Pesticides, History, and Classi Fication

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CHAPTER 3

Pesticides, History, and Classification


YUSUF ABUBAKAR • HABIBU TIJJANI, PHD • CHUKWUEBUKA EGBUNA, BSC, MSC •
CHARLES OLUWASEUN ADETUNJI, PHD • SMRITI KALA, PHD • TOSKË L. KRYEZIU •
JONATHAN C. IFEMEJE, PHD • KINGSLEY C. PATRICK-IWUANYANWU, PHD

INTRODUCTION insecticide, or nematicide for the reason that it con-


Pesticide is any substance or mixture of substances used to trols mites, insects, and nematodes, respectively.
prevent, destroy, or control pest including insects, fungus, Aside from established chemicals employed as insec-
rodents or, unwanted species of plants causing harm dur- ticides, other traditional means are also employed to
ing production and storage of crops [1]. The word “pesti- decrease the growth of insect or limit their activities.
cide” is a broad term that includes insecticides, herbicides, Some of these compounds are generally meant for other
fungicides, and rodenticides that may be used to kill some purposes but are being used as insecticides. They
specific pests. Pesticides are classified according to the include alcohols and oils. Alcohols are used as surface
sources of origin as either being a chemical pesticide or compounds for the control of mosquito larvae. It is
biopesticides. Biological pesticides are host specific. They the active ingredient in Agnique, a known larvicidal
are highly specific in the sense that it acts on the target product. The aim for the uses of alcohol is to reduce sur-
pest and strongly related organisms, whereas chemical face tension of water, thus reducing the adherence of
pesticides are nonspecific with wide range of activities mosquito larvae or pupae leading to their drowning
on a large group of nontarget organisms. Biopesticides and death. Oils similarly are useful for surface applica-
are environmentally friendly because they are less toxic, tions. However, they prevent supply of oxygen for the
decomposed easily, and required in small quantities. survival of the larvae or pupae. The use of this water sur-
Chemical pesticides cause several environmental pollu- face control has several advantages because their actions
tion because they are quite toxic and may not be biode- are more physical than conventional insecticides that
gradable. More so, biopesticides are of important are more biochemical in actions. These ensure that the
advantage being less susceptible to genetic modification organisms do not develop pesticide resistance.
in plant populations. This confirms the little chance of
pesticide resistance in pests, which is hardly encountered
in case of chemical pesticides. Chemical pesticides are HISTORY
further subdivided into organochlorine, organophos- Ever since ancient times, human civilizations have tried to
phate, carbamate, and pyrethroids. Biopesticides are group apply the most effective and less time-consuming ap-
of pesticides derived from natural materials such as ani- proaches for cultivating and preserving their food re-
mal, plant, and microorganism (bacteria, viruses, fungi, sources. An actual illustration of this is how they
and nematodes). They include microbial pesticides, plant cultivated venomous and nutritious vegetation in the
incorporated protectants, and biochemical pesticides. same place due to the shielding effect of toxic plants for in-
Pesticides act through several mechanisms. Some sect elimination. Correspondingly, throughout this period,
are termed growth regulators as they either stimulate elemental sulfur has also been used. These would be the
or retard the growth of pest, while repellents are initial methods for removing pests for several millennia.
known to repel pests, and attractants attract pests or Later on came the Ebers papyrus, one of the oldest
chemosterilants, which sterilize pests. Pesticides with still existing documents that contain some of the prep-
a wide range of activities and used to control more aration techniques for the removal of insects from
than one class of pests are difficult to classify [2]. Ex- foods. In parallel, traditional Chinese medicine also
amples are aldicarb, which is used in Florida citrus uses primitive sulfides. It is likewise interesting to note
production and may be considered an acaricide, that Homer’s epic work “Odysseus,” written around the

Natural Remedies for Pest, Disease and Weed Control. https://doi.org/10.1016/B978-0-12-819304-4.00003-8


Copyright © 2020 Elsevier Inc. All rights reserved. 29
30 PART I Green Approach to Pest and Disease Control

