Introduction

• All stabilizers and thickeners are hydrocolloids = hydrophilic

and are dispersed in solution as colloids
• Usually hydrocolloids provide the desired functionality at levels
<2%, some of them even give sig. influence on textural and
organoleptic properties at <1%
• Roles: control moisture and provide structure and texture, flow,
stability and eating qualities of food products
• Inhibit crystallization (sugar and ice), stabilize foam and emulsion,
improve (reduce stickiness) of icings on baked goods, and control
release of flavors
 Global market share of hydrocolloids
“The hydrocolloids market is projected to reach $7,911.1 Million by 2019. In 2013, the market was dominated by
North America, followed by Europe. The Asia-Pacific market is projected to grow at the highest CAGR with the
rapid growth in food & beverage industries in developing countries, such as India and China. Increasing
consumer awareness on health, diet, nutrition, and natural products is driving the market”.
http://www.marketsandmarkets.com/Market-Reports/hydrocolloid-market-1231.html

Based on the applications in food products: dairy & frozen products > confectionery > meat &
poultry products > beverages > bakery products > sauces & dressing > others
Functional properties
 Viscosity
• thicken the water for adding body, texture and mouthfeel of
food products such as syrup (low calorie syrups)
• Usually used in systems where the oil/fat content is
reduced/eliminated by water substitution (example: reduced-
fat salad dressing)
 Stability

• Stabilize and prevent separation the

(reduced fat) emulsion
• To control ice crystal formation in ice
cream (usually stabilized with carrageenan,
locust bean gum and guar gum)
Schematic interaction protein-polysaccharide on an emulsion (a) no
added polysaccharide, (b) bridging flocculation at low polysaccharide
levels, © steric stabilization saturated coverage of polysaccharide, (d)
emulsion gel with droplets immobilized in entangled polysaccharide
network
 Suspension

• Keep particles immobilized in suspension (so that

the particles won’t make separation and settling)
• Example: xanthan gum in salad dressing
 Gelation
• Ability to gel (with varied texture from
soft, elastic to hard and brittle gel) and
solidify fluid products
• Example of product : gelled milk
desserts
• Examples of gelling agents: carrageenan,
pectin, gelatin, agar, alginates with
calcium,
• Synergistic combination; xanthan gum
and locust bean gum don’t gel
individually but will together working
synergy and form a strong cohesive gel
 Gelation
Thermoreversible gelling agents Thermally irreversible gelling agent
• Gelatin • Alginate‘
• Agar • High methoxy pectin
• Kappa carrageenan • Konjac mannan
• Ioata carrageenan • Locust bean gum
• Low metoxyl pectin
• Gellan gum
• Methyl cellulose and
hydroxypropilmethyl cellulose
• Xanthan gum and locust bean gum
or konjac mannan
 Nutritional and nutraceutical

• hydrocolloids as source of dietary fiber

• potential benefits:
 weight loss program,
 cholesterol reduction
 to cancer risk prevention.

See Phillips and Williams (2009) Handbook of hydrocolloids pp 77

 Source of hydrocolloids
Botanical:
Tree gum exudates: gum Arabic, gum karaya, gum ghatti, gum tragacant
Plants: starch, pectin and cellulose
Seeds: guar gum, locust bean gum, tara gum, tamarind gum
Tubers: konjac glucomannan

Algae
Red seaweeds: agar, carrageenan
Brown seaweeds: alginate

Microbial: xanthan gum, curdlan, dextran, gellan gum, cellulose

Animal: gelatin, caseinate, whey protein, soy protein, egg white protein, chitosan

See Phillips and Williams (2009) Handbook of hydrocolloids pp 30

 Gum Arabic (acacia gum)
• Natural gum, a dried exudate obtained from the
stems and branches of Acacia senegal or A. seyal
Raw gum
trees (grown in Sudan, Nigeria and Chad)
• The 3rd largest hydrocolloids used by industry
Crushing (57000 tons, 2008)
• Highly branched arabinogalactan (galactose 44%,
arabinose 27%, rhamnose 13%, glucuronic acids
Dissolution in water
14,5%, 4-0-methylglucuronic acid 1.5%) that
gives a low viscosity together with a central
protein fraction providing good emulsion
Filtration
properties
• Applications: confectionery products, flavored oil
Heat treatment
emulsions, capsules and health foods (soluble
fiber source with prebiotic properties)

