# Solid state complexation of natural organic dyes with Al(III): electronic and vibrational spectroscopies

Sylvie Blanc, Tu Khai Nam Nguyen, Kevin Bourhis, Eve Péré, Carole Mathe, Catherine Vieillescazes

► To cite this version:

Sylvie Blanc, Tu Khai Nam Nguyen, Kevin Bourhis, Eve Péré, Carole Mathe, et al.. Solid state complexation of natural organic dyes with Al(III): electronic and vibrational spectroscopies. 30th European Congress on Molecular Spectroscopy, Aug 2010, Florence, Italy. hal-05367779

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# Solid state complexation of natural organic dyes with Al(III): electronic and vibrational spectroscopies

Sylvie Blanc
Tu Khai Nam Nguyen
Kevin Bourhis
Eve Péré

Carole Mathe

Catherine Vieillescazes

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Institut Pluridisciplinaire de Recherche
sur l'Environnement et les Matériaux

Equipe Chimie Physique

Laboratoire de Chimie Bioorganique et des
Systèmes Moléculaires Vectoriels

Equipe Chimie Appliquée à l'Art et à l'Archéologie
# Yellow of Avignon : short history

## Characteristics

* Yellow dyes extracted from fruits of *Rhamnus* species

* Tinctorial properties known since the Antiquity

* Employed in artistic paintings as yellow lakes

* Production in the area of Avignon (commercial place)

<figure><img src="image_9.png" /></figure>

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Livre des Jeux of Alphonse le Sage
1282 Escorial's Library

## History

* Lateran Council of 1215 discrimination of the Jews using yellow dye (until the 18th century)
# Preparation of Avignon yellow lakes (Stil-de-grain)

## Marcucci's «recipe»

* Powdering of dried immature *Rhamnus* berries

* Maceration under agitation during 24-48 hours

* Filtration to remove the residues

* Addition of alum ($KAl(SO_4)_2$, 12 $H_2O$)

* Precipitation of the mixture with an alcalinic carbonate

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /></figure>

## Physico-chemical explanation provided

* Extraction of the dye during the maceration

* Complexation of the dye by the metallic ion $Al^{3+}$ contained in alum

* Precipitation of the complex with an elevation of the pH from 5 to 12

↔ formation of an inorganic matrix of amorphous aluminium hydroxide including the organic dyes

L. Marcucci, Saggio analytico-chimico sopra i colori minerali, 2nd ed., Rome (1816), 120-121
# Objectives

* Extraction and characterization of the natural dyes

<figure><img src="image_13.png" /></figure>

* Preparation of lakes without solvent

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* Characterisation of the materials by spectroscopy

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<figure><img src="image_16.png" /></figure>
# Yellow dyes of *Rhamnus catharticus*

## ♦ Optimization of the extraction process

* quantity of *Rhamnus* berries

* solvent

* temperature

* time

H₂O

⇒ 1 h (maceration)
room T

## ♦ Separation and identification by HPLC-PDA

<figure><img src="image_17.png" /><figcaption>Rhamnétine-3-O-rhamninoside</figcaption></figure>

<figure><img src="image_18.png" /><figcaption>Quercitrin</figcaption></figure>

⇒ Two major extracted molecules : quercetin derivatives
# Natural and quercetine lake

A precipitate obtained by mixing
dye+alun+carbonate in solution

## ♦ Natural lake

### Optimization of conditions

<figure><img src="image_19.png" /></figure>

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## ♦ Quercetine lake

### Parameters of preparation

$$[Q]=10^{-3} \text{ M}; [\text{Alun}] = 7 \text{g L}^{-1}$$

Immediate precipitatipn at pH = 7 ($\text{Na}_2\text{CO}_3$)

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$$\text{[berries]}=0.015\text{g L}^{-1}; [\text{Alun}] = 9\text{g L}^{-1}; \text{pH} = 7$$

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### Quercetin : chromophore model
# Quercetin in solution

## Acid-base properties

<figure><img src="image_24.png" /></figure>

Several protonation sites

<figure><img src="image_25.png" /></figure>

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Absorption spectrum versus pH

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Al(III) complexation

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Several coordination sites

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Several complexes

1 cation : AlQ, AlQ₂, AlQ₃,

2 cations : Al₂Q, Al₂Q₃

# Solid state properties?

L. Dangleterre, J.P. Cornard, C. Lapouge, Polyhedron 27 (2008) 1581; T.L. Lin, B.Z. Yan, G.F. Hu, M. Wang, Chinese Chemical Letters 17 (2006) 937; R.F.V. De Souza, W.F. de Giovani, Spectrochim. Acta, Part A 61 (2005) 1985; X. Chang, S. Wang, H. Luo, G. Gong. J. Fluoresc. 13 (2003) 421; J.P. Cornard, J.C. Merlin, J. Inorg. Biochem. 92 (2002) 19; A.C. Gutierrez, M.H. Gehlen, Spectrochim. Acta, Part A 58 (2002) 83; E.A. Saad, L.H. Khalil, M.T.M. Zaki, A.A.A. El-Ella, Microchim. Acta 140 (2002) 87; H. Deng, G.J. Van Berkel, J. Mass Spectrom. 33 (1998) 1080
# Quercetin powder

