CHEMISTRY IN EVERY CUP

Autor: Emma Davies

Coffee has a conflicting reputation - is it a guilty pleasure or a lifesaving elixir?

It is hard to avoid stories about the latest must-eat food to join the anticancer brigade. First it
was select vegetables and berries, then red wine, dark chocolate and coffee. Newspapers
frequently tell us that antioxidants ’fight (nasty) free radicals’, and the words ’polyphenol
antioxidants’ have entered the mainstream. Swiss food giant Nestlé even sells a coffee called
Nescafé Green, advertised as containing ’high levels of naturally occurring polyphenol
antioxidants which can help protect the body’s cells from day to day damage’. The coffee
contains unroasted (green) coffee beans in a bid to boost antioxidant levels.

Coffee is indeed one of the richest sources of phenolics in the western diet and can potentially
pack a strong antioxidant punch, in theory protecting cells if the body’s natural mechanisms fail
to keep levels of reactive oxygen species under control. Yet the story is far more complex than a
simple battle between antioxidants and free radicals. All of the antioxidant-rich products, from
red wine to coffee, have far subtler modes of action than previously thought, says Alan Crozier, a
plant biochemist at the University of Glasgow, UK.

KILL OR CURE?

We are used to thinking that coffee must be bad for us - a guilty pleasure - and many try their
utmost to kick the habit. Yet some epidemiological studies, which involve questioning people
about daily coffee intake and following their health over a period of years, suggest that regular
coffee drinkers are less likely to get various cancers, including liver, colon, oral and
oesophageal. In 2008, a team of researchers from Harvard Medical School in Cambridge, US,
and the University of Madrid, Spain, led by Esther Lopez Garcia, assessed data from two major
US epidemiological studies following more than 125 000 people over two decades. They
concluded that regular coffee consumption was ’not associated with an increased mortality
rate’. In fact, taking into account risk factors such as body size, smoking and specific diseases,
the team suggested that people who drank more coffee were actually less likely to die within the
decades of the study because of a lower risk of cardiovascular disease.

Coffee has been suggested to help protect against gout (by lowering uric acid levels), tooth
decay and gallstones. And so the list goes on. In particular, there is mounting and strong
evidence for coffee providing some protection against type 2 diabetes.

ACID HOUSE

Coffee contains a tremendous number of chemicals, with over 1000 aroma compounds. If you
are looking for antioxidants, the most abundant phenolic compounds in coffee are chlorogenic
acids (CGAs), which account for up to 12 per cent of the dry weight of green unroasted coffee
beans. Much of coffee’s bitter taste comes from CGAs, which also cause the acid reflux that is
sometimes experienced by coffee drinkers.

CGAs form in the coffee plant by esterification of trans-cinnamic acids (mainly caffeic, ferulic
and p-coumaric acids) with hydroxyl groups on quinic acid. The resulting conjugated CGA
structures are known as caffeoylquinic acids, feruloylquinic acids and p-coumaroylquinic acids
respectively.
Up to half of the CGAs in green coffee beans degrade during high-temperature roasting, which
causes a host of chemical reactions. Some of the CGAs hydrolyse to form free phenolic acids or
dehydrate to bitter-tasting chlorogenic acid lactones. Others are involved in Maillard browning
reactions to give a wide range of compounds including brown coloured and very bitter-tasting
antioxidant polymers called melanoidins.

The concentration of CGAs in a cup of brewed coffee varies hugely, from about 20-675mg per
cup - compared with 20-60mg in an average cup of tea. CGA levels not only depend on roasting
time and temperature, but also on the coffee beans - Arabica beans have lower levels of CGAs
than Robusta - and the brewing method. Decaffeinated coffee contains similar levels of
phenolics to caffeinated coffee, and can contain higher levels, thanks to a concentration effect
that occurs during decaffeination, says Yi-Fang Chu, who leads the coffee and wellness
research group in the US at Kraft Foods Global.

