DIFFERENT MICROSTRUCTURES OF BINARY GELS FOR FOOD APPLICATIONS

Marcela Jarpa PhD Student Supervisor: L. Chen

PROTEINS & POLYSACCHARIDES

Proteins and polysaccharides play a key role in

the structure formation and stabilisation of food systems.

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Protein/polysaccharide interactions and systems

Below

Above

Protein-Polysaccharide gels
Gels have been classified in three types :
I.

Interpenetrating networks (incompatibility)

II.

Phase-separated networks (incompatibility)

III. Coupled networks (compatibility)

I.

Interpenetrating networks (IPN)

An Interpenetrating gel comprise two or more

independent polymer networks. Individual polymer networks interact with each other through topological entanglement. Interlocked structures by crosslinks

Basic synthesis methods for IPN

A. Sequential IPN

B. Simultaneous IPN
Adapted from Sperling, L. H. (1994)"Interpenetrating Polymer Networks: An Overview."

Whey protein/ Locust Bean Galactomannan (WPI/LGB)

(Monteiro et al.,2005)

Objective:
Study the influence of the molecular mass of

galactomannan on whey protein gelation.

Method

Results
A. The effect of LBG on
WPI 11% WPI 11% + LBG LMw

11% WPI solution

WPI solutions at 11% do not

gel. Addition of galactomannan of any Mw at low concentration, does not change the microstructure (phase separation). Addition of galactomannan of higher Mw and concentration (0.7%), forms an incipient IP gel.

WPI 11% + LBG HMw (0.7%)

Results
B.

The Effect of LBG on 14% WPI Gels. Addition of medium range Mw galactomannan changes the microstructure (phase separation) at low concentration. Increasing the polysaccharides concentration and/or Mw promote gel formation at lower temperature. G reaches higher values as the polysaccharide concentration and/or Mw increase

WPI 14%

WPI 14% + LBG MMw

WPI 14% + LBG HMw (0.7%)

Conclusions
Differences in the molecular weight of the

polysaccharide have a significant influence on the gel microstructure.

At 11% WPI, below the gelation threshold of the

protein alone, the presence of the non-gelling polysaccharide induces gelation to occur.
At higher protein concentration, the main effect of

the polysaccharide was a re-enforcement of the gel.

Protein-Polysaccharides gels
I. II.

Interpenetrating networks (incompatibility) Phase-separated networks (incompatibility)

III. Coupled networks (compatibility)

II. Phase-separated network

Consist of a gel matrix filled with particulate

inclusions. Some degree of demixing occurs prior to gelation. First and second component network will be separated spatially. Bigger polymer concentration

Synthesis Method
Incompatibility between polymers One component gel faster than the second one. The second one aggregates within the pores of

the supporting network

Gelatin / Dextran
(Butler et al. 2003)

Objective:
Study the microstructure formation and

evolution in a gelatin/dextran mixture, over a range of temperatures.

Method

Results
Small-Angle Light Scattering and Turbidity
The kinetics of phase separation depends on temperature. At temperatures below 18 C, the gelation kinetics is sufficiently rapid to trap the structure as soon as the phase separated morphology formed. At temperatures above 20 C , the gelation is slower, allowing a coarsening process for long periods of time: There was a time-delay of up to tens of minutes between reaching the quenched temperature and the onset of phase separation.

Results
Polarimetry
optical rotation at the onset of phase separation

in the delayed samples demonstrate the coil to helix transition in gelatin occurs at temperatures below about 30 C. Also suggest, that a certain degree of helix formation was required to trigger phase separation.

Results
Confocal Laser Scanning Microscopy.
Evolution of the microstructure in a sample held at 26C for 26, 29,41,and 62 min. 1 2

Conclusions
Depending on temperature, the formed gel will have

a very clear droplet morphology (over 20C), or a typical diffuse morphology of early stages of phase separation (below 18C).
The time-delay phenomenon demonstrated the

phase separation only occurred once a certain amount of ordering of the gelatin molecules is achieved.

Protein-Polysaccharides gels
I. II.

Interpenetrating networks (incompatibility) Phase-separated networks (incompatibility)

III. Coupled networks (compatibility)

III. Coupled networks

Defined as those in which chains of different

polymers interact directly to form the network. Large attractive interaction between the components Junction zones

Junction zones

Schematic representation of the complexing between oppositely charged polymers

Compactness of proteinpolysaccharide complexes

Tolstoguzov,V. (2003). Food Hydrocolloids 17,1-23.

