SEM at

lower magnification.

S8a S8b

S9a S9b

S9c S9d

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Figure S10a.CD Spectra of stilbene in dioxane and water; b) CD spectra of sodium cholate at 8mM and 16mM.

200 250 300 350 400 450 500 550 600

-0.4

-0.2

0.0

0.2

0.4

mde

g

Wavelength (nm)

Dioxane Watera

200 250 300 350 400 450 500 550 600

-0.4

-0.2

0.0

0.2

mde

g

Wavelength (nm)

8MM 16mM

b

8

Spectral data

1H NMR of CPA (6)

13C NMR of CPA (6)

O

CNO

9

1H NMR (Z)-3-(4-(dimethylamino)phenyl)-2-(4-hydroxyphenyl)acrylonitrile (1)

HO

CNN

13C NMR (Z)-3-(4-(dimethylamino)phenyl)-2-(4-hydroxyphenyl)acrylonitrile (1)

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Mass spectrum of (Z)-3-(4-(dimethylamino)phenyl)-2-(4-hydroxyphenyl)acrylonitrile (1)

Exact mass 264.13

Mass obtained in positive mode 265.1266 (M+1)

1H NMR of (2Z,4E)-5-(4-(dimethylamino)cyclohexa-2,4-dien-1-yl)-2-(4-

hydroxyphenyl)penta-2,4-dienenitrile (3)

NCN

OH

(1)

HO

CN N

11

13C NMR of (2Z,4E)-5-(4-(dimethylamino)cyclohexa-2,4-dien-1-yl)-2-(4-

hydroxyphenyl)penta-2,4-dienenitrile (3)

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Mass spectra of (2Z,4E)-5-(4-(dimethylamino)cyclohexa-2,4-dien-1-yl)-2-(4-

hydroxyphenyl)penta-2,4-dienenitrile (3)

Exact mass290.142

Mass obtained in positive mode 291.0769 (M+1)

1H NMR of stilbene-cholesterol (2)

O

OOH

H

H

N NC

13

13C-NMR of stilbene-cholesterol (2)

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Mass spectra of stilbene cholesterol (2)

Exact mass676.46

Mass obtained in positive mode 677.3047(M+1)

1H NMR of diene-cholesterol (4)

O

OOH

H

H

NNC

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13C NMR of diene-cholesterol (4)

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Mass spectra of diene cholesterol (4)

Mass obtained in positive mode 702.7087 (M+1)