1 Polysaccharides

• Introduction of polysaccharides
• Polysaccharide sources and characterization
• Polysaccharide structure analysis
• Functions of polysaccharides
• Selecting polysaccharides for food applications
2
Polysaccharides: Introduction

Definitions of polysaccharides
• “Polysaccharide” is the name given to a macromolecule consisting of a
large number of monosaccharide residues joined to each other by
glycosidic linkages.

• Polysaccharides composed of only one kind of monosaccharide are

described as homopolysaccharides (homoglycans). Similarly, if two or
more different kinds of monomeric unit are present, the class name
heteropolysaccharide (heteroglycans) may be used.

• A general term for a homopolysaccharide is obtained by replacing the

ending “-ose” of the sugar name by “-an”. For example: xylan for
polymers of xylose, mannan for polymers of mannose, and galactan for
polymers of galactose. Cellulose and starch are both glucans, as they
are composed of glucose residues

Adapted from IUPAC Nomenclature of Carbohydrates (1996) http://www.chem.qmul.ac.uk/iupac/2carb/

3 Polysaccharides: Introduction

Shorthand Notation
 Glycosyl units are represented by the first 3 letters of their names, except
for glucose which is Glc
 Sometimes D is omitted; if it is an L sugar, the L is put in the designation
 Ring size: p or f
 Uronic acids are indicated by a suffix A
  and  are designated where appropriate
 Examples
 Cellobiose = -Glcp(14)-Glc or Glcp1,4Glc
 Lactose = -Galp(14)-Glc or Galp1,4Glc
 Maltose = -Glcp(14)-Glc or Glcp1,4Glc
 Gellan = [3)--D-Glcp-(14)--D-GlcpA-(14)--D-Glcp-(14)--L-
Rhap-(1 ]n
4 Polysaccharides: Introduction
Classification of Polysaccharides

Polysaccharides by source
• Seaweed extracts: Agars, alginates, carrageenans
• Higher plant cell walls insoluble: cellulose
• Higher plant cell wall soluble: pectin
• Higher plant seeds: cereal starch, guar gum, locust bean gum
• Higher plant tuber & root: potato starch, tapioca starch
• Higher plant exudates: gum arabic, gum tragacanth
• Microorganism: Xanthan gum, Gellan gum
• Derived: modified starch, carboxymethyl cellulose, propylene glycol
alginate
5 Polysaccharides: Introduction
Classification of Polysaccharides
Polysaccharides by structure
• Linear: amylose, cellulose, pectin, alginates
• Short branched: guar gum, locust bean gum, Xanthan gum
• Branch-on-branch: amylopectin, gum arabic, arabinoxylan
Polysaccharides by monomers
• Homoglycans: starch, cellulose
• Diheteroglycans: agars, alginate, carrageenans,
• Triheteroglycans: Xanthan, Gellan, arabinoxylan
Polysaccharides by charge
• Neutral: amylose, amylopectin, cellulose, guar gum
• Anionic: alginates, pectin, carrageenans, Gellan, gum arabic, Xanthan
• Cationic: chitosan
6 Polysaccharides: Introduction

Molecular weight and degree of polymerization

 Molecular weight (MW):

 The mass of one molecule of the substance, relative to the

“unified atomic mass unit” (equal to 1/12 the mass of one atom
of carbon-12)

 Degree of polymerization (DP):

 The number of monomeric residues in a polymer molecule

 “Chain length”, expressed in DP, is used to quantify the size

of polysaccharide chains
7 Polysaccharides: Introduction

Polydisperse and polydispersity

GGGGGGGGG
GGGGG This collection of molecules is polydisperse
GGGGGGGGGGGGG

Polydispersity index (PDI):

 Ratio of the weight average molecular weight to the number average
molecular weight
 Indicating the overall distribution of individual molecular weight in a
batch of polymers
 PDI equal to 1 indicates only one length of polymer is present
 In polysaccharides (e.g. starch), PDI may vary significantly.
8 Polysaccharides: Introduction

Number average molecular weight (MN)

 MN = iNiMi/iNi , where Ni is the number of molecules of

molecular weight Mi

 Can be determined by osmometry, end group titration,

and colligative properties

 MN is more weighted by the small molecules in the

molecular population
9 Polysaccharides: Introduction

Weight average molecular weight (MW)

