R A W M AT E R I A L S 5
G E L AT I O N O F H & F P E C T I N S 11
Pectin 11
Gelling Mechanisms 12
S Y N E R E S I S B E H AV I O U R 38
T H E S TA N D A R D I Z AT I O N O F H & F P E C T I N S 42
C L A S S I C , C O M B I A N D A M I D P E C T I N S A N D T H E I R A P P L I C AT I O N 50
G E N E R A L C A L C U L AT I O N S A N D D E S I G N O F F O R M U L AT I O N S 64
F O O D L E G I S L AT I O N 69
2 Low-Calorie Products
Dietetic Products
71
73
3
INDIVIDUALITY IS OUR STRENGTH 74
Cooking jams, jellies and marmalades using The quality criteria for jams and marmalades Fresh fruits, for cost as well as seasonal reasons,
fruits, sugar, pectin and edible acids is one of are decisively determined by the flavour, co- are only used in smaller quantities for the
the oldest food preserving processes known to lour and consistency as well as state of preser- manufacture of finished products. Thus, the
mankind and presents a way of making food vation and distribution of fruits. These proper- largest amount of fruits for production purpo-
stable by increasing the content in soluble ties depend to a high degree on the raw mate- ses are either frozen, heated (canned) or pre-
solids. The shelf-life of the products gained by rials used, with special importance given to the served with sulphur dioxide.
this method depends on the following criteria proper selection of suitable fruits. The
as regards their stability to microbial spoilage: characteristic nature of the finished product is The most important quality criteria for fruits
● Perfect hygienic operating conditions, such further determined by the addition of sugars, used are:
as production units, filling and production pectin and edible acids. ● optimal state of ripeness
system. ● full fruity flavour
● Perfect hygienic raw materials and packa- The German Fruit Jams Regulation gives the ● variety-specific colour
ging materials. following definition for the required condition ● no blemishes (no spots, no bruises)
● A high sugar content (min. 60% soluble of the raw materials: ● sufficient consistency (solidity of form)
solids in jams, jellies and marmalades), ● soluble solids content in agreement with
which causes a lowering of the free water Fruits: quality standards
by hydration. Fresh, sound, not spoiled fruit, containing all ● perfect hygienic condition of raw materials
● Sufficient pasteurization or chemical preser- its essential constituents, after cleaning and and packaging
vation of low-calorie fruit spreads, jams, removal of blemishes and sufficiently ripe.
jellies and marmalades (less than 60% solu- Chestnut for the purpose of the regulation is
ble solids). the fruit of the sweet chestnut tree (Castanca Fruit Pulp (pulp):
● A low pH-range (pH 2.6-3.2) when using ● Cooking temperature: sativa). The term ”fruits” is extended for the The edible part of the whole fruit, peeled or
a rule, of 80-85% water. The main constituents, portance. Generally speaking, the insoluble blackberries 44 0.48 3.3-3.6 1.09 (C)
besides water, are carbohydrates, furthermore parts of fruits are especially rich in calcium. red currants 29 0.93 3.0-3.1 2.14 (C)
gooseberries 29 0.62 2.7-3.1 2.37 (C)
organic acids, polymer carbohydrates such as However, the total calcium amount is not
pectins and starches, nitrogenous compounds, available to pectin, but only part of it, the Table 1: 1) Souci-Fachmann-Kraut: Die Zusammensetzung der
M: calculated as malic acid Lebensmittel, Nährwert-Tabellen 1989/1990, Wissen-
minerals, vegetable phenols, flavours and so-called ”free calcium”. The remaining
C: calculated as citric acid schaftliche Verlagsgesellschaft mbH Stuttgart 1989
vitamins. calcium ions, or ”bound calcium”, are solidly 2) K. Herrmann: Obst, Obstdauerwaren und Obster-
fixed to complexing agents. zeugnisse, Verlag Paul Parey 1966
Liquid sugar is an aqueous solution of sucrose and sucrose in the finished product. Its addi- its. Its relevance as a sugar substitute consists maltitol 0.65-0.68 *
with a minimum of 62% soluble solids and a tion improves the texture (smoother consisten- in its insulin independent metabolism and di- lactitol 0.30-0.35 *
maximum amount of 3% invert sugar related cy of the finished product). Dried glucose syrup gestion, which makes it suitable for dietetic
xylitol 0.00 *
to soluble solids (ss). may also be used instead of glucose syrup. food products for diabetics. The calorific value
of fructose is determined at 17KJ/g (or Table 2:
* the figures indicate the factor by which the sugar
Invert liquid sugar is an aqueous solution of Glucose syrups may be of different composition 4kcal/g), equal to sucrose or glucose. The
substitute in question tastes sweeter than sucrose.
sucrose, partially inverted in hydrolysis, in depending on the various possible methods sweetening power of fructose is higher than from: Süßungsmittel im Überblick (a summary of swee-
which the amount of invert sugar does not employed in large-scale productions. The pro- that of sucrose. Fruit sugar is normally traded teners), Gordian 88/4, p. 72ff.
preponderate and the following criteria are duction, however, always starts with a partial as fruit sugar have a laxative effect.
given: a minimum of 62% soluble solids and no starch hydrolysis. The application of the enzyme syrup with 70% ss. Sweeteners:
less than 3% but no more than 50% invert glucose isomerase has greatly extended the Sweeteners are natural or synthetic compounds
sugar related to soluble solids. range of available glucose syrups. This enzyme Polyols or sugar alcohols form the main group which have no or, compared to their sweete-
causes the conversion of part of the glucose of sugar substitutes. The physiological benefit ning power, only a negligible calorific value.
