The evolution of chemical defenses in plants is linked to the emergence of chemical substances that

are not involved in the essential photosynthetic and metabolic activities. These
substances, secondary metabolites, are organic compounds that are not directly involved in the
normal growth, development or reproduction of organisms,[25] and often produced as by-products
during the synthesis of primary metabolic products.[26] Examples of these byproducts include
phenolics, flavonoids, and tannins.[27] Although these secondary metabolites have been thought to
play a major role in defenses against herbivores,[5][25][28] a meta-analysis of recent relevant studies has
suggested that they have either a more minimal (when compared to other non-secondary
metabolites, such as primary chemistry and physiology) or more complex involvement in
defense.[29] Furthermore, plants can release volatile organic compounds (VOCs) to warn other plants
in the area of stressful conditions. These toxic compounds can be used to deter the herbivore or
even attract the herbivore's predator. Finally, some plants can also produce plant defensive proteins,
which upon ingestion, end up poisoning the herbivore.

Plants can also communicate through the air. Pheromone release and other scents can be detected
by leaves and regulate plant immune response. In other words, plants produce volatile organic
compounds (VOC) to warn other plants of danger and change their behavioral state to better
respond to threats and survival.[30] These warning signals produced by infected neighboring trees
allow the undamaged trees to provocatively activate the necessary defense mechanisms. Within the
plant itself, it transmits warning, nonvolatile signals as well as airborne signals to surrounding
undamaged trees to strengthen their defense/immune system. For instance, poplar and sugar maple
trees demonstrated that they received tannins from nearby damaged trees.[30] In sagebrush,
damaged plants send out airborne compounds, such as methyl jasmonate, to undamaged plants to
increase proteinase inhibitor production and resistance to herbivory.[30] Further observations
illustrated that damaged plants release various VOCs and hormones to receiver plants as a form of
communication for defense and regulating their immune system.

The release of unique VOCs and extrafloral nectar (EFN) allow plants to protect themselves against
herbivores by attracting animals from the third trophic level. For example, caterpillar-damaged plants
guide parasitic wasps to prey on victims through the release of chemical signals.[31]The sources of
these compounds are most likely from glands in the leaves which are ruptured upon the chewing of
an herbivore.[31] The injury by herbivores induces the release of linolenic acid and other enzymatic
reactions in an octadecanoid cascade, leading to the synthesis of jasmonic acid, a hormone which
plays a central role in regulating immune responses. Jasmonic acid induces the release of VOCs
and EFN which attract parasitic wasps and predatory mites to detect and feed on
herbivores.[32] These volatile organic compounds can also be released to other nearby plants to be
prepared for the potential threats. Studies have shown that the volatile compounds emitted by plants
are easy to be detected by third trophic level organisms as these signals are unique to herbivore
damage.[31] An experiment conducted to measure the VOCs from growing plants shows that signals
are released instantaneously upon the herbivory damage and slowly dropped after the damage
stopped. It was also observed that plants release the strongest signals during the time of day which
animals tend to forage.[31]

Since trees are sessile, they've established unique internal defense systems. For instance, when
some trees experience herbivory, they release compounds that make their vegetation less palatable.
The herbivores saliva left on the leaves of the tree sends a chemical signal to the tree's cells. The
tree cells respond by increasing the concentration of salicylic acid (hormone) production.[33] Salicylic
acid is a phytohormone that is one of the essential hormones for regulating plants' immune
systems.[34] This hormone then signals to increase the production of tree chemicals called tannins
within its leaves.[33] Tannins affect palatability and digestibility of vegetation while also increasing the
concentration of growth hormones, encouraging new leaf growth.[33] The increased production of
tannins makes it difficult for deer to digest, which makes the leaves less appealing to eat. The
research experiment done by Bettina Ohse, et al. found that a group of field-grown saplings of
European beech and sycamore maple trees could sense whether it was specifically a deer eating at
its leaves. The scientists realized saliva caused an increase in tannin concentration, due to their
experiment of having broken leaves that contain saliva and ones that do not. The leaves that
contained the deer saliva showed an increase in tannin and experienced an increase in the growth
of the leaves of the tree, but the leaves without the deer saliva did not experience these
changes.[33] The increase in tannin concentration is one internal mechanism that trees use to combat
mobile predators, like deer. This tannin increase is done by the trees' immune system and is a key
defense strategy used by plants of all kinds.