Spray/ Spray drying Roller drying

agglomeration
Gum Arabic structure and application
• Confectionery:
• molded candies; hard texture
acacia gum (35%) sucrose (30%),
glucose (25%) and water, flavoring
and colorant (10%)
• Chewy candy: sucrose and glucose
(74%), hydrogenated vegetable fat,
flavor and acid (5%), gelatin (1%)
and Arabic gum (1%)
• Sugar free candies: added 2-5%
Arabic gum (for reducing
hygroscopicity, recrystallization and
stickiness) based on sorbitol,
maltitol and mannitol
• Tableting
 Starches and its derivatives
Modified to
Native starch
Unsuitable for most application
• inadequate process tolerance for
commercial manufacturing
• inadequate shelf stability for
retail distribution
• Typical processing will lead to a
loss in viscosity
• Prolonged holding will lead to
deterioration, especially with
repeated freezing and thawing.
Functional improvements through modification
Modification Effects
Crosslinking Retains viscosity despite heat, acid and shear
Monosubstitution Improved stability to cold storage
Reduced gelation
Reduced gel temperature for low moisture foods
Improved emulsification properties
Acid-thinning Reduced hot-paste viscosity, improved gelling
Oxidation Improved batter adhesion
Dextrinization Emulsification
Increased stability
Reduced viscosity
Improved film forming
Re-drying Improved flow and moisture binding
Oil addition Holds shape for molding
Pregelatinization Dissolves and thickens without heat
Modification Effects
Annealing Increased gel temperature
Increased enthalpy
Narrowed gel temperature range
Heat-moisture Increased gel temperature
Reduced swelling
Increased stability, broadened gel temperature range
Reduced enthalpy
Dry heat Increased viscosity
Increased process tolerance
Increased gel temperature range
Shear Higher gel strength
Improved stability
Cold gelling
Radiation Increased gel temperature
Improved stability
Reduced viscosity
Solvents Pregelatinization, thin-thick properties
 Example of application of (modified) starch in food products

Modified corn starch as thickener in baked beans, hoi-sin sauce, and yoghurt

Modified corn starch as gelling agent with sodium alginate in apple pie filling
 Seaweeds polysaccharides-AGAR
• AGAR obtained from red seaweeds Rhodophyceae with main
species Gelidium (produced the highest gel strength agar) and
Gracilaria
• Structure: repetitive units of D-galactose and 3-6, anhydro-L-
Gelidium galactose and a low sulfate ester content
• Gelling power is obtained from the hydrogen bonds formed
among its linear galactan chain.
• Concentration for gelation 0.2%, doesn’t need cations to gel,
gel point ranges 28-31oC (Gelidium) and 29-42oC (Gracilaria)
and melting point 80-90oC (Gelidium) and 76-92oC (Gracilaria)
Gracilaria
• Agar forms gel over a wide pH range, but it can be hydrolyzed
by acid at high temperature
 Structure of agar

Agarose

Two components:
• Agarose = the gelling fraction, a neutral polymer, β-1,3-linked- D-galactose and α-1,4-
linked 3,6-anhydro-L-galactose
• Agaropectin, a charged, the non gelling fraction, is a sulfated polysaccharide (3% to 10%
sulfate), composed of agarose and varying percentages of ester sulfate, D-glucuronic
acid, and small amounts of pyruvic acid
• Ratio agarose to agaropectin varies among seaweed specieis, Agarose normally represents
at least two-thirds
 Synergy, incompatibility and applications
Synergy Incompatibility with:
• Gelidium agar with locus bean and carob • Tannic acid and other proton scavenger
• Agar with high sugar concentration such as potassium iodide, guanidine,
(>60%) urea and sodium thiocyanate

Application in food products

• Agar is GRAS; it is used in baked goods and baking mixes (0.8%), confections and
frostings (2.0%), soft candies (1.2%) and all other food categories (0.25%)
• It has been used in ice cream, milk shake, sherbet, custard pudding, cakes, pie filling,
flat icing, meringue, cookies, candy, fruit jelly dessert, jam and jellies, processed
cheese, fermented dairy products, ets
 Alginates
• Alginic acid is a copolymer of the
building blocks β-d-mannuronic acid (M)
and its C-5 epimer, α-l-guluronic acid
(G), linked together to form a linear
polysaccharide with (1,4)-glycosidic
bonds
• Extracted from brown seaweeds: Laminaria
hyperboria, L. digitate, L. japonica, Ascophyllum
nodosum etc
• It has unique properties: cold stability, cold
setting gels, non-melting gels and freeze
thaw stable gels
 Alginate properties
• To make water-soluble and stable
alginate, the alginic acid is transformed
to alginate salts
• Dissolution of alginate: to apply alginates
effectively it may be done by careful addition
material during high shear mixing/ pre-blending
with other food materials (sugar) before
addition to liquid system
• It develops viscosity when hydrated in aqueous
solution and gels with addition of calcium
• Viscosity: depend on the length of alginate
molecules involved, composition of aqueous
system (presence of salt, high sugar/polyols,
non-solvent-alcohol,.
• Gelation: form gel with ion calcium; at slightly
acid pH (fruit jam) alginate gel will be an acid-
type gel/ mix calcium/acid gel
• Syneresis: low molecular weight alginates show
less syneresis than gels of HMW alginates
 Alginate applications
• Restructured food: restructured onion rings
(0.82%)
• Bakery creams and fruit fillings; to prevent
from leaking out of the pastry during baking
• Dessert jellies and mousse
• Thickening of gravies etc
• Stabilizing of ice cream, food emulsions-
sauces-salad dressings, low fat-spread
• Stabilizer, thickener, and gelling agent in dairy
products: canned cream, chocolate mousse,
yoghurt, bakery creams, milk shake, etc
• Encapsulation, film former
Carrageenan

