24 r o a s t May | June 2014 25

Making a Case for

Chlorogenic Acid
by R. Luke Harris and Christian Axen
C
afeine is bitter. Yet the vast
majority of cofee fanatics and
professionals would be loath
to deny themselves the cafeine buzz that
is, arguably, the only reason cofee was
popularized by Kaldi and his goats in the
frst place.
In other words, we accept the bitterness of
cafeine in our cofee because it presents us
with something stimulating. But cafeine
is not the only biologically active bittering
agent present in the delightful elixir that is
your passion and your livelihood.
Bitter
End
the
continued on page 26
26 r o a s t May | June 2014 27
continued on page 28
In their paper, Correlation Between Cup Quality and Chemical
Attributes of Brazilian Cofee, published in the scientifc journal Food
Chemistry, Adriana Farah and colleagues present their analytical
chemistry investigation of the Rio of-favor. According to Farah,
the unpleasantness of Rio-like cofee is usually described as a
pungent, medicinal, phenolic or iodine-like favor associated with
a musty, cellar-like odor, which at its extreme, is characterized as
anintolerable taste and smell. Farah and colleagues data show
that with increasing abundance of chlorogenic acidsor CGAsin
light and mediumroast cofee, the cup quality decreases markedly,
including a much more prominent Rio of-favor. Higher cafeine
levels were also associated with lower cup quality, but these negative
favor associations of cafeine were only observed in mediumroast
cofee, not in light roast, and to a lesser extent than for CGAs.
For better or for worse, the role of CGAs and cafeine in cofee
favor is unavoidable. As roasters already know, it is possible to
infuence the amounts of these compounds in the cup because levels
of such chemicals decline with longer heat application for darker
roasts. But there are so many other aspects of cofee favor and
aromasweetness and sourness to name only twoso isolating these
two compounds and attributing favor characteristics to themis an
oversimplifcation. That said, when it comes to cafeine and CGAs, is
bitter better?
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
CGAs, Caeine and Oxidative
Stress in Plants and Animals
Dr. Terry Graham, a professor of human health and
nutritional sciences at the University of Guelph in
Ontario, Canada, spoke with us about the biological
importance of cafeine and CGAs in the human diet.
Dr. Grahams message is that chronic cofee intake
over a lifespan has largely benefcial efects for human
health. Most scientists attribute these positive efects to
antioxidant content of cofee, and one particular group
are the derivatives of chlorogenic acid, he says. What is
the basis for this antioxidant beneft of CGAs?
Oxidative stress is a chemical process that
occurs in plants and animals, promoting damage
to key biochemical constituents of cells and tissues,
including DNA. Damaged DNA speeds up aging and
can lead to mutations. In cofee trees and other plants,
environmental stressors, such as excess direct exposure
to sun or extreme cold, impair the plants metabolic
functions, resulting in oxidative stress. CGAs are a major
28 r o a s t May | June 2014 29
continued on page 30
component of plant antioxidant defenses,
which protect themagainst the resulting
biochemical damage. Many plants produce
CGAs and related chemicals for this reason, but
green cofee beans contain more CGAs than any
other edible plant product, except perhaps for
the leaves of Ilex paraguariensis, fromwhich mat
teas are made.
In 2010, Ana Fortunato and colleagues
at the University of Alberta with the
phrase, Cafeine bad, cofee good,
implying that CGAs are primarily
responsible for counteracting the
negative efects of cafeine in human
health. Seven years later, we asked him
if he would still say the same thing.
Cafeine pushes the metabolismtoward
a Type 2 diabetic state for hours, says
Graham. With this negative efect in
mind, he says, With regards to cafeine,
I would now have to modify this a
little and say, Cafeine mainly bad.
However, There are likely some positive
neural health efects [of cafeine]. Dr.
Grahamrefers to evidence that chronic
cafeine consumption may have positive
health efects on some aspects of brain
function, such as memory and aging.
With cofee, I would now say
damn good, as there is strong evidence
for not only reduced risk for Type 2
diabetes, but also some cancers and
neurological conditions. Actually,
the story with Type 2 diabetes is not
so straightforward. Says Graham, It
is impossible to compare cafeine and
cafeinated cofee. Cafeine is obviously
biologically active, but cofee contains
many other bioactive substances. Just as
these thousands of bioactive substances
complicate cofee favor and aroma, they
afect its physiological efects, too.
