AN T H O C Y A N IN S -PO L Y S A C C H A R ID E S

NA N O C O M P L E X E S F O R FO O D AP P L IC A T IO N
Inês Pereiraa, Ana Fernandesa, Nuno Mateusa, Victor de Freitasa Food and Natural Products

a) Requimte-LAQV: Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto - Rua

do Campo Alegre, s/n, 4169-007 Porto

IN T R O D U C T IO N [1-3]
RESULTS AND DISCUSSION
• Anthocyanins are polyphenolic pigments that present a great potential as natural
Higienização e Cuidado com Infeção
Ultraviolet-Visible Spectroscopy (UV-Vis)

colorants and functional ingredients.

• Their application in foodstuffs is currently encouraged to fulfill the consumers’

request towards natural, safe and healthy foodstuffs.

• Their color stability, processability and biological activity are highly affected after
their transformation procedures.

• Main goals: Develop polyelectrolyte nano/microcomplexes of anthocyanins,

using polysaccharides extracted from algae as building blocks, to stabilize these • At pH 3.00 and 3.50, the adition of l-Carg
pigments. induces a hyperchromic and hypsochromic
effect on the Cy3Glc spectrum.

• At pH 4.00, and in this conditions, the Cy3Glc

spectrum does not suffer any changes.

Isothermal Titration Calorimetry (ITC)

Red seaweed l-carrageenan 80
(l-Carg) 60 H
40 G
20
pH 4.00 S

kJ.mol-1
pH 3.00 pH 3.50 0
-20

ME T H O D S [4-6] -40
-60
-80
-100

00

50

00
Anthocyanins Extraction and Purification

3.

3.

4.
pH

pH

pH
KD (mM)
pH 3.00 10.0 ± 0.1
pH 3.50 29.0 ± 3.0
H2O pH 4.00 83.1 ± 0.6
(HCl 0.1 M)

• The reaction is a spontaneous exothermic process, impulsionated by enthalpy, suggesting the

existence of interaction between opposite charges.
Cyanidin-3-glucoside
C18 & Toyopearl (Cy3Glc)
• The results indicate some molecular conformational alterations that disfavors the system.
Equipamentos de Proteção Individual
• Increasing the pH values of the system results on the decrease of affinity between the molecules.
Nano/micro Complexes Formation
Dynamic Light Scattering (DLS)
Cy3Glc l-Carg
Size PDI Zeta Potencial
Soluble Complexes 300
pH 3.00
0.8
pH 3.00
0
pH 3.00
pH 3.50 pH 3.50 -10 pH 3.50
0.6
200 pH 4.00 pH 4.00 pH 4.00
Size (nm)

z (mV)
-20
PDI

0.4
Agitation -30

Heat
Insoluble Complexes 100
0.2
-40
Centrifugation
0 0.0 -50
0.2 0.3 0.4 0.6 0.8 1.0 0.2 0.3 0.4 0.6 0.8 1.0 0.2 0.3 0.4 0.6 0.8 1.0

Ratio Ratio Ratio

• Complexes’ size and PDI increases with the addition of l-Carg, while the zeta potencial becomes
more negative.

Ultraviolet-Visible Spectroscopy Isothermal Titration Calorimetry • Increasing the pH of the medium provokes an increment on PDI values and makes the zeta
(UV-Vis) (ITC) potential more negative.
Soluble Complexes: pH 4.00
Cy3Glc
pH 3.00 Cryo Scanning Electron Microscopy (SEM)
pH 3.50
0.1 mM pH 4.00
pH 3.00
pH 3.00 pH 4.00
l-Carg
6 mM

l-Carg
5 mL

Cy3Glc
1 mM
Soluble Complexes:
pH 3.00
pH 3.50 Soluble Complexes Insoluble Complexes
pH 4.00
T = 25 ̊C
• Soluble complexes assume the shape of esferic nanoparticles and the insoluble complexes form
a polymer mesh, with higher dimensions.
Dynamic Light Scattering Cryo Scanning Electron Microscopy
(DLS) (SEM) • Alterations in the solutions’ pH values provoke changes in the medium homogeneity.

Plunged into sub-cooled

nitrogen
Soluble Complexes
CO N C L U S IO N
pH 3.00 & 4.00

Size
Sublimation at -90 °C for
120s
• Anthocyanins/carrageenan’s complexes were successfully developed and
Cy3Glc
PDI
Zeta Potencial
characterized.
Coated with Au/Pd Insoluble Complexes
1 mM pH 3.00 • Their interaction is mainly due to hydrogen bonding
+
l-Carg and their opposite charges.
Soluble Complexes: Cy3Glc (1 mM) + l-Carg
pH 3.00 Ratio (l-Carg:Cy3Glc) = 0.6
pH 3.50
pH 4.00 • Future work: characterize insoluble complexes, evaluate
the complexes’ stability and perform biological assays.

RE F E R E N C E S : [1] Scalbert, A. & Williamson, G. 2000. J Nutr 130: 2073. [2] Manach, C. et al. 2005. Am J Clin Nutr 81: 230. [3] Luo, Y. et al. AC K N O W L E D G E M E N T S : The authors thanks the support by AgriFood XXI I&D&I project (NORTE-01-0145-FEDER-000041) cofinanced by
2020. J Agr Food Chem 68: 12993. [4] Azevedo, J. et al. 2010. Food Chem 119: 518. [5] Klimaviciute, R. et al. 2015. Carbohyd Polym 129: European Regional Development Fund (ERDF), through the NORTE 2020 (Programa Operacional Regional do Norte 2014/2020. A.F would
70. [6] Navikaite, V. et al. 2016. Carbohyd Polym 148: 36. like to thank the FCT for their research contracts (CEECIND/00029/2018/CP1545/CT0010).