DIGESTIVE JUICES

Crozier’s coffee work was originally sponsored by Nestlé, whose chemists synthesised CGA
metabolites to help understand the reaction and degradation pathways in the body. The theory is
that quinic acid cleaves from the CGA in the small intestine to release caffeic and ferulic acids,
which go on to form glucuronides and are also metabolised to sulfates. ’We know from analysing
the ileal fluid that a mixture of the parent compounds and some of the metabolites pass from
the small to the large intestine,’ explains Crozier. ’In the colon, some are absorbed as parent
compounds, together with sulfates and glucuronides, but most are chopped up by colonic
bacteria to form simple phenolic acids.’

The ferulic and caffeic acids form phenolic acids such as dihydroferulic acid or dihydrocaffeic
acid. ’People are starting to get interested in the impact of these things on colonic health,’ says
Crozier. There are some suggestions that the compounds could act as prebiotics, stimulating
the gut bacteria.

There is growing evidence that compounds broken down in the colon form a key part of the
’bioavailability equation’ of flavonoids and related compounds that not only occur in coffee, but
also in vegetables and other beverages, says Crozier. What is more, the colon-derived phenolic
acids appear to have in vitro anti-inflammatory activity, and to protect human nerve cells against
oxidative damage, says Crozier. Some of the phenolic acids are also thought to be involved in
helping to prevent regular coffee drinkers from developing type two diabetes.

BLOOD SUGAR

Kraft’s Chu is greatly interested in exactly how coffee could help prevent diabetes. In his in vitro
experiments on human fat cells, coffee doubled the levels of glucose uptake. In the body, such
an increase in uptake would lower glucose levels in the blood. But it is not yet clear which coffee
compounds induce cells to take up more glucose. Chu has ruled out caffeine, which had no
effect on fat cells when applied alone, and CGA concentrations do not seem to correlate with
levels of cell stimulation. Identifying which compounds stimulate the glucose uptake and
determining whether the effect is related to their ability to bind to insulin receptors is of
’significant nutritional and pharmacological importance’, says Chu.

Chu has tested the ability of coffee to protect neurons, at least in vitro, and found that treatment
with either green or roasted coffees protects cells against oxidative stress induced by hydrogen
peroxide. The roasted coffee was far better at protecting cells than green coffee, perhaps
because it has 30 times more lipophilic antioxidant activity. Chu’s team, which included
researchers from National Yang-Ming University in Taiwan, suggests that lipophilic antioxidants
such as chlorogenic acid lactones are key to coffee’s apparent neuroprotective effects, possibly
because the brain is such a lipid-rich organ. Chu stresses that more work is now needed to
identify ’key neuroprotective coffee bioactives’.

Chu’s team has also studied coffee’s anti-inflammatory effect on cells in the lab. The main
putative anti-inflammatory components are chlorogenic acids, he says. Yet in experiments with
pure CGA, Chu was unable to achieve the same results as with coffee. ’The pure compound
does not have the same level of inflammatory inhibition as whole coffee, so we propose that
there is a matrix effect whereby components of coffee work together to provide benefits,’ says
Chu.

CAFFEINE IN THE BLOODSTREAM

Caffeine is known to improve memory and the speed with which our brains process information.
It binds to some of the same receptors as adenosine, a compound that promotes sleep,
amongst other things. Caffeine is a non-selective antagonist at A1 and A2A adenosine receptors in
the heart and the brain, having an opposite effect to adenosine and producing a stimulant
effect.

There is also a suggestion that caffeine can perhaps benefit those suffering from Alzheimer’s
disease. The theory is that blocking the A2A receptors weakens the damage caused by beta-
amyloid, the peptide that accumulates in the brain with Alzheimer’s. Giving caffeine to mice
engineered to have the disease limited their levels of beta-amyloid and increased adenosine
levels.4 Human studies have not brought out strong links between caffeine and Alzheimer’s
although analysis of Finnish data on 1409 people over 21 years led by Marjo Eskelinen at the
University of Kuopio, Finland, suggested that people who drank 3-5 cups of coffee per day had a
greatly reduced risk of developing Alzheimer’s or dementia.

