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.
http://www.siskiyous.edu/
http://www.mn.uio.no
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
Adapted from Sperling, L. H. (1994)"Interpenetrating Polymer
Networks: An Overview."
A. Sequential IPN
B. Simultaneous IPN
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
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% WPI 11% + LBG LMw
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. Interpenetrating networks (incompatibility)
II. 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
3 4
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. Interpenetrating networks (incompatibility)
II. 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
Tolstoguzov,V. (2003). Food Hydrocolloids 17,1-23.
Schematic representation of the
complexing between oppositely charged
polymers
Compactness of protein-
polysaccharide complexes
-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
Soluble complexes
Interpolymeric
complexes
Cluster-cluster
aggregation
Gel
Polysaccharides: coils
Proteins: circles
A two-step mechanism for gel formation.
Step 1 Step 2
pH
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!