Chemistry in sport including stadiums

0:06Skip to 0 minutes and 6 secondsSports and fitness plays a major part of our lives and has been greatly
influenced by developments in Chemistry. When participating in our favourite sports, we regularly interact with
a range of modern synthetic materials. In sports that use specialised equipment, such as golf, the impact of
developments in Chemistry has been most obvious - over 100 years ago hickory wood shafts were used, this
was followed by use of steel and aluminium, whereas today, composite fibres or polymers, including Kevlar,
are typically used to propel golf balls faster and with greater accuracy.
0:41Skip to 0 minutes and 41 secondsBut it is not just golf, nearly every sport relies on modern materials to
produce high-performance equipment - whether it be tennis, football, cricket, canoeing, or skiing, polymers,
composites and other advanced materials are commonly used - high-performance describes materials that are
stronger, more resilient and lighter-weight than traditional materials, including wood and steel. When watching
sport it is of course the athlete’s talent that inspires and enthuses us - athletes are faster and stronger than
ever - and Chemistry plays a key role in their training, competition and recovery. Using the right equipment and
choosing the appropriate sports drink, could mean the difference between winning a gold or a silver medal.
1:24Skip to 1 minute and 24 secondsAlthough not all athletes can win medals, from time to time, they all suffer
from injuries - it is estimated that around 65% of runners are injured in an average year. To help recover from a
fall, twist or sprain, cold sprays, antiseptics, anaesthetics, anti-inflammatory medicines, not to mention plasters,
bandages and sleeves, have an important part to play. Our tour of Chemistry in Sports looks at landmark
developments in sports equipment, medicines and nutrition. This includes improvements in safety, such as
protective clothing made from polyethylene and polycarbonates. We will also look at the more controversial use
of performance-enhancing medicines, including stimulants, diuretics and most famously of all, anabolic
steroids.
2:11Skip to 2 minutes and 11 secondsThis topic helps to showcase the range of career opportunities available to
chemists - many of our York Chemistry graduates go on to be polymer chemists, formulation chemists, organic
chemists and materials scientists, and some go on to be analytical chemists - it is the advances in analytical
chemistry that ensures modern techniques including gas chromatography-mass spectrometry can detect
minute amounts of banned drugs, in an athlete’s blood or urine.

Welcome back to the course and our fourth and final week of study, which explores chemistry in sport!

Modern construction materials have transformed the design and performance of sports venues, whether it be a
stadium, a velodrome or an aquatics centre. Venues can be built more quickly, stand the test of time better,
and have lower energy usage. For example, the setting time of concrete can be formulated with additives – it
can be set more quickly to reduce the building time, or more slowly if it needs to stay liquid for longer to allow it
to be pumped further. Admixtures are specially formulated products that are added in small amounts to
concrete, mortar or grout during the mixing process to change the concrete properties in the plastic and/or
hardened state. These admixtures were used, for example, to speed up the construction of the Beijing olympic
village, tennis centre and aquatics centre.

Chemistry also provides the paints and coatings that protect surfaces from the weather and other damage, and
provide a decorative finish. Many modern coatings are ‘greener’ than traditional paints, and can protect just as
well – if not better. Traditional paints are derived from fossil-fuels and release large amounts of volatile organic
compounds (VOCs), as the paint dries and cures, which has environmental impacts. For example, for Bayer
Leverkusen’s football stadium in Germany, poly(aspartic acid) coatings were used to protect the metal girders
from corrosion. The coatings dry more quickly and thicker layers can be applied, so fewer coats are needed,
and as there is less solvent to be evaporated, they are more environmentally friendly.

Poly(aspartic acid): an amino acid polymer

Poly(aspartic acid) (or PASA) is a large molecule, called a polymer, made up of repeating aspartic acid subunits
(called monomers). The aspartic acid monomers are linked together by heating – they react to
form amide bonds on loss of water. First, loss of water forms a five-membered ring called a succinimide, and
multiple dehydration reactions form a polysuccinimide. This polymer is then treated with aqueous sodium
hydroxide which attacks either C=O bond of the imides in a series of nucleophilic acyl substitution reactions – the
term α unit or β unit is used according to which C=O bond of the imide is attacked.

This is just one of the more complicated ways of linking together subunits to form a range of useful polymers,
which we will explore in subsequent sections. First, we will introduce polymers and why they are important in
sports, including use in protective equipment where strong, tough materials are required – ‘hard’ chemistry in
action!

Take a look at this undergraduate video, made by Hannah as part of our first year undergraduate
macromolecules course, about golf balls.

https://youtu.be/Zln_K6HuoVA

For a beginning-of-week teaser, see if you can identify the 8 pieces of protective sports equipment in the collage
in the downloads section below and post your answers.

Protectiveequipcollagequiz.pdf
A general introduction to polymers and their use in micelles

0:06Skip to 0 minutes and 6 secondsPolymers are extremely large molecules that are essential to our existence -
for example, our bodies contain proteins, which are polymers of amino acids. To make polymers, small
molecules, called monomers, need to be joined together. We will see that there are two ways of doing this, one
called addition or chain polymerisation, the other called condensation or step-growth polymerisation. Addition
polymerisation usually employs alkenes, such as ethene or styrene, which can be linked together using
different reaction conditions. In contrast, condensation polymerisation uses monomers containing two
functional groups, such as a diol reacting with a dicarboxylic acid to form a polyester.
0:50Skip to 0 minutes and 50 secondsPolyesters have a wide range of uses from clothing to bottles, films, and
liquid crystal displays; in sports equipment their uses range from surfboards to canoes, skis and skateboards.
The word polymer is obtained from the Greek words for many or ‘poly’ and parts or ‘mer’. So a polymer is a
large molecule made up of smaller, repeating units of monomers, or ‘parts’. Polymers can be either naturally
occurring, such as cellulose or peptidoglycan, or artificial like nylon or Kevlar. The different monomers used to
make a polymer chain will give the polymer its distinctive properties. For example, using many branching alkyl
groups in the monomer will result in a flexible, low-density structure.
1:38Skip to 1 minute and 38 secondsIf less branching chains are used then the polymers can align themselves
closer together and form a more rigid plastic. Using groups that are able to form hydrogen bonds to each other
allows for a flexible material, which is extremely tough due to the combined strength of many hydrogen bonds
between different polymer chains. Some polymers can consist of more than one type of monomer. These
polymers are so-called co-polymers and the arrangement of the different monomers can be alternating,
random or in blocks of the same monomer. The properties of the individual monomers can often be applied to
those of the overall polymer.
2:17Skip to 2 minutes and 17 secondsFor example, a group of hydrophilic monomers, which interact with water,
can be bonded to a group of hydrophobic monomers that do not interact with water. This block co-polymer now
contains a hydrophilic block and a hydrophobic block. When placed with other polymers of the same type, into
water, the polymers will naturally aggregate to form micelles - structures where the hydrophobic monomers are
protected from interactions with water by the outer hydrophilic monomers. Research is underway at York to
create inversed micelles. That is to say micelles that contain a hydrophilic interior and a hydrophobic exterior
allowing for polar molecules to be encapsulated within non-polar solvents. These micelles could have a range
of uses.
3:05Skip to 3 minutes and 5 secondsIt has been suggested that micelles could be used as a novel form of drug
delivery. The drug, protected inside a micelle of co-polymers, can be delivered to the target site more
successfully. When the target site is reached an alteration in pH, solubility or external intervention such as
application of radiation or other compounds can be used to open the micelle and allow for the medicine held
inside to be released directly at the target site. We will now investigate how polymers are used in the sporting
industry - to create materials that are tailor-made to be lighter, stronger and more aerodynamic than those
traditionally used.
3:46Skip to 3 minutes and 46 secondsIn the world of high performance sports every gram that can be shaved off
a piece of equipment can mean the difference between a gold or silver medal!

Teflon and serendipity

Teflon® is the trademark name for a family of fluorinated polymers that includes
poly(tetrafluoroethene), PTFE ([–CF2–CF2–]n). PTFE was first made by accident by the American
chemist Roy Plunkett when he was working on the development of new non-toxic refrigerants for the
chemical company DuPont. Plunkett used pressurised cylinders of gaseous tetrafluoroethene
(F2C=CF2) in his research and on one occasion, on the morning of 6 April 1938, he found that there was
no pressure in the cylinder but it weighed the same as when filled with gas. On opening the cylinder,
he found a waxy white solid had formed.

To his surprise, Plunkett found that the F2C=CF2 had polymerized in the bottle to form PTFE. PTFE has some
remarkable properties. It is inert to virtually all chemicals as it contains only strong C–F and C–C bonds, and it
is considered the most slippery material in existence because the surface is covered with fluorine atoms that do
not interact with atoms in other compounds. These properties have made PTFE a particularly useful polymer.
PTFE tubes hold cables and wires in aircraft and cars, in medicine it is used in reconstructive and cosmetic
facial surgery, and it has become a household name through its use as a coating on non-stick cookware.

Similarly, Bob Gore wasn’t attempting to improve outdoor clothing when he created Gore-Tex®. Working in his
father’s Teflon factory in the late 1960s, he was simply trying to make more efficient use of the plastic by
stretching it. He found that pulling Teflon filled it with air pockets. The pockets that appeared in his ‘expanded
poly(tetrafluoroethene) (ePTFE)’ were 700 times larger than a water vapour molecule but 20,000 times smaller
than a droplet. Gore reasoned that if you made a fabric out of ePTFE, you could block out rain while still
venting steamy perspiration, with the added bonus of wind protection. Since the first jacket was made in 1977,
ePTFE has found use in products ranging from heart patches to space suits.

A significant number of other notable scientific discoveries have, like Teflon, been made by chance, or
serendipitiously. This includes the world’s first artificial sweetener, saccharin (which is 300-400 times sweeter
than sugar), discovered by Dr James Schlatter, who, when cleaning lab glassware accidentally tasted a powder
on his fingers (he had been making saccharin in connection with an anti-ulcer project). Also vulcanised rubber,
formed when Charles Goodyear accidentally dropped a mixture of rubber, sulfur, and lead onto a hot stove.
More recently, there is Viagra, developed by Pfizer, initially as a new treatment for angina (a heart condition
that constricts the vessels that supply the heart with blood). Trials in people were disappointing, but, volunteers
started coming back and reporting an unusual side effect!

Are you are aware of any other serendipitous chemical discoveries? If so, which is your
favourite?
Cleaning products

We have seen that polymers containing a hydrophilic head and a hydrophobic tail can
aggregate to form a direct or normal micelle in water. Smaller-sized molecules, such as
sodium salts of fatty acids like stearic acid, CH3(CH2)16CO2H, can also form micelles. The
charged end of sodium stearate (–CO2– Na+) is hydrophilic and binds to water, while the long
hydrocarbon chain (CH3CH2CH2CH2CH2…) is fat-loving and sits inside the micelle sphere.
Sodium stearate, CH3(CH2)16CO2– Na+, is used in soap as it dissolves oil molecules, which
carry dirt. When soap and oil molecules are mixed, the micelles break up and reform to
position the oil molecules inside the micelles, within the fat-loving interior. When you rinse
off soapy water, it takes the oil with it!

Soaps are made from natural products (stearic acid is found in animal and vegetable fats), while
similar (more modern) synthetic compounds, often salts of sulfonic acids (RSO3– Na+), such as
sodium lauryl sulfate and sodium laureth sulfate, are called detergents.