 MW = iNi(Mi)2/iNiMi, where Ni is the number of molecules

of molecular weight Mi

 Can be determined by light scattering, small angle neutron

scattering (SANS), X-ray scattering, and sedimentation
velocity

 MW is more weighted by the large molecules

10 Polysaccharides: Introduction

Polydispersity index = MW/MN

11 Polysaccharides: Introduction

An example of MW,MN, and polydispersity index

Mi (DP) Ni NiMi Ni(Mi)2

100 10 1,000 100,000

10 10 100 1,000

 20 1,100 101,000

MW = iNi(Mi)2/iNiMi 101,000/1100 = 91.8 (DP)

MN = iNiMi/iNi 1,100/20 = 55 (DP)

So, polydispersity index = 91.8/55 = 1.67

12 Polysaccharides: Introduction
Chain length distribution of starch: HPSEC & FACE
High performance size-exclusion chromatography Fluorophore-assisted carbohydrate electrophoresis
13 Polysaccharides: Introduction

A case study: eel feed & http://fishology.bl

ogspot.com/2012/
polysaccharides 08/eel.html

Eel feed Eel food

http://www.japantimes.co.jp/life/2013/07/13/travel/hot-weathers-cold-comfort-for-eels/
14 Polysaccharides: Introduction

Eel eats fish or fish meal

Major components of eel feed dough:

• Fish meal: white fish meal or red fish meal, ~70%

• Pre-gelatinized potato starch or/and tapioca starch, as

binder, ~25%

• Nutrients (minerals, yeast, etc.) and others, ~5%

15 Polysaccharides: Introduction

Eel feed: big dough shared by hundreds of eels

• All ingredients are blended and added with water. After

kneading, a big dough forms
• The dough is thrown in water; eels race to the dough and
bite
• The dough needs to be cohesive enough to stay in large pieces

Eels are very picky with their foods: they do not

like a dough that is not elastic enough
16 Polysaccharides: Introduction

We want to cut the cost of eel feed

• Usually white fish meal (~$600/MT) is used for eel feed.

The project was to replace white fish meal using red fish
meal (~$400/MT)

• However, red fish meal contains much higher lipid (fatty

acids) amount than white fish meal. The dough with red
fish meal has low elasticity and may easily dissemble in
water

• And eels don’t want to eat it…

17 Polysaccharides: Introduction

The reason:
• In red fish meal, lipid is hydrolyzed by
lipase, and fatty acids are released at a
much higher amount
• Fatty acids form starch-lipid complex with
amylose of starch
• Gel structure of dough is damaged by
starch-lipid complex, and the
viscoelasticity is partially lost
We either had to remove lipid from fish meal,
or enhance the gel strength of potato starch by
adding additional binders
Buleon et al., Int. J. Biol.
Macromol. (1998) 23, 85
So, our strategy was to…
18 Polysaccharides: Introduction

To add non-starch polysaccharides (food gums)

as binders to the dough system, in order to
improve gel strength, cohesiveness, and elasticity
19 Polysaccharides: Introduction

To increase the viscosity, we tested:

• Carboxymethyl cellulose (CMC)
• Guar gum
• Locust bean gum
• Alginate, agar, carrageenans
• Pectin
• Xanthan gum
• Konjac flour
• Gum arabic
To increase the gel strength, we tested:
• Locust bean gum + Xanthan gum
• Locust bean gum + carrageenans
• Modified starches
20 Polysaccharides: Introduction

We found, with up to 1% level:

• Some gums improved the cohesiveness (less sticky
dough) and retain water better, but the dough was
not elastic
• Some gums had no observable effects
• Some gums reduced the gel formation of potato
starch, and resulted in reduced cohesiveness and
elasticity
• Gelling agents basically had no effect on the
overall gel strength or elasticity of dough
21 Polysaccharides: Introduction

Some fundamental questions are:

• What are the interactions among polysaccharides,
lipids, and protein?

• What are the interactions among starch and non-starch

polysaccharides?

• What are the interactions between two gel networks,

e.g. starch gel network & LBG-Xanthan gel network?

