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Supporting Information
Self-assembly of sodium and potassium betulinates into hydro- and organo-gels: Entrapment and removal studies of fluorophores and synthesis of gel-gold nanoparticle hybrid materials
Braja Gopal Bag,* Shib Shankar Dash
Department of Chemistry and Chemical Technology, Vidyasagar University,
Midnapore 721102, West Bengal, India
Email: [email protected]
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
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Table of Contents Pages
1. Figure S1 and S2: Optical micrograph images of salts 2 and 3 S3
2. Figure S3: SEM images of dried self-assemblies of 2 S4
3. Table S1: Thermodynamic parameters of sodium betulinate 2 S5
4. Figure S4: ln K vs 1/T (K) plot of 2 and 3 S6
5. Figure S5 and S6: FTIR images of 1, 2 and 3 S7
6. Figure S7: POM images of 3 loaded with Rhodamine B S8
7. Table S8: Fluorescence Emission spectra of potassium betulinate 3 S8
8. Figure S9: UV-visible spectra obtained during dye removal studies S9
9. Figure S10: Structure of the chemicals present in the bark extract of Ziziphus jujube S10
10. 1H and 13C NMR of sodium betulinate 2 S11
11. 1H and 13C NMR of potassium betulinate 3 S12
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Figure S1: Optical micrographs of potassium betulinate 3: (a, b) 1.67% w/v in water; (c) 2.8% w/v in EG-water (1:1v/v) and (d) 1.9% w/v in DMF-water (1:1 v/v)
Figure S2: Optical micrographs of sodium betulinate 2 (2.1% w/v) in EG-water (1:1 v/v)
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Figure S3: SEM images of dried self-assemblies prepared from a hydrogel of sodium betulinate 2 (0.71 % w/v).
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Calculation of thermodynamic Parameters:
The thermoreversible melting of a gel can be expressed as:
Gel liquid
The equilibrium constant can be expressed as:
K = [Gelator]/ [Gel]
Assuming unit activity of the gel, the equilibrium constant can be expressed as:
K = [Gelator]
The Gibbs free energy change during gel melting can be expressed as:
G = - RT lnK =H – TS, Hence, lnK = -H/R. (1/T) + S/R
Table S1: Thermodynamic parameters (Ho, So, Go) at 298 ºK of the sodium
betulinate gel melting in different liquids.
Liquids kJ/mol S J/mol/K G kJ/mol
DMSO-water 76.01 202.36 15.71
DMF-water 58.71 154.39 12.7
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The gel melting temperature (Tgel) increases with increasing concentration of the “solutes”. A plot of ln K vs 1/T allowed us to calculate the thermodynamic parameters. Representative plots for gel in DMSO-water (1:1v/v) and DMF-water (1:1v/v) for both 2 and 3 were given in the figure below:
Figure S4: ln K vs 1/T (K) plot of (A) 2 in DMSO-water; (B) 2 in DMF-water; (C) 3 in DMSO-water and (D) 3 in DMF-water.
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Figure S5: FTIR spectra (a) powder sample of betulinic acid 1; (b) dried self-assemblies prepared from a hydrogel of 2 and (c) powder sample of 2.
Figure S6: FTIR spectra (a) powder sample of betulinic acid 1; (b) dried self-assemblies prepared from a hydrogel of 3 and (c) powder sample of 3.
4000 3500 3000 2500 2000 1500 1000 500
20
30
40
50
60
70
80
(c)
(b)
(a)
15481559 (COO-)
Inten
sity (a
.u)
Wave no (cm-1)
4000 3500 3000 2500 2000 1500 1000 5000
20
40
60
1541 (COO-)
(c)
(b)
(a)
1539
Inten
sity (
a.u)
Wave no (cm-1)
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Epifluorescence Microscopy: The epifluorescence microscopy images revealed the entrapment of rhodamine B on the self-assemblies of potassium betulinate 3 in water.
Figure S7: (a-b) Self-assemblies of potassium betulinate 3 loaded with rhodamine B in water: (a) under normal light; (b) under fluorescence light.
Figure S8: Fluorescence Emission Spectra: (a) rhodamine-B (c = 0.03 mM) in phosphate buffer (0.01 M, pH = 7.2); (b) in the presence of a hydrogel obtained from potassium betulinate 3 after 4 hours. Upon excitation at 554 nm (rhodamine B), emission spectra appeared at 581.4 nm. Decrease of fluorescence intensity with time indicated the removal of rhodamine-B dye from the aqueous buffer solution.
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Figure S9: (a, b) UV−visible spectroscopy of CF solution kept in contact with the hydrogels of sodium betulinate 2 (2.5% w/v) and potassium betulinate 3 (2.5% w/v) respectively; (c, d) UV−visible spectroscopy of NR solution kept in contact with the hydrogels of sodium betulinate 2 (2.5% w/v) and potassium betulinate 3 (2.5% w/v) respectively, Inset: left: structure of the dye molecules, right: photograph of vials at different times.
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Figure S10: Probable structures of compounds present in the bark extract of Ziziphus jujube, as evident from the mass spectral analysis.
O
O
OH
OH
OHOH
OH
Quercetin
OH
O OH
Betulinic acid Betulonic acid
O
O OH
OH
Beta-sitosterol
OHOHOH
O OH
Gallic acid
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