Invert sugar syrup is an aqueous solution of into fructose. The glucose syrups produced in of these sugar substitutes is their suitability for Their sweetening power is by far greater than
sucrose partially inverted in hydrolysis, which this way have higher fructose volumes and thus diabetics (insulin independent metabolism) as that of sucrose.
is dominated in its composition by the amount greater sweetening power as starter syrups. well as their partially anti-cariogenic effect and
of invert sugar present and which meets the Depending on the fructose share, these syrups lower calorific value. Comparison of the sweetening power of
sweeteners in relation to sucrose
aspartame
130-200 *
200-250 *
9
glucose related to soluble solids are, for exam- cyclamate 30-40 *
These sugar solutions are characteristic for ple, used in production.
saccharine 450-500 *
their relatively low viscosity, temperature tole-
sucralose approx. 600 *
rance and the fact, that they do not crystallize Dextrose is made by starch hydrolysis. It is of
even at a low temperature. They affect the practically no importance in jam manufacture, Table 3:
* the figures indicate the factor by which the sugar
microbiological stability of the product positi- since dextrose tends to crystallize and lends a
replacer in question tastes sweeter than sucrose.
vely owing to the higher osmotic pressures dull and mat appearance to the products. from: Süßungsmittel im Überblick (a summary of swee-
teners), Gordian 88/4, p. 72ff. resp. Handbuch Süßungs-
mittel, Behr’s Verlag
Different amounts of pectin may be extracted The molecular structure of pectins is composed
from various raw materials: of D-galacturonic acid molecules, which are
10 Pomace 10-15%
Sugar beet chips 10-20%
Citrus peels 20-35%
linked to each other in alpha-1-4-glycosidic
formation to polygalacturonic acid. Part of the
carboxyl groups is methoxylated with methanol.
11
Apples and citrus fruits have always been of Neutral sugars like arabinose, galactose and
superior importance for the production of pectin xylose, which are linked as side chains to the
No sugar is added to these products, they only destined for the manufacture of jams, jellies pectin macromolecule, as well as the interrup-
contain the sugar from the fruits they are ma- and marmalades. The highly valuable pectin tion of the main chain by rhamnose make
de from. substances are present in the pulp and, in espe- pectin a heteropolysaccharide.
of chain links a pectin molecule boasts, which which are ruptured by the incorporation of
is kept intact by extremely sensitive production rhamnose or by the branching of the chain.
process. COOCH3 OH
Different types of chain associations exist which O
O O
If all carboxyl groups of the polygalacturonic are determined by the degree of esterification.
OH OH
acid are free, i.e. not methoxylated, one gets For high methylester pectins, two decisive fac- O O
pectic acid, its salts are called pectates. tors initiate gel formation:
H+
OH C
Pectic acid in nature is methoxylated (or esteri- 1. The addition of sucrose or other sugars has O O–
fied) in different degrees with methanol and a dehydrating effect on the pectin molecules, COOCH3 OH
O
thus becomes pectin. If the degree of esterifi- which facilitates the approach of the polymer O O
cation is higher than 50%, it is called high chains and enables a cross linkage of the OH
OH O
methylester pectin, with less than 50% it is hydrogen bridges. O
called low methylester pectin.
OH C
Fig. 3: Dissociation of carboxyl groups O OH
2. A lowering of the pH in the medium sup- Methylester groups are the hydrophobic part
12 13
Fig. 1: Section of a pectin molecule presses the dissociation of free carboxyl groups of a pectin molecule. Hydrophobic forces push
and thus reduces the electrostatic repulsion them into aggregate formations, while they
between the chains. The mechanism described are constantly striving to keep the contact sur-
above is referred to in literature as ”sugar-acid- face with water as small as possible. Moreover,
gelling mechanism”. hydrogen bridges are formed, e.g. between
non-esterified carboxyl groups, at a sufficiently
Recent studies, however, have shown that high low pH-value in the gel and the dissociation of
methylester pectins are stabilized in the gel by the carboxyl groups is largely suppressed.
a combination of hydrophobic interactions and
hydrogen bridge bondings, which means that
the term ”sugar-acid-gelling mechanism” requi-
res a closer definition.
HO HO
O O
O O O O
–
HO –
HO
HO O COO HO
– O COO
–
O O O O O
OH OH
Ca2+ Ca2+
HO HO
O O O
O O
–
OOC –
O OH –OOC –
O OH
O OH O OH
O O
O OH O OH
soluble
solids
Fig. 4: Structure of [ºBrix]
connecting zones of 80
HM pectins
75
14 According to Oakenfull and Scott (1984), the over free, non-methoxylated carboxyl groups
70
pre-gelled 15
hydrogen bridge bondings are the responsible decreases and if the pH is too high, the number gelled
factor in the stabilization of a pectin network, of interfering factors (-COO-) decreases as well 65
but without the hydrophobic interaction of the (in case of a too high product pH, dissociated
liquid
methylester groups, gelation would not occur carboxyl groups interfere with the network
60
for energetic reasons. formation). This affects the gelling-pH-range. If
the degree of esterification is extremely high,
55
The higher the degree of esterification, the the suppression of dissociation does not matter
3.6 3.4 3.2 3.0 2.8 2.6 pH
greater the impact of hydrophobic forces in the anymore.
gelation. The number of hydrogen bridges Fig. 6: Setting range of high esterified pectins
amid groups are present, that means the more pectin may prevent the formation of brittle Deuel, H., Huber, G., Leuenberger, R. (1950): Über das
Geliervermögen von Polygalakturonsäuremethylester,
links are possible, the firmer the resulting gels gels and the crystallization of sugar and dex-
Helvetica Chimica Acta, Vol. 33, p. 1266ff.
will be. trose. Rees, D.A., and Welsh, E.J. (1977): Sekundär- und Tertiär-
struktur von Polysacchariden in Lösungen und Gelen,
Angewandte Chemie, Band 89, S. 228-239.