Qualitative and quantitative metabolites[edit]

Secondary metabolites are often characterized as either qualitative or quantitative. Qualitative
metabolites are defined as toxins that interfere with a herbivore's metabolism, often by blocking
specific biochemical reactions. Qualitative chemicals are present in plants in relatively low
concentrations (often less than 2% dry weight), and are not dosage dependent.[citation needed] They are
usually small, water-soluble molecules, and therefore can be rapidly synthesized, transported and
stored with relatively little energy cost to the plant. Qualitative allelochemicals are usually effective
against non-adapted generalist herbivores.

Quantitative chemicals are those that are present in high concentration in plants (5 – 40% dry
weight) and are equally effective against all specialists and generalist herbivores. Most quantitative
metabolites are digestibility reducers that make plant cell walls indigestible to animals. The effects of
quantitative metabolites are dosage dependent and the higher these chemicals' proportion in the
herbivore's diet, the less nutrition the herbivore can gain from ingesting plant tissues. Because they
are typically large molecules, these defenses are energetically expensive to produce and maintain,
and often take longer to synthesize and transport.[35]

The geranium, for example, produces the amino acid, quisqualic acid in its petals to defend itself
from Japanese beetles. Within 30 minutes of ingestion the chemical paralyzes the herbivore. While
the chemical usually wears off within a few hours, during this time the beetle is often consumed by
its own predators.[36][37]

Antiherbivory compounds[edit]
Further information: Secondary metabolite
Plants have evolved many secondary metabolites involved in plant defense, which are collectively
known as antiherbivory compounds and can be classified into three sub-
groups: nitrogen compounds (including alkaloids, cyanogenic
glycosides, glucosinolates and benzoxazinoids), terpenoids, and phenolics.[38]

Alkaloids are derived from various amino acids. Over 3000 known alkaloids exist, examples
include nicotine, caffeine, morphine, cocaine, colchicine, ergolines, strychnine,
and quinine.[39] Alkaloids have pharmacological effects on humans and other animals. Some
alkaloids can inhibit or activate enzymes, or alter carbohydrate and fat storage by inhibiting the
formation phosphodiester bonds involved in their breakdown.[40] Certain alkaloids bind to nucleic
acids and can inhibit synthesis of proteins and affect DNA repair mechanisms. Alkaloids can also
affect cell membrane and cytoskeletal structure causing the cells to weaken, collapse, or leak, and
can affect nerve transmission.[41] Although alkaloids act on a diversity of metabolic systems in
humans and other animals, they almost uniformly invoke an aversively bitter taste.[42]

Cyanogenic glycosides are stored in inactive forms in plant vacuoles. They become toxic when
herbivores eat the plant and break cell membranes allowing the glycosides to come into contact
with enzymes in the cytoplasm releasing hydrogen cyanide which blocks cellular
respiration.[43] Glucosinolates are activated in much the same way as cyanogenic glucosides, and the
products can cause gastroenteritis, salivation, diarrhea, and irritation of the
mouth.[42] Benzoxazinoids, such as DIMBOA, are secondary defence metabolites characteristic of
certain grasses (Poaceae). Like cyanogenic glycosides, they are stored as inactive glucosides in the
plant vacuole.[44] Upon tissue disruption they get into contact with β-glucosidases from the
chloroplasts, which enzymatically release the toxic aglucones. Whereas some benzoxazinoids are
constitutively present, others are only synthesized following herbivore infestation, and thus,
considered inducible plant defenses against herbivory.[45]

The terpenoids, sometimes referred to as isoprenoids, are organic chemicals similar to terpenes,
derived from five-carbon isoprene units. There are over 10,000 known types of terpenoids.[46] Most
are multicyclic structures which differ from one another in both functional groups, and in basic
carbon skeletons.[47] Monoterpenoids, continuing 2 isoprene units, are volatile essential oils such
as citronella, limonene, menthol, camphor, and pinene. Diterpenoids, 4 isoprene units, are widely
distributed in latex and resins, and can be quite toxic. Diterpenes are responsible for
making Rhododendron leaves poisonous. Plant steroids and sterols are also produced from
terpenoid precursors, including vitamin D, glycosides (such as digitalis) and saponins (which lyse red
blood cells of herbivores).[48]