A clear example of how one could
draw the completely incorrect conclusion
about cofee consumption is that
cafeine leads to insulin resistance,
thereby promoting a diabetic state, and
[the logical] extension of this fnding
to cofee would be that cofee increases
the risk for Type 2 diabetes. However,
many excellent studies demonstrate
the opposite: chronic consumption of
cafeinated cofee decreases the risk for
Type 2 diabetes in a dose-dependent
manner, Dr. Grahamsays.
Dr. Shearer elaborates on this
argument: The more cofee consumed,
the lower the risk [of developing Type
2 diabetes]. This has been shown in
various populations worldwide.
One of the reasons why cafeinated
cofee doesnt pose a serious long-term
risk for developing diabetes and related
trees fromfve cofee varieties, including
catua, which had been grown at a range
of temperatures decreasing from25
degrees C/77 degrees F down to as low as
4 degrees C/39 degrees F. In response to
this cold stress, the catua trees increased
their production of CGAs by around 30
percent, and increased their production
of cafeic acid by around 39 percent. In
general, plants produce considerably
more CGAs when exposed to sun and cold,
with combined exposure to sun and cold
resulting in the most dramatic increases
so shade helps to reduce cold-induced
increases in CGAs.
As mentioned by Dr. Graham, some of
the major efects of CGAs on our bodies are
related to the same antioxidant functions
for which plants produce them. In our
bodies, the parallels to cold and sun
exposure are things such as eating the
wrong foods (think transfats or saturated
fats), smoking cigarettes, sufering
traumatic injury or sufering an infection.
We also experience oxidative stress all of
the time, just by living and breathing, as a
byproduct of natural metabolic processes.
Just like plants, our bodies produce
antioxidant compounds to combat oxidative
stress, thereby slowing our aging and
providing us with some protection against
the efects of our sometimes-lacking diets
and sedentary lifestyles. For even better
protection we have to supplement our own
antioxidant supply through the foods we
consume.
In the average North American diet,
cofee is responsible for 50 to 60 percent
of daily antioxidant consumption, says
Dr. Jane Shearer, an associate professor of
kinesiology and medicine at the University
of Calgary. A cup of blueberries has more
antioxidants than [the same volume
of] cofee. The problemis that most
individuals dont consume enough fruits
and vegetables on a daily basis. On the
other hand, and fortunately for cofee
professionals, individuals readily consume
multiple servings of cofee per day.
The Better of Bitter
Previously, in 2007, Dr. Grahamhad
humorously concluded a visiting lecture
published the most recent report available
about the important antioxidant role of
CGAs in protecting cofee plants fromcold
stress, found in the Journal of Plant Physiology.
In their study, titled Biochemical and Molecular
Characterization of the Antioxidative systemof
Cofea sp. Under Cold Conditions in Genotypes with
ContrastingTolerance, Fortunato and colleagues
analyzed the contents of CGAs in 1.5-year-old
conditions is that CGAs protect us against
the negative efects of cafeine. CGAs
slow the movement of sugars fromour
gut into the blood, and also promote the
uptake of sugar fromthe blood into the
liver, thereby reducing glucose levels in
the blood. The net efect of CGAs, then,
is to counteract the pro-diabetes efects
of cafeine; compare this to non-diet
colas that deliver high levels of glucose and
cafeine simultaneously. Over many years,
daily consumption of colas poses a huge risk
for developing metabolic diseases because
there are no CGAs in cola to blunt the efects
of cafeine. Well take CGAs in our cofee any
day, thank you very much.
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
30 r o a s t May | June 2014 31
Caeine and CGAs in Coee
Brews: Our Experiment
Cafeine and CGAs work alongside each other in our bodies,
sometimes collaborating and sometimes competing.
Their benefts for the cofee trees, their infuence on
cofee favor, and this metabolic dance they performin
the human body got us thinking about how we brew our
cofee.
We performed an experiment to compare the levels of
cafeine and CGAs in cofee brews, prepared using diferent
methods: machine drip, manual pour-over and press pot.
