Procedia Food Science 1 (2011) 12 – 16

11th International Congress on Engineering and Food (ICEF11)

Interfacial adsorption and shear flow properties of gum

arabic-sodium caseinate mixtures
Bibiana Bonilla-Reyna, María G. Sosa-Herrera, Laura P. Martínez-Padillaa*
Universidad Nacional Autónoma de México, FES Cuautitlán. Laboratorio de Propiedades Reológicas y Funcionales en Alimentos,
Av. Primero de mayo s/n, Cuautitlán Izcalli, Edo. de México, 54740 México

Abstract

This work discusses rheological and physicochemical properties of sodium caseinate and gum arabic, in aqueous
media (25°C). All the systems showed low viscosity values and Newtonian behaviour in the shear rate range studied.
From particle size distribution, a limited thermodynamic compatibility was observed since hydrocolloids mixtures
showed particles size between the values from the systems alone. Interfacial tension measurements at equilibrium at
the air-water interface, revealed that the binding affinity of arabic to the air water interface is very low compared to
that of caseinate. The adsorption critical concentration could be deduced as a function of aqueous solutions
composition. In competitive adsorption experiments involving simultaneous adsorption of the hydrocolloids from a
bulk mixture, sodium caseinate displaced gum arabic from the interface at both polysaccharide concentrations,
changing the adsorption critical concentration.

© 2011 Published by Elsevier B.V. Open access under CC BY-NC-ND license.

Selection and/or peer-review under responsibility of 11th International Congress on Engineering and Food (ICEF 11) Executive
Committee.

Keywords: Emulsion; sodium caseinate; whey concentrate; rheology; stability

1. Introduction

Protein/polysaccharide mixtures are commonly found in the food industry as thickeners for low fat
food. Within of applications, these biopolymers are used to formulate emulsion-based food systems.
Products like ice cream, milk shakes, milk desserts, salad dressing and mayonnaise are some examples.
Interactions between proteins and polysaccharides play an important role in the structure and stability of
processed foods; control or manipulation of these macromolecular interactions is a key factor in the
development of novel food processes and products [1].

*
Corresponding author. Tel.: 52-555-623-2038; fax:+52-555-623-2026
E-mail address: lpmp@unam.mx.

2211–601X © 2011 Published by Elsevier B.V. Open access under CC BY-NC-ND license.
Selection and/or peer-review under responsibility of 11th International Congress on Engineering and Food (ICEF 11) Executive Committee.
doi:10.1016/j.profoo.2011.09.003
 Bibiana Bonilla-Reyna et al. / Procedia Food Science 1 (2011) 12 – 16 13

Because proteins are amphiphilic and exhibit a high tendency to adsorb to air-water and oil-water
interfaces, they primarily function as emulsifiers in foods [2]. On the other hand, hydrocolloids, which are
hydrophilic random coil-type high molecular weight polymers, are primarily used as thickening agents in
foams and emulsions. However, it has been reported that some polysaccharides have interfacial properties
[3].
Caseinates are in particular demand as functional food ingredients, due mainly to their surface
properties [4], these proteins are currently used in a variety of products, including those of low pH such as
imitation cheeses and yoghurt. Commercial sodium caseinate is a variable multicomponent mixture
containing four major constituents, D s1, D s2, E, and N-casein, in the proportion 3:0.8:3:1 by weight [5].
Gum arabic is a heteropolysaccharide containing a small amount of proteinaceous material (around
2%) [6], the carbohydrate part has highly branched structure consisting of a 1,3-linked E-D-galactose core
with extensive branching through 3- and 6-linked galactose and 3-linked arabinose. A feature of gum
arabic is its ability to form an adsorbed film at the oil-water interface whose surface viscoelasticity is
rather insensitive to dilution of the aqueous phase [7].
It is known that proteins and polysaccharides exhibit limited thermodynamical compatibility and
undergo phase separation; thus, in systems containing both proteins and hydrocolloids to make up an
interface, it is conceivable that these surface-active macromolecules may compete for adsorption. In this
work we studied the shear flow, the particle size distribution and the interfacial adsorption of gum arabic
at two different concentrations, alone and in mixture with 2% sodium caseinate, to elucidate about
competitive adsorption at the air-water interface.

2. Materials & Methods

2.1 Materials

Sodium caseinate (Lactoprot, Germany), §96% dry matter, and gum arabic (Coloides naturals de
México), §94% dry matter, were used without any pretreatment. All concentrations are given as a weight
percentage. Caseinate systems (2%) an arabic samples were prepared at room temperature, by stirring for
60 minutes. Blends for protein-polysaccharide were made by mixing equal parts of duplicate aqueous
solutions of individual components.

2.2 Flow properties

A stress rheometer (LS100, Paar Physica) with a double gap concentric cylinder (DG10, 48 and 50 mm
internal and external diameter, respectively, 36 mm length and radii ratio of 1.0417 was used. Flow
curves were obtained by using two up-down step programs. The temperature was maintained at 25 r
1°C.