Phenolics, sometimes called phenols, consist of an aromatic 6-carbon ring bonded to

a hydroxy group. Some phenols have antiseptic properties, while others disrupt endocrine activity.
Phenolics range from simple tannins to the more complex flavonoids that give plants much of their
red, blue, yellow, and white pigments. Complex phenolics called polyphenols are capable of
producing many different types of effects on humans, including antioxidant properties. Some
examples of phenolics used for defense in plants
are: lignin, silymarin and cannabinoids.[49] Condensed tannins, polymers composed of 2 to 50 (or
more) flavonoid molecules, inhibit herbivore digestion by binding to consumed plant proteins and
making them more difficult for animals to digest, and by interfering with protein absorption
and digestive enzymes.[50]

In addition, some plants use fatty acid derivatives, amino acids and even peptides[51] as defenses.
The cholinergic toxin, cicutoxin of water hemlock, is a polyyne derived from the fatty acid
metabolism.[52] Oxalyldiaminopropionic acid is a neurotoxic amino acid produced as a defensive
metabolite in the grass pea (Lathyrus sativus).[53] The synthesis of fluoroacetate in several plants is
an example of the use of small molecules to disrupt the metabolism of herbivores, in this case
the citric acid cycle.[54]

Mechanical defenses[edit]

The prickles on the stem of this raspberry plant serve as a

mechanical defense against herbivory.
See the review of mechanical defenses by Lucas et al., 2000, which remains relevant and well
regarded in the subject as of 2018.[55] Many plants have external structural defenses that discourage
herbivory. Structural defenses can be described as morphological or physical traits that give the
plant a fitness advantage by deterring herbivores from feeding.[56] Depending on the herbivore's
physical characteristics (i.e. size and defensive armor), plant structural defenses on stems and
leaves can deter, injure, or kill the grazer. Some defensive compounds are produced internally but
are released onto the plant's surface; for example, resins, lignins, silica, and wax cover
the epidermis of terrestrial plants and alter the texture of the plant tissue. The leaves of holly plants,
for instance, are very smooth and slippery making feeding difficult. Some plants
produce gummosis or sap that traps insects.[57]

Spines and thorns[edit]

A plant's leaves and stem may be covered with sharp prickles, spines, thorns or trichomes- hairs on
the leaf often with barbs, sometimes containing irritants or poisons. Plant structural features like
spines, thorns and awns reduce feeding by large ungulate herbivores (e.g. kudu, impala, and goats)
by restricting the herbivores' feeding rate, or by wearing down the molars.[58] Trichomes are
frequently associated with lower rates of plant tissue digestion by insect herbivores.[56] Raphides are
sharp needles of calcium oxalate or calcium carbonate in plant tissues, making ingestion painful,
damaging a herbivore's mouth and gullet and causing more efficient delivery of the plant's toxins.
The structure of a plant, its branching and leaf arrangement may also be evolved to reduce
herbivore impact. The shrubs of New Zealand have evolved special wide branching adaptations
believed to be a response to browsing birds such as the moas.[59] Similarly, African Acacias have
long spines low in the canopy, but very short spines high in the canopy, which is comparatively safe
from herbivores such as giraffes.[60][61]

Coconut palms protect their fruit by surrounding it with multiple

layers of armor.
Trees such as palms protect their fruit by multiple layers of armor, needing efficient tools to break
through to the seed contents. Some plants, notably the grasses, use indigestible silica (and many
plants use other relatively indigestible materials such as lignin) to defend themselves against
vertebrate and invertebrate herbivores.[62] Plants take up silicon from the soil and deposit it in their
tissues in the form of solid silica phytoliths. These mechanically reduce the digestibility of plant
tissue, causing rapid wear to vertebrate teeth and to insect mandibles,[63] and are effective against
herbivores above and below ground.[64] The mechanism may offer future sustainable pest-control
strategies.[65]

Thigmonastic movements[edit]
Thigmonastic movements, those that occur in response to touch, are used as a defense in some
plants. The leaves of the sensitive plant, Mimosa pudica, close up rapidly in response to direct
touch, vibration, or even electrical and thermal stimuli. The proximate cause of this mechanical
response is an abrupt change in the turgor pressure in the pulvini at the base of leaves resulting
from osmotic phenomena. This is then spread via both electrical and chemical means through the
plant; only a single leaflet need be disturbed. This response lowers the surface area available to
herbivores, which are presented with the underside of each leaflet, and results in a wilted
appearance. It may also physically dislodge small herbivores, such as insects.[66]

Carnivorous plants[edit]
Carnivory in plants has evolved at least six times independently, some examples include the Venus
flytrap, pitcher plant, and butterwort.[67] Although many outside of the scientific community usually
believe these plants excel in defenses, many of these plants have evolved in poor nutrient soil. In
order to get sufficient nutrients in these conditions they must use an alternative method.[68] They use
insects and small birds as a way to gain the minerals they need through carnivory. Carnivorous
plants do not use carnivory as self-defense, but to get the nutrients they need.