-Lactoglobulin/ Xanthan Gum

(Laneuville et al, 2006)

Objective:
Determine the mechanism and kinetics of the

electrostatic gelation of native -lg/ xanthan gum mixtures in aqueous solution.

Method

Gel

Results
The higher protein concentration, the faster

structuration process, and the weaker gels. The lower the pH at high protein concentration, the weaker the gel after an optimal ph.

Phase contrast micrographs of the microstructure of -lg/xanthan gum gels for (a) r=2, (b)r=5, and (c) r=15

Results
Best results for -lg/Xhantan gum ratio: 2 and 5

Evolution of the storage () and loss () modulus during gelation for lg/xanthan gum mixtures at (a) r=2 and (b)r=5. The dotted lines indicate the gelation time. The acidification curves () and the IEP of lg (pH 5.1)(*) are also presented.

Results
A two-step mechanism for gel formation.
Step 1 pH Step 2

Soluble complexes

Interpolymeric complexes

Cluster-cluster aggregation

Gel

Polysaccharides: coils Proteins: circles

Results
The total biopolymer concentration at which

gelation was obtained was extremely low (0.1 wt %) compared to the usually tested concentrations for protein-polysaccharide mixed gels (4-12 wt %).
The gel is formed without applying any

treatment to denature the protein (e.g. heating, enzymatic hydrolysis)

Conclusions
A two-step mechanism for gel structuration

is proposed.
The -lg/xanthan ratio had an important

effect on the reaction rate and the stability of the gels.

SUMMARY
Three main gel structures could be form when

protein and polysaccharides are mixed in aqueous solution: IP, Phase-separated, and Coupled networks.
The different structures depending on the nature

and strength of interactions between polymers and, also, depend on their properties.
Polymer gelling properties are impacted by

presence of other polymers in the medium, sometimes producing synergistic effects.

SUMMARY
In mixed gels, usually, the minimum concentration

of gelation is lower than those of solutions of both individual gelling agents

The control of gelation process in binary gels

allows the formation of a wide range of microstructures and different applications.

Applications
Creation of tailor-made structures for

specific food applications:

Surimi based products, meat replacers, dairy

products, fat replacers, heat sensitive foods, and microencapsulation.

References

Butler, M. F. & Heppenstall-Butler, M. (2003). Delayed Phase Separation in a Gelatin/Dextran Mixture Studied by Small-Angle Light Scattering, Turbidity, Confocal Laser Scanning Microscopy, and Polarimetry

Biomacromolecules , 4, 928-936 Clark, A.H. (2000). Biopolymer gelation - The structure property relationship. Gums and Stabilisers for the food industry , 10, De Kruif, C. G., & Tuinier, R. (2001). Polysaccharide protein interactions. Food Hydrocolloids, 555-563. Jones, O., Lesmes, U., Dubin, P., & McClements, D. (2010). Effect of polysaccharide charge on formation and properties of biopolymer nanoparticles created by heat treatment of B-lactoglobulin-pectin complexes. Food Hydrocolloids, 374-383. Laneuville et al. (2006). Gelation of Native -Lactoglobulin Induced by Electrostatic Attractive Interaction with Xanthan Gum.Langmuir, Vol. 22, No. 17. Monteiro, S.,Claudia Tavares, Dmitry V. Evtuguin, Nuno Moreno, and J. A. Lopes da Silva (2005). Influence of Galactomannans with Different Molecular Weights on the Gelation of Whey Proteins at Neutral pH. Biomacromolecules, 6, 3291-3299 Neirynck, N. et al. (2007). Influence of pH and biopolymer ratio on whey proteinpectin interactions in aqueous solutions and in O/W emulsions. Colloids and Surfaces A: Physicochem. Eng. Aspects, 99-107. Sperling, L. H. "Interpenetrating Polymer Networks:An Overview." In Interpenetrating Polymer Networks, Edited by Klempner, 3-38. Washington, DC: American Chemical Society, 1994. Tolstoguzov, V. (2003). Some thermodynamic considerations in Food Formulation. Food Hydrocolloids 17,1-23. Turgeon, S., & Laneuville, S. (2009). Protein+Polysaccharide and Complexes: From Scientific Background to their Application as Functional Ingredients in Food Products. In I. T. Edited by: Stefan Kasapis, Modern Biopolymer Science. (pp. 327-363). London: Elsevier.

Acknowledgement
Dr. L. Chen (supervisor)
Dr. F. Temelli and Dr. T. Vasanthan (committee members)

THANK YOU!