Food Polymers: The Importance of Being Big

What are polymers?

Polymers are large molecules generated by chemically linking together many smaller
molecules called monomers. The monomers link together, or polymerize, into a polymer by
specific chemical reactions between functional groups. Each monomer must thus contain at least
two reactive groups or regions so that the chemical linking reaction can occur indefinitely. If the
monomers contain only two reactive groups, then linear polymers are formed. A good model for
this process is the linking together of beads in a chain (recall pop-it beads, small hollow spheres
that had a hole at one end and a knob at the other that fits into the hole…). If the monomers
contain three or more reactive groups, then branched polymers can form.

Polymers can vary in complexity depending upon the number, the kinds, and the order (or
sequence) of the monomers in the macromolecule; the manner in which the monomers are linked
together (the chain topology) also influences the polymer properties.
Number of monomers: Polymers can contain as few as 50 or as many as 108 monomers.
Large proteins in your muscles contain about 2000 amino acids; large starch (amylopectin)
molecules contain 105 to 106 sugar monomers; individual DNA molecules in your cells contain
about 2x108 nucleotide bases and are about 4 cm (about 1.5 inches!) long.
Kinds of monomers: Synthetic plastics are simple polymers made by polymerizing a
single kind of monomer. Polyethylene is polymerized ethylene (CH2=CH2) while polystyrene
(the plastic in foam cups) is polymerized styrene. Most biopolymers are more complex, typically
made of different kinds of monomers: proteins are made of twenty different amino acids; DNA is
made of four different nucleotide bases. Starch and cellulose, however, are made entirely of
glucose monomers; they differ because of differences in the specific linkage that connects them.
Order or sequence of monomers in chain: The true complexity of biopolymers becomes
apparent when considering the possible order of monomers in the linear polymer. Although
polyethylene can only vary in terms of its size (number of monomers), a polymer made from two
or more different monomers can vary in terms of its sequence. Polymer sequence is most
important when describing proteins and, of course, the DNA which codes the sequence
information for the protein. Consider a small protein containing 100 amino acid monomers.
There are actually 20100  10130 possible proteins of this size if we consider all the possible ways
that the 20 amino acids can be ordered in this protein. (Consider the first monomer in the
sequence, there are 20 possible amino acids that can be at this position. There are also 20
possible amino acids for the second monomer and 20 possible for the third, and 20 possible for
the fourth, etc. There are thus 20x20x20x20…x20 = 20100 possible proteins containing 100
amino acids.) Despite this potential complexity, each protein is a unique sequence.
Topology of polymer chain: Polymers can be linear (most synthetic plastics) or they can
be branched (starches). The extent and degree of branching can vary enormously. Most
synthetic polymers are linear; however, a new class of synthetic polymers, dendrimers, has very
extensive branching structures. Proteins are linear polymers, as is DNA. Starches have variable
topology. Amylose is primarily linear with only a very few (less than 1%) branching points
while amylopectin is more heavily branched, containing about 4% branch points.
Properties of food polymers
The physical and chemical properties of polymers are the result of the chemical
properties of the monomers (polarity, acidity, chemical reactivity), the size of the polymer, the
specific topology of the polymer chain, and in the case of proteins and some other biopolymers,
the linear sequence of monomers.

Chemical properties. All food polymers are polar because they are made up of polar
monomers (sugars, amino acids) and thus interact strongly with water. They are thus either truly
water soluble or bind water tightly. Many food polymers are also acids and/or bases. Proteins
contain many acidic (carboxyl) and basic (amino) groups and are thus charged at the pH of food
(neutral or slightly acidic). The chemical reactivity of a polymer is solely due to the reactivity of
the groups in the monomers of which it is made.

Size. The size of a polymer has a great influence on its physical properties. Large water
soluble molecules can dramatically affect the viscosity of aqueous solutions. Only a small
quantity of cornstarch, for example, can turn a thin fluid liquid into a thick viscous gravy. The
larger the polymer, the greater is its ability to modulate the flow properties of a solution. This is
because larger (longer) polymers have large effective sizes in solution (large effective
hydrodynamic volumes).

Topology. The degree of branching in a polymer influences the ways in which the
polymer can interact with water and with itself. Branched polymers also have a smaller effective
hydrodynamic volume for their mass due to their being less extended; they thus have a smaller
effect on water viscosity.