Pilnik, W. (1980): Pektine, in ”Gelier- und Verdickungs-
mittel in Lebensmitteln”, Forster Pub., Zurich
Ionization constant
pka 3 5.4
Table 4: Important data on lactic acid, tartaric acid and citric acid
From: Genußsäuren und Salze (edible acis and salts); Anwendung und Wirkung in Lebens-
mitteln (application and effect in food)/Publ. Fachgruppe Lebensmittelchemie und Gerichtl.
Chemie i.d. GDCh. (Editor: G. Wieder) – Hamburg, Behr, 1989
(Lebensmittelchemie, Lebensmittelqualität, Vol. 14).
Citric acid: Low Methylester Pectins – Gelling Behaviour: Concentration of Soluble Solids:
Citric acid is naturally present in a great num- On the other hand, if the pH-value in fruits is The gel formation of low methylester pectins Chart 8 on page 24 shows how the breaking
ber of fruits. It is crystalline and dissolves well too low, it can be increased in order to prevent must be seen as follows: strength of a gel changes with increasing cal-
in water. Citric acid as a weaker acid than tar- pre-gelation. cium dosage as a function of the different solu-
taric acid, but stronger than lactic acid. The When small amounts of calcium ions are added, ble solids contents. At a soluble solids content
flavour of the citric acid is naturally sour and If the aim is a stabilization of the pH-value the pectin chains start to bond over calcium of 60%, hardly no calcium ions are required to
harmonious. This acid, too, is preferred to be within strict limits, as is the case for jams, one bridges. With increasing calcium ion concentra- form a firm gel, while at 20-30% of soluble
added as 50% aqueous solution. profits from the specific properties of fruit tion, gelation sets in. In case of an exceeded solids major amounts of calcium become neces-
acids to form excellent buffer systems with dosage of calcium ions, calcium pectinate will sary. The lower the soluble solids content in a
If the acid value is too high (pH-value under their salts, e.g. in the combination citric acid precipitate under the given gel forming condi- gel, the higher the calcium requirement in order
2.8) the gel elasticity will be increased and the and sodium citrate. tions, which is referred to as ”pre-gelling”. to achieve proper gelation is. The gel strength
gels become firm and brittle. If the acid value is in these samples has been determined with the
low (pH-value above 3.3) the gel structures be- As a rule, fruit acids are added to the cooking The gel texture will then lose its elasticity, be- Herbstreith Pektinometer by testing the
come very soft. When exceeding a certain pH batch towards the end of the cooking process. comes more pasty and shows a lower breaking breaking strength.
limit, gelation is no longer possible. This prevents pre-gelling, which might occur if strength. The precipitation of calcium pectinate
1800 30% ss calcium ion requirement in order to achieve the filling temperature. The higher the filling
20% ss
1600 sufficiently firm gels. temperature, the more calcium ions can be in-
corporated in the gel network without causing
1400
An increased concentration of buffer substan- pre-gelation.
1200
ces, especially with a strong binding effect on The amount of the calcium dosage does not
1000 calcium as e.g. exists for the salts of citric acid, only control the firmness of the gel, but also its
800 will, similar to a raise in the pH, require a si- rheological and sensory properties.
400
200
Chain
Effect of the type of sugar: association
Not only the concentration, but also the type The rise in pH will lead to an increased number
of sugar or sugar substitute used will affect of charged particles in the gel which dissociate
gelation. Thus, the calcium requirement to the pectin molecules even more strongly. The
Ca2+
Effect of the Product’s pH: An increased concentration of calcium ions pro- Ca-pectinate
The increase of the pH-value in a gel must be vides more bonding points between the pectin precipitation Fig. 9: Gelation of low
methylester pectins in
followed by an increase of the amount of cal- molecules and will thus keep the gel strength dependence on calcium
cium ions required within the gel to achieve intact. ion concentration
Gels of section II show in their majority viscous pumped but still hot and liquid, they have an
influences, they are spreadable, stable gels unlimited high viscosity and behave like solids.
with a high regeneration potential after mecha- Owing to this, fruit pieces will neither rise nor
nical stressing and show very little tendency to settle, but remain ”cast” in position in the gel.
syneresis. In the sensory respect as well, viscous This is understood by ”good fruit distribution”.
I II III IV components influence the flavour. These are
mgCa2+/g Pectin gels that will melt in the mouth and have a Fruit pieces regularly distributed in the gel are
fruity, sweet taste which is very pronounced. considered a quality feature of jams.
Fig. 10: Breaking strength of pectin gels in dependence on
added calcium ions (Section I-IV)
The reaction of pectins with calcium ions in- The yield point cannot be substituted by a high
creases the setting temperature and results in a viscosity. Indeed, a high viscosity delays the
Rheology and Sensorics: Section I: yield point at a higher temperature. rising of fruits but will not prevent it.