Both soaps and detergents help to clean surfaces in another way. Water molecules have a
tendency to stick together (through hydrogen bonding, HO–H- - - - -OH2) rather than sticking to other
surfaces; this is known as the surface tension of water. Surface tension is the reason why water
droplets are spherical in shape, as a sphere is the shape that minimizes surface tension among
water molecules. In the cleaning process, surface tension must be reduced so water can spread
and wet surfaces. Soaps and detergents weaken the surface tension in water – by attempting to
move away from the water molecules, the fat-loving ends of the molecules push up to the surface.
This weakens the hydrogen bonds holding the water molecules together at the surface. The result
is a break in the surface tension of the water.

As soaps and detergents reduce the surface tension of water, allowing ‘wetting’ of a dirty surface,
they are called surfactants (or surface-active agents). Surfactants are ingredients in numerous
cleaning products, from shampoos to shower gels, including commercially available products A–E.

A: Aqua, Sodium Laureth Sulfate, Sodium Chloride, Cocamidopropyl Betaine, Glycerin, Parfum,
Pyrus Malus Fruit Extract, Benzophenone-4, Tetrasodium EDTA, Sodium Benzoate, Citric Acid,
Sodium Hydroxide, Potassium Sorbate, Sodium Sulfate, CI 19140, CI 42090.

B: Aqua, Sodium Laureth Sulfate, Cocamidopropyl Betaine Mentha Arvensis (Peppermint) Leaf
Oil, Lauryl Glucoside, Melaleuca Alternifolia (Tea Tree) Leaf Oil, Sodium Chloride, Lactic Acid,
Styrene/Acrylates Copolymer, Tetrasodium Glutamate Diacetate, Sodium Benzoate, Benzotriazolyl
Dodecyl p-Cresol, BHT, Limonene, CI 42090, CI 19140.

C: Aqua, Sodium Laureth Sulfate, Sodium Chloride, Cocamidopropyl Betaine, Citrus Medica
Limonum (Lemon) Peel Oil, Melaleuca Alternifolia (Tea Tree) Leaf Oil, Citrus Sinensis (Orange)
Peel Oil Expressed, Citrus Aurantium Bergamia (Bergamot) Fruit Oil, Polyquaternium-7, Sodium
Benzoate, Tetrasodium Glutamate Diacetate, Lactic Acid, Styrene/Acrylates Copolymer, C11-15
Pareth-7, C11-15 Pareth-40, Benzotriazolyl Dodecyl p-Cresol, Citral, Citronellol, Limonene, CI
19140, CI 14700.
D: 5-15% Anionic Surfactants, Oxygen-Based Bleaching Agents, <5% Enzymes, Nonionic
Surfactants, Optical Brighteners, Perfume, Phosphonates, Polycarboxylates, Soap, Zeolites,
Butylphenyl Methylpropional, Geraniol, Hexyl Cinnamal.

E: Aqua, Hydrated Silica, Glycerin, Sorbitol, PVM/MA Copolymer, Sodium Lauryl Sulfate, Aroma,
Cellulose Gum, Sodium Hydroxide, Sodium Fluoride, Carrageenan, Triclosan, Sodium Saccharin,
Mica, Limonene, CI 77891, CI 42090.

Based on the list of ingredients, which of the products A–E would you most like to have in your sports
locker?

What complex formulations! Along with the surfactants and water (or aqua), which is the solvent in which all the
ingredients are mixed, there are typically:
• stabilisers – such as glycol distearate (which gives a pearlescent effect) keep the ingredients blended so each
drop has the right mixture of ingredients
• foaming agents – such as cocamidopropyl betaine provide the satisfying suds during washing
• preservatives – such as sodium benzoate stop microbial contamination
• texture agents – such as sodium chloride to adjust the thickness of the end product
• colour and fragrance agents – produce long-lasting scents ranging from (yellow) fresh lemon to (green) cool
mint
• pH adjustment – such as acids (e.g. citric acid) and/or bases (e.g. sodium hydroxide) to achieve the target pH

Here are the identities of products A-E:

A: Apple shampoo
B: Mint and tea shower gel
C: Lemon shower gel
D: Bio washing powder
E: Toothpaste

Did you make the right choice?

Tools of the trade: making polymers

There are a wide variety of polymers available in the world and an even greater number of monomers,
which make up these polymeric chains. Understanding how monomers react to form polymeric chains
and which monomers should be used to modify a polymer’s properties is crucial to developing our
understanding of polymer science.

Chain growth polymerisation

The most basic polymers consist of just a single monomer. For example, poly(ethene) (or polyethylene) is
formed from ethene. Polymers made by joining together alkenes (that contain C=C bonds) are typically
achieved through chain polymerisation, involving radical intermediates.

The first step is called the initiation step and involves the formation of a reactive radical species with an
unpaired valence electron that adds to the C=C bond in the monomer.

One of the most common radical sources is benzoyl peroxide (C14H10O4). The weak O–O bond of the peroxide
bond breaks via homolytic cleavage (homolysis) when heated or exposed to ultraviolet radiation. Homolytic
fission gives two alkoxyl radicals (RO•).

The alkoxyl radical adds to the C=C bond in the alkene monomer to form a new carbon-centred radical, in
a propagation step. Addition occurs because the new O–C bond that is formed in the product is stronger than
the C=C bond that is broken in the monomer. The carbon-centred radical then adds to another C=C bond in
another monomer. Subsequent addition reactions can take place, so the length of the carbon chain increases.

It is possible for two carbon-centred radicals in different chains to react with one another, thus
stopping either chain from growing any further by reacting with further monomer units; this is
a termination step called combination. Alternatively, one carbon-centred radical can “steal” a
hydrogen atom from another through a reaction called abstraction. This produces both saturated
and unsaturated products, in equal amounts, and this type of termination reaction is called
disproportionation. In chain growth polymerisation a range of polymer lengths are formed due to
the variable times at which termination occurs.
This type of reaction is useful for monomers with C=C bonds or similar functional groups.

Step growth polymerisation

Some polymers rely on condensation reactions, where two functional groups form a covalent bond in the
product, through the loss of a small molecule, such as water. The resulting polymers are commonly called step
growth polymers.

Such polymers can be formed using a co-polymerisation method where two different monomers, with two
functional groups, react to form a continuous chain. These functional groups react together indefinitely in order
to give long polymer chains with high molecular masses. These chains are classed as alternating copolymers.

Polyesters
To form polyesters, monomers containing a carboxylic acid and alcohol group can be mixed and heated with an
acid catalyst in order to form ester linkages. Water is lost in each esterification step and so a series of
condensation reactions forms the polyester. Condensation reactions will continue to occur until all of the free
monomer units have been used up, thereby resulting in a long chain. If additional monomer units are added
then condensation reactions will begin again. The polymer polyethylene terephthalate, abbreviated PET, is
used to make plastic bottles for soft drinks and water, and is the most widely recycled plastic.

As shown below, to make a polymer like PET, the esterification step involves a nucleophilic acyl substitution
reaction. The OH group of the alcohol (or diol) acts as a nucleophile, attacking the carbonyl carbon of the
carboxylic acid (or diacid). An acid is used to protonate the carboxylic acid as this converts it into a stronger
electrophile (it is now positively charged), that is more readily attacked by the alcohol. Notice that the H + is
regenerated at the end of the reaction and so acts as a catalyst - it increases the rate of the esterification
without itself undergoing any permanent chemical change.
Polyamides
Another copolymer is Kevlar – a diacyl chloride reacts with a diamine, in a series of nucleophilic acyl
substitutions, to form the polyamide (notice the presence of repeating -C(=O)NH– groups).

Kevlar, when spun into a fibre, is five times stronger than steel and has half the density of fibreglass. These
properties ensure it is widely used in sport, including in racquet sports, where it ensures that strings break less
frequently.

A related polyamide is nylon 66, -[C(=O)(CH2)4C(=O)NH(CH2)6NH]n-, made from two monomers each
containing 6 carbon atoms. These monomers are called adipoyl dichloride (ClC(=O)(CH2)4C(=O)Cl) and
hexamethylenediamine (H2N(CH2)6NH2). This polymer has high mechanical strength, rigidity, good stability
under heat and chemical resistance. Nylon clothing is lightweight, silky, attractive and smooth. Since it does not
absorb moisture or odours readily, it is in demand for the production of athletic clothing.
You may have seen the ‘nylon rope trick’ where a solution of a diacyl chloride in an organic solvent floats on
top of an aqueous solution of the diamine. As nylon forms at the interface, it can be pulled as fast as it is
produced forming a long thread. Nylon rope is twice as strong as rope made from natural fibres such as hemp
and it weighs less.

https://youtu.be/lNWc6xUf6U4

Polymetallocarbosilanes
Monomers that have three or more functional groups will form infinitely large 3-D networks of interlinking
polymers. This method is used to create viscous polymer gels as well as to strengthen polymer chains through
cross-linking. For example, silicon-titanium tetra-functional group polymers, and similarly substituted structures,
are called polymetallocarbosilanes. They can be used to create heat-resistant paints and protective coatings.
Now you try
From the partial structures of the polymers shown below, identify the monomer or monomers that are used in
their synthesis.

(a) –CH(CH3)–CH2–CH(CH3)–CH2–CH(CH3)–CH2–

(b) –C(CN)(CO2CH3)–CH2–C(CN)(CO2CH3)–CH2–C(CN)(CO2CH3)–CH2–

(c) –CO–CH2–CH2–CO–NH–CH2–CH2–NH–CO–CH2–CH2–CO–NH–CH2–CH2–NH–

See if you can identify the 9 different polymers comprising the everyday products in the
collage in the downloads section below. Post your answers – we look forward to seeing
your results.

Everydaypolymers.pdf
Modelling polymers
0:06Skip to 0 minutes and 6 secondsA polymer is a large molecule made up of numerous small building blocks,
called monomers. These monomer building blocks are joined together to form chains that are long and straight,
or slightly branched, or highly interconnected. For example, linking together molecules of ethene, the simplest
alkene, forms poly(ethene), or polythene. As just one type of monomer is used this is classed as a
homopolymer. When two different types of monomers are joined in the same polymer chain, the polymer is
called a copolymer. For example, linking together molecules of ethene with ethenyl ethanoate, which contains
both alkene and ester groups, gives poly(ethylene vinyl acetate) or PEVA.
0:47Skip to 0 minutes and 47 secondsIn PEVA, there are different ways in which the monomers could be linked -
if they are linked alternately, it is called an alternating copolymer. In contrast, a block copolymer has long
sequences of the same monomer unit, whilst, as the name suggests, for random copolymers the two
monomers are linked in any order. Linear copolymers consist of a single main chain whereas branched
copolymers consist of a single main chain with one or more polymeric side chains. If the side chains have a
different structure to the main chain we call this a graft copolymer. With so many variations, it can be tricky to
visualise the different structures of polymers, so in this activity we will model their structures using paper clips.
1:32Skip to 1 minute and 32 secondsA paper clip will represent the monomer, which can be linked together, in
different ways, to simulate the way monomers join up to form polymers. Start with using the same type of paper
clips to model a linear homopolymer, then change it to a branched homopolymer - consider how the different
chains can pack together - and then model a crosslinked homopolymer. Also, consider how different chains
can twist and bend to form a tangled arrangement like cooked spaghetti tangled up on a plate. Now move on to
using two different paper clips to model copolymers - alternating, random and then graft. There are some
limitations to using paper clips, including the fact that it gives a two-dimensional model, whereas polymers
make three-dimensional lattices.
2:16Skip to 2 minutes and 16 secondsNevertheless the designs can be effective and fun to make! Be creative
and take a picture of your favourite design, naming the polymer type and post your results - we look forward to
seeing your stationery model!