Previous studies have already quantifed the concentrations
of cafeine and CGAs in cofee. However, they have mostly
focused on the total amount of cafeine and CGAs found
in cofee beans, and the extractions have been performed
using conditions that do not yield drinkable cofee, such
as organic extraction with methanol, the use of very high
cofee-to-water ratios, and dwell times of up to a few hours
in duration. Our goal was to measure these compounds in
cofees that had been freshly roasted, ground and brewed
with human consumption in mind.
continued on page 32
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
photo by Mark Shimahara
Method
CGA
mg/mL
Cafeine
mg/mL
CGA per
240-mL cup
Cafeine per
240-mL cup
Technivorm 0.773 0.522 185.5 125.3
Technivorm 0.890 0.518 213.7 124.2
Technivorm 0.604 0.512 145.0 122.9
Technivorm 0.588 0.479 141.0 115.0
Technivorm 0.427 0.463 102.5 111.2
Pour-over 0.400 0.444 96.1 106.5
Pour-over 0.399 0.449 95.8 107.9
Pour-over 0.483 0.442 115.8 106.1
Pour-over 0.508 0.462 122.0 110.8
Pour-over 0.449 0.441 107.7 105.9
Press Pot 0.458 0.489 109.9 117.4
Press Pot 0.449 0.428 107.8 102.6
Press Pot 0.441 0.421 105.8 101.0
Press Pot 0.422 0.416 101.2 99.8
Press Pot 0.366 0.372 87.9 89.2
AVERAGE 0.510 0.457 122.5 109.7
Standard
Deviation
0.15 0.04 35 10
Table 1.
Chlorogenic
acid (CGA) and
caeine contents
in freshly
roasted coee
brews prepared
using machine
drip, pour-over
and press pot
methods.
32 r o a s t May | June 2014 33
We performed our experiment
onsite at the Prince George campus
of the University of Northern British
Columbia (UNBC). Cofee (Ethiopia wet
process Guji Oromo) was purchased
green fromSweet Marias in Oakland,
Calif., and roasted within two months
of receipt. Specifcally, we used a
Behmor 1600 counter-top roaster
on a P4D programwith appropriate
adjustments, 1/4-, 1/2- or 1-pound.
Green cofee batches were roasted to a
city level, with the cooling cycle started
at the end of frst crack.
First crack start and end times
were consistent within a few seconds
across batches of the same size. Cofee
samples were brewed in 650-mL
volumes according to SCAA standards
using a cofee-to-water ratio of 0.068,
with freshly ground cofee that had
been roasted one to two days before
brewing.
Using a TechnivormMoccamaster
for machine drip, a Hario V60 Buono
kettle for pour-over, or a stainless
steel Frieling press pot, each brew was
prepared with a four-minute extraction
in fltered and freshly boiled water at
90.595.6 degrees C/195204 degrees
F. Once brewed, the samples were
cooled immediately in an ice bath, and
then 3 mL of each brew sample was
transferred to a separate plastic tube.
We drank the rest.
Our analytical chemistry methods
were a modifcation of the methods
described previously by Luiz C. Trugo
and Robert Macrae in their paper
Chlorogenic Acid Composition of Instant
Cofees, published in the journal
Analyst (1984), as well as JK Moon
and colleagues in their article Role of
Roasting Conditions in the Level of Chlorogenic
Acid Content in Cofee Beans: Correlation
with Cofee Acidity, published in the
Journal of Agricultural and Food Chemistry
(2009). We carried out a number of
chemical steps to isolate and purify
the CGA and cafeine fromour brew
samples. Alan Esler, the analytical
chemistry support specialist in UNBCs
continued on page 34
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
Figure 1a.
CGA Concentrations Classied by
Brew Method (mg per 8-ounce cup)
Figure 1b.
Caeine Concentrations Classied by
Brew Method (mg per 8-ounce cup)
34 r o a s t May | June 2014 35
continued on page 36
central equipment laboratory, then
determined the CGA and cafeine
contents of the samples using an
Agilent Liquid Chromatograph1100
high-performance system. Each
sample was analyzed twice, using
diferent ultraviolet light detection
wavelengths: once to quantify CGA (at
325 nm) and once to quantify cafeine
(at 275 nm). The quantifcations of
CGA and cafeine, respectively, were
performed using the linear regression
equation of the concentration and
peak area of standard CGA and
cafeine solutions prepared using
pure standards of these chemicals
purchased fromSigma-Aldricha
life science and high technology
company. All measurements were
performed in triplicate.
Experimental Data
CGA and cafeine concentrations of
our Technivorm, pour-over and press
pot brews are shown in Table 1 on
page 31. Overall, across all three brew
methods, the CGA concentration in
the brew samples varied from0.366 to
0.733 mg/mL brewed cofee, with an
average of 0.510 mg/mL. The cafeine
concentration in the brew samples
varied over a slightly narrower range,
from0.372 to 0.522 mg/mL of brewed
cofee, with an average of 0.457 mg/
mL. According to Dr. Shearers 2008
work, Cofee, Glucose Homeostasis, and
Insulin Resistance: Physiological Mechanisms
and Mediators, published in the
journal Applied Physiology, Nutrition, and
Metabolism, a standard 8-ounce cup of
cofee (240 mL) contains CGAs in the
range of 88250 mg, and an average of
130 plus or minus 20 mg of cafeine.
