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Abstract
Surface-active polysaccharides are attracting increasing interest for use in a variety of applications. Amongst these, methylcellulose (MC)
and hydroxypropyl methylcellulose (HPMC) have been developed, in part, for their foam and emulsion stabilising properties, together with
their water holding and viscosity enhancing properties. The aim of this research is to quantify the competitive adsorption between proteins
and MC/HPMC, as they are often used together in many applications, and the results of potential effects of competition are unknown.
Two proteins were compared; b-lactoglobulin (BLG) and b-casein (BCAS). BLG forms an elastic interface, whereas BCAS does not.
Hence, BCAS is displaced by surfactants more easily than BLG. The surface rheology, surface tension and foam stability of the mixed
protein:polysaccharide systems were determined to elucidate the mechanism and consequences of competition.
In contrast to surfactants, both MC and HPMC formed highly elastic interfaces, more elastic even than BLG. Both HPMC and MC were
more surface active than the proteins, therefore at higher MC and HPMC concentrations, the polysaccharides began to dominate the
interfacial properties. Whereas surfactants reduce the elasticity of the protein adsorbed layer, the elastic properties of the polysaccharides
enhanced the overall strength of the interface, which will potentially result in more stable foams.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Methylcellulose; Hydroxypropyl methylcellulose; b-Lactoglobulin; b-Casein; Interface
1. Introduction
The formation and stability of foams and emulsions is a key
quality parameter in a wide range of applications. Particularly
in food since consumer perception of quality is strongly
influenced by appearance. Foam and emulsion functionality is
strongly influenced by the surface and interfacial properties of
the surface-active components in the system (Dickinson,
2001). Therefore, the role that these ingredients play is vital for
the formation and stability of food foams and emulsions. In
addition, the competition between the different surface-active
species can also be important for the functionality offoams and
emulsions. Competitive adsorption phenomena between
proteins and surfactants have been found to have a major
impact on foam and emulsion stability (Coke, Wilde, Russell,
& Clark, 1990; Dickinson, Owusu, & Williams, 1993).
* Corresponding author. Tel.: C44 1603 255258; fax: C44 1603 507723.
E-mail address: peter.wilde@bbsrc.ac.uk (P.J. Wilde).
1
Current address: AZTI (Instituto Tecnologico Pesquero y Alimentario)
Txatxarramendi Ugartea, z/g, 48395 Sukarrieta/Bizkaia, Spain.
0268-005X/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodhyd.2004.10.013
486
3. Methods
3.1. Surface tension
Surface tensions at the airwater interface of solutions of
protein and polysaccharides were measured using the
pendant drop technique. In this technique, surface/interfacial
tension was calculated from the size and shape of a drop
hanging from the tip of a syringe. The mathematical
treatment of pendant drop shape is based on the fundamental
equation of capillarity, which relates the interfacial/surface
tension to the pressure difference across a surface and to the
two principal radii of curvature of the surface at that point
(Ambwani & Fort, 1979). Droplets of the aqueous phase were
held by the tip of a syringe (diameter, 0.7 mm). The image
was digitised with a Pulnix TM500 monochrome camera
(resolution, 512!512 pixels) using a MuTech MV200 frame
grabber and a personal computer. The shape of the drop was
analysed by computer image analysis (Hansen & Rodsrud,
1991). Surface tension was also determined by the Wilhelmy
plate method. This apparatus consisted of a home-constructed tensiometer, which was made by a 10 g force
transducer (HBM, GmbH, Darmstadt, Germany) and a
25 mm wide roughened glass plate. The measuring system
was calibrated with a known weight before any contact
between plate and sample surface. Accuracy was estimated at
better than 0.1 mN/m. Surface tension was monitored at
room temperature for between 10 and 20 min, according to
the adsorption rate of each solution.
2. Materials
3.2. Surface rheology
Methyl cellulose (Methocel Premium A15, mean molecular weight 14 kDa, methyl substitution between 27.5
and 31.5%) and HPMC (Methocel HPM 450, mean
487
Fig. 1 shows the results of preliminary surface rheological experiments designed to check for adverse storage or
temperature effects on the surface properties of 0.1% MC
and HPMC solutions. Fig. 1a shows the surface shear elastic
modulus (G 0 ) after 30 min adsorption time, following
Fig. 1. Effect of storage time and temperature on the surface shear elasticity
of MC (B) and HPMC (:) after 30 min adsorption as a function of (a)
storage time and (b) temperature.
488
Fig. 4. Effect of HPMC concentration on (a) surface tension and (b) surface
shear elasticity of solutions containing: no protein (!, B); or 10 mM bcasein (6) or b-lactoglobulin (&). Open circles represent surface tensions
measured by the Wilhelmy plate technique for comparison.
489
490
5. Conclusion
The competitive adsorption of MC and hydroxypropylmethyl cellulose with two different proteins (BCAS and
BLG) was investigated. BCAS appeared to be displaced
through simple competitive adsorption, more easily than
BLG. Some synergism appeared to take place between the
adsorbed polysaccharides and BLG, resulting in greater
values of surface elasticity in the mixtures. Complex
adsorption behaviour of HPMC alone had a strong influence
on the competition with the proteins, resulting in complex,
non-linear concentration dependent behaviour. This underpinning knowledge of the complex surface behaviour of
these mixtures should allow the design of protein:polysaccharide mixtures with enhanced functionality.
Acknowledgements
The authors would like to thank Fraser Hogg, Dr Neil
Carr, and Dr Alan Holmes for their funding and support, and
to Dr Annette Fillery-Travis for her help and advice for this
project. PJW also acknowledges BBSRC for support
through the Core Strategic Grant to the Institute.
References
Ambwani, D. S., & Fort, T. (1979). Pendant drop technique for measuring
liquid boundary tensions. In R. J. Good, & R. R. Stromberg (Eds.),
Surface and colloid science (pp. 93119). New York: Plenum Press.
Benichou, A., Aserin, A., & Garti, N. (2002). Proteinpolysaccharide
interactions for stabilization of food emulsions. Journal of Dispersion
Science and Technology, 23(13), 93123.
Bos, M. A., & van Vliet, T. (2001). Interfacial rheological properties of
adsorbed protein layers and surfactants: a review. Advances in Colloid
and Interface Science, 91(3), 437471.
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