• Extracted from red seaweeds:

Kappaphycus alvarezii (Cottonii) and
Euceuma denticulatum
• A high-molecular weight linear
hydrophilic polysaccharide
comprising repeating disaccharide
units of galactose and 3,6-
anhydrogalactose (3,6 AG), both
sulphated and non-sulphated, joined
by alternating α-(1,3) and β-(1,4)
glycosidic links
Carrageenan
properties
 Carrageenan application
• Water gelling applications: water dessert gels and cake glazes, sliced meats, salad dressing
• Dairy and protein applications: milk puddings, crème dessert, mousse. At very low
concentration: 100-200 ppm are used to stabilize and prevent separation of dairy products:
milk shake, ice cream mix etc
 Cellulose derivatives
• Cellulose constructs about 1/3 of all vegetable matter, 40-50% of wood and
85-97% of cotton.
• Cellulose derivatives (are usually used wood and cotton as raw materials):
 sodium carboxymethyl cellulose (CMC)
 Methyl cellulose and hydroxypropylmethyl cellulose
 Hydroxypropyl cellulose
 Ethyl cellulose
• Today, application of cellulose gum exceeds 20000 metric tons
 CMC, structure and its
properties

• CMC is (hot and cold) water soluble, anionic cellulose derivate, insoluble in organic solvent
• Light tan to white, odorless, tasteless, free-flowing powder, fairly hygroscopic
• Highly pure (>99.5%) of CMC = cellulose gum , it is GRAS
• Solubility depends on the chain length, less DP more soluble in water
• Viscosity: the longer chain length the higher viscosity
• It tends to agglomerate and lump when introduced to water, so need high agitation or pre-blending
to dry ingredients
• High water holding capacity: 42.3 g/g; stable over wide pH range (not less than 3.0), stable to salts
 CMC-applications
• Beverages: ready to drink, dry mix and concentrates, protein beverages
• Bakery: tortillas, bread, cakes and sweet goods, instant noodles, icing, frostings
and glazes
• Dairy desserts: ice cream, and frozen desserts, whipping cream and whipped
toppings
• Processed foods: meat analogues, meat, fish and poultry products, syrups, sauces
and soups, fried foods, encapsulation and films
 Gelatin
• Is a proteinaceous material obtained from animal connective tissue (skin or
bones) of animal species: beef, pork, fish and poultry using hydrolysis in acid
(type A) or basic (type B)
• It hydrates readily in warm/hot water to give low viscosity solutions with a
good whipping and foaming properties
• After cooling, the network of polypeptide chains associates slowly to form
clear, elastic gels and syneresis free.
• The melting point is <37oC, melt in the mouth and give smooth textures
with excellent flavor release
 Extra cellular protein contain 3
heliical chain polypeptides @ 1000
amino acids with glycine present in
every 3 residues

https://www.google.co.id/search?q=gracilaria&biw=1047&bih=511&source=lnms&tbm=isch&sa=X&ved=0CAYQ
 Commercial gelatin
• Available in: fine powder to coarse granules, sheets or
flakes
 Production, characteristics of gelatin
Pig Fish skin Beef bone poultry