<figure><img src="image_32.png" /></figure>

## Structure

<figure><img src="image_33.png" /></figure>

Dimer

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Dihydrate

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## DRUV

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broadening of the
absorption band
with increasing
concentration

<figure><img src="image_37.png" /></figure>

Monomer ↔ dimer?

Rearrangement of water molecules?

G.Z. Jin, Y. Yamagata, K. Tomita, Acta Cryst. C46 (1990) 310; M. Rossi, L.F. Rickles, W.A. Halpin. Bioorg. Chem.14 (1986) 55
J.P. Cornard, J.C.Merlin, A.C. Boudet, L. Vrielynck, Biospectroscopy (1997) 3 183
Quercetin powder

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DRIFT

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modifications around the carbonyl group with [Q]

Rupture of intermolecular hydrogen bond
Dimer ↔ Monomer

G.Z. Jin, Y. Yamagata, K. Tomita, Acta Cryst. C46 (1990) 310; M. Rossi, L.F. Rickles, W.A. Halpin. Bioorg. Chem.14 (1986) 55
J.P. Cornard, J.C.Merlin, A.C. Boudet, L. Vrielynck, Biospectroscopy (1997) 3 183

Solid state complexation of natural organic dyes with Al(III):electronic and vibrational spectroscopies
Solid state complexation of quercetin with Al(III)

Cation

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DRUV

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↔ Complexation
only with AlCl₃
Solid state AlCl₃ complex : DRUV

◆ Kinetics

<figure><img src="image_42.png" /></figure>

complete reaction
in few hours

◆ Al(III) concentration

<figure><img src="image_43.png" /></figure>

<figure><img src="image_44.png" /></figure>

↔ two absorption bands around 450 and 490 nm
Solid state AlCl₃ complex : Raman

<figure><img src="image_45.png" /></figure>

$$ \text{Al}^{3+} \leftrightarrow \text{water molecules} \\ \text{phenol coordination} $$

J.P. Cornard, J.C. Merlin, A.C. Boudet, L. Vrielynck, Biospect, 3 (1997) 183; T. Teslova1, C. Corredor, R. Livingstone, T. Spataru, R.L. Birke, J.R. Lombardi, M. V. Cañamares, M. Leona, JRS 38 (2007) 802
# Solid state AlCl₃ complex in Al(OH)₃ Matrix

## ➤ Dilution of quercetin

<figure><img src="image_46.png" /></figure>

Dimer characteristics

→ Quantitative analysis

## ➤ Al(III) complex

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Modification of the
complex reflectance
with Al(OH)₃

No complexation but interaction between complex and Al(OH)₃
Solid state AlCl₃ complex and quercetin lake

◆ Classical quercetin Lake :

precipitate obtained by mixing
quercetin +alun+carbonate in solution

$$
[\text{Q}] = 10^{-3} \text{M}; [\text{Alun}] = 30 \text{g L}^{-1}
$$

$$
\text{Immediate precipitatiopn at pH = 7 (Na}_2\text{CO}_3\text{)}
$$

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◆ Solid state quercetin lake :

$$
(Q + \text{AlCl}_3) + \text{Al(OH)}_3
$$

$$
[\text{Q}]=[\text{AlCl}_3]=10^{-4} \text{ M}
$$

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Similar UV-Visible reflectance spectrum
Conclusion

◆ Identification of the yellow dyes of *Rhamnus catharticus*

➢ Quercetin as chromophore model for Avignon Lake

◆ Quercetin powder

➢ monomer and dimer observed by DRIFT and DRUV

◆ Solid state complexation of quercetin with AlCl₃

➢ observed by DRUV

➢ reaction with water molecules showed by Raman

◆ Complex dilution in Al(OH)₃

➢ interaction between the complex and the matrix

◆ Solid state quercetin lake

➢ similar reflectance spectrum as classical quercetin lake
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Thank you for your attention

Sylvie Blanc

Tu Khai Nam Nguyen, Kevin Bourhis, Eve Péré
Carole Mathe, Catherine Vieillescazes

Solid state complexation of natural organic dyes with Al(III):
electronic and vibrational spectroscopies