Sequence. The sequence of a protein determines the way in which this polymer folds up
in aqueous solution. Proteins contain many different kinds of amino acids. Some of these
contain side chains that are non-polar (phenylalanine, leucine, etc.) and thus not water soluble.
The protein will thus adopt a conformation, a three-dimensional shape for the polymer chain, that
segregates these non-polar groups away from water. The protein is said to fold up into a specific
shape that is determined by the sequence of amino acids in the polymer. All of the biological,
and many of the food, functionalities of the protein are influenced by the protein conformation.
Common Food Polymers (Food Hydrocolloids)
Look for these names on the labels of foods that you buy (they will usually be at or near
the end of the list, indicating that they are added in very small quantities).

Protein:

Gelatin (isolated from bones and skin of vertebrates)

Carbohydrate and modified carbohydrate:

Agar (isolated from seaweed)

Algin or Alginate (isolated from brown algae)
Amylopectin (a kind of starch, isolated from starch)
Amylose (a kind of starch, isolated from starch)
Carboxymethylcellulose (modified cellulose, isolated from wood, etc.)
Carrageenans (isolated from seaweed)
Furcellaran (isolated from seaweed)
Guar (or guaran) gum (isolated from legume seed)
Gum Arabic (exudate of Acacia tree from Middle East)
Gum Ghatti (exudate of tree from India)
Gum Tragacanth (exudate of Astragalus, a Middle Eastern shrub)
Karaya gum (exudate of tree from India)
Locust bean gum (isolated from carob bean, the seed of a Mediterranean evergreen tree)
Pectin (isolated from fruit and other plants)
Starch & Modified Starches
Xanthan gum (extracellular exudate of Xanthomonas bacteria)
Functions of polymers in foods
The physical properties of any food containing starch or protein are modulated
extensively by the polymeric properties of these biomolecules. A clear example of this is the
thickening of gravies by the addition of cornstarch or flour. The long chain starch molecules are
dissolved in the aqueous phase and dramatically increase the viscosity of the liquid. The result is
a thick liquid that effectively coats other foods like mashed potatoes or meat.

Food polymers (also called hydrocolloids) have many important functional roles in foods.
These include:

Generate and maintain foam structure in bread dough. The foam-like structure of bread
is generated by the growth of CO2 gas bubbles formed by fermentation by yeast. The surfaces of
these bubbles are formed from wheat proteins called glutens that act as elastic films to entrap the
gas. Upon heating, the walls of the gas cells are stabilized by the formation of many
intermolecular interactions that solidify the material into a stable foam.

Modulate solution viscosity and texture. Long linear polar polymers bind water tightly
and impede its flow by forcing the water to move with the polymer. A good model for this is a
bowl of cooked pasta noodles in water. Quick set puddings and pie fillings are examples of the
extent to which polysaccharide polymers can modulate the texture of liquids.

Stabilize foams and emulsions. Polymers can bind to the air/water interface in foams or
the oil/water interface in emulsions and stabilize these interfaces. The polymers can do this
because they have many different groups, some of which can interact with the non-polar air or
oil phase and some of which can interact with the polar water phase. The polymers become
entangled and form a felt-like layer or film on the surface that is strong and elastic and thus
stable. Interfaces stabilized by polymers are thus more stable than those stabilized by small
molecules.

Form elastic gels. Many food polymers have the remarkable ability to interact in three
dimensions to generate elastic solids called gels. Gelatin is the best known hydrocolloid with
this ability. Hot gelatin solutions will slowly set into to soft elastic solids at temperatures below
about 30C even at concentrations below 1% by weight of the solution (solid gelatin can thus be
99% water and 1% gelatin). Gelation is the result of non-covalent crosslinks between two or
more individual strands of the gelatin protein polymer. These crosslinks, which form
spontaneous due to specific interactions among the gelatin polypeptides, weave the gelatin
polymers into a three-dimensional random network that binds water tightly and confers solidity
to the largely aqueous solution.
 Gelation & the Sol-to-Gel Transition
Long polymers such as proteins and carbohydrates can form thick solutions upon
dissolution in water. Gelatin and starch are well known examples. We refer to these viscous
solutions as sols. Under specific conditions of temperature, pH, and the presence of certain ions,
however, these sols will form solid solutions known as gels. This sol to gel transition can occur
slowly or rapidly and can be initiated by a small change in solution conditions. The underlying
molecular changes (and corresponding macroscopic changes) are complex, however, and reflect
specific molecular interactions among the polymers.