Mimicry and camouflage[edit]

Further information: Mimicry in plants
Some plants mimic the presence of insect eggs on their leaves, dissuading insect species from
laying their eggs there. Because female butterflies are less likely to lay their eggs on plants that
already have butterfly eggs, some species of neotropical vines of the genus Passiflora (Passion
flowers) contain physical structures resembling the yellow eggs of Heliconius butterflies on their
leaves, which discourage oviposition by butterflies.[69]

Indirect defenses[edit]

The large and directly defensive thorn-like stipules of Vachellia

collinsii are also hollow and offer shelter for ants, which indirectly protect the plant against
herbivores.
Main article: Tritrophic interactions in plant defense
Another category of plant defenses are those features that indirectly protect the plant by enhancing
the probability of attracting the natural enemies of herbivores. Such an arrangement is known
as mutualism, in this case of the "enemy of my enemy" variety. One such feature
are semiochemicals, given off by plants. Semiochemicals are a group of volatile organic
compounds involved in interactions between organisms. One group of semiochemicals
are allelochemicals; consisting of allomones, which play a defensive role in interspecies
communication, and kairomones, which are used by members of higher trophic levels to locate food
sources. When a plant is attacked it releases allelochemics containing an abnormal ratio of
these herbivore-induced plant volatiles (HIPVs).[70][71] Predators sense these volatiles as food cues,
attracting them to the damaged plant, and to feeding herbivores. The subsequent reduction in the
number of herbivores confers a fitness benefit to the plant and demonstrates the indirect defensive
capabilities of semiochemicals.[72] Induced volatiles also have drawbacks, however; some studies
have suggested that these volatiles attract herbivores.[70] Crop domestication has
increased yield sometimes at the expense of HIPV production. Orre Gordon et al 2013 tests several
methods of artificially restoring the plant-predator partnership, by combining companion planting and
synthetic predator attractants. They describe several strategies which work and several which do
not.[73]

Plants sometimes provide housing and food items for natural enemies of herbivores, known as
"biotic" defense mechanisms, as a means to maintain their presence. For example, trees from the
genus Macaranga have adapted their thin stem walls to create ideal housing for an ant species
(genus Crematogaster), which, in turn, protects the plant from herbivores.[74] In addition to providing
housing, the plant also provides the ant with its exclusive food source; from the food bodies
produced by the plant. Similarly, several Acacia tree species have developed stipular spines (direct
defenses) that are swollen at the base, forming a hollow structure that provides housing for
protective ants. These Acacia trees also produce nectar in extrafloral nectaries on their leaves as
food for the ants.[75]

Plant use of endophytic fungi in defense is common. Most plants have endophytes, microbial
organisms that live within them. While some cause disease, others protect plants from herbivores
and pathogenic microbes.[76] Endophytes can help the plant by producing toxins harmful to other
organisms that would attack the plant, such as alkaloid producing fungi which are common in
grasses such as tall fescue (Festuca arundinacea), which is infected by Neotyphodium
coenophialum.[66][77]

Trees of the same species form alliances with other tree species in order to improve their survival
rate. They communicate and have dependent relationships through connections below the soil called
underground mycorrhiza networks, which allows them to share water/nutrients and various signals
for predatory attacks while also protecting its immune system.[78] Within a forest of trees, the ones
getting attacked send communication distress signals that alerts neighboring trees to alter their
behavior (defense).[78] The tree and fungi relationship is a symbiotic relationship.[78] Fungi, intertwined
with the trees' roots, support communication between trees to locate nutrients. In return, the fungi
receive some of the sugar that trees photosynthesize. Trees send out several forms of
communication including chemical, hormonal, and slow pulsing electric signals. Farmers
investigated the electrical signals between trees, using a voltage-based signal system, similar to an
animal's nervous system, where a tree faces distress and releases a warning signal to surrounding
trees.