In a given formulation, which means that su- The calcium concentration in section I is very
gars and sugar concentration, pectin concen- low: fruit preparations in this area are highly In resting condition, once the jams have been
tration and type of fruits and fruit quantity are viscous or slightly gelled. filled in containers and are no longer stirred or
constant, gels become increasingly more firm
with higher amounts of calcium. Section II:
The firmness may be assessed by testing the Gels in this area have only just started gelation
breaking strength with the Herbstreith or are already gelled. The gels are very smooth
Pektinometer. and spreadable. Rheologically speaking, they
may be characterized by their visco-elasticity as
However, an increase in calcium concentration follows:
does not only raise the breaking strength of
Gel strength
high and at the given filling temperature pre- vity and with that the calcium need for forming
gelling will occur. The gel strength decreases, a gel network and the resulting setting tempe-
the consistency is mushy or pasty, syneresis rature.
occurs and the yield point is lowered. The tex-
Elastic-brittle texture
Sensitivity levels of low methylester, amidated pectins with differing calcium sensiti-
amidated pectins: vity at different filling temperature
Low sensitivity: The texture and the firmness of the final pro-
Low methylester, amidated Pectin Amid AF 005, Pectin Amid CF 005 duct can be decisively influenced by the selec-
citrus pectin ted filling temperature.
32 33
Fig. 14: Texture of gels, manufactured with low methylester, amidated pectins with differing calcium sensitivity in
dependence from filling temperature
To form elastic gels, gel preparations which are calcium ions for gelation, however then it
manufactured with pectins with medium and shows a high tolerance towards fluctuations of
low reactivity require a certain amount of the calcium content resulting in a homogenous
LMA pectin with high calcium
calcium ions whereas gels, which are manufac- gelation over a wide working range.
reactivity
tured with a reactive pectin, already form an
LMA pectin with low calcium
reactivity elastic gel at minor addition of calcium ions As a result, low methylester, amidated pectins
which might come from the fruits or the drin- with high calcium reactivity such us Pectin
Increasing calcium concentration king water. Amid CF 020 or Pectin Amid AF 020 are excel-
pH 3.2 pH 3.6 lently suited for the use in products with a low
In contrast to pectins with low and medium sugar content such as sugar reduced fruit pre-
Fig. 15: Breaking strength (Herbstreith Pektinometer Mark IV) of gels (40% ss, 1.0% pectin), manufactured at diffe-
reactivity, the curve progression of pectin with parations or delicatessen products.
rent pH-values with low methylester, amidated pectins with differing calcium reactivity in dependence from calcium
ion concentration high reactivity is plain and the breaking
strength of the gels changes over a wide range Pectins with very high reactivity such as Pectin
only little. Amid CF 025 or Pectin Amid CB 025 are suited
d) Gelling properties of low methylester, ami- Gelling behaviour at 20% ss among others for glaze, spray nappage or jelly.
dated pectins with differing calcium reactivity With rising calcium ion concentration the At low soluble solids contents (0-20% ss) the
at different soluble solids content breaking strength, determined with the reactive pectin requires a certain amount of
Besides the pH-value of the product also the Herbstreith Pektinometer Mark IV, increases,
soluble solids content is an important parame- the texture of the gels becomes firmer and
ter for choosing low methylester, amidated more elastic.
pectins. When altering the soluble solids con- 20% ss
tent, low methylester, amidated pectins show Over the whole range investigated the high
different gelling properties in dependence reactive pectin results in firmer gels at compa-
from their calcium reactivity. Thus, depending rable calcium ion concentration than pectins
Fig. 16: Breaking strength of gels (20% ss, 1.0% pectin, pH-value 3.2), manufactured with low methylester, amidated
pectins with differing calcium reactivity in dependence from calcium ion concentration
Syneresis Behaviour elastic as well as viscous phases. The greater throughout the molecule due to the production
the elastic and the smaller the viscous phase in method. Enzymes, which cause a clustered
a gel, the greater the sensitivity of gel textures demethoxylation, are not active in the raw
to mechanical stressing and their inclination to material pomace, contrary to other raw mate-
In general, syneresis is an undesired phenome- High Methylester Pectins (HM Pectins): syneresis are. rials, e.g. citrus peels.
non for jams and other fruit preparations and
depends on many factors. It is described more Gelled products with HM pectins have, as a The ratio of elastic and viscous phases in pectins The most frequent cause for syneresis is the
closely in the following: rule, a soluble solids content of at least 60%. is determined by the degree of esterification series of unsuitable production conditions
At these high soluble solids, the manufactured and their sensitivity to multivalent ions. which may be summarized by the term
Pectin is supposed to immobilize the free water products should not show any syneresis under ”pre-gelling”.
in the product. If the desired water binding optimal conditions, that is if the gel is not Very high methylester pectins form very elastic
effect is not completely achieved in gel produc- destroyed. gels with high setting temperatures. Medium Pre-gelling will always occur if the filling
tion or during further processing of the gel, methylester pectins form elastic gels with temperature for the gel has been set too low.
gels show a tendency to shrink and to release Syneresis to a minor extent may occur in the greater viscous phases and lower setting tem- The reason for this may be (at correct pectin
fluid, which is called syneresis (the pectin normal consumption of gelled products, e.g. in peratures. Due to the greater viscous phase, dosage):
chains approach each other too closely and household consumption and especially if a gel medium methylester pectins are less sensitive
squeeze the originally bound water out of the is stirred or pumped. to mechanical stressing, show less inclination
gel network). to syneresis and result in more spreadable gels. ● that the sugar concentration is too high
HM pectin gels are not able to regenerate their ● that the acid dosage (which causes the pH
Based on the different gelling mechanisms, gel texture after mechanical destruction. Once Another reason for high gel elasticity is ion in the product to be too low) is too high or
syneresis must be differently assessed in high the texture of these gels has been damaged, sensitivity, which occurs also in high methyl- ● an unsuitable type of pectin, e.g. a pectin
and low methylester pectins. syneresis sets in and becomes more pronounced ester pectins as a function of raw materials and that sets too fast.
during a longer storage period. production methods. Ion sensitivity is probably
also influenced by the way the free carboxyl This may be remedied by correcting the sugar
groups are distributed in the pectin molecule. and acid concentrations, and by matching the
A clustered appearance of free carboxyl groups filling temperature and the type of pectin.