The solution solidifies due to the formation of a three-dimensional molecular network

among the polymer chains. The network is held together by crosslinks among 2 or 3 individual
chains. These crosslinks can be non-covalent interactions among the polymer chains or they can
result from covalent bonds between two or more chains. The former types of crosslinks are
generally reversible while the latter are generally irreversible.

Gelatin: Gelatin is made by extracting the protein collagen from the skin and bones
remaining after butchering pigs and cattle. The process generally involves solubilizing the
proteins using acid or base for long periods, followed by several cycles of purification. The
resulting solution is pure collagen with a range of molecular weights. The strength of the jelly
formed from the collagen is affected by the purity of the gelatin (higher purity makes better jelly)
and the molecular weight distribution (larger molecular weight makes more rigid gel).
In gelatin, the crosslinks probably result from the formation of regions in which 3
individual “gelatin” polymers (individual polypeptide chains made from collagen) form a triple
helical region much like a three-stranded piece of rope. The formation of these triple helical
regions is spontaneous at temperatures below about 30C. Only small regions of the polymers
can form triple helical junctions, however, due to the many possible interactions that occur
among all of the many different polymer chains (about 3x1018 per gram of gelatin). The end
result is the spontaneous formation of a 3D polymer network that completely fills the aqueous
solution giving it the solidity and elasticity of a true solid. The gel forming abilities of gelatin
are remarkable: an aqueous solution containing about 1% gelatin is a solid at room temperature.
Collagen gels form slowly due to the complex nature of the crosslinks that hold the gel
together. Since each crosslink involves the entangling of three chains (each of which may be
involved in other crosslinks), the formation of the gel is a complex process involving the
movement of many polymer chains; crosslinks are thus slow to initiate (nucleate) and grow in
size slowly.

Alginate: Algin is a structural carbohydrate polymer isolated from brown seaweed

(kelp). It is composed of two different sugars, mannuronic and guluronic acid. The
carbohydrate is water soluble and solutions of alginate are highly viscous.
Alginate can form a rigid gel in the presence of calcium ions. These ions bind to
carboxyl groups on the guluronic acid sugars on adjacent chains of the alginate. The gels form
rapidly because the crosslinks form rapidly; mobile calcium ions bridge adjacent strands of algin
containing essentially pure strands of polyguluronic acid.
 Gelatin Gelation: Thermal Gels
Purpose:
This exercise demonstrates gel formation in gelatin, a thermally reversible gel.

Materials:
Gelatin (Knox or Jello)
Two 500 mL beakers (1-2 cup measuring cups)
Heat source (to dissolve gelatin)
Large container for ice water bath
Thermometer (to measure near 30C)
Food Coloring
Eye droppers or squirt bottles

Gelatin preparation:
Dissolve gelatin as described on package, except make the gelatin at least three times the
recommended concentration (for example, dissolve two packages of Knox gelatin in 1.5 rather
than four cups water).
Color the gelatin solution with a few drops of food coloring. Your choice of colors.
Cool the gelatin solution to about 35C.

Formation of gelatin balls and worms:

Prepare an ice water bath. Use excess ice to ensure that the bath remains at 0C for at
least ½ hour.
Place a beaker (cup) of water in the ice bath and wait for the water in the beaker to
equilibrate to 0C. The idea is to have ice water without ice cubes floating in it.
Using the dropper or a squirt bottle, squirt the gelatin solution slowly into the ice water.
If you make single drops, these will form solid balls. If you squirt a stream of gelatin solution
into the ice water, it will make a gelatin “worm”.

Observations and Points for Discussion:

Note that the gelatin balls and worms are initially soft. They will slowly harden as they
continue to polymerize by forming more triple helical crosslinks. If you leave them in a
refrigerator overnight they will harden more fully. This is a reflection of the complex events
occurring in the gel during formation of crosslinks. Many large collagen molecules must form
many triple helical junctions. These complex events take time.
The food coloring will diffuse out of the gelatin balls and worms. This happens because
the colors are small molecules that are not linked to the gelatin in any way. These molecules can
move through the empty spaces in the gel matrix.
The gel matrix is mostly water (more than 95% in this demo; more than 98% in regular
gelatin). Yet it is a solid. This is characteristic of gels of all kinds. The solidity of the gel is a
reflection of the 3D network of individual protein polypeptide strands that tightly bind water.
 Alginate Gelation: Chemical Gels

Purpose:
This exercise demonstrates gel formation in alginate, a natural biopolymer that undergoes
a sol to gel transition induced by binding calcium ions.