The Finnish study was by no means the only one to suggest that caffeine may help to stop a
decline in brain activity with old age. In the Three City study, carried out in the French cities of
Bordeaux, Dijon, and Montpellier between 1999 and 2001, over 9000 people aged over 65 were
questioned about their levels of tea and coffee consumption and their mental agility assessed
using standard tests. When a team of French researchers led by Karen Ritchie at Montpellier
University analysed the data, it suggested that there was a ’significant relationship’ between
higher caffeine intake in women without dementia and ’lower cognitive decline over time’.
Curiously, no relationship was found between caffeine intake and cognitive decline in men. 6 Not
to worry - a team led by researchers at the National Institute for Public Health and the
Environment in Bilthoven, the Netherlands, suggests that ’consuming coffee reduces cognitive
decline in elderly men’ based on analysis of data from a 10-year study of men from Finland, Italy
and the Netherlands.

CARCINOGENS IN COFFEE

Of course, there are negatives. For example, coffee contains 4-methylimidazole, which the US
National Toxicology Program (NTP) has identified as a carcinogen. The compound is used to
manufacture many products, from dyes to agricultural chemicals and rubber. But it can also
form through the Maillard reaction in foods and drinks, particularly those with a caramel flavour
such as Cola.7 The levels of 4-methylimidazole in cola drinks are similar to those in coffees, says
Takayuki Shibamoto, at the Department of Environmental Toxicology at the University of
California, Davis, US.

’Understanding how the chemical forms in coffee and how to prevent it from forming is not easy,’
says Shibamoto. Nevertheless, he is committed to the task, largely because the compound is
listed by the California Environmental Protection Agency as a ’Proposition 65 carcinogen’ in
California, US. This means that food or drink products known to contain levels of the chemical
exceeding the 16ug per day consumption limit must be labelled as such.

The original NTP study suggested that 4-methylimidazole caused cancer in mice fed up to
1250ppm of the compound for two years, equivalent to up to 170mg/kg of body weight for the
mice. A 60kg person drinking a whole 591ml (20 fl oz) bottle of cola would only ingest 3.3ug/kg of
4-methylimidazole, says Shibamoto, so coffee drinkers would be likely to have even less
exposure.

Then there’s the suspected carcinogen acrylamide (2-propenamide), which is highly water-
soluble and also thought to come from the Maillard reaction. Last March the European
Chemical Agency added acrylamide to its ’list of substances of very high concern’. Acrylamide
formation peaks at some point in the roasting process before decreasing significantly. The
degree of roasting is therefore a key factor in determining acrylamide content, says Rita Alves,
from the University of Porto in Portugal.

Alves and her team have analysed acrylamide levels in espresso coffee and shown that light
roasts contain significantly more acrylamide than dark ones. Bean type also appears to affect
acrylamide levels and Robusta espressos contain almost twice as much acrylamide as
their Arabica counterparts, says Alves. She estimates that what she calls a ’moderate’ espresso
consumer who drinks 3-5 cups per day will probably ingest about 4-6ug of acrylamide per day.

Alves admits that it is nigh on impossible to cut acrylamide levels in coffee without affecting
quality, but suggests opting for higher levels of Arabica beans and a darker roast. A short
espresso rather than a ’lungo’, which takes twice as long to prepare, may also have a lower level
of acrylamide because the chemical has less opportunity to transfer to the drink, she says.

SWINGS AND ROUNDABOUTS

So many chemicals to think about. If you already enjoy drinking coffee, it is nice to think that you
might be doing yourself some good. Do you take milk? Or sugar? If so, you may be changing the
antioxidant chemistry. Crozier has already shown that adding cream to strawberries slows
absorption of antioxidants and studying the effects of additives on the bioavailability of coffee’s
antioxidants is next on the agenda for many coffee chemists.

Whatever the science may be, coffee certainly gets the brain into gear in the morning and gives
much pleasure. Just remember the key word that is never far from a nutritionist’s lips when it
comes to red wine and coffee: moderation.

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Link: https://www.chemistryworld.com/features/chemistry-in-every-cup/3004537.article