40 41
A sugar-pectin-water gel with 65% soluble For determining the breaking strength and the
solids and a pH-range of about 2.0 is manufac- texture with the Herbstreith Pektinometer a
tured for this purpose. The gel is cooled under nearly optional gel is put on strain up to the
defined conditions (25°C [77°F] 24 hours). After destruction of the gel network. The force
cooling, the gel is released from its mould and necessary for this effect is measured in depen-
the percentage of sagging under its specific dence from time.
gravity is measured with the so-called Exchan-
ge Ridgelimeter after exactly 2 minutes. A Gel The simple handling, good reproducibility and
with a 23.5% sagging is considered a standard above all the great flexibility regarding the
gel. recipe are the advantages of this method. With
that gels can be assessed which are exactly
The grading of pectin is calculated according to adjusted to the particular application.
the following formula:
Fxa But, fruit spreads containing fruit components
°USA-Sag =
b can only be assessed reproducibly if the fruits
a = amount of sugar in the gel (650g) are finely ground or at least relatively small
b = amount of pectin in the gel (4.33g) and distributed homogeneously.
A sagging of 23.5% is equal to factor F = 1 and For determination of the breaking strength and
the °USA-Sag = 150. Gels which sag more the texture with the Herbstreith Pektinometer
strongly (weaker gels) are corrected by a factor the gel preparation is filled into a standardized
< 1; gels which sag less strongly are calculated measuring beaker with shear insert. After a
with the correcting factor > 1. A table has been defined time this shear insert is pulled out of
compiled with these factors. the gel and the force necessary herefore is
measured. From the resulting force-time-dia-
The method described has served as commercial gram the following information is obtained:
Fig. 20: Ridgelimeter (USA-Sag-Method)
basis for high methylester pectins for many
years. However, this method is not undisputed, The maximum value is the force which is neces-
Elastic-viscous gels for example require a smal- Determination of Texture Properties using the
ler force to be disrupted resp. broken and Oscillating Rheometer
therefore their breaking strength is relatively The above mentioned texture constant K
low. which is used together with the Herbstreith
As elastic-viscous gels have an inner cohesion, Pektinometer Mark IV for determining the tex-
a low but steady power input is necessary to ture properties of pectin gels correlates very
pull the shear insert out of the gel. Therefrom well with the so-called dynamic Weißenberg
a relatively large integral area in the force- number W’ (Windhab, 1990) which can be
time-curve results. determined by using the oscillating rheometer.
From the ratio of breaking strength, i.e. the The determination of the dynamic Weißenberg
maximum force, and integral of the force-time- number W’ is a comparatively extensive rheo-
curve a relatively low value for the texture metric method in which the ratio between
constant K is obtained. Sensorily the gels are elastic (G’) and viscous shares (G’’) of a pectin
assessed very easy to spread and homoge- gel is determined by a special oscillating
neously firm with high mouthfeel. measurement mode (W’ = G’ : G‘’).
Elastic gels show high breaking strength values, Pectin gels are visco-elastic substances, which
thus they require a high power input for means they are predominantly elastic. How-
breaking. Elastic gels break into single frag- ever, they additionally possess more or less
ments when ruptured. Therefore after breaking high viscous shares which have a very signifi-
only a small power input is necessary to pull cant influence on texture.
The determination of setting time according to then measured in the sample. The sample is
Joseph and Bayer (Joseph, G.H., Bayer, W.F., not destroyed in the process.
1949) has proved to be simple and easy to carry
Fig. 23: Visco-elastic substance (phase displacement between 0°-90°) out without any technical input. If the sample is in a liquid state, the viscous
References: Joseph, G.H., Bayer, W.F. (1949): Food
phase is dominant and the phase displacement
Technol. 3, 18-22
between the curve of the applied force and the
response movement amounts to approx. 90°C
The texture, that means appearance and struc- starts to gel and the higher the filling tempera- In this method a gel preparation is produced (194°F) If the sample has become a firm gel, the
ture of the gel surface, the sensorily felt firm- ture in the production process has to be fixed. according to the Ridgelimeter method. The set- elastic forces are paramount and the resulting
ness when spooning and spreading, and the If the setting temperature of the product is ting process is observed under defined cooling phase displacement between curves approaches
haptic impression (mouthfeel) of fruit spreads higher than the fixed filling temperature, pre- conditions. The time at which gelation starts, is 0. If viscous and elastic phases are balanced,
are determined by the ratio of elastic and gelation will occur, that means the products measured and defined as setting time. one gets a so-called sol-gel-transition or gel
viscous properties. The higher the elastic shares already starts gelling before the filling process. point. The angle of shift between phases will
in a gel, the higher is the dynamic Weißenberg The mechanical treatment during the filling Due to the less practice-oriented recipe para- then amount to 45° and the corresponding
number W’. process irreversibly destroys the gel network meters (no buffer salts, pH-value approx. 2.2) temperature is defined as the setting tempera-
already formed resulting in a partial loss of the the measured values correlate only to some ture.
The texture of gels with a high dynamic final gel strength in the product. extend with practical experiences.