Materials:
Sodium Alginate (Keltone LV)
Two 500 mL beakers (1-2 cup measuring cups)
Calcium Chloride
Food Coloring
Eye droppers or squirt bottles

Alginate preparation:
Materials for the alginate experiment can be acquired from Tic Gums
(www.ticgums.com); ask for the University Kit.
Dissolve alginate in water to make a 2% solution (2 g into 100 mL). Preparation of an
alginate solution is quite tricky because the alginate will readily form nearly insoluble clumps.
The best method is to slowly pour the alginate powder into a rapidly stirring liquid. A blender
works fine. If you have a stir plate, use the highest possible spin setting. The first time you do
this on your own, make the alginate solution the day before. This will let you stir overnight if
clumps develop.
Color the alginate solution with a few drops of food coloring. Your choice of colors.

Formation of alginate balls and worms:

Prepare a solution of 5% (wt/wt) calcium chloride in water.
Pour about 50-100 mL of this solution into a container (any sort will do).
Using the dropper or a squirt bottle, squirt the alginate solution into the CaCl2 solution. If
you make single drops, these will form solid balls. If you squirt a stream of gelatin solution into
the ice water, it will make a gelatin “worm”. The alginate gels immediately upon contact with
the salt solution.

Observations and Points for Discussion:

Note that the alginate balls and worms initially have liquid centers. They will harden
throughout after a few minutes in the CaCl2 solution as they polymerize further. The surface
hardens first because the Ca+2 must diffuse from the surface into the balls and worms.
Polymerization is rapid because crosslinks form when two alginate strands become linked
together into the eggbox structure by mobile Ca+2 ions.
The food coloring will diffuse out of the alginate balls and worms. This happens because
the colors are small molecules that are not linked to the alginate in any way. These molecules
can move through the empty spaces in the gel matrix.
The gel matrix is mostly water (about 98%). Yet it is a solid. This is characteristic of
gels of all kinds. The solidity of the gel is a reflection of the 3D network of individual protein
polypeptide strands that tightly bind water.
 Hydrated Cornstarch: Viscous Flow
Purpose:
This exercise demonstrates the unusual flow properties and texture of a concentrated
solution of cornstarch in water.

Materials:
Cornstarch
Small bowls
Water
Food Coloring (optional)

Preparation of Thick Cornstarch Solution:

Pour about 1/2 cup of cornstarch into a bowl. Slowly add about an equal volume of
water, slowly stirring the mixture. Stop when the solution becomes a very thick liquid that flows
very slowly in response to tipping the bowl or mixing.
You may make colored solutions by adding a few drops of food coloring (color optional)
to the water before adding it to the cornstarch.
The solution you have made is often called Oobleck (after the Dr. Suess book
Bartholomew and the Oobleck).

Observations and Points for Discussion:

The thick cornstarch solution has a very interesting physical property: its rate of flow is
comparable to the rate at which a person can move. The solution thus has properties
intermediate between those of a solid and those of a liquid: if flows through your fingers if you
hold it but you can role it into a ball and play catch with it. Whether the solution acts like a
liquid or acts like a solid thus depends upon the speed with which it is stressed (the rate of your
interaction with it).
The rate of flow of this solution is slow because the relaxation time of the cornstarch
polymer at the low water content is very slow. (The relaxation time is the time it takes the
polymer solution to respond to some external stress (external force).) This property of the
solution can be easily demonstrated by pushing against the thick solution either slowly or
quickly: the solution responds like a liquid to slow pushing and breaks like a weak solid with fast
pushing.
It is possible to observe the slow mixing of two colored cornstarch solutions. Make two
colors of solution and pour them into the same bowl. The solutions will remain separate and
distinct for many minutes (you can partly mix them to make a colorful swirl pattern). After
several minutes, however, the edges of the solutions will start to blur as the solutions slowly mix.
(The rate of this mixing is quite sensitive to the thickness of the solution.)