Polysaccharide-Surfactant Interactions

Lindman, B., Carlsson, A., Gerdes, S., Karlstroem, G., Piculell, L., Thalberg, K., et al. (1993). Polysaccharide-surfactant systems interactions, phase diagrams and novel gels. In Dickinson, E., Walstra, P. (Eds). Food Colloids and Polymers Structure and Dynamics, Cambridge, UK Royal Society of Chemistry, pp. 113-125. 

B. Lindman et al. Polysaccharide-Surfactant Systems Interactions, Phase Diagrams,... 

It was seen that anionic surfactants interact with the positive charge of cationic polysaccharides even at concentrations well below the surfactant s cmc. There is a rapid increase in the viscosity of 1.0 wt% polyquaternium-10 solutions as the anionic surfactant begins to neutralize the charge on the cationic polymer (Fig. 26). As shown earlier (Fig. 22), this solution viscosity response is characteristic of the cationic HEC/anionic surfactant combination and does not appear to occur in the juxtaposed anionic cellulose/cationic surfactant combination. 

Sano, H., Sohma, H., Muta, T, Nomura, S., Voelker, D. R., Kuroki, Y. Pulmonary surfactant protein A modulates the cellular response to small rough polysaccharides by interaction withCD14. J. Immunol. 1999,163(1), 387-395. 

In the past [4-6] it was common to characterize amphiphiles according to their major performance in food systems (1) emulsification and stabilization, (2) protein interactions, (3) polysaccharide complexation, (4) aeration, and (5) crystal structure modification of fats. Such classifications correlate the surfactant chemical structure to its interaction (chemical or physical) with substrates such as fats, polysaccharides, and proteins. It was confirmed fhat certain surfactants interact molecularly with macromolecules, forming complexes and/or hybrids, and alter the macromolecular behavior at the interface. Such activity is an important new contribution of cosurfactants to the surface performance of other surfactants [7]. Such interactions are sometimes a very important contribution of amphiphiles to food systems. 

Let us consider now the case of a specific ionic polysaccharide. The unique properties of complexes of the cationic chitosan with non-ionic sorbitan esters provides an interesting example. Grant and co-workers (2006) have established that mixtures of chitosan and surfactant form emulsion-like solutions and/or creams, where the surfactant component is present as droplets or micelle-like particles and the chitosan solution acts as the system s continuous phase. It was established that the length and the degree of saturation of the surfactant hydrocarbon chain have a significant impact on the development of the chitosan-surfactant complexes. Moreover, an optimal distance between the chitosan s protonated amine groups is required for effective interactions to occur between the polysaccharide and the sorbitan esters. 

In an OAV emulsion system containing a mixture of surfactant + polysaccharide, the stability behaviour will generally depend on two sets of factors (i) the nature of the surfactant-polysaccharide interactions at the surface of the emulsion droplets, and (ii) the surfactant-polysaccharide interactions in the aqueous medium between the droplets (Dickinson et ah, 1993 Dickinson, 2003 Aoki el al., 2005 Klinkesom et ah, 2004 Chuah et ah, 2009). 

It is important to understand the characteristic interactions involved at an interface containing each of the main types of surface-active molecules, i.e., biopolymers (proteins, polysaccharides) and low-molecular-weight surfactants (lipids). But that is not the whole story. In real food systems there are almost always mixed ingredients at the interface. So it is necessary to understand what sorts of mixed interfacial structures are formed, and how they are influenced by the intermolecular interactions. 

In general, surface activity behaviour in food colloids is dominated by the proteins and the low-molecular-weight surfactants. The competition between proteins and surfactants determines the composition and properties of adsorbed layers at oil-water and air-water interfaces. In the case of mixtures of proteins with non-surface-active polysaccharides, the resulting surface-activity is usually attributed to the adsorption of protein-polysaccharide complexes. By understanding relationships between the protein-protein, protein-surfactant and protein-polysaccharide interactions and the properties of the resulting adsorbed layers, we can aim to... 

The term food colloids can be applied to all edible multi-phase systems such as foams, gels, dispersions and emulsions. Therefore, most manufactured foodstuffs can be classified as food colloids, and some natural ones also (notably milk). One of the key features of such systems is that they require the addition of a combination of surface-active molecules and thickeners for control of their texture and shelf-life. To achieve the requirements of consumers and food technologists, various combinations of proteins and polysaccharides are routinely used. The structures formed by these biopolymers in the bulk aqueous phase and at the surface of droplets and bubbles determine the long-term stability and rheological properties of food colloids. These structures are determined by the nature of the various kinds of biopolymer-biopolymer interactions, as well as by the interactions of the biopolymers with other food ingredients such as low-molecular-weight surfactants (emulsifiers). 

In Part Four (Chapter eight) we focus on the interactions of mixed systems of surface-active biopolymers (proteins and polysaccharides) and surface-active lipids (surfactants/emulsifiers) at oil-water and air-water interfaces. We describe how these interactions affect mechanisms controlling the behaviour of colloidal systems containing mixed ingredients. We show how the properties of biopolymer-based adsorption layers are affected by an interplay of phenomena which include selfassociation, complexation, phase separation, and competitive displacement. 

For the analysis of water-soluble polymers (such as surfactants, oligosaccharides, PEGS, lignosulfonates, polyacrylates, polysaccharides, PVA, cellulose derivatives, PEG, polyacrylic acids, polyacrylamides, hyaluronic acids, CMC, starches, gums) and for separations of oligomers and small molecules, columns that are comprised of macroporous material with hydrophilic functionalities may be used. The requirement for these columns in SEC mode is to eliminate or minimize ionic and hydrophobic effects that make aqueous SEC (otherwise known as GFC) very demanding. The interaction of analytes with neutral, ionic, and hydrophobic moieties must be suppressed. It is often necessary to modify the eluent (addition of salt) in order to avoid sample-to-sample and sample-to-column interactions that can result in poor aqueous SEC separations and low recoveries. 

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