Process acid acid Alkaline Acid

Duration 1 week 1 week 3 months 1 week

Type gelatin A A B A

Bloom (g) 100-200 200-270 100-250 100-240

Viscosity (mPa s) 1.8-4.8 + 2.8-4.5+hydrolysed 2.8-5.2 0.75-3.5

hydrolyzed
Isoelectric point >7.5 7.0-9.5 4.7-5.2 >8.0

Usages Food, pharma Food, pharma Photo, food, Food, pharma

pharma
 Pectin
• Is polysaccharide that naturally found in the middle lamella and primary walls
of most land plants cells and commercially is extracted mainly from citrus
peel and apple pomace. Around 1/3 of cell wall dry material are pectin
• Two forms: high methyl- (HM) and low methyl-esterified pectin (LM)
• HM pectin: forms gel in high soluble solid and acidic system
• LM pectin: forms gel in a broader pH and soluble-solids range, but requires
the presence of cations for gelling
• World market pectin and used:
status: GRAS
 Pectin structure
• A linier polysaccharide of α-1-4 linked anhydro-galacuronic acid with partial
methyl esterification of the carboxyl groups

• Native pectin has more complex structure with arabinose, galactose,

rhamnose and xylose.
Commercial pectin composition
 Pectin characteristics
• Stability: if exposed to un-suitable pH and temperature, pectin is easily degraded : de-
esterification and de-polymerization
• Optimal pH: 3.5-4.0
• At 20oC pectin solution is stable for months, at 60oC stable for days, at higher temperature it
may loss in jelly grade.
• Solubility: soluble in water, insoluble in alcohol and organic solvents. It is difficult to hydrate,
need a high speed mixer to preparing a pectin solution up to 10%; or pre-blend with dry
materials. Sodium pectinates are more soluble than pectic acid
• Viscosity: depends on concentration
• Gelation: the ability to gel and its gel strength increase with increasing molecular weight. HM
pectin gels in acidic and present of sugar; LM gel in broader pH, lower sugar level but need
cation (calcium)
• Emulsifying properties: b/c of acetyl groups presence.
• It doesn’t show synergism with other hydrocolloids
 Pectin application

• High- and low- sugar jams and jellies

• Baking jams
• Fruit toppings and gelling powder/sugar
• Fruit preparations for yoghurt (to make fruit evenly distributed in a large container, reduce fruit color
migration)
• Confectionery
• Beverages (acidified and fermented milk deinks, fruit beverages,)
• Dairy
Xanthan gum
• An extracellular polysaccharide secreted by
Xanthomonas campestris
• Primary structure: a linier 1-4-β-D-glucose
backbone with a trisaccharide side chain on
every other glucose at C-3 containing a
glucuronic acid residue linked 1-4 to
terminal mannose unit and 1-2 to a second
mannose that connects to the backbone
 Preparing xanthan gum solutions
• Gum xanthan is water soluble
• Gum particles must be well dispersed (to avoid clumping
and partially swollen lumps of gum) and gum must be
properly hydrated to have optimum functionality.
 under high shear mixing conditions.
 or pre-mix with other dry ingredients (sugar, starch
and salt) with ratio 10:1 or 5:1 (1=xanthan) to help
disperse the xanthan gum
 Avoid mix xanthan with alcohol, glycerol or oils and
salt solution >2%
 Make xanthan paste (6% solids)
 Xanthan gum characteristics
• Xanthan gum has ability to develop an extremely high viscosity even at low concentration
• Xanthan solution is stable during heating, even in the presence of salts and acids
• The viscosity decreases with increasing temperature, but it recovers upon cooling
• The viscosity of xanthan solution is stable in wide range of pH (>2 to <11)
• Hydrated xanthan has very good salt tolerance (up to 20-30% salt)
• Synergy with galactomannans (locust bean gum, guar gum, tara gum, cassia gum) and
glucomannans (konjac mannan)
 Xanthan gum applications
• Dressing and sauces (the largest application); xanthan stabilizes
emulsion and suspends particles and spices. Pseudo-plastic flow
properties of xanthan gum makes dressing easy to pour, pumping and
reduce splashing during filling. Cold stability enables use in dry mixes
and in cold processed dressing
• Bakery products: xanthan improves the even distribution of solid
particles, increases self life (retards stalling) and maintains a soft
texture of baked product.
• Dairy products: it improves smoothness and reducing syneresis, helps
air retention of aerated desserts, and reduced color migration between
layers of layered desserts
• Instant mixes: very rapid hydration of xanthan gum is ideal for dry
mix products: beverages, soups and desserts
Konjac mannan (glucomannan-porang)
• Obtained from 4-5 y old tubers of Araceae;
Amorphopallus konjac (Japan, China, Indonesia), A.
oncophyllus (Indonesia)
• Mannan = 8-10% of raw tuber
• Mannan is a heteropolysaccharide consisting of β-D-
glucose (G) and β-D-manose (M) with ratio G/M is
1-1.6
Konjac mannan application