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Electronic Supplementary Information for
Manuscript ID NJ-ART-02-2017-000661
New Journal of Chemistry
Complexation behaviour of caffeic, ferulic and p-coumaric acids towards aluminium cation: a combined experimental and theoretical approach
Amerigo Beneduci, Emilia Furia*, Nino Russo and Tiziana Marino
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
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Figure S1. UV absorption spectra of caffeic acid (a), ferulic acid (b) and p-coumaric acids (c).
Figure S2. UV spectra at pH=3.5 of 0.1 mM ferulic acid free (line 1) and of the complexes formed between ligands and AlCl3
0.1 mM (line 2).
a
b
c
1 2
Wavelenght (nm)
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Figure S3. UV spectra at pH=3.5 of 0.1 mM p-coumaric acid free (line 1) and of the complexes formed between ligands and AlCl 0.1 mM (line 2).
3
Figure S4. 1D 1H-NMR spectra of caffeic, p-coumaric and ferulic acid at pH 3.5.
1
2
Wavelenght (nm)
Ferulic acid
p-Coumaric acid
Caffeic acid
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Figure S5. 1D 1H-NMR spectra of ferulic, p-coumaric and caffeic acids at pH 3.5 in the 6.3-7.8 ppm spectral range.
c
a
b
c c
a,b
d
c a
b
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pH = 4.5
pH = 3.5
Figure S6. 1H-NMR spectra of ferulic acid at different pH.
pH = 4.5
pH = 3.5
Figure S7. 1H-NMR spectra of p-coumaric acid at different pH.
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Figure S8. Up-field shift of the 1H-NMR doublet of the β-proton of ferulic and p-coumaric acids plotted as a function of
increasing concentration of Al3+ at pH 3.5.
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Figure S9. Four “Gouterman’s orbitals” of the lowest energy caffeic acid complex.
Figure S10. Four “Gouterman’s orbitals” of the lowest energy ferulic acid complex.
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Figure S11. Four “Gouterman’s orbitals” of the lowest energy p-coumaric acid complex.
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Table S1. Main excitation energies (∆E), oscillator strengths ( f) and MO contribution (%) computed for free ligands ,
calculated at (TD)-M052X/6-31G* level of theory, in aqueous solution.
Acids MO contribution ∆E f
Bands nm eV Caffeic S1
S2
S3
S4
HL (70%)
H-1L(53%); HL+1 (45%)
H-4L (50%);H-1L+1(41%9
H-> L+5 (63%); H-1 L+1 (27%)
277
213
195
177
4.48
5.83
6.36
7.00
0.704
0.572
0.211
0.119
Ferulic S1
S2
S3
S4
HL (70%)
H-1 L (54%); HL+1 (46%)
H-1L+1(44%); H-5L
(24%) H-1L+1(36%);
HL+5(58%)
279
214
194
178
4.44
5.60
6.38
6.94
0.683
0.669
0.186
0.163
p-Coumaric S1
S2
S3
S4
HL (70%)
H-1
L(60%);HL+1(37%) H-
1L+1(46%)
H-1L+1 (48%)
273
204
192
175
4.53
6.08
6.46
7.08
0.7596
0.3435
0.2929
0.3097