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Hydrocolloids

Pectins in Protein:
Stabilisation of Cultured Milk and
Milk-Juice Beverages
P
By Claus Rolin ECTIN is widely used as a age and helps create a smooth
stabiliser of beverages that drinkable texture 2 .
contain protein under the
condition of low pH. Examples Pectin as a stabiliser in
Without a stabiliser, low include drinkable yoghurt, bever- acidified milk products
pH milk drinks are prone ages containing both milk and In general, the regime of com-
to protein separation, fruit juice, soft-drinks that con- positions and conditions with
with consequently tain milk protein as a minor in- which pectin is used for stabilis-
unpleasant mouthfeels, gredient, and beverages contain- ing acidified milk products ranges
ing soy protein and fruit juice. from 8.5% MSNF through less
during storage. With their
The latter were recently described than 1% MSNF (MSNF or milk
ability to form a hydrated in this magazine 1. solids non fat refers to the part of
network of protein and As an example of a dairy bev- the solids of milk that are not fat;
calcium ions, citrus pectins erage, a recommended recipe for 8.5%, corresponding to about
are ideally placed to a raspberry-flavoured long shelf- 3.4% total protein, the natural
stabilise the texture of life yoghurt drink may be found amount in bovine milk). Typical
in the box below. The homogeni- acidities range from pH of about
long shelf-life acidified
sation that is part of the procedure 3.7 to about 4.4. In order to pro-
milk culture beverages. is strongly recommended since it vide the appropriate balance be-
reduces the necessary pectin dos- tween freshness and tartness, the

Raspberry Yoghurt Drink with GENU pectin type YM-115-H


Order of Ingredients % Notes
addition • It is important that pH is adjusted to
A • GENU pectin type YM-115-H 0.40 4.0 ± 0.2.
• Sugar 12.00 • Homogenisation upstream is necessary
• Water 26.43 in order to disintegrate any lumps of
yoghurt, and ensure interaction between
B • Yoghurt, 3% fat, 3.4% protein 60.00 the negatively charged pectin and
positively charged caseins before the heat
C • Raspberry concentrate 65° Brix 1.00 treatment.
• Flavour – EW Raspberry S-301867 0.15 • Full fat yoghurt may be substituted by
• Colour – Fusgaard Red 10980 FL 0.015 low or non-fat yoghurt.

Process
1) Prepare the pectin solution by dispersing pectin powder mixed with part of the sugar into 70°C
water using a high speed mixer, e.g. Tetra Almixer.
2) Mix yoghurt with water and pectin solution. Add the rest of the sugar. Mix for minimum 10 minutes
3) Add concentrate, flavour and colour while stirring.
4) Homogenise at 60°C, 180/50 bar. Homogenise at high temperature because the yoghurt
contains 3% fat.
5) Pasteurise at 90°C for 15 seconds.
6) Cool to approx 15°C.

FOOD & BEVERAGE ASIA FEB/MARCH 2005


Hydrocolloids

pH of formulations typically follows the MSNF; the reason, the use of a stabiliser is highly recommended
higher the MSNF, the higher is the typical pH. with all beverages containing milk protein at low
The use of pectin as a stabiliser of acidified milk pH, and it is (except in rare specific cases) strictly
protein was described in 1959 by Doesburg and necessary with heat-treated long shelf life products.
DeVos 3 and in more detail in 1982 by Glahn 4. The
application started to become commercially signifi- Citrus pectin and milk protein:
cant in Japan from about 1980. It later spread to an electrostatic attraction
other countries and it is today a global application Pectin consists of water-soluble relatively elon-
consuming in the order of magnitude of 5,000 MT gated polymeric molecules, which possess carboxyl
of pectin annually. For many years, the understand- groups. At the pH of acidified milk beverages, about
ing of the molecular mechanism was very incom- half of these carboxyl groups are dissociated, i.e.
plete, but the commercial importance has inspired they bear a negative charge. Several kinds of pectin
a number of research studies 5-10 that together have are available commercially: these are principally
brought a more comprehensive picture. classified into HM-pectin and LM-pectin based on
Some may ask why molecules and mechanisms whether the natural methyl esterification of the car-
are interesting considering that the technology for boxyl groups is above or below 50%.
many years has been successfully practiced based The preferred pectin grades for acidified milk
on empirical knowledge. Well, curious and scien- stabilisation belong to the HM-pectin group: they
tifically minded people (like the honourable read- are of citrus origin, and they create viscous
ers of this honourable magazine!) usually have a pseudoplastic solutions with Ca ++ -rich liquids such
craving for knowing mechanisms. It is no unpro- as, for example, the serum of typical acidified milk
ductive luxury: it helps to develop intuition and un- drinks 2,5. This thickening effect is known to involve
derstanding about what to do and what
to avoid when formulating acidified milk
drinks. And it explains why pectin works
so well for the application. So the remain-
der of this article seeks to provide the
essence of the recent scientific findings.

