supporting information - royal society of chemistry · 2015. 6. 3. · supporting information...

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Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly in water and application in drug delivery Krishnamoorthy Lalitha, a Y. Siva Prasad, a C. Uma Maheswari, a Vellaisamy Sridharan, a George John, b Subbiah Nagarajan* a a Organic Synthesis Group, Department of Chemistry & The Centre for Nanotechnology and Advanced Biomaterials, School of Chemical and Biotechnology, SASTRA University, Thanjavur - 613401, Tamil Nadu, INDIA Fax: 04362264120; Tel: 04362304270; E-mail: [email protected]. b Department of Chemistry, the City College of New York. 160 Convent Ave. New York, NY 10031. Electronic Supplementary Material (ESI) for Journal of Materials Chemistry B. This journal is © The Royal Society of Chemistry 2015

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Page 1: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Supporting Information

Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly in water and application

in drug deliveryKrishnamoorthy Lalitha,a Y. Siva Prasad,a C. Uma Maheswari,a Vellaisamy Sridharan,a George John,b Subbiah Nagarajan*a

a Organic Synthesis Group, Department of Chemistry & The Centre for Nanotechnology and

Advanced Biomaterials, School of Chemical and Biotechnology, SASTRA University, Thanjavur

- 613401, Tamil Nadu, INDIA Fax: 04362264120; Tel: 04362304270; E-mail:

[email protected] Department of Chemistry, the City College of New York. 160 Convent Ave. New York, NY 10031.

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry B.This journal is © The Royal Society of Chemistry 2015

Page 2: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Table S1: Vegetable oil/Solvent used for gelation studies

S.No Oil/Solvent 4a 4b 4c

1 Hazelnut P P P

2 Sesame P P P

3 Jojoba P P P

4 Olive P P P

5 Soyabean P P P

6 Linseed P S S

7 Light paraffin P P P

8 Heavy paraffin P PG PG

9 Dodecanol I S S

10 Ethanol P P S

11 n-Butanol P S S

12 Octanol P S S

13 Toluene I I I

14 Cyclohexane I I I

15 n-heptane I I I

16 Ethylene glycol I I I

17 Ethanol+water S S PG

18 DMSO S S S

19 DMF S S S

20 DMSO+water S PG G

DMF+water S S S

S – Soluble; I – Insoluble; P – Precipitation; PG – Partial gel formation

Calculated quantity of gelator was taken in a separate glass vial and about 20-30 μL of

DMSO was added. The vials were heated to dissolve the compounds and then distilled water was

added drop wise. The formation of cloudy white solution was observed which was again heated to

get clear homogeneous solution and cooled to room temperature to form hydrogel. Gel formation

has been observed within 5-6 h. The thermorevesibility of these gels were confirmed by repeating

heating and cooling experiments.

Page 3: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Figure S1 Photograph of the hybrid hydrogel formed from compound 4c.

Figure S2. Morphology of self-assembled fibers formed from 4c in acidic pH.

Page 4: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Figure S3 - Zetasizer report of 4c, average diameter of micelles is 197nm

Figure S4. Photographs of the gel (a) without curcumin (B) with curcumin drug (C) curcumin

loaded gel in acidic buffer pH 4

Page 5: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Position [°2Theta] (Copper (Cu))20 30 40 50 60 70

Counts

0

100

200

300

A-D

Figure S5. WAXD data for gel.

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1

2

Figure S6. 1H NMR spectra of (a) gelator, 4c in DMSO-d6 and (b) gel formed by 4c in DMSO-d6-D2O (1:2

ratio).

(a)

(b)

Page 6: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Copies of 1H and 13C spectra

01234567891011f1 (ppm)

-0.0

01

0.85

40.

878

0.89

91.

252

1.25

91.

271

1.29

01.

300

1.59

11.

641

1.95

01.

965

1.97

61.

984

1.99

92.

010

2.01

92.

034

2.04

52.

587

2.61

22.

638

5.32

55.

334

5.34

45.

355

5.36

45.

379

5.39

3

6.80

16.

821

6.84

7

7.43

07.

456

9.82

7

11.0

47

OHCH3

O

Page 7: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

020406080100120140160180200f1 (ppm)

14.1

222

.67

27.1

727

.24

29.0

029

.16

29.2

129

.25

29.3

429

.44

29.6

329

.67

29.7

229

.74

30.6

631

.80

32.6

236

.44

117.

0711

8.85

120.

50

129.