Weißenberg number (W’ = 15-20) is elastic- On the basis of setting time/setting tempera-
brittle, the gels show a structured, rough sur- On the other hand, products, which contain This becomes very clear when observable reac- ture the high methylester pectins are usually
face and often a slightly higher tendency to whole fruits or fruit pieces, require a compara- tions with ions, mostly bivalent cations such as divided into the following groups:
syneresis. tively high setting temperature as these pro- calcium ions, are already expected due to the
ducts are intended to gel quickly after the fil- low degree of esterification or due to the raw ● rapid set (rs)
Gels with a small dynamic Weißenberg number ling process in order to prevent the contained material (as for citrus pectins by a blockwise ● medium rapid set (mrs)
(W’ = 5-10) are elastic-viscous, easy to spread fruits or fruit pieces from floating and with distribution of carboxyl groups). ● slow set (ss)
Customized Pectins for Specific Control of Generally, citrus pectins form highly elastic, Classic Pectins: An Example for Formulation Parameters and
Sensory and Rheological Properties of Jams, even brittle gels with a relatively high tendency The Classic Pectins of interest in this area receive Technology:
Jellies and Fruit Preparations: to syneresis. Apple pectins, on the other hand, a letter coding in their nomenclature, which is Jam with 62% soluble solids, pH at 3.0:
Increased quality demands on jams, jellies and form elastic gels with a certain amount of ”AF”, ”A” stands for ”apple” as raw material If Pectin Classic AF 101 is used for this purpose,
fruit preparations are not only limited to the viscosity, to which they owe their good and ”F” for the application area ”fruits”, also the product will, under the given parameters,
gel strength, but also include in a rising degree spreadability with low tendency to syneresis, ”C” for ”citrus” as raw material. show a very high setting temperature. To avoid
consistency, texture and syneresis behaviour. which, in turn, also influences the taste of the pre-gelling, it must be possible with the tech-
What is regarded as the optimal consistency by gels. Apple pectin gels melt in the mouth, and All high methylester Classic Pectins listed here nology applied to fill at a very hot state. The
consumers in one country and for a certain the fruity-sweet flavour is intensively perceived. are suitable for jams and marmalades with texture of the gels is highly elastic, the sprea-
product, may be quite different in other places. more than 60% soluble solids, but also the low dability is poorly developed. To lower the set-
In some countries, for example, special products Based on these properties, H&F supply Classic methylester Pectin Classic AF 802 may be ting temperature and to improve spreadability,
are expected to be of very firm and brittle gels, Apple and Citrus Pectins for a great variety of applied. Which type is suitable in a specific pectins with a lower degree of esterification
in other countries, easily spreadable gels are product designs. case depends on: are used instead. On the other hand, if the same
clearly preferred (Swiss consistency). Of extra product should be produced with a higher pH-
jam, however, consumers in general expect a Furthermore, H&F have also developed Combi ● the formulation value of e.g. 3.3, then Pectin Classic AF 101 has
firmer consistency than for e.g. compote or Pectins (apple/citrus), which differ from tradi- ● the production technology certain advantages compared with other pec-
spoonable fruit desserts. tional pectins due to their production method ● the texture requirements tins. This pectin, due to its high degree of este-
and properties. To produce Combi Pectins, rification, shows still a good setting at a higher
Pectins are the preferred gelling and thickening pomace and citrus peels are extracted jointly in With a declining degree of esterification the pH-value and, owing to the higher product pH,
agents for jams, jellies and fruit preparations, a fixed mixing ratio, which depends on the setting temperature of these gels also drops, if the setting temperature will be lowered and
because these are already originally and natu- intended finished product. their manufacure happens under the same con- the texture becomes smoother.
rally present in fruits thus resulting in a natural ditions and according to the same formulation.
48 texture.
50g Pectin solution 5% (= 0.25%) Procedure: pectins form gels with a sometimes firm, even
450g Fruit Gels which are manufactured with Pectin Clas- brittle gel texture, because fruit pieces or fruit
A Production of pectin solution (mix pectin
420g Sucrose, crystalline sic AF 504 show a very spreadable texture and fibres that might contribute to the gel’s
dry with a part of sucrose, stir into water
200g Glucose syrup (15% dextrose, an extremely low tendency to syneresis. smoothness, are missing.
and heat to approx. 90°C).
15% maltose, 13% maltotriose)
x ml Citric acid solution 50% to adjust B Mix fruit, glucose syrup and sucrose and
the pH-value heat to approx. 90°C.
50 450g Fruit
420g Sucrose, crystalline
200g Glucose syrup (15% dextrose,
A Production of pectin solution (mix pectin
dry with a part of sucrose, stir into water
450g Fruit juice, approx. 12% ss
410g Sucrose, crystalline
200g Glucose syrup (15% dextrose,
A Mix the pectin with approx. 100g sucrose
from total sucrose amount.
51
and heat to approx. 90°C).
15% maltose, 13% maltotriose) 15% maltose, 13% maltotriose) B Stir mixture ”A” into fruit juice and boil
x ml Citric acid solution 50% to adjust B Mix fruit, glucose syrup and sucrose and x ml Citric acid solution 50% to adjust until the pectin has dissolved completely.
the pH-value heat to approx. 90°C. the pH-value C Add the remaining sucrose and the glucose
C Add the hot pectin solution and cook to syrup and cook to final soluble solids.
Input: approx. 1150g final soluble solids. Input: approx. 1065g
D Add the citric acid solution to adjust the
Output: approx. 1000g Output: approx. 1000g
D Add the citric acid solution to adjust the pH-value.
ss: approx. 63% ss: approx. 63%
pH-value: 3.0-3.1 pH-value. pH-value: 3.0-3.1 E Adjust filling temperature to trading unit
E Adjust filling temperature to trading unit size.
size.
loped for the preparation of cranberries. It gives rate calcium addition in a soluble solids range x ml Citric acid solution 50% to adjust completely.
these products a very smooth texture and also of approx. 40-55%. In order to reach optimal the pH-value C Add the remaining sucrose and the glucose
provides a good fruit distribution. gelling properties, the addition of calcium may Input: approx. 1035g syrup and cook to final soluble solids.
become necessary for fruit spreads below Output: approx. 1000g D Add the citric acid solution to adjust the
Besides these standard pectin types, H&F have 40% ss depending on fruit type, pectin and ss: approx. 55% pH-value.
developed in close cooperation with their processing parameters. pH-value: approx. 3.1-3.3 E Adjust filling temperature to trading unit
customers specifically designed, customized size.
pectin types.