Chemists often build molecular models using plastic rods and balls to represent different atoms and
their bonding. It can often be easier to visualise the symmetry, shape and potential bonding
interactions of a molecule when you have the 3-D model on hand to rotate.

In order to aid your understanding of how different types of polymer can be formed we are going to use
paperclips to represent individual monomers. When joined together they will form different variations of polymer
chains.

The following items will be required:

 A large number of paperclips, preferably of different size and colour.

First take a set of paperclips all of the same size or colour. These all represent the same molecule. Joining
them together shows how many of the same monomer can be used to form a long, polymer chain. If you had
many of these chains adjacent to each other they would pack closely together and so you would have a high-
density polymer.

Add some paperclips at regular intervals to act as side chains to the main polymer chain. This would represent
a lower-density polymer as the steric hindrance of the side chains prevents the polymer chains from packing as
closely together.

Let’s start a new polymer chain and this time include two different types of monomers. You may differentiate
your monomer molecules through using paperclips of different types, sizes or colours. If you have a large
enough collection of paperclips at your disposal then you can make all of the types of polymer listed below and
then compare them.
First put your paperclips together in a random order. This would indicate two monomers which are able to react
with both themselves and the other available monomer. Next create a chain of alternating monomers. These
monomers might be bi-functional. The functional groups they possess can only react with the functional groups
on the other monomers. Finally create a block co-polymer which consists of a length of a single type of
monomer followed by another length of the other monomer. As each monomer might have different properties
these are carried into the properties of the polymer. Most commonly one monomer will be hydrophilic and the
other monomer will be hydrophobic. This creates a polymer with a hydrophilic section and a hydrophobic
section.

As we have seen, polymers with discrete hydrophilic and hydrophobic sections can aggregate into micelles
when placed in water. They will have a hydrophilic exterior and hydrophobic interior. The interior can be used
to house drugs for targeted delivery or to “capture” oil and dirt when used in soaps and washing-up liquids.

If you have any remaining paperclips then you can investigate the effects of cross-linking between chains.
Connect separate polymer chains together through the regular placement of cross-linking bond paperclips and
you should get a sheet of paperclip chains. Is the sheet strong enough to hold the weight of a tennis ball? Can
you join the chains close enough to hold a marble?

When you are done we would love to see your results! Upload a picture of your models using our
open Padlet (we have included some examples from a previous course to help inspire you) and/or
on Twitter or Instagram hashtag #FLchemistry.

Polymer structure and properties

When designing a polymer for a particular application, there are a number of factors that affect the physical
properties of a polymer, and so need to be considered. For example, the viscosity, strength and toughness of a
polymer depend on its molecular weight (this is determined by the number of repeating units in the polymer
chain and the molecular weight of the repeating unit). The lower the molecular weight of a polymer, the lower
the viscosity and the mechanical strength. On increasing molecular weight, due to increased entanglement of
chains, a polymer becomes more viscous and tougher, which makes the processing of the polymer more
difficult.

Also, polymer chains can attract one another encouraging them to stick together, using secondary bonds
or intermolecular forces. Take, for example, the polyamide Kevlar. Its strength comes from strong
intermolecular forces between adjacent chains of the Kevlar polymer. One intermolecular force is hydrogen
bonding, which describes the electrostatic attraction between some hydrogen atoms in –NH– groups in one
chain and the oxygen atoms in –C(=O)– groups in another chain. Additional strength is derived from stacking
interactions between the benzene rings in different chains.

Another factor that needs to be considered is tacticity. This term is used to describe the way pendent groups
on a polymer chain are arranged on a polymer backbone. The tacticity of a polymer is determined by what side
of the polymer chain the pendant groups are on (i.e., are all of the groups pointing towards us, or are some
pointing away from us). This is important because the relative position of the groups can have dramatic effects
on the physical properties of the polymer.

Tacticity arises when there are chiral carbons in the polymer chain backbone. For example, this occurs in free
radical polymerisation of propene, H2C=CH(CH)3, to form poly(propene), [–CH2–CH(CH)3–]n. When a propene
monomer adds to the end of the growing polymer chain, the monomer can either join the pendant CH 3 group
on the same side as all of the other CH3 groups, or it can join the pendant CH3 group on the side away from the
nearest pendant CH3 group. If propene adds to the polymer backbone with the pendant CH3 group on the same
side as the previous CH3 group, this is called isotactic. If propene adds so that its CH3 group adds to the
opposite side of the previous CH3 group, it is called syndiotactic. If there is no order to the way the CH3 group
adds, (completely random) the polymer is said to be atactic (see the pdf in the downloads section below).
The tacticity has a dramatic effect on the physical properties of poly(propene). Atactic poly(propene) has little
order in the polymer backbone and it is called an amorphous polymer. The polymer chains move across each
other when it is pushed or pulled, so it has some flexibility and elasticity. Isotactic poly(propene) has long-range
order, which adds mechanical strength and crystallinity. It is called a semicrystalline polymer and it is a stiffer
material. The demand for these polymers resulted in the development of a range of catalysts (by Karl Ziegler
and Giulio Natta) that can selectively prepare atactic or isotactic poly(propene).

Is it possible to illustrate intermolecular forces and/or tacticity in your paperclip model?

4.5_Tacticity.pdf
Understanding the role of polymers in sports equipment
0:06Skip to 0 minutes and 6 secondsSports equipment is continually evolving. Traditionally, sports equipment
was made from natural materials, such as metals, wood, twine and even ox-gut. The limited supply of these
materials meant that only a small proportion of the population played sports. Today, chemists have developed
new, cheaper synthetic materials, which allow most people to play. The new materials also enhance the
performance of those playing sport - for example, polymers combined with natural compounds from rubber
have been used to create golf balls that travel a greater distance, have higher abrasion resistance, and
improved firmness. We will see that nanomaterials, including carbon nanotubes, are now being routinely
incorporated into various sports equipment to add extra strength and stiffness, durability and to reduce weight.
0:59Skip to 0 minutes and 59 secondsAlthough polymers and synthetic materials are most often associated with
the equipment and clothing worn by competitors there are, in fact, many additional, supporting uses for
polymers. These range from applications in playing surfaces, balls and pucks, to waterproof clothing for
spectators and fans. Synthetic playing surfaces are incorporated into many professional leagues including the
NFL (American football), EHL (Field Hockey) and International Tennis Opens. On AstroTurf pitches linear low-
density polyethylene (abbreviated as LLDPE) is used. LLDPE retains a similar structure to low-density
polyethylene (LDPE) but mixes 1-butene monomers with ethene monomers in order to produce a more ordered
structure. Meanwhile, for tennis and similar court sports, an ethylene-propylene-diene backbone, incorporating
an ethylidene norbornene structure, is used.
1:57Skip to 1 minute and 57 secondsThis forms an elastic polymer, which gives courts grip for competitors and
increased bounce for tennis balls in order to provide the best performance possible.. In order to reduce
bouncing pucks during ice hockey games, pucks are kept in freezers as they are made of vulcanised rubber
that becomes more elastic when warmed. Vulcanised rubber consists of a rubber polymer of cellulose or
isoprene, which has been treated with sulfur under high pressures and temperatures. The result is a durable
structure of cross-linked polymers that are rigid and durable. Wimbledon championship tennis balls undergo an
even more rigorous pre-game warm-up where they must adhere to hand-tested bounce, weight and
compression guidelines. Their protective felt coating is often made from dyed wool or synthetic nylon.
2:49Skip to 2 minutes and 49 secondsBoth polymers contain amide bonds. The properties of some polymers
allow for them to work under high stress and pressure whilst maintaining their shape. As such they are
essential materials in high performance sports where other compounds would be unable to hold their own. For
example, PVC (poly(vinyl chloride)) has a similar structure to polyethene except for a single hydrogen
substituted for a chlorine atom. Over 140,000 m2 of PVC was used in the construction of venues for the
London Olympic Games, comprising of flooring for basketball, badminton and table tennis courts as well as
roofing and canopies in stadiums. High performance PVC crashmats are used in martial arts to provide a tear
resistant surface under which impact padding can be layered.
3:40Skip to 3 minutes and 40 secondsAlternatively, Zylon is an integral component of high-performance sails. It
has high tensile strength and is very resistant to stress creep where materials are deformed over time. Many
novel polymers and synthetic materials are first trialled in sports equipment to monitor their effectiveness
against impacts, friction and stress. This allows for new materials to undergo rigorous testing whilst potentially
providing a competitive edge. Only once these materials have been certified as both effective and safe for use
is their incorporation into other areas, such as structural and aeronautical engineering, considered.
Enhancements in sports technology are commonly adapted for public use over time, especially in sectors such
as motor technology.
4:30Skip to 4 minutes and 30 secondsNano-particles of copper oxide (CuO), zinc oxide (ZnO) and zirconium
oxide (ZrO2) are used in lubricants to reduce wear and friction whilst carbon nano-fibre brakes, first trialled in
Formula 1 racing cars, have a longer lifetime and provide greater thermal resistance than cast-iron brake discs.

The optimum design of sports equipment requires the application of a number of disciplines, from
anatomy to materials science, for enhanced performance, to make the equipment as user-friendly as
possible and to avoid injury. In designing sports equipment, the various characteristics of materials
must be considered including strength, ductility, density, fatigue resistance,
toughness, modulus (damping), and cost. If we want a material that features the highest possible
stiffness for the least possible weight, we would select low density materials with the highest specific
stiffness.
Spandex (or Lycra®) is an interesting stretchy elastic artificial fibre. It is used to make sports clothing including
wetsuits, and with other fibres to make comfortable clothing with a snug fit, that helps to support muscles. Its
structure has a stretchy section that makes it soft and rubbery, and a rigid section (containing substituted
benzene rings and urea, –NHCONH–, functional groups) that makes it tougher than rubber. Different chains
can form hydrogen bonds (C=O IIIIIIII H–N) to one another that align the rigid segments in different chains in the
fibres. Spandex is lightweight but doesn’t get damaged by sunlight, sweat or detergents - all of which can make
other materials wear out.

To meet the requirements of sports equipment, the materials of choice often consist of a mixture of
material types, typically metals, ceramics, polymers, and composite concepts. Composite
materials are made from two or more materials with different chemical and physical properties, that
when combined, produce a material with characteristics different from those of the individual
components. For example, carbon-fibre-reinforced composites are superior to metals in imparting
high forces to a ball. To reduce the vibration upon impact, racket handles are constructed of
multiple carbon-fibre-reinforced layers wrapped around a soft inner core, which is often an injected
polyurethane foam or honeycomb construction. A polyurethane is formed, for example, by reacting
a diisocyanate with a diol.
https://youtu.be/wVNeoy2WLm4

In the Paralympics, some sprinters have made use of prosthetic devices featuring carbon-graphite feet bolted
to carbon-composite sockets, that provide the right balance of stiffness and flex at a substantially reduced
weight compared to conventional materials such as wood. The arrangement acts like a springboard, with the
runner punching the track with each step forward, catapulting the athlete more efficiently than if they were
running on two human feet. In the 2018 Winter Paralympics, a new prosthetic leg, called the Ottobock ProCarve,
was designed with a powerful pneumatic spring and a large air-filled cylinder at the ankle joint which acts as a
shock absorber, and is perfect for tough sports like snowboarding.