7413

0.00

133.

58

153.

78

161.

80

195.

80

OHCH3

O

Page 8: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

-0.0

02

0.85

40.

877

0.89

81.

287

1.30

31.

318

1.33

91.

566

1.58

81.

614

1.63

91.

663

2.58

62.

612

2.63

8

6.80

26.

817

6.82

26.

843

6.84

8

7.43

27.

458

9.82

9

11.0

45

OH

CH3

O

Page 9: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

020406080100120140160180200f1 (ppm)

14.1

3

22.7

129

.25

29.3

829

.44

29.5

429

.67

29.7

130

.67

31.9

436

.45

117.

0711

8.84

120.

49

133.

57

153.

82

161.

79

195.

78OH

CH3

O

Page 10: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

0.00

0

0.78

40.

808

0.83

11.

192

1.21

61.

240

1.31

71.

341

1.35

11.

364

1.60

41.

901

1.93

01.

950

2.62

02.

646

2.67

1

4.30

74.

331

4.35

44.

378

5.27

35.

276

5.30

5

7.06

77.

073

7.09

67.

423

7.42

87.

451

8.44

9

O

O

O

OCH3

CH3

Page 11: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

020406080100120140160180200f1 (ppm)

14.2

322

.63

27.1

227

.19

28.9

529

.11

29.1

529

.34

29.6

629

.69

30.8

336

.26

41.6

5

61.4

761

.80

77.2

7

115.

7211

6.19

116.

88

125.

4712

9.22

129.

6712

9.99

148.

7115

1.30

155.

4015

7.01

163.

25

166.

60

O

O

O

OCH3

CH3

Page 12: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

0.00

0

0.80

80.

827

0.85

01.

182

1.23

41.

318

1.34

21.

365

2.61

92.

645

2.67

1

4.30

84.

332

4.35

64.

379

7.07

47.

097

7.20

17.

422

7.42

77.

445

7.45

0

8.45

0

O

O CH3

O

OCH3

Page 13: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

020406080100120140160180200f1 (ppm)

1.02

14.1

214

.24

22.6

929

.19

29.3

629

.41

29.5

229

.62

29.6

529

.69

30.8

531

.92

36.2

9

61.8

3

115.

7311

6.20

125.

50

129.

23

148.

7515

1.33

155.

4115

7.06

163.

26

O

O CH3

O

OCH3

Page 14: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

-0.0

00

3.66

63.

684

4.82

94.

848

4.86

6

7.43

17.

456

7.48

17.

521

7.54

87.

737

7.74

27.

765

7.77

07.

789

7.79

47.

987

7.99

28.

013

8.01

8

8.92

98.

984

O

NH

OH

OH

OH

O

O

Page 15: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

0.00

00.

011

0.88

8

1.25

41.

319

1.90

0

2.73

72.

759

3.80

13.

808

5.30

55.

316

7.20

17.

267

7.27

67.

282

7.57

47.

602

8.86

3

9.73

5

O

NH

OH

OH

OH

O

OCH3

Page 16: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

-20020406080100120140160180200f1 (ppm)

13.1

1

21.6

526

.23

28.1

928

.37

28.7

129

.84

30.7

435

.32

61.3

261

.68

76.2

8

115.

0511

5.36

115.

93

125.

00

128.

70

147.

7115

0.38

153.

74

160.

4216

2.04

O

NH

OH

OH

OH

O

OCH3

Page 17: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

01234567891011f1 (ppm)

0.00

0

0.85

20.

875

0.89

6

1.32

0

1.64

01.

666

2.71

92.

744

2.77

0

3.73

33.

752

4.82

74.

848

7.15

97.

184

7.21

6

7.63

57.

662

8.87

5

9.53

2O

NH

OH

OH

OH

O

OCH3

Page 18: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

020406080100120140160180200f1 (ppm)

13.6

6

22.0

828

.59

28.7

328

.80

28.9

129

.03

29.0

630

.30

31.3

135

.69

38.7

4

61.6

862

.34

115.

3411

5.85

116.

88

125.

50

129.

21

147.

7815

0.59

154.

15

160.

6516

2.01

O

NH

OH

OH

OH

O

OCH3

Page 19: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Mass spectra of compound 4b

Page 20: Supporting Information - Royal Society of Chemistry · 2015. 6. 3. · Supporting Information Stimuli Responsive hydrogel derived from Renewable Resource: Synthesis, Self-Assembly

Mass spectra of Compound 4c