• How do polysaccharide-lipid-protein interactions affect

the physical properties of dough?
22 Polysaccharides: Introduction

We also tested other approaches, e.g. converting fatty

acids to substances with reduced impact on starch gel
structure. However, the “red fish meal for eel feed” still
seems to be a good challenge
23 Polysaccharides: sources and characterization

Polysaccharides from seed, tuber, or root: Starch

• A most abundant carbohydrate
• Major component of human diet
Amylose • Various digestibility
• Numerous applications as ingredients
• Comprising linear molecules, amylose,
& branched molecules, amylopectin
• Subjected to genetic, chemical, physical,
and enzymatic modifications
Amylopectin
• Subjected to acidic and enzyme
hydrolysis to maltodextrins and syrups
• Basic ingredient of many food and non-
food industries
Adopted from: http://www.oci.unizh.ch/edu/lectures/material/AC_BII/Kap14/kap14.html
24 Polysaccharides: sources and characterization

Polysaccharides from seed: Guar gum

http://en.wikipedia.o
rg/wiki/Guar_gum

http://guargum-sd.com/ http://www.guarglobal.com/oppo
rtunity/guar-global-markets

• Galactomannan obtained from the seed of guar plant, Cyanaposis tetragonolobus, mostly
in India and Pakistan
• Chains of (14)-linked -D-mannopyranosyl units, with averagely 1.8 chain units
attached with single -D-galactopyranosyl units via (16)-linkages
• Distribution of side units is relatively even along the main chain
• Neutral polysaccharide with molecular weight: 150,000 – 1,500,000
• Soluble in cold water
• Showing pseudoplastic (shear thinning) behavior in solution
• Does NOT form gel with xanthan gum
• US $2,000-10,000/Ton (Corn starch: US $550-650/T)
25 Polysaccharides: sources and characterization

Polysaccharides from seed: Guar gum

http://www.guarglobal.com/opportunit http://en.wikipedia.org/wiki/Hydraulic_fracturing
y/guar-economics

• Shale oil and gas extraction industries consume the majority of guar gum for Hydraulic fracturing (fracturing of rock
by a pressurized liquid, fracking)
• Fracking is conducted once in the life of the well and greatly enhances well productivity
• In the past 60 years, 2.5 million hydraulic fracturing jobs have been performed on oil and gas wells worldwide, more
than one million of them in the US
• Fracture fluid contains water-soluble gelling agents (e.g. guar gum) to increase viscosity and effectively deliver the
proppant (sands, ceramics, etc.)
• Conventional linear gels are used: e.g. CMC, guar and its derivatives
• Borate-crosslinked: guar-based fluids cross-linked with boron ions, to provide high viscosity at pH 9 to carry
proppants. After the fracturing the pH is reduced to break the gel
• Organometallic-crosslinked fluids: also to crosslink guar gum
26 Polysaccharides: sources and characterization

Polysaccharides from seed: Locust bean gum

http://www.jpbsonline.org/viewimage.asp?img=JPh
http://www.gumtech.com/products/ProductInfo
armBioallSci_2012_4_3_175_99013_u2.jpg
.php?product=Locust%20Bean%20Gum

• Galactomannan obtained from the seed of carob tree, Ceratonia

siliqua, around the Mediterranean Sea
• Chains of (14)-linked -D-mannopyranosyl units, with
averagely 3.9 chain units attached with single -D-
galactopyranosyl units via (16)-linkages
• Distribution of side units is highly uneven along the main chain
• Neutral polysaccharide with molecular weight: 400,000 -
1,000,000
• Requires heating to hydrate completely
• Showing pseudoplastic behavior in solution
• Forms gel with xanthan gum
• US $25-30 / Kg (seed $7000/T) http://vasugum.com/locust-bean-gum/
27 Polysaccharides: sources and characterization

Polysaccharides from seed: Tara gum

• Galactomannan obtained from the seed of Tara shrub, Caesalpinia spinosa, mostly in
northern Africa and South America (Peru)
• Main chain of (14)-linked -D-mannopyranosyl units, with single -D-galactopyranosyl
units attached with average 3 main chain units via (16)-linkages
• Molecular weight may fall between 300,000 to 1,000,000
• 70% soluble in cold water and 100% hydrated at >80C
• Showing pseudoplastic behavior in solution
• Difficult to form gel with xanthan gum
• US $8.00-9.00/kg

http://en.silvateam.com/Products-Services/Food-Ingredients/Tara-gum/Production-process
28 Polysaccharides: sources and characterization

Polysaccharides from tuber: Konjac flour

• Glucomannan obtained from the tuber of Amorphophallus konjac grown in Asia
• Chain of mannose and glucose units in a molar ratio of 1.6:1 connected with -(14)-
linkages. One acetyl group presents at the C-6 for about 6 to 20 sugar units
• Neutral polysaccharide with molecular weight: 200,000 - 2,000,000
• Swells in cold water, fully hydrates after heating
• Showing pseudoplastic behavior in solution http://www.ricepl
ex.com/Konjac-
Root-
• US $5.30-5.50/kg Glucomannan-
Powder.html

http://www.glucomannan.com/
http://en.wikipedia.org/wiki/Konjac