Ethical implications of emerging materials

So, amazing improvements have been made in those sports where equipment is critical. However, the use of
advanced materials in sports equipment presents some ethical questions. We can clearly enhance behaviour
by allowing the use of advanced materials, but where should the line be drawn, or should there be no
restrictions? Can we ensure that athletes are competing and not the advanced materials? Also, should we
allow competition at the highest level to be only affordable to the elite because of the high cost of modern
equipment?

What do you think?

Ski waxes
Concerns over cost is not the only reason to ban sports equipment. Take skiing, where applying a wax can
help make the skis glide faster over the snow. The wax, particularly those containing fluorinated compounds,
provides a smooth hydrophobic, or water-repelling surface, that helps skis glide over the snow. However, the
International Ski Federation has recently banned the use of fluorinated waxes from elite competitions. Not
because of improved performance, but because of environmental and health concerns. Fluorinated waxes
belong to the family of per- and polyfluoroalkyl substances, called ‘forever chemicals’, because they do not
break down naturally in the environment. So, the search is on for environmentally-friendly alternatives.
The role of polymers in cycling, canoeing and badminton
Polymers are often trialed in sport for properties which can be beneficial in other areas of science and
technology. So, let’s look more closely at some specific examples. The following polymer, known as
Vectran, is a perfect example of how polymers tested in sports equipment can find applications in
other industries.

Vectran is a polyester characterised by aromatic rings on both monomer constituents. It has a relatively high
melting point of 276-330 °C, depending on the thickness of the strand, and resists creep, a property where
ropes and cables deform over time due to the tensile pressure placed on them. In sporting equipment Vectran
was first introduced as synthetic stringing for badminton racquets. The notable impact resistance and
high tensile strength result in a strong yet lightweight racquet head which allows for more powerful shots by the
player. A 67 centimeter racquet can weigh as little as 87 grams (that is, much less than an average bar of
soap)!

Carbon-fibre-reinforced polymer
In both high-performance and non-competitive canoeing, carbon-fibre-reinforced polymer (CFRP) is the optimal
construction material for canoe paddles and oars. Poly(acrylonitrile) or PAN is the main polymeric component
of carbon fibre. The poly(acrylonitrile) fibres are spun before being heated in air, fusing the polymer into a series
of pyridine rings (fully unsaturated 6-membered rings with a nitrogen atom) at approximately 700 °C.

Slowly heating the polymer to 600 °C expels hydrogen gas and fuses adjacent polymer chains
together. At conditions up to 1300 °C multiple chains can fuse together, eliminating more hydrogen,
and also nitrogen, leaving a pure sheet of interlinked carbon atoms. The high temperatures and
pressures involved in this process align the microscopic crystals which the carbon sheets form all
along the same axis as the fibre. Carbon fibre has a thickness of 5-10 micrometres in a fibre (a
micrometre is one millionth of a metre). As such, the overall structure is very resistant to bending
or stretching pressures.
The high cost of production has proven a key limitation in the widespread adoption of carbon fibre, but recent
work has shown that adding a small amount of graphene to the production mixture could not only make carbon
fibre more affordable, but possibly stronger and stiffer at the same time. Graphene consists of a single atomic
layer of carbon, arranged in a honeycomb lattice. The individual sheets in graphite (which is used in pencils)
are graphene. Interestingly, graphene has been shown to be the strongest material ever studied, being over
200 times stronger than steel. It is estimated that it would take an elephant standing on a pencil to break
through a single sheet of graphene with the thickness of plastic wrap! At the 2018 Winter Olympics the GB
team won a bronze medal in skeleton, using a skeleton sled made of a graphene-enhanced composite
material. (In contrast, at the 2022 Winter Olympics, the disappointing performances of the GB skeleton team
was blamed on poor equipment.)

An epoxy resin
Mixing carbon fibre with an epoxy resin will add further strength to its structure and allow for it to be coated in
abrasion- or further chemically-resistant layers. Epoxy resins are very strong polymers that can withstand high
temperatures. They are formed by the nucleophilic attack of phenols (or deprotonated phenols) on epoxides,
leading to opening of the strained three-membered ring. This forms a prepolymer that can be reacted with
nucleophiles, such as triamines (e.g. H2NCH2CH2NHCH2CH2NH2) – each of the three amine groups can react
with an epoxide on a prepolymer. As the three amine groups can each react with different molecules of the pre-
polymer, this forms a densely cross-linked structure that is very strong.

Polycarbonates
Alternatively, polycarbonates contain the carbonate functional group (O-(C=O)-O) and are commonly formed
from acid chloride (RCOCl) precursors and bisphenol A. The monomers are linked together by
multiple nucleophilic acyl substitutions where HCl is lost as a by-product. The resultant polymer layers are flexible
and non-brittle. These are properties that allow them to be moulded into shape as a solid sheet without cracking
or breaking, for example, for use in canoe and kayak hulls.
This property is also desirable in safety equipment used in both cycling and motorcycling crash helmets. The
outermost polycarbonate “shell” is able to absorb some of the impact energy by deforming and flexing slightly.
Were the shell too rigid it would either be brittle and shatter or transfer much of the impact energy to your skull
inside the helmet. As such the slightly malleable (pliable) polycarbonate shell absorbs much of the initial impact
with a soft, foam, expanded polystyrene (EPS) interior to mitigate any remaining energy from a collision.

On the subject of bisphenol A (C15H16O2), or BPA, you may be aware of the health concerns over the use of
this chemical. It mimics the estrogen hormone, estradiol, and some animal studies have shown that BPA
affects fetuses and newborns. Even human studies have linked BPA to a range of health issues. In 2017 the
European Chemicals Agency concluded that BPA should be listed as a substance of very high concern due to
its properties as an endocrine disruptor (i.e., a chemical that interferes with our hormones). BPA is present in
many household products, from food packaging to toilet paper and linings of beverage cans. Although our
bodies quickly remove BPA, its ubiquitous use in so many consumer goods means that the substance
persists. A 2003-2004 National Health and Nutrition Examination Survey found detectable levels of BPA in 93%
of 2517 urine samples from people aged six years and older. Concerns about the health effects of BPA have
led many manufacturers to replace it with substitutes, such as bisphenol S (BPS, C 12H10O4S), although there
are safety concerns over these too. So, the search and research continues.

Nanotubes
Further research into polymers continues to inspire cutting-edge breakthroughs in both pure chemistry and
applications in medical and industrial settings. For example, research has suggested that nanotubes, involving
compact tubes of bonded carbon atoms, have a variety of potential applications such as: a super-strong
industrial fibre, an alternative to copper conduction wire, and a novel delivery method for targeted
chemotherapy.

Take a look at this super video by Oli, one of our former students, on badminton, made as part of our first year
undergraduate macromolecules course.

https://youtu.be/YhDVVD8-Ol0
The role of polymers in sports protection equipment
Injuries are a common sight in sports, particularly those with contact rules. The fast pace of the game
and competitive nature of the athletes can lead to rash challenges, pulled muscles and over-exuberant
celebrations.

Though professional football (soccer) players would have you believe that they are the most injury prone of all
athletes, they are, in fact, in little danger relative to those who play other sports. In 2009, Stanford Children’s
Health attributed just 88,000 injuries in children under 14 in the US to football, compared to 200,000 attributed
to cycling and 215,000 attributed to American football. Regardless, protection against the balls, sticks and
opposing players of nearly all sports has seen substantial development from early wooden and cotton plates to
today’s advanced foams and impact polymers.

The mouth
Amongst the most vital areas to protect are the neck, face and mouth. Though keeping a set of pearly whites
will be most people’s primary concern, the gum and mouth guards of today also help reduce the risk of
concussions and tongue injuries resulting from impacts to the jaw. The most common mouth guards available
are “boil and bite” types. These are heated in order to be shaped to fit a user’s teeth and then form a more
resistant solid on cooling. Their main component is poly(ethylene-vinyl acetate) or PEVA, made from the
polymerisation of ethene with vinyl acetate.

PEVA is used as a shock-absorber in other areas such as in the soles of shoes or hockey pads.
Other mouth guards are available to professional athletes which involve using alginic acid, a gum-
like polymer, to make a tooth mould and then fashioning a comfortable gum shield which perfectly
fits the wearer. The additional cost associated with acquiring a custom mould means it is
sometimes prohibitive to amateur athletes; though they provide greater protection than “boil and

bite” products.
The head
There are an estimated 3.8 million sports-related concussions each year in the United States and the hard
contact hits in American football leagues contribute heavily towards this figure. Movements of the brain, even
by millimetres, can strain the nerve cells and connections within the white-matter of the brain. This can
irreversibly damage nerve endings and lead to loss of memories or reduced motor control. Currently the
helmets used in American football are tested to withstand a linear impact and reduce the risk of skull fracture. A
combination of inner foam padding, typically made of polyurethane, and hard plastic (typically a polycarbonate)
or composite outer layers means that they can reduce the force from a direct impact very well. For example, on
impact, the polycarbonate will flex to absorb some of the force and so less force is exerted on the head.

However, few impacts are purely direct, linear forces. The majority arise from rotational hits which not only
impact the skull but also twist it, putting considerable strain on the brain. In order to try and counter these
additional forces testing is underway on MIPS, or a multi-directional impact system. A plastic layer is inserted
below the traditional helmet padding, allowing the helmet to float above the plastic layer and absorb some of
the rotation from the force of a non-linear impact. The new impact reduction system can reduce rotational
forces acting on the head by between 15 and 55%. These reductions may be the difference between walking
away from a tackle or being left with a debilitating injury. The technology is now used in over 120 brands,
including skiing, snowboarding and cycling protective equipment.

The shoulders
Now let’s move on to shoulder pads - they are made of a soft polyethene foam and a hard polyethene shell.
The hard shell is high-density poly(ethene) (or HDPE) - the polymer chain has no branching, which makes it
dense and, as the chains are arranged close together, intermolecular forces (called London dispersion forces,
which are short-lived electrostatic attractions) can form between the chains, making the material strong. If
you stretch a plastic grocery bag (made of polyethene), you will see that the length increases and the width
decreases. This breaks apart the intermolecular forces and straightens out the polymer chains. The covalent
bonds in the polymer remain intact until the plastic rips. (Talking of plastic bags, you might like to try this water
in a bag party ‘trick’.)

On the other hand, the foam is softer as there is branching in the polymer chains - the branching gives more
flexibility to the material and it is called medium-density polyethene. Low-density polyethene (or LDPE) has the
greatest amount of branching, giving the greatest flexibility, and it is the weakest polymer. It has a low density
which helps to ensure that the pads are lightweight so players can move freely.

The hands
For more adventurous sports such as rock climbing, sailing and white water rafting, hand protection is essential
in order to keep skin from being cut, blistered or burnt. However, gloves must still retain the flexibility and motor
control to make deft adjustments whilst further providing grip in wet or icy conditions. For this reason, many
protective gloves are manufactured with a combination of neoprene (made by polymerising chloroprene) for
chemical resistance and lightweight breathability and flexibility; as well as silicones for water and heat
resistances.
Polydimethylsiloxane (PDMS) is commonly formed by hydrolysis of dimethyldichlorosilane
(C2H6Cl2Si) – this involves a series of nucleophilic substitution reactions. Stronger Si–O bonds are
formed in place of the weaker Si–Cl bonds. The methyl groups on the silicon atoms of silicone can
be varied, by using different chlorosilanes, to give a wide variety of structures, as well as to
provide cross-linking in order to form more rigid, overlapping silicone polymer chains.

