Whats a phenolic compound?

A secondary product that contains a phenol group

- a hydroxyl functional group on an aromatic ring.

OH

Phenolics are a chemically diverse group: many

different properties and functions.

Biosynthesis of phenolics

Shikimic acid pathway is most common in plants. Converts simple

carbohydrates into aromatic amino acids. Not present in animals.

Most plant phenolics are derived from cinnamic acid

formed from phenylalanine by phenylalanine ammonia lyase
(PAL) enzyme.
PAL activity is inducible: fungal infection, low nutrient levels, high light

PAL

Major types of phenolics

1. Simple phenolics - e.g. coumarins
2. Lignin - 2nd most abundant compound in plants
3. Flavonoids - two aromatic rings, 2 pathways
anthocyanins, flavones/flavonols
4. Condensed tannins
polymerized flavonoids
5. Hydrolyzable tannins
made of phenolic acids and sugars
smaller molecules than condensed tannins

1. simple phenolics
Fig. 13.10

Involved in
defense against
insect herbivores
and fungi, some may
have allelopathic
function.

Simple phenolics
Caffeic acid
& ferulic acid
implicated in
allelopathy.
Fig. 13.11

Psoralen is one
of several
phototoxic
furanocoumarins,
(UV activated)

Furoanocoumarins can certain light wavelengths.

(common in Umbelliferae family celery,
parsnip)
Leaf rolling insects
Insects usually roll
leaves for protection
from predation and
to create a habitat
Sometimes insects
roll leaves to prevent
furanocourmarins
from being activated

Furanocoumarins can bind to DNA or

react with lipids and proteins

Simple phenolics

Fig. 13.11

2. Lignin
Second most abundant compound in plants.
Highly branched polymer of phenylpropanoid groups
(benzene-C3)

- often found in vessel elements, tracheids, and

stems; confers structural support. Primary
structural
role!
- Secondary role as a herbivore deterrent by
reducing digestibility of plant matter
- also difficult for microbes to degrade; its
presence slows litter decomposition.

3. Flavonoids - basic structure is two aromatic

rings joined by a 3C bridge.
Fig. 13.10

a) anthocyanins
b) flavones
c) flavonols
d) isoflavonoids

Fig. 13.13

Flavonoids
a) Anthocyanidins and
anthocyanins are pigments
that give plant tissues
red, blue, and purple
color.
Pollinator attraction
Disperser attraction

Flavonoids continued
b & c) flavones and flavonols
UV absorbing
protection against UV (280 - 320 nm)
insect pollinator attraction

How we see the golden

eyes

How honeybees see golden eyes

UV absorbing flavonols are present
in the inner part of petals

d) Isoflavonoids
common in legumes
antimicrobial properties
also involved in signalling
e.g. attracting rhizobia

Rhizobium is attracted to
legumes through signaling
by isoflavanoids released
from roots.

Tannins

Condensed
-formed by polymerization of flavonoid units
-common in woody plants
Hydrolyzable
- contain phenolic acids: gallic acid, & simple sugars
- smaller molecules than condensed tannins
- more easily hydrolyzed and degraded
Tannins reduce growth and survival of many different
kinds of herbivores
Also act as antioxidants - eat your isoflavonoids Johnny!

Many foods contains tannins (e.g. tea, red wine)

and have some healthy side effects for humans
(e.g. disallowing constriction of blood vessels)
Tannins also make protein less digestible.
Animals can sense high levels of tannins in their
food and opt for another food resource (e.g.
mule deer, beavers).
High levels of tannins in diet can actually kill some
animals.

Condensed tannins
are polymerized
flavonoids.

Hydrolyzable tannins are made of phenolics and sugars.

Fig. 13.15

The term tannin is derived from the tanning process

in which raw animal hides are preserved by rubbing
tannins on them. The tannins help to complex the
proteins and keep them from degrading.
This protein-binding property of tannins lends them
their toxicity to herbivores.
tannins can bind digestion enzymes in the gut of
herbivores.
tannins also form complex polymers when bound
to proteins which are difficult to digest, thus
decreasing the nutritional value of the plant
material.

Tannins can reduce nutritional value of tissues

by binding to proteins, making them less digestible.

Fig. 13.16

Care for a spot of milk in your tea?

Creosote bush, Larrea tridentata

Leaves are 10-25% phenolic resin.

40% of resin is NDGA (nordihydroguaiaretic acid),
remainder is o-methylated flavones and flavonols.
Deters insect herbivory. Mammalian herbivores
select older leaves (less resin).

QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

Active compounds in creosote leaves.

NDGA and similar compounds.
Amino acids.
Flavonoids.
Volatile oils.
Triterpenes.
Saponins.

QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

USDA formerly used NDGA as an antioxidant to prevent rancidity in food.

Now known to cause liver and kidney disease in lab animals.
Creosote has long been used in traditional Native American and Mexican
herbal medicine

Creosote applications in herbal therapy

To dissolve urinary kidney stones.
Anti inflammatory for respiratory ailments (asthma) and
arthritis
To eliminate gallstones
Against urinary infections
For the treatment of venereal disease
As an abortifacient
Against diabetes
Bronchitis and colds
Rheumatism
Against some types of cancer
As a mouthwash against tooth decay and halitosis

QuickTime and a
TIFF (Uncompressed) decompressor
are needed to see this picture.

After life effects of phenolic compounds.

Plant litter decomposition, and release of nutrients
from decomposing litter, are strongly influenced by
the chemical composition of the litter.
Litter higher in tannins and lignin decomposes more
slowly.
Decomposition
rate

Lignin/Nitrogen ratio

Bill Shakespeare, secondary chemist