The perils of unstabilised


milk protein
If milk is acidified, the casein micelles
lose their ability to stay apart and they
turn into particles that tend to stick to-
gether. In those varieties of yoghurt that
are normally eaten with a spoon, this is
desirable, because in the course of stick-
ing together, the particles form a network,
which is stable in the sense that it does
not re-arrange further into a dense curd
phase and a whey phase.
In a beverage, on the other hand, there
is no such coherent network (unless a sta-
biliser is added, see later), and the ag-
gregation of particles thus results in mac-
roscopic phase separation. In mild cases
this may mean a tendency towards slight
whey-off and a chalky mouthfeel. In se-
vere cases it may result in total separa-
tion into sediment and clear liquid, and
this is typically observed if one attempts
to heat-sterilise an acidified milk system
without the aid of a stabiliser. For this

FOOD & BEVERAGE ASIA FEB/MARCH 2005


Hydrocolloids

bridging by calcium ions of pec-


tin parts that possess high pres-
ence of carboxyl groups. On the
other hand, HM-pectin contains
fewer parts of this kind than LM-
pectin, which is commercially de-
veloped for making strong gels in
the presence of Ca ++.
When the pectin is added to
the yoghurt, it becomes attracted Shear
to the surface of the protein par-
ticles predominantly due to elec-
trostatic attraction 6,7 between the
negatively charged pectin and
positively charged areas on the
protein surface. The shear during
preparation has two effects: it dis-
rupts aggregates of particles, and
it transports pectin to the parti- Figure 1: Symbolic illustration of the preparation of an acidified milk drink
cles 8. Homogenisation is particu- stabilised with pectin. The situation to the left represents the situation before
larly effective in both respects 9. shear is applied. The protein particles, represented as blue dots, exist in
While the mixture is sheared rather large aggregates. Pectin, represented as reddish curved lines, also
aggregates to some extent. By shear, the aggregates are shredded and the
and pectin becomes bound to the
pectin is smeared on the outside of the smaller aggregates. The right side of
particle surfaces, the water-bind- the illustration symbolises the situation after the shear with pectin wrapping
ing property of the pectin makes in the smaller aggregates and starting to build a network.
the protein particles much more
hydrated and less sticky towards
each other than they were in the
absence of pectin. For this reason
they do not re-aggregate so rap-
idly and the shear (homogenisa-
tion) in the presence of pectin
thus efficiently reduces the aggre-
gate size (see figure 1).

A network of calcium
bridges
Once the preparation has be-
come finalised and conditions
again become quiescent, a thin
network rapidly builds up (see
figure 2). This network arrests the
protein particles, prevents them
from accidentally bumping into
each other, and prevents them Figure 2: Symbolic illustration of a pectin-stabilised acidified milk drink. The
from settling 8,10 The final bever- protein aggregates are illustrated as groups of blue dots surrounded by a
age contains a network in which pectin-enriched zone (dark yellow) that at further distance from the
all pectin takes part 8; but it is not aggregates becomes thinner (light yellow). The idea is that the pectin-zones
surrounding each particle can connect to each other and form a coherent
all of the pectin that is directly
network. It is intended to illustrate principles only, the relative dimensions are
bound to the protein particles – not necessarily correct.
some pectin is bound to other pec-
tin through calcium bridges. presence of pectin that is not directly attached to ca-
In typical beverages of relatively low MSNF this sein is crucial for the stability, because the particles

FOOD & BEVERAGE ASIA FEB/MARCH 2005


Hydrocolloids

with bound pectin are too few and too small to em- August 2004, p. 16
brace the entire liquid volume8. For this reason, bever- 2. P.E. Glahn & C. Rolin, Food Ingred. Eur. Conf. Proc.
ages of low MSNF require almost the same dosage of 1994, p. 252
pectin as beverages of high MSNF; if only pectin di- 3. J.J. Doesburg & L. DeVos, 5th Intern. Fructsaftkongress,
rectly bound to casein were crucial for the stability, Wien 1959, p. 32
one should have expected the necessary dosage to be 4. P.E. Glahn, Prog. Food Nutr. Sci. 6 (1982) 171
roughly proportional to the MSNF. 5. P.E. Glahn & C. Rolin, Gums Stabilis. Food Ind. 8
In conclusion, the use of pectin for stabilisation of (1996) 393
acidified milk beverages relies upon a highly complex 6. A. Parker, P. Boulenguer & T.P. Kravtchenko in K.
mechanism. It involves a compulsory adsorption proc- Nishihari & E. Doi (eds.) Food Hydrocolloids, Structures,
ess, a compulsory network formation, and a blending Properties and Functions, Plenum Press 1994, p. 307
process that depending upon the amount of shear af- 7. R. Tuinier, C. Rolin & C.G. de Kruif,
fects the size of the suspended particles as well as the Biomacromolecules 3 (2002) 632
localisation of the stabiliser. 8. R.H. Tromp, C.G. de Kruif, M. van Eijk & C. Rolin,
Based on this mechanism, we can understand why Food Hydrocoll. x (2003) Y
citrus pectin has become a preferred ingredient. This 9. F. Sedlmeyer, M. Brack, B. Rademacher & U. Kulozik,
is because it on one hand possesses carboxyl groups Intern. Dairy J. 14 (2004) 331
that are attracted to positively charged areas on the 10. P. Boulenguer & M.A. Laurent in F. Voragen et al.
protein particles as well as to each other by Ca-bridges, (eds.) Advances in Pectin and Pectinase Research, Kluwer
but on the other hand it is a material that is water-solu- Academic Publishers, 2003, p. 467
ble and thus embraces much water when it forms a Enquiry No: 047
network with protein and Ca-ions.
Claus Rolin holds a PhD from The Technical University
Literature of Denmark and has been employed in CP Kelco since
1. R. Valli & S. Bülow Riis, Food & Beverage Asia, 1984.

FOOD & BEVERAGE ASIA FEB/MARCH 2005

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