These materials have all had a tangible impact on reducing the number of impacts and injuries sportspeople
receive. It is often said that safe fun is the best fun and with modern polymers paving the way in advancing
sport science, this old motto is becoming more and more relevant.

Take a look at one of our undergraduate videos, on polymers in sport, by Oliver, made as part of a first year
undergraduate macromolecules course.

https://youtu.be/lDdHJZJl8xA
How polymers have advanced football, rugby and cricket
Football, or soccer, is one of the most common sports in existence. This stems mainly from the nature
of the game requiring no aides to playing, such as sticks, bats or clubs; simply the football itself. The
most common football is arranged in a “Buckyball” configuration consisting of twenty hexagons and
twelve pentagons. The “Buckyball” shape is named after the architect and designer Buckminster
Fuller, who pioneered geodesic dome architecture.

“Buckyball” is also used in chemistry to describe a certain member of the fullerene family. Fullerenes are
spheres made up of carbon atoms with a hollow core. Buckminsterfullerene, C60, was the first identified and
categorised by Harold Kroto, Richard Small and Robert Curl, who all received the 1996 Nobel Prize in
Chemistry for their work. The “Buckyball” shares the same pattern of pentagons and hexagons as a modern
football.

Polyurethanes
Footballs, however, are not made purely out of carbon atoms! The oldest surviving football dates from around
1540 and is constructed from a pig’s bladder surrounded by an outer layer of cow hide. It is only half the
diameter of a standard football used today. Modern footballs retain a similar construction method with an
inflatable bladder and leather exterior. However, these are often made of polymers rather than traditional animal
hides. For example, the outer “leather” of a modern football is often made from polyurethanes. Polyurethane
monomers are joined through urethane (or carbamate) linkages which are formed when an alcohol reacts with
an isocyanate group (R–N=C=O) – the alcohol (ROH), or an alkoxide ion (RO–), is a nucleophile that adds to
the electrophilic carbon in the isocyanate.

Polyisoprene
Meanwhile the inner “bladder” of the ball is constructed from polyisoprene, formed by polymerisation of
isoprene using, for example, a Ziegler-Natta catalyst (involving a complicated reaction mechanism).

Different catalysts give different amounts of cis-1,4- and trans-1,4-polyisoprene – cis-1,4-polyisoprene, which is
also called isoprene rubber, is a major ingredient of natural rubber. trans-1,4-Polyisoprene is also known as
gutta percha, which shares a name with the tree the latex is sourced from. The ratio of cis-:trans- influences the
properties of the polymer. cis-Polymer chains cannot be packed tightly together, whereas chains of the trans-
polymer can. This means that the cis-polymer has fewer cross-links and the separate polymer chains can slip
more – making a stretchy, rubbery polymer (the same as that from the rubber tree). The trans-polymer is much
harder and is sometimes used in golf ball coverings.

Poly(butylene terephthalate)
In football there is little danger from a ball impact and players generally wear limited shin-guards to protect from
tackles. However, in cricket the cork and leather ball can travel at speeds up to 80-100 mph (129-161 kph).
This can lead to forces of over 8000 N on the ball, equivalent to the force required to lift a mass of 800 kg from
the ground (around the average weight of a cow).

In order to provide adequate protection against fast balls, cricket leg pads that batters and wicketkeepers wear
are made from a coating of a high-impact polyester, called poly(butylene terephthalate) or PBT. PBT can be
formed from a polycondensation reaction (you will see that water is a byproduct) between terephthalic acid
(C8H6O4) and butane-1,4-diol (C4H10O2). Notice that PBT has a similar structure to poly(ethylene terephthalate),
or PET, which we have seen used in protective clothing previously (and is discussed later). PBT is less rigid
than PET (it has a longer flexible carbon chain between the benzene rings), but has a higher impact resistance
making it ideal for use in flexible padding.

As with PET, PBT must be mixed or coated with a UV stabilizer such as a benzotriazole (C 6H5N3),
as polymers can be susceptible to breakdown when exposed to intense ultraviolet (UV) radiation.
These additives generally absorb UV radiation much more strongly than the polymers that they
protect. Therefore, the outer coating of cricket pads provides not only a flexible and fitting shape,

but also a high degree of impact and environmental resistance.

Tackle bags
Impact resistance is also crucial in contact sports such as rugby where tackles, especially at higher levels, can
hit with considerable force. Training in order to tackle effectively and safely is often done through the use of
training pads known as tackle bags. These tackle bags must be able to absorb the force generated by a
tackling player whilst protecting the player holding the bag. In order to remain both light enough to carry yet
flexible enough to absorb the force of an incoming tackle, the interior of these bags is constructed from foam
polymers.

Most foam is constructed from polyurethanes with a blowing agent injected during the mixing process. Previously,
chlorofluorocarbons (CFCs) were the molecules of choice for injection as they are non-toxic and have good
thermal insulation properties. However, concerns over their environmental impacts, especially on reduction of
atmospheric ozone, led to a decrease in their use and liquid carbon dioxide is now the commonly used,
inexpensive alternative. As the blowing agent evaporates it expands and forms bubbles within the foam
structure, leading to a low-density, lightweight product. These foams give tackle bags their flexible structures,
providing a force-absorbing layer, which allows players to practice against a safe target to hone their skills.
With the re-introduction of rugby to the 2016 Olympic games after a 92-year absence there has been renewed
enthusiasm to encourage participation in the sport at junior and amateur levels. For every sport where injuries
are prevalent, especially in young athletes, training with equipment designed to keep users safe is paramount
to increasing retention of players and maintaining the health of participants.

Take a look at one of our undergraduate videos, on football, by Brandon, made as part of a first year
undergraduate macromolecules course.

https://youtu.be/Z6trTiq47F0

Advertising polymers
0:07Skip to 0 minutes and 7 secondsIn England alone, around 16 million people aged 16 and over play sport at
least once a week. These people all benefit from Chemistry - from the equipment, clothing and footwear used,
through to the surfaces laid in sports venues. However, it is probably fair to say that the important role of
modern synthetic materials in sport is not necessarily recognised and appreciated by those who play it. For
example, how many football players realise they are kicking a football with a covering of polyurethane, rather
than leather, as leather has a tendency to absorb water causing the ball to become heavy? This activity is an
opportunity for us to champion this cause by promoting the positive impact of high-performing polymers in an
advertising campaign.
0:51Skip to 0 minutes and 51 secondsPick a piece of sports equipment, clothing or footwear of your choice and
make a poster to advertise the chemistry behind it. Keep it simple by focusing on the impact of just one modern
material, noting the beneficial properties it provides - for example, it may provide lightness, durability, strength
and/or flexibility. You could pick cycling, and advertise modern carbon fibre bike frames, or athletics and the
modern hard wearing and bouncier polyurethane all-weather tracks, or perhaps the polyamide fluffy outer
covering of tennis balls that reduce aerodynamic drag, whilst providing resistance to wear and abrasion.
Alternatively, you could focus on how polycarbonate is often used in riding and biking helmets, helping protect
riders competing in equestrian and cycling competitions. The choice is yours.
1:41Skip to 1 minute and 41 secondsBe creative and use an eye-catching image and distinctive clear and
concise lettering - perhaps a promotional poster for one of your favourite films will inspire you? Make a pdf of
your poster, and share with our learning community - it will be interesting to see what you pick! Don’t forget to
add your reason for picking your ‘star material’. Let’s show the sports world that Madonna was right when she
said that ‘we are living in a material world, a material, a material, a material world.’

Almost every day you will see a commercial or product placement of some sort. Many companies
invest heavily in their marketing and advertising departments in order to promote their products as
widely as possible. This holds true for sporting products.

However, even without a budget stretching into the millions of pounds it is possible to create effective and eye-
catching advertisements for all sorts of sporting items. Therefore, why not have a go at making your own advert
for a product of your choice:

The following items will be required:

 Paper, pens and other stationary for a hand-drawn poster.

 Computer with a word processor or similar software.

Choose a product that you use or simply one that you are interested in. Highlight the benefits of your chosen
product over competitors and try to encourage people to take up your chosen sport and use the product you
are advertising. You could also take a picture and demonstrate where different polymers have been used.
Remember to upload your advert to see if anyone would want to buy your merchandise. If you’re
feeling particularly creative then why not invent a brand new product or company!

When you are done we would love to see your results! Upload a picture of your advert
using our open Padlet (we have included examples from a previous course to help inspire
you) and/or on Twitter or Instagram hashtag #FLchemistry.

Alternatively, you could come up with a slogan, or short promotional blurb, advertising your polymer
and share this in the comments (below). You might like to take inspiration from two popular advertising
slogans for ‘plastic’, namely, Mastercard’s clever For Everything Else, There’s MasterCard and Don’t Leave
Home Without It from American Express.

Plasticisers
When you have selected your chosen product, look out for the presence of plasticisers. A plasticiser is a
substance which when added to a material, usually a polymer, makes it flexible, resilient and easier to handle.
For example, polyvinyl chloride (PVC), [-CH2CHCl-]n, is an extremely hard plastic, and to make it more flexible,
plasticisers are added. These are small organic molecules that embed themselves in-between the PVC
polymer chains so they cannot interact with each other as well. This reduced interaction ensures that the
polymer is more pliable. In PVC, the most common plasticisers are a class of esters called phthalates (the most
common being bis(2-ethylhexyl) phthalate or DEHP, a diester with the chemical formula C 24H38O4). They are
the preferred plasticiser found in, for example, trainers, because of their strong performance, cost-effectiveness
and durability. The characteristics of an individual phthalate often make it well-suited to a specific product,
allowing manufacturers to meet unique requirements for its use (function and safety specifications),
appearance (texture, colour, size and shape), durability and wear.

Phthalates are only slightly volatile, and so tend not to evaporate and they have little or no odour. Despite this,
there has been some concerns over the presence of phthalates in ‘new car smell’. The reason for the concern
is that some of these compounds have been found to interfere with normal sexual development in male rats.
Some scientific studies have indicated that phthalates behave as endocrine disruptors in human beings, that is,
they interfere with our normal hormonal mechanisms. Consequently, the use of phthalates with relatively low
molecular weights has been restricted in the European Union. In contrast, scientific studies on phthalates with
high molecular weights (called high phthalates) have concluded that they do not pose a risk to human health at
typical exposure levels.

The health concerns associated with phthalates, coupled with the fact that they are not chemically bonded to
polymers and so can leach out into the environment, have inspired the development of alternatives and this
continues to be an active area of research.
For the record
The impact of chemistry on sport is nicely illustrated by the 100 metres sprint. At the Berlin Olympics, in 1936,
Jesse Owens ran the race in 10.3 seconds. This is slower than Usain Bolt’s record of 9.58 seconds in 2009.
However, Owen’s track surface was made of cinders, he wore heavier and less flexible leather shoes, and his
“starting block” consisted of two holes in the cinders that he had to dig with a trowel. According to a
biomechanics analysis, if Owens had used a real starting block, worn modern shoes, and run on a rubber-
polyurethane surface, he would have been within a single stride of Bolt!

To illustrate the point, this clip shows how a modern sprinter can maximise the use of the starting block.

https://youtu.be/xXqGZamvZjw

So, without new technology, peak human performance has not increased by that much over the
years.
PET recycling
The polyester PET (or polyethylene terephthalate) has a wide range of uses from footballs to car
bumpers, bottles, surfboards and clothing - indeed, some sports shirts are ‘100% polyester’. In
clothing, PET has a big advantage over the more traditional cotton fibres, as it absorbs much less
water. Around 40 million tonnes of PET are made in the chemical industry each year. Of this, around
65% is used to make fibres (commonly called Terylene or Dacron), 30% for packaging and 5% for film.