2.3 Particle size

Particle size distribution of the samples was measured using a Malvern Zetasizer Nano (Malvern
Instruments Ltd.). Protein and polysaccharide systems yield satisfactory photon counts without dilution.

2.4 Interfacial tension

A pendant drop tensiometer PAT-1 (Sinterface Technologies) was used to measure the air-water
interfacial tension. Normally, a pendant drop of oil is formed at the tip of a capillary. The silhouette of the
drop is cast onto a CCD camera and digitized. The digital images of the drop are recorder over time and
14 Bibiana Bonilla-Reyna et al. / Procedia Food Science 1 (2011) 12 – 16

fit to the Young-Laplace equation to accurately determine interfacial tension. All experiments were
performed at 25°C.

3. Results & Discussion

The steady shear flow of aqueous systems of the hydrocolloids alone and in mixtures shows Newtonian
behaviour in the shear rate range studied. Viscosity values are reported in Table 1. An increase on
viscosity was observed as a result of a higher molecular concentration of hydrocolloid. With regard to the
rheological properties of gum arabic in water, it behaves as Newtonian fluid in the concentration and
shear rate interval tested, due to the highly branched arabinogalactan components [8,9]. Sodium caseinate
solutions showed Newtonian behaviour and the lower viscosity values, agree on the general
characteristics of low concentration systems [10].

Table 1. Viscosity of aqueous systems of sodium caseinate, gum arabic and mixtures, 25ºC

Sample Viscosity Newtonian

(Pa.s) Shear rate r2
-1
(s )
-3
Caseinate (Ca)2% 2.3 x 10 1.2 - 300 0.999
Gum arabic (AG) 5% 3.0 x 10-3 1 - 100 0.998
-3
Gum arabic 10% 7.1 x 10 1 - 100 0.999
Ca 2% - AG 5% 5.2 x 10-3 1 - 100 0.999
-3
Ca 2% - AG 10% 11 x 10 1 - 100 0.999

The particle size distributions of gum arabic 5%, sodium caseinate 2% and the mixture are show in
Figure 1. Caseinate forms aggregates around 300 nm in size. In the case of gum arabic sample, this
displayed the largest size that can be attributed to molecular associations [8]. A general point to note from
Figure 1 is that in mixture, the particle size distribution exhibit a trimodal distribution were some larger
particles than gum arabic, and some shorter particles than caseinate are presents, indicating changes on
the sodium caseinate and gum arabic aggregation as well as the formation of some intermediate
complexes, probably because of a thermodynamic effect.

18

C a s e in a t e 2 %
16
A r a b ic g u m 5 %
C a 2 % -A G 5 %
14

12

10

8
Intensit (%)

0
10 100 1000 10000

d ia m e t e r ( n m )

Fig. 1. Particle size distributions of sodium caseinate (Ca) and gum arabic (AG), alone and its mixture (Ca2%- AG5%)
 Bibiana Bonilla-Reyna et al. / Procedia Food Science 1 (2011) 12 – 16 15

Figure 2 shows the results of the air-water interfacial tension measurements at equilibrium for sodium
caseinate and gum arabic alone on aqueous solutions at 25°C. From this experimental data, the adsorption
critical concentration (ACC) can be deduced as a function of aqueous solutions composition. The ACC
was obtained analytically by the cut point of the lines at low and high hydrocolloid concentrations. The
value of ACC is higher for gum arabic than for sodium caseinate, but in mixture the ACC value was near
to the caseinate, which is more hydrophobic [11]. This indicates that the mixed polymer film was
undergoing some major structural/compositional reorganization due to adsorption-displacement processed
occurring between the gum arabic and sodium caseinate.

ACC

ACC
ACC

Fig. 2. Adsorption critical concentration of sodium caseinate and gum arabic, 25ºC

It has been known that gum arabic is surface active and has the ability to stabilize emulsions [12]. The
adsorption isotherm (not showed) indicates that gum arabic was rapidly adsorbed to the air-water
interface initially owing to its high bulk concentration. However, the binding affinity of gum arabic to the
air water interface is very low compared to that of sodium caseinate, since it was subsequently displaced
or desorbed from the interface by the adsorption of the late arriving casein molecules and the system
reached a new equilibrium value. The surface load at saturated monolayer coverage conditions is far
greater than for sodium caseinate. In spite of this high surface load, the maximum reduction in surface
tension of water, of gum Arabic film is lower than caseinate film, clearly indicating that it is not as
surface active as proteins.

4. Conclusion

Supporting on his high adsorption critical concentration, the maximum reduction in surface tension of
water of gum arabic systems, clearly indicating that it is not as surface active as sodium caseinate,
however, it appears that its unsaturated monolayer is able to block sodium caseinate from the interface.

Acknowledgements

This study was financed by a grant obtained from DGAPA-UNAM (project IN 119110).
16 Bibiana Bonilla-Reyna et al. / Procedia Food Science 1 (2011) 12 – 16

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Presented at ICEF11 (May 22-26, 2011 – Athens, Greece) as paper FMS914.