How to Incorporate Pectins into the Product If sugar solutions or sugar syrups are used, pre-mixing mixer pre-mixing mixer
approx. approx.
Batch: pectin may also be suspended in 10 times the 500 min-1 500 min-1
The production of pectin solutions by way of a amount of liquid sugar/sugar syrup while stir-
suitable system is the best possibility to add ring slowly. This suspension may then be incor-
standardized pectin to the cooking process. porated into hot water with at least 80°C
(176°F), which results in a 3-5% pectin solution.
If only slow-speed mixers are available, the product product
batch batch
pectin is mixed with about 5 times the amount If pectin is directly added to the product batch,
of sugar and this mixture is dissolved in water i.e. not as pectin solution, this is best achieved
with a temperature of at least 80°C (176°F). In with the above mentioned pre-mix of pectin
Production of pectin solutions
this way, a 3-5% pectin solution can be pro- and 5-10 times the amount of sugar or a suspen-
duced. sion with liquid sugar or sugar syrups. In this
pectin ingredients
case it is important to observe that the soluble
If a dissolver with high-speed mixer is available solids content in the batch during the dissolving
(more than 1.500rpm), pectin is added while of pectin is not above 30%, since it otherwise
pre-mixing mixer
the mixer is running and the water temperature interferes with the solubility. approx.
500 min-1
is at least 80°C (176°F), directly poured into the
mixer flux and dissolved. Depending on the
type of pectin, pectin solutions of 5-7% may be
produced.
water
Nowadays, 7-10% pectin solutions can be pro-
duced, on modern injection mixers. Flowchart pectin
water water
Fig. 24: Incorporation of Pectin into the product batch/scheme high-speed dissolving equipment
oils and fats such as mono- and diglycerides of capping under vacuum with headspace sterili- steam
edible fatty acids may be added during cooking. zation guarantees germ-free filling and perfect
stability during storage. Before closing the jars,
The pectin solution is then metered and further suitable measures for the sterility of the pro-
pectin solution
reduced by boiling under vacuum until the duct surface during the filling process are re-
acid solution
desired final soluble solids content is reached. commended. UV-radiation of the empty jars or
Due to the low cooking temperatures, which the caps before filling is also indicated to pro- cooling water
H2O
may be as low as 65°C (149°F), slow to medium tect against secondary infections.
rapid set pectins are applied in this process.
After filling and capping, the jars pass through
Once the final soluble solids content is reached, a tunnel cooler and are sprinkled with cold
the batch will be vented and acid is added. The water which lowers their temperature to
temperature of the cooked material increases 40-50°C (104-122°F). The rapid lowering of the cooler
in this process, before discharging it should temperature prevents caramelization and co-
vacuum vessel
reach 80-85°C (176-185°F) in order to guarantee lour changes in the filled article (centreburning)
steam
germ-free filling. and brings the product into a temperature ran-
ge, in which gelation is initiated and an
Sophisticated cooking systems with flavour optimal gel texture may be slowly formed.
recovery condense the volatile aroma compo-
nents from the escaping steam and return After cooling and labelling, the products go H2O vacuum pump
them to the cooking batch before its discharge. into packaging. Before distribution, however,
labelling
filling machine + tube cooler machine final
cap closer packaging
General Calculations
and Design of Formulations Ray path on the Abbe refractometer
1. Ocular lens
2. Objective lens
3. Reflecting prism
Soluble Solids Content and Refractometry:
1 4. Amili prisms
5. Objective lens
The soluble solids contents of raw materials c1 6. Scale
7. Reflecting mirror
and finished products are important parame-
8. Illumination prism
ters for the calculation and design of jam, jelly 9. Measuring prism
and marmalade formulations. They indicate 10. Reflecting mirror
what amounts of dissolved solids (sugar, acids,
pectins, salts, etc.) are contained in anhydrous 2
form in 100g of mass. Thus an anhydrous sub-
α
3
stance, for example, consists of 100% ss, a fruit
with 10% soluble solids and 90% water has a
soluble solids content of 10%. To measure the
Medium 1
ss content, a refractometer is used. 4
Medium 2 7
Fig. 28: Optical design of a hand refractometer Fig. 29: Hand refractometer
sample
small
refraction
64 65
large
refraction
prism lens scale lens
Table 5:
The following legal provisions and regulations With the exception of food additives, the Fruit
Raw Material Volume ss Content Soluble Solids are valid in Germany for fruit jams, jellies and Jams Regulation describes finally and bindingly
marmalades on the basis of the ”Lebensmittel- the composition of food products which are
Fruit 45.0kg approx. 10% 4.5kg
Sugar 51.0kg approx. 100% 51.0kg und Bedarfsgegenständegesetz” (German Food marketed by the designation extra jam, jam,
Glucose syrup 80% ss 5.0kg approx. 80% 4.0kg Law): extra jelly, jelly, marmalade and chestnut purée.