PET can be made by heating ethane-1,2-diol (C2H6O2) with dimethyl terephthalate, a diester with the chemical
formula C10H10O4 (or with benzene-1,4-dicarboxylic acid, C8H6O4). The reaction involves multiple nucleophilic
acyl substitution reactions. For each reaction, an oxygen atom in the diol attacks the carbon atom in the C=O
bond of the methyl ester (–CO2CH3). This gives an unstable intermediate that, after transfer of a proton, breaks
down to form the C=O bond of a new ester, kicking out methanol (CH 3OH) as a leaving group. As the monomers
are joined together by loss of a small molecule by-product, namely methanol (CH3OH), this is an example of
a condensation polymerisation.

Linking together benzene rings ensures that PET has a rigid structure, leading to high melting points and great
strength. PET is called a thermoplastic as it softens when heated and hardens when cooled. It can go through
many heating/cooling cycles with no significant change to the chemical structure, and so it can be recycled. It is
the most recycled plastic packaging material in Europe. Life-cycle analyses for PET-recycling systems have
evaluated their net environmental impacts and these find greater positive environmental benefits for
mechanical recycling over landfill or incineration with energy recovery.

The market for bottled drinks has increased the need for PET and in the UK, around 15 million plastic bottles
are used every day. For recycling, the PET bottles are collected, cleaned, sorted and processed to reuse the
polymer. The amount of PET recycling is on the increase, but, controversially, recycled PET is typically used to
make products including textiles, such as clothing (including sports clothing) and carpets, rather than bottles.
Some people argue that PET should be recycled back into bottles because of the enormous demand for plastic
bottles. Also, plastic bottles can be recycled more than once whereas, for example, carpets cannot. Others
argue that, because the recycled PET for bottles needs to be of higher quality, the process requires more
energy and is less cost-effective than recycling PET for use in alternative products. There is also a concern that
the use of recycled PET in, for example, drinks bottles, may be controversial among consumers.

What do you think? Join in the discussion below.

Edible packaging
A group of students was recently awarded a prestigious design prize for coming up with a neat way to package
water, in an edible bubble called Ooho!. To create a water sphere, you dissolve sodium alginate
(a polysaccharide isolated from seaweed) in water, then drop some of this solution into another solution of
calcium chloride in water. This sphere will hold the water in place, and the students’ modified version of this
technique makes larger, tougher spheres of water. So, perhaps this could help put an end to plastic
packaging? In the future, when you buy a drink, perhaps it will come in its own edible glass?

Getting recycled polymers on track

It is interesting to see that many athletics tracks use recycled rubber in their composition, thereby helping to
reduce the waste that ends up in landfill or is incinerated. Tyres are strong and flexible and can be ground into
crumbs, cleaned and incorporated into the bottom layer of the track, which is not visible and does not come into
contact with the athletes (it is also commonly used in many playgrounds as a safe cushioning flooring). Tyre
rubber (containing cis-1,4-polyisoprene) has excellent viscoelastic properties (viscoelastic materials dissipate
part of the energy of impact, while conserving enough to provide a suitable reaction force to help propel the
athlete forward) and, when combined with new rubber material on the track surface, which protects it from
oxidation, it can provide a safe and fast running track.

Did you know that Nike used recycled plastic bottles to make the shirts of a number of national football teams,
including England, in the last three FIFA World Cups? Going forward, it is anticipated that there will be a greater
emphasis on sustainability in sports materials. Take tennis balls, which are designed to be non-biodegradable,
single-use, disposable products, especially at the professional level. Today, companies are starting to address
these sustainability and waste issues by creating eco-conscious balls, such as those that include recycled
material. There is also a proposal to use recycled tennis balls to protect buildings from earthquakes!

Take a look at this video by Alex, made as part of a first year undergraduate macromolecules course, on plastic
recycling.

https://youtu.be/NrZ_CmmVcnk
Understanding medicines in sport
0:06Skip to 0 minutes and 6 secondsFootball players and supporters will know how effective an old-fashioned
cold soggy sponge can be in treating a bruised ankle on a chilly winter’s day. Some injured footballers
miraculously return to action within just a few seconds of treatment! For those more seriously injured, the
‘magic sponge’ will, unfortunately, not work and other more scientific approaches are needed. Whereas
repairing muscle or ligament tear may require surgery, for more minor injuries, ‘chemical magic sponges’ are
often effective. Today, qualified physiotherapists carry bags with a wide array of sprays, tablets, gloves and
bandages, which are designed to deal with professional athletes’ injuries. A particularly common injury is a
minor bruise or an ankle or elbow sprain.
0:55Skip to 0 minutes and 55 secondsTo treat such injuries a cold spray is often used, which acts to deaden the
pain and also reduce the swelling. Hydrocarbons, such as butane and 2-methylpropane (or isobutane), are
popular ingredients as they have low boiling points. In aerosol cans the hydrocarbons are stored at 2-8 times
normal atmospheric pressure - when you let a gas escape from 8 times its normal pressure into the air, it
expands enormously and cools down drastically, hence the cooling effect when sprayed on an injury. In contact
sports such as football, hockey and rugby, cuts and scrapes are particularly common. To treat these injuries,
antiseptic sprays are commonly used. These sprays provide relief by soothing and numbing the area while
helping to prevent infection.
1:43Skip to 1 minute and 43 secondsActive ingredients include local anaesthetics such as lignocaine (lidocaine),
which act by blocking nerve impulses from reaching the brain. Once inside the nerve cell, the amine group of
lignocaine is protonated, and the positively charged lignocaine molecule then moves into a sodium channel.
Sodium channels allow Na ions to move
2:05Skip to 2 minutes and 5 secondsinside and outside the cell: they are crucial for nerve transmission. To
transmit a nerve impulse along a nerve, sodium ions move through the cell membrane to the inside of the cell
through the sodium channel. But if a protonated lignocaine molecule is in the way, the movement of sodium
ions is blocked and the nerve impulse cannot be transmitted to the brain. The pain from acute injuries, such as
ligament sprains and muscle strains, is thought to be due to the body’s inflammatory response following the
injury. The body responds by clearing away injured debris and dead cells, to make way for the healing process
to start.
2:46Skip to 2 minutes and 46 secondsPain and swelling caused by the inflammation also keep the athlete from
using the injured part and protect it from further injury. However, it is thought that the inflammatory response is
often excessive and prolonged and, as a result, anti-inflammatory drugs are used to minimise the body’s
response. The most common of these are non-steroidal anti-inflammatory drugs (or NSAIDs), such as
ibuprofen. Ibuprofen works by preventing an enzyme (called cyclooxygenase) from making compounds called
prostaglandins. We produce prostaglandins in response to injury and these would otherwise go on to cause
pain, swelling and inflammation. Ibuprofen has a chiral centre and it is sold as a racemic mixture, or a racemate
- which is a mixture containing equal amounts of each enantiomer.
3:33Skip to 3 minutes and 33 secondsAt first sight this is surprising as only one of the enantiomers is the
biologically active component, which is responsible for stopping prostaglandin formation. Interestingly, within
the body, there is an enzyme that converts the biologically inactive enantiomer into the active enantiomer. As it
is easier and cheaper to produce a racemic mixture, there is little point in looking to market the single
biologically active enantiomer. A much more controversial treatment of inflammation is the use of cortisone
injections. Cortisone is a steroid present in the body, which has completely different actions to the anabolic
steroids used to enhance sports performance. Cortisone is a potent anti-inflammatory drug that can be used to
treat certain joint, ligament or tendon injuries where there is lots of inflammation.
4:22Skip to 4 minutes and 22 secondsBut cortisone injections must be used with caution. Repeated cortisone
injections were at times used in the joints (often knees) of professional athletes to keep them playing rather
than attending to the underlying problem. There is still debate about the effectiveness of these injections today.
Going forward, further scientific investigation, comparing new products or treatment methods to the current
standards of care, will no doubt lead to innovations that provide more effective treatments, which are cost-
effective, returning athletes to the playing field even quicker than before.
To protect cuts and abrasions, traditionally, flexible cloth bandages are used. These are typically made
from cotton. After scouring and bleaching, cotton is 99% cellulose. Cellulose is a polymer made up of a
long chain of glucose molecules all linked together by C-1 to C-4 oxygen bridges, called glycosidic
bonds, formed on elimination of water. The cellulose chains within cotton fibres tend to be held in
place by hydrogen bonding, which occurs between the hydroxyl groups (–OH) of adjacent sugar
molecules.

Today, an alternative to cotton is ‘spray on bandage’ or liquid bandages. The spray contains a polymer such as
PVP/VA, which binds to the skin and forms a temporary protective coating over the injury. It is easy to remove
the bandage because the polymer is water-soluble. When water is applied it dissolves! Liquid bandages can
stick better than plastic or fabric adhesive bandages to many hard-to-bandage areas, including knuckles and

between fingers.

Research in this area continues, and a new algae-based polymer, called Vetigel, has been developed that
stops profuse bleeding within seconds. It was invented in 2010 by Joe Landolina, when he was just 17 years
old. (This reminds me of Maria Elena Grimmett who, at the age of just 14, became the youngest person
published in the Journal of Environmental Quality for designing reusable polymer beads to remove
sulfamethazine (an antibiotic) from rivers, streams and groundwater.)

What sporting injuries would you most like to solve using chemistry-based inventions?

To cool or not to cool, that is the question

As mentioned in the video, cooling the site of an injury, or cryotherapy, is often used to treat acute sports
injuries. Putting an ice pack on a pulled muscle can help to relieve pain and is called cooling-mediated
analgesia (or pain relief). But how effective is it? Unfortunately, the lack of appropriate randomized and blind
model studies means that we cannot definitively say how effective cryotherapy is. It is generally advised to
continue to use such therapy soon after acute sports injuries and their surgical treatment occur. Does adding
an ice-pack or cold-spray work for you?
Understanding the role of polymers in nutrition
The global sports nutrition industry is estimated to grow to a net worth of around $81.5 billion by 2023.
Aggressive marketing, changing consumer preferences and the increase in social media following of
sports celebrities and lifestyle bloggers may explain the increasing demand for performance sports
foods and drinks.

As such many corporations and private enterprises have attempted to enter the lucrative market with a mixture
of organic and synthetic foodstuffs. We will examine some of the common polymeric ingredients in these
sports-targeted products.

Sports drinks
Maltodextrins are short polymer chains consisting of two to twenty D-glucose monomers – the D-glucose units
are linked together by acetal functional groups. They are produced by the partial hydrolysis of starch, which is a
much longer polymer containing many more D-glucose units linked together. The hydrolysis of starch occurs
under acidic aqueous conditions – protonation of the bridging acetal oxygen forms a good leaving group (step 1)
that is kicked out by the second hemiacetal oxygen (step 2). Water then adds to the positively charged
intermediate (step 3), then on loss of a proton (step 4), the component D-glucose units are formed.

The structure of D-glucose can be drawn in different ways, but most commonly it is shown as a six-membered
ring. Notice the three secondary alcohols, the primary alcohol, and the hemiacetal functional group, as well as
the presence of five chiral centres.

The glucose monomers are a quick and steady source of energy, which is taken post-workout in order to restore
blood glucose levels and provide energy for protein anabolism – the synthesis of complex protein molecules
used for construction of muscle tissue from amino acid building blocks.