Based on the same cofee cup size,
our data is remarkably similar, with
CGAs in a range from87.9 to 213.7 mg
per 8-ounce cup, and cafeine at an
average of 109.7 plus or minus 10 mg
per cup.
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
Figure 2a.
CGA Concentrations Classied by Batch Size
(mg per 8-ounce cup)
Figure 2b.
Caeine Concentrations Classied by Batch Size
(mg per 8-ounce cup)
36 r o a s t May | June 2014 37
Finding Meaning in the Data
We plotted the data found in Table 1 as graphs of CGA or cafeine
contents according to brew method. As shown in Figure 1a and
1b on page 32, it seems that brew method might actually afect
the amount of CGA and cafeine in the cup, with machine drip
resulting in the highest levels of CGA and cafeine, manual pour-
over resulting in intermediate levels, and press pot resulting in
the lowest levels.
continued on page 38
THE BITTER END | Making a Case for Chlorogenic Acid (continued)
Even though our data are remarkably close to that reported
by Dr. Shearer, we were curious as to why our values were so
variable despite our eforts to achieve consistency across roasts,
brews and HPLC analyses. Cafeine exhibited a relatively tighter
range of values, regardless of brew method, which might mean
that cafeine content is more dependent on the cofee beans
themselves, rather than the roast or brew method. With CGAs,
on the other hand, the efect of roasting on variations in CGA
levels is well established in the scientifc literature, with longer
heat application times leading to the breakdown of CGAs into
diferent molecular structures.
CGA does not appear to have
one action in the body, but
many. One very surprising role
may be to feed the millions of
bacteria living in our gut.
Dr. Jane Shearer, University of Calgary
photo by Mark Shimahara

www.dailycoffeenews.com
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specialty cofee
professionals.
38 r o a s t May | June 2014 39
Consequently, we thought that perhaps the variation
in CGA content could be due to variations in the roasting
conditions. We plotted the data fromTable 1 again, this time
according to the 1/4-pound, 1/2-pound or 1-pound size of the
roast batch. As seen in Figures 2a and 2b on page 34, as we
expected, cup contents of CGA and cafeine also appear to vary
with roast batch size. Thus, an alternative explanation for the
CGA and cafeine contents we measured is that their levels
decreased with the longer heat application required for larger
batches in the Behmor roaster.
The most direct implication of our experiment for roasters
is that larger batches and longer roast times will probably
result in lower CGA and cafeine contents in brewed cofee.
Of more general interest to cofee professionals, fanatics and
consumers may be the possibility that diferent brew methods
can afect the cup contents of these biologically important
compounds.
The Bitter End
Cofee is a mess of chemicals, and in this sense, it is
probably a bit of a mistake to think too hard about the role of
cafeine and CGAs as bittering agents in our cofee. Rather,
for the fnal word on CGAs and cafeine, lets switch fromthe
mouth to the, um, other end.
Not long ago, a friend contacted one of the authors to ask,
You know about chlorogenic acid, right? I just read that it
induces recto-sigmoid motility. What does that mean? Well,
to put it delicately, recto-sigmoid refers to the end of the
human digestive system, and motility refers to movement, so
CGA is one of the reasons why many cofee drinkers experience
some degree ofshall we sayregularity associated with their
morning cup.
This brings us back to the question of cofee and human
health. On this point, Dr. Shearer also explains that CGAdoes
not appear to have one action in the body, but many. One very
surprising role may be to feed the millions of bacteria living
in our gut. Gut bacteria break down and metabolize many of
the phenolic compounds found in cofee. Having healthy
gut bacteria has been shown to prevent disease and maintain
health.
So, thanks in large part to CGAs, perhaps to cafeine,
cofee is good for you, but most defnitelyto borrow fromDr.
Grahambecause it tastes so damn good.
R. LUKE HARRISis an assistant professor at the School of Health
Sciences and an adjunct professor in the Northern Medical Programat the
University of Northern British Columbia. He can be reached via e-mail at
cafe.luke@gmail.com.
CHRISTIAN AXEN is an analytical chemist in Calgary with a
Bachelor of Science in chemistry fromthe University of Northern British
Columbia. He can be reached at chris.axen@gmail.com.
THE BITTER END | Making a Case for Chlorogenic Acid (continued)