Pectin 0.3kg approx. 100% 0.3kg
Acid 0.2kg approx. 100% 0.2kg The ”Konfitüren-Verordnung” (the German Fruit Except these food additives, the regulation
101.5kg 60.0kg Jams Regulation), (Verordnung über Konfitüren describes the production and condition of these
und einige ähnliche Erzeugnisse vom 23.10.2003 products and lists the admissible raw materials
kg total ss x 100% 60kg x 100% [BGBl. I. S. 2151] in its current version). This and the optional ingredients.
= = 95.2kg theoretical yield
% of set ss 63%
regulation implements the EC Fruit Jams Direc-
tive (Council Directive of 20.12.2001 – 2001/113/ All products covered by the regulation must
Soluble Solids Content in %
EEC – on the approximation of the regulations have a minimum soluble solids content of 60%.
Table 6: of the Member States relating to fruit jams, Products, for which the sugar is completely or
jellies and marmalades and chestnut purée partially replaced by sweeteners, are excluded
Raw Material Average Range of
Variation [OJ L 10/67] in its current version) into German herefrom.
Apples 14.7 10.0-19.6 legislation.
Cherries, sweet 17.2 14.0-20.2
Plums 16.3 12.1-21.3
As regards low-calorie and/or dietetic fruit jams,
Peaches 13.5 10.9-13.8
jellies and marmalades, these are governed The minimum quantity of fruits to be used is
Apricots 14.7 10.7-17.3
additionally by the ”Nährwertkennzeichnungs- different for the various products depending
Strawberries 10.5 7.6-15.9
Raspberries 15.5 14.0-16.0 Verordnung” (Nutritional Labelling Regulation) on the type of fruit and the additional designa-
Blackberries 15.3 13.0-17.8 (Verordnung über nährwertbezogene Angaben tion ”extra”:
Red Currants 15.3 10.4-18.6 bei Lebensmitteln vom 25.11.1994 [BGBl. I. S.
Gooseberries 12.7 11.1-14.9 3526] in its current version) and the ”Zusatz-
Sweeteners:
Low-calorie jams, jellies and acesulfame-k E 950 1000
marmalades aspartame E 951 1000
70 aspartame-acesulfame-salt
cyclamate
E 962
E 952
1000
200
71
sucralose E 955 50
Amid AF 005 32-40% 10-16% const. gelling strength amidated apple pectin, fruit preparations Amid AF 020 27-32% 18-23% const. gelling strength amidated apple pectin, fruit preparations,
E 440 low calcium reactivity (ss 50-65%, pH 3.0-3.5) E 440 high calcium reactivity jellies
(ss 10-40%, pH 3.0-4.0)
Classic CF 201 > 70% - 150 +/- 5°USA-Sag citrus pectin, jams, marmalades and Amid CF 010 30-36% 14-20% const. gelling strength amidated citrus pectin, jams, marmalades,
const. breaking strength rapid set fruit preparations E 440 medium calcium low-calorie fruit
const. setting time (ss > 58%, pH 2.9-3.3) reactivity preparations,
E 440 fruit spreads
72 73
(ss 30-55%, pH 3.0-3.5)
Classic CF 301 65-70% - 150 +/- 5°USA-Sag citrus pectin, jams, marmalades and
const. breaking strength medium rapid set fruit preparations
const. setting time (ss > 58%, pH 2.9-3.3) Amid CF 020 27-32% 18-23% const. gelling strength, amidated citrus pectin, jams, marmalades and
E 440 E 440 high calcium reactivity fruit preparations
(ss > 58%, pH 2.9-3.3)
Classic CF 401 60-66% - 150 +/- 5°USA-Sag citrus pectin, jams, marmalades and jams, marmalades,
const. breaking strength slow set fruit preparations low-calorie fruit prepa-
const. setting time (ss > 58%, pH 2.9-3.3) rations, fruit spreads
E 440 ss 10-40%, pH 3.0-4.5)
Amid CF 025 24-29% 21-25% const. gelling strength amidated citrus pectin, jams, marmalades,
Classic CF 501 55-61% - 150 +/- 5°USA-Sag citrus pectin, jams, marmalades and E 440 very high calcium low-calorie fruit
const. breaking strength extra slow set fruit preparations reactivity preparations,fruit
const. setting time (ss > 58%, pH 2.9-3.3) spreads
E 440 (ss 10-30%, pH 3.0-4.5)
Amid CF 005 32-40% 10-16% const. gelling strength amidated citrus pectin, jams, marmalades,
E 440 low calcium low-calorie fruit Table 9: DE° = Degree of esterification/A° = Degree of amidation
reactivity preparations, fruit
spreads
(ss > 55%, pH 3.0-3.5)
Pectins by Herbstreith & Fox have enjoyed a Furthermore, we also supply our customers
worldwide reputation over many decades. with formulations and technical service, as e.g.
Constantly improving production methods and for the manufacture of high quality jams, jellies
high quality standards have decisively contri- or marmalades.
buted to our present success in the world mar-
ket. This development has always been charac- For this purpose, specific pectins are integrated
terized by innovative thinking and farsighted by our technological experts in the most advan-
research. tageous way in the composition and optimi-
zation of formulations.
Today, we are in a position to offer pectins
which can be used in all foreseeable areas of The analysis of your finished products also con-
application. Consistent production and quality tributes successfully to assure a high and con-
controls with state-of-the-art analytical instru- sistent quality of your product, or even permits
ments guarantee a regular high quality of our conclusions as regards potential improvements
pectins. of your finished articles.
This positive and continuous progressive New and promising product ideas should not
approach has not only been upheld in the face fail because of formulation or production
of challenges, which our staff in research and specific problems. This is what we stand for.
development have faced successfully many Keeping in mind the producer, the product and
times, but also by the great variety of require- the consumer.
ments brought to us by our customers, the
74 users.
Corporate Group
www.directeam.de