Maltodextrin polymers are preferred over taking glucose monosaccharides as the polymer solution will have a
lower osmolarity than the monosaccharide solution. Osmolarity is a measure of the number of particles per litre
of solution. With the glucose monomers of maltodextrin linked in a polymer chain, the same total number of
monomers will have a lower osmolarity in maltodextrin. Water tends to move from areas with a low osmolarity,
where a low concentration of molecules is dissolved in solution, to an area of higher osmolarity where a greater
number of molecules are dissolved in solution. Therefore, due to the difference in osmolarity between the
glucose solutions in the intestine and the blood, maltodextrins are more likely to be absorbed than a simple
glucose solution (i.e. pass from the intestine into our bloodstream).
Many sports drinks have a high energy content due to the carbohydrates dissolved in them. Although these
additional carbohydrates are beneficial, overloading a drink with too high a concentration of carbohydrates can
reduce the rate of uptake of another essential nutrient, namely, water.

Water makes up approximately 60% of the average adult’s body mass and is an essential solvent used to
transport nutrients in the blood plasma. Playing sports or exercising under hot conditions can result in an
increase in sweating and, eventually, dehydration.

In order to provide an adequate water supply to the body, drinks with a low carbohydrate content are preferred.
A low number of carbohydrates leads to a very low molarity, encouraging water to be absorbed by the body
(where blood molarity is greater).

Sodium ions, often sourced from common salt (NaCl), can aid the uptake of other nutrients and are often found
in high concentrations in sports drinks (10-25 mmol/L) relative to non-specific commercial soft drinks (1-2 mmol/L).
A high salt intake in a diet, with little exercise, can result in dangerous increases in blood pressure. However,
the main problem for salt within sports drinks is its unpalatable taste. Though greater sodium ion
concentrations would increase nutrient absorption, a balance must be struck between this efficiency and the
unpleasant taste that can result from salty beverages.

Protein shakes
Whilst carbohydrates provide the energy for exercise and protein formation, they do not provide the building
blocks of proteins – namely, the amino acids. Proteins are polymers made of amino acid monomers. Each
amino acid shares an identical basic structure with an alternating side chain (typically represented as R)
providing the variation seen in amino acids.

Of the twenty amino acids found in the proteins of our body, nine are considered “essential” as they cannot be
synthesised by our bodies and therefore must be acquired from the food we consume.

To ensure that these “essential” amino acids are present, as well as to provide a sufficient amount of amino
acids to synthesise muscle protein, bodybuilders often consume protein supplements. These come in the form
of the amino acid monomers themselves or as complex proteins, as found in popularised protein shakes, which
contain all of the amino acids required by the human body.

The amide (or peptide) bonds that link together amino acids in peptides are formed from reactions between the
amine groups (–NH2) and carboxylic acid groups (–CO2H) in different amino acid molecules. Water is formed
as a by-product and so this is called a condensation reaction. The reaction mechanism involves a nucleophilic
acyl substitution – the amine acts as the nucleophile and the carbonyl carbon is the electrophilic site. To make a
peptide in the laboratory, often an acid catalyst is used, which protonates the carbonyl group of the carboxylic
acid, making it a stronger electrophile.

Alternatively, under certain conditions, protein chains can be broken into their constituent amino acids by
reaction with water in a hydrolysis reaction. This involves the breaking of bonds using water and, as such,
protein chains ingested from food can be broken into their substituent amino acids and then re-formed into the
protein polymers which make up our body.

As products are continually refined in order to find the mixtures and concentrations most effective at improving
exercise and sporting performance (including reducing muscle fatigue), the basic requirements of carbohydrates
and proteins will still remain essential for everyone. Both those partaking in vigorous exercise and living their
daily lives.

Controversial marketing
The marketing of sports drinks and protein powders is a controversial topic. For example, the British Dietetic
Association (BDA) has stated that marketing for some protein powder products is both “wrong and immoral”. The
American Heart Association says water is best for hydration and adds, “Sports drinks with electrolytes, may be
useful for people doing high intensity, vigorous exercise in very hot weather, though they tend to be high in
added sugars and calories.” Recently, in the UK, a number of supermarkets banned the sale of energy drinks
(with high levels of sugars and caffeine) to children under 16.

Have any of you tried sports drinks? If so, are they your favourite choice for hydration or do
you prefer water or something else?
Making a natural plastic
0:06Skip to 0 minutes and 6 secondsAmazingly, from the early 1900s until about 1945, milk was commonly used
to make various plastic ornaments, ranging from buttons, beads and other jewellery, to fountain pens, and
comb and brush sets. The plastic, called milk plastic, or more usually casein plastic, was even used to make
jewellery for Queen Mary of England! First milk was converted into curds, which were hardened on soaking in a
solution of methanal in water. This activity explores making curds from cow’s milk. Milk contains a family of
proteins called casein - proteins, are comprised of long chains of amino acids that are linked together by amide
bonds, called peptide bonds. Casein makes up around 80% of the proteins found in cow milk.
0:52Skip to 0 minutes and 52 secondsThese proteins group together to form sphere-like structures called casein
micelles, which form a suspension in milk. These micelles consist of casein molecules, together with ions
including calcium, and they have negatively charged groups on the outer surface. On addition of ethanoic acid,
or vinegar, the negatively charged groups in the casein micelles are protonated. This causes them to come
apart and the proteins forming the micelle are no longer soluble and they form a precipitate of small white blobs
- as the proteins clump together into a mass called curd. This process occurs naturally when milk sours. So,
this activity involves adding vinegar to hot cow milk, and stirring it, to make curds.
1:35Skip to 1 minute and 35 secondsCollect and dry the curds, and thoroughly knead it, like dough, to make a
shape, or put it in a mould. You can colour it by mixing it with a food colouring, before letting it dry for at least
24 hours to form a hard object of your choice, which should be related to chemistry. Alternatively, when dry,
you can it colour and decorate it using marker pens. You might like to try other common household acids, such
as lemon juice - does this work as well as vinegar? What about adding the vinegar to hot milk at different
temperatures? Use a thermometer to record the temperature and find out what is the best temperature for
forming the maximum amount of curds.
2:12Skip to 2 minutes and 12 secondsAlso, what about using other types of milk, such as skimmed milk? Take a
picture of your chemistry-related object and post your results - we look forward to seeing your findings, from
this ‘hard’ experiment.

We are going to make a natural plastic using proteins. Casein is a mixture of proteins found in cow’s
milk which can be extracted through the following method and then moulded into whatever shape you
want.

The following ingredients will be required:

• Fresh cow’s milk
• 1-5% strength vinegar
• A variety of food colourings

The following items will be required:

• A measuring cup
• A measuring spoon or tablespoon
• A selection of pans for heating
• A stirring spoon
• A strainer or sieve
• A roll of paper towels
• A selection of ice cube or cookie trays and moulds

Ensure that you read through all of the instructions below before beginning the experiment so that you
understand exactly what will happen at each step.

Step 1: Measuring and heating

Measure out approximately 1 cup (236 ml) of milk and pour into a saucepan. Heat until the milk becomes
warm. However, do not heat excessively as the milk should not be left to boil.
Step 2: Addition of vinegar and food colouring
Measure out one tablespoon of vinegar. Add the vinegar to the warm milk and stir until the milk cools. At this
point you can add some food colouring of your choice in order to add some colour to your protein moulds. Here
we used green and red food colouring as well as doubling the volume of both milk and vinegar used, in order to
process a larger batch of casein.

Step 3: Collection of precipitate

Once the milk has cooled some casein should have precipitated out of the solution. (The acid protonates the
negatively-charged casein micelles in milk and the neutral protein precipitates - even acidic drinks like Red
Bull or Coca Cola can be used.) Pour the milk through the strainer and collect any solid product. Dispose of any
remaining milk down the sink.

The solid product is known as casein and contains a variety of proteins. Transfer the solid product to a piece of
paper towel and fold the towel onto the casein in order to dry the product.

Continue transferring the casein to fresh paper towels until most of the water has been removed.

Step 4: Moulding
Take the resulting casein and press the solid into any shape you want. Securing the casein into a mould or ice
cube tray allows specific shapes to be made. A more detailed product can be achieved by slowly layering
casein into the mould. Push down firmly in order to compact the solid each time.

Once placed into an appropriate mould the casein should be left to continue to dry. Warm areas between 30-40
°C, such as above radiators or in greenhouses, are ideal for storing the mould.

The final product should be cast into a shape based on the mould into which it was placed. The solid is hard
but sometimes brittle and so should be handled relatively carefully. Casein is non-toxic, however, we would not
recommend consuming the results of the experiment.

Although the solid result may be ready after a few hours, leaving the casein in a mould for up to four days will
result in the driest and strongest structure. Here we see shapes less than a day after being made. Although
they are solid they are still “moist” and easily develop fractures as they have not fully dried.

After being left for over a week the shapes become very hard but also experience a slight shrinking in size. Be
sure to account for this by using larger moulds if you want plastic objects of a specific size.
When you are done we would love to see your results! Upload a picture of your creation on
our open Padlet (we have included some examples from a previous course that we hope will
help inspire you) and/or on Twitter or Instagram hashtag #FLchemistry.

Safety

 Take care when warming milk – warm milk can cause scalds. Take care when separating
protein solid from warm milk and pour all warm milk down the sink once it is separated from
the protein.
 Avoid ingesting casein. It is strongly recommended that you do not consume any of the
casein that you extract. Dispose of any casein in a food or general waste bin after use.

Biodegradable
Casein is a biopolymer. That is, it is a polymer produced by living organisms and it is biodegradable.
Biopolymers are capable of being degraded under atmospheric conditions by, for example, hydrolysis of ester
or amide bonds by bacteria or other living organisms (i.e. the reverse of the condensation polymerisation
process in which they were formed). The end products are water, carbon dioxide, and biomass (plant or animal
material used for energy production). Biodegradable polymers can be either natural or synthetic.

Polysaccharides, such as starch and cellulose (40% of all organic matter is cellulose), represent the most
characteristic family of natural biodegradable polymers. Glucose units in starch and cellulose are held together
by acetal linkages (RO-CH(R)-OR), called glycosidic bonds. Cellulase enzymes found in fungi and bacteria can
catalyse the hydrolysis of the glycosidic bonds to break down the polymer, ultimately, into glucose units. (In the
laboratory, to speed up the hydrolysis reaction of polysaccharides with water, the reaction is heated with an
acid or base catalyst. This process is used in the food industry to peel, for example, vegetables such as
tomatoes. Heating vegetables with a sodium hydroxide solution dissolves the cell walls and weakens the
polysaccharide (cellulose and pectin) network in the skins.)

In contrast, a polymer like poly(ethene) is typically classed as not biodegradable. There is nothing in the natural
environment that will easily break down this polymer and so it persists for many years (conventional
poly(ethene) bags were found to be intact after three years buried in soil or submerged in the sea). Eventually,
poly(ethene) will be broken down by, for example, the action of sunlight, heat and moisture. The long lifetime is
because poly(ethene) is a long chain alkane, [–CH2–CH2–CH2–CH2–]n. Alkanes are unreactive compounds
because they contain strong, non-polar C–H and C–C bonds.
Biodegradable or compostable?

As consumer demand for sustainable products grows, you may well have seen an increased use
in the terms ‘biodegradable’ and ‘compostable’ in marketing products. These terms are often
used interchangeably, which is unfortunate as they don’t mean the same thing. For biodegradable
polymers it is important to note that the length of the biodegradation process depends on
environmental parameters such as humidity and temperature. So, claiming that a material is
biodegradable without any further context (i.e., in what timeframe and under what environmental
conditions) is misleading to consumers. Reputable companies will often make more specific
claims, primarily certifying that their biopolymers are compostable. Compostable polymers are a
subset of biodegradable polymers, defined by the standard conditions and timeframe under which
they will biodegrade. For example, one biodegradable polymer that is compostable is polylactide
(PLA), [–CH(CH3)–CO2–]n, which is used to make food packaging. This polymer is certified to
European Standard EN13432, which means it must break down under industrial composting
conditions in less than 12 weeks.

Instructions (1).pdf
Banned drugs in sport
0:06Skip to 0 minutes and 6 secondsThe use of chemistry in sport is most controversial when it comes to
performance-enhancing drugs. Perceived benefits to athletes who use these drugs include an increase in
strength, endurance, aggressiveness and enhanced concentration. Prohibited substances can therefore give
athletes an unfair competitive advantage, or harm their health, and their use is contrary to the spirit of sport.
Banned drugs in sport include stimulants, diuretics and most famously of all, anabolic steroids. The use of
banned drugs affects nearly all sports and to help catch cheating athletes, random drug tests have proved to
be a useful weapon. Classes of banned drugs in sport include stimulants, diuretics and most famously of all,
anabolic steroids.
0:55Skip to 0 minutes and 55 secondsBack in 1988, Canadian sprinter Ben Johnson was dethroned after
breaking the 100 metres world record because the anabolic steroid stanozolol was found in his urine. Athletes
have taken anabolic steroids in particular, because they work for a long time in the body. More recently, the
steroids THG (tetrahydrogestrinone) and DMT (desoxymethyltestosterone) have hit the headlines. Subtle
structural differences can have important biological effects. For example, in THG, having an ethyl group, rather
than methyl group at position 17, allows it to pass through the liver and into the bloodstream without being
deactivated, so it can be administered orally.
1:38Skip to 1 minute and 38 secondsThey were the first ‘designer steroids’ to be marketed as performance-
enhancing drugs to both athletes and bodybuilders - they have a similar impact to testosterone, increasing
strength, muscle bulk and stamina - and were designed, synthesized, and distributed only to beat the standard
drug testing methods. These counterfeit steroids were identified by isolation, their structures were determined
using analytical methods, and finally, authentic compounds were prepared in the lab and compared to the
counterfeit steroid. To detect the presence of banned drugs in an athlete’s blood or urine, gas chromatography-
mass spectrometry is often used. In the GC-mass spectrum spectrum of DMT particularly prominent and
characteristic peaks at m/z 143 and 130 are found, which allows its identification.
2:30Skip to 2 minutes and 30 secondsHowever, this method cannot be used to identify THG, as this compound
decomposes on heating in the GC-MS spectrometer, and it remained undetected by sport doping control urine
tests for several years, until a specific method was established in 2003. Natural human proteins are another
class of high-profile banned drugs - for example, EPO (erythropoietin) stimulates the body to make more red
blood cells, which carry oxygen. EPO is made of 165 amino acids and four carbohydrate groups (or sugars).
Athletes who use it get an endurance boost, which makes it popular in sports like cycling, cross-country skiing,
and distance running. Alternatively, HGH (human growth hormone), composed of 191 amino acids, help
athletes build muscle and bone, adding strength and power.
3:28Skip to 3 minutes and 28 secondsAs these proteins occur naturally, their detection is a challenge and relies
on techniques that tell the difference between the natural and artificially introduced versions - for example, the
Lasne test exploits subtle differences in the carbohydrate groups present within human EPO and the banned
EPO protein, which is made from hamster cells. Stimulants act on the central nervous system to speed up
parts of the brain and body - adrenaline or epinephrine is an example of a naturally occurring stimulant in the
body. Some athletes may use stimulants, like adrenaline, to help increase alertness, reduce tiredness, lose
weight, and also increase their competitiveness and aggressiveness.
4:14Skip to 4 minutes and 14 secondsFamously, in the 1994 football World Cup, Diego Maradona, was banned
from playing because he tested positive for ephedrine, which has a very similar structure to adrenaline.
Diuretics, sometimes called water pills, increase the rate of production of urine, which may dilute and mask the
presence of a banned substance in the urine. Diuretics, including furosemide, are called ‘masking agents’ as
these compounds are taken with the purpose of hiding or masking the presence of specific illegal drugs that
are screened for doping testing. As they cause dehydration, they can help athletes to lose weight rapidly.

Using drugs to cheat in sport is not new, but it is becoming more effective. Despite the health risks,
and despite the regulating bodies’ attempts to eliminate drugs from sport, the use of illegal substances
is still occurring. So is cheating here to stay? Drugs are against the rules, but we define the rules of
sport – if we made drugs legal and freely available, there would be no cheating.

Arguments for legalising performance-enhancing drugs include audiences being able to see the best
performances possible – as athletes approach the limit of what can be achieved, further improvements require
performance-enhancers. Clothing and equipment are being specially designed for athletes, and some argue
that there should be no distinction between the equipment and an athlete’s body. Others argue that drug
testing does not work - most athletes are relatively unlikely to ever undergo testing and so it does not always
catch the guilty (fewer than 2% give a positive result).

Arguments against legalising performance-enhancing drugs mention the health risk to athletes, that allowing
drugs promotes unhealthy behaviour and that athlete safety must be our prime concern. Some say that taking
part is what counts, not the winning, and that drugs are against the spirit of sport, that celebrates fair play and
honesty. Presumably this would then lead on to drug advertising and sponsorship?

So, what do you think - should performance-enhancing drugs be accepted in sports?

Analysing the evidence

We have seen the importance of using mass spectrometry to analyse organic compounds, including identifying
banned drugs, so why not have a go at analysing mass spectra in the extension activity in the downloads
section below. A bit like Sherlock Holmes (the fictional private detective), you will be identifying ‘clues’ in the
spectra to identify the ‘culprit’ (the organic compound).

Also, take a look at this short clip about the research interests of one of my York colleagues, Professor Jane
Thomas-Oates, which shows some of the specialist kit and equipment in modern biological mass spectrometry.

https://youtu.be/hg7r4wTueKs

massspectrometryexercise.pdf
End of week summary

Whether it is a carbon fibre vaulting pole, javelins with spiral tails, golf balls with special
dimple patterns, stiffer carbon fibre tennis rackets, or bicycles with new types of wheels,
chemistry plays a major part in the race to go “further and faster”.

In 2009, a study found that while better equipment had allowed 100 metre runners to go just 4 per
cent faster, both pole vault and javelin performance had improved by about 30 per cent – indeed,
javelins had to be redesigned to reduce performance (in the 1980s they were being thrown so far
that authorities feared for public safety). In cycling, research has shown that moving from a
traditional wool jersey (which takes up liquid and gets heavy and sticky) to a full-body Lycra
skinsuit gives at least a minute advantage over a 40 km (24.9 miles) distance – so, a significantly
reduced time in a long-distance race like the Tour de France.
Also, data on an athlete’s movement style, vital signs, psyche, fitness level, diet, sleep and
previous injuries are collated to produce individual risk profiles which helps reduce the risk of
injuries. Even when an injury occurs new chemical therapies accelerate the healing process.

Interestingly, research has shown that, in the absence of injury, athletes across a variety of sports –
including football (soccer), American football and hockey – have healthier brains than non-athletes.

So, how did you find the final week? Is there anything that remains unclear?
Over the week, was there any course content that really surprised you? Perhaps being able to
make casein plastic from just milk and vinegar, or the wide range of polymeric materials used in
sports equipment?

What is your highlight of the week?

In Europe around 40% of people claim to practice a sport on a regular basis, with running and
cycling at the top of the list. An active and healthy life is increasingly valued in our society, and so
there is a continuing need to develop even more sophisticated sports equipment. For example,
perhaps cycling could see the advent of spray-on clothing that keeps riders dry and safe, but also
light, as well as sensors to monitor a rider’s physiological changes and “phase-change” tyres that
vary their tread depending on the terrain? There are certainly some promising developments in
new sports materials, such as a multi-layered elastic material called C3, that are being optimised to
protect against a range of different types of impacts. (Also, for the armchair ‘sports’ fans, look out
for those polycarbonate Fidget Spinners that have proved to be such a popular toy.) Further ‘hard’
research will no doubt follow!

So, in sport, what future chemical innovations would you most like to see?

Everyday Chemistry Collage – Get Involved!

Why not contribute to our course collage! Take a photo of the ingredients on the
container/packet of a product at home, which is related to sports, such as a sports drink, an
energy bar or your preferred locker room shampoo or deodorant – alternatively, what about a label
on your favourite sports clothing or footwear. Upload your photo on our open Padlet (we have
included examples from a previous course to help inspire you) and/or
on Twitter or Instagram hashtag #FLchemistry. (See the downloads section below for the course
collages from previous years – can we have a more diverse array this year?) Please include the
name of the product, the country where it was bought, and your initials. We will then collate them
to make a unique eeDc course collage with contributions from (hopefully) all of our learners! A
nice end-of-course keepsake.

Do you spot any of these ingredients?

Benzophenone-4 (Sulisobenzone) (C14H12O6S): A sunscreen that protects the skin from the harmful
effects of the sun. It is used to protect cosmetics and personal care products from deterioration by
absorbing, reflecting, or scattering UV rays.
Benzyl salicylate (C14H12O3): A natural fragrance ingredient and ultraviolet light absorber.
Butane and isobutane (C4H10): These gasses are used as propellants in aerosol deodorants.
C.I. Disperse Red 356 (C26H20O5): A bright dye that was developed by ICI and introduced in 1975
for the dyeing of polyester.
Elastane: Another name for spandex or lycra (a polyether-polyurea copolymer), known for its
exceptional elasticity (an elastane fibre can be stretched up to almost 5 times its original length!).
Since it is lightweight and does not restrict movement, it is most often used in athletic wear. This
includes such garments as swimsuits, bicycle shorts, and exercise wear. It is not damaged by
sunlight, sweat or detergents, all of which can make other materials wear out.
Phenoxyethanol (C8H10O2): A preservative that prevents the growth of bacteria and enhances
shelf-life of personal care products. This alcohol is a solvent found in over 80% of ballpoint pen
formulations and it is also used in insect repellent, antiseptics and fish sedatives!
Steareth-2 (C22H46O3): A waxy substance (comprising polyethylene glycol ethers of stearic acid)
that acts as an emulsifier. If an ingredient like Steareth-2 were not added to some personal care
products, the ingredients would separate like some salad dressings.
Sucralose (Splenda) (C12H19Cl3O8): An artificial sweetener found in energy bars, which has the E
number E955. Sucralose has a sweetness potency of about 600 times that of sucrose, so very
small amounts of it can be used to sweeten foods and beverages. Unlike sucrose, sucralose is not
digested or metabolised for energy, therefore, no calories are obtained from sucralose, and it does
not affect blood glucose levels.
Whitening agent: Cotton fabrics for clothing normally contain natural yellow/brown tones. To mask
these tones, a whitening agent is used. These are organic compounds, such as disodium
distyrylbiphenyl disulfonate (C28H20Na2O6S2), which absorb invisible UV light in ambient lighting and
emit visible blue light. The emitted blue light combines with the yellow/brown tones in the cotton to
produce white light, so making the fabric appear whiter.

mooc_collage.pdf

eeDC_Collage_Draft_1.pdf

Ingredients_lists.pdf
End of course summary

Week_1_summary.pdf

Week_2_summary.pdf

Week_3_summary.pdf

Week_4_summary.pdf