same time, describes the use of substances to remove that are untreated. They are effective in killing of weeds
insects. even with partial spray coverage of the pesticide. They
Around 1500's, the early stages of the use of the effectively penetrate the plant tissues and pass via plant
“para-pesticides,” namely mercury and arsenic, vascular system to kill target pests. In addition, few pes-
emerged. These substances were used until the start of ticides are considered locally systemic and pass only to a
synthetic pesticide era (1940 and beyond), initially for distance that is not far from the point of contact. Such
the destruction of food reserves during the World War insecticides include 2,4-dichlorophenoxyacetic acid (2,
II and later on as precious tools for cultivating processes 4-D) and glyphosate [3].
of foods consumed daily. It is crucial to note that
through this time, several scientists have highlighted Nonsystemic Contact Pesticides
the adverse effects of pesticides on human health The nonsystemic pesticides are also known as contact
when used for a long time. For instance, the drastic in- pesticides, as they produce the desired effect when
crease in the number of lymphoma patients is a topic they come in contact with the pest. Nonsystemic pesti-
that would be discussed until today [1e3]. cides must come into physical contact with the pest for
it to be active. Pesticide enters the body of pests via
Present Era their epidermis while in contact which result to death
A vital event in the history of pesticides represents the by poisoning. These pesticides must not necessarily
discovery of the initial modern pesticide: dichloro- penetrate the tissues of the plant and consequently
diphenyl-trichloroethane (DDT) by Paul Muller in not transported via the vascular system of the plant.
1939. This revelation granted him years later the Nobel Contact pesticides include paraquat, diquat, and
Prize in Medicine, primarily because of the decrease of dibromide.
the damages caused by pesticides in agriculture and like- Stomach poisoning pesticide enters the pest’s body
wise health-related problems such as malaria or typhus. via their mouth and to the digestive system resulting
Despite its sensation, the use of DDT would not last to death by poisoning. These insecticides kill the vector
long. In 1962, the book “Silent Spring” by author by destroying the midgut (or stomach) of the larvae, for
Rachel Carson, elaborated the harmful effects of DDT. example, malathion.
Immediately after that, numerous states banned the Fumigants are pesticides that act or kill the target
use of DDT in favor of lower risk organophosphates pests through production of vapor. These pesticides
and carbamates in the forthcoming years. form poisonous gases after application. The vapor
Presently, there are still public concerns about the formed enter the body of pests through their respiratory
consequences of using pesticides in health (especially system (tracheal) via spiracles, which result, to death by
in old people and children). In contrast, because of poisoning. Most of their active ingredients are in liquid
the exponential growth of the population in the last de- form when packaged under high pressure and change to
cades, global production of pesticides is growing at the gases when they are released. Fumigants are used for the
same trend [2]. In the meantime, according to the new removal of pest from stored product such as fruits, veg-
EU regulations, producers are required to minimize the etables, and grains. It is also useful in controlling pests
manufacture of pesticides to decrease the number of in soil.
serious illnesses in the population. However, high Repellents also belong to this class of pesticides.
attention is now being dedicated to the arrival of Their uniqueness is the ability to repel the pest and
pesticide-resistant herbs, a factor that will definitely not exactly kill, but they are distasteful enough to
have a high impact in the future [1e3]. keep pests away from treated areas. They also interfere
with the ability of pests to locate crop. Repellants are
useful in public health applications to prevent mosqui-
toes and bloodsucking insects including ticks and black
GENERAL MODE OF ENTRY OF PESTICIDES
flies from biting pets, livestock, or humans.
The mode of entry of pesticides can either be systemic or
nonsystemic.
USEFULNESS OF PESTICIDES IN
Systemic Contact Pesticides COMMERCIALIZED AGRICULTURE
Pesticides with systemic contact are absorbed by ani- The use of pesticides has gained the attention of several
mals or plants and transferred to tissues that are not stakeholders, farmers, scientists, governments, and
treated. Systemic herbicides pass through the plant agroindustries. The usefulness of pesticides were
and can reach in the areas of leaves, stems, or roots summarized:
CHAPTER 3 Pesticides, History, and Classification 31

1. Pesticides have been highlighted as an effective such as organic agricultural practices and bio-
weapon of man for the management of agricultural pesticides [8].
pests affecting the increase in agricultural produc- 5. The high cost of production and the socioeco-
tion. The process of applying these pesticides has led nomic aspect of the pesticides have discouraged so
to a drastic reduction of insect pests, diseases, and many investors most especially taking into
weeds that can strikingly decrease the amount of consideration the standard benefit:cost ratio [9].
harvestable agricultural yield and economic margin. The blend of secondary pest outbursts, insect
2. The utilization of pesticides has resulted in enhanced resistance, government rules, and legal clashes over
agricultural production of quality foods. For example, well-being and the surroundings, consistently have
the consumption of diet having fruit and vegetables repercussions for the economics of unadventurous
prevail over impending risks from consumption of pesticide utilization.
low residues of pesticides available in some agricul- 6. The registration of most pesticides has been
tural crops after application of pesticides [4]. observed to be very tedious, time consuming, and
3. The application of pesticides helps in the preserva- highly demanding with a lot of requirements. This
tion of wood from destruction by termites and other has resulted to a lot of economic challenges due to
wood-boring insects as well as in controlling the the high costs implication involved in research and
spread of malaria vector, the Anopheles mosquitoes development necessary for utilization that has led
[5]. to less preference of pesticides for control of agro-
4. The reception of pesticides for the management of nomic pests.
agricultural pests by farmers has boosted and 7. The health challenges and food safety issue have
encouraged several scientists and researchers to become paramount most especially during post-
divert most of their energy into more research and harvest storage of agricultural crops whenever
growth in the pesticide subsector. This has led to the pesticides are used to prevent the incident of agri-
discovery of more types of pesticides with different cultural pest, that is, Gamalin 20 and malathion.
modes of action. This includes acute poisoning, chronic poisoning,
neurobehavioral effects, developmental and
reproductive effects, carcinogenic effects, and
PROBLEMS ASSOCIATED WITH THE USE OF immunological effects. Most farmers in developing
PESTICIDES country do not allow the pesticides to decay before
Some of the demerits of pesticide use include the they are being send to market and most consumers
following: do not wash these agricultural produces before
1. The consequence of environmental pollution that consumption that has led to the accumulation of
has led to uncontrolled outward influence on the ingestion of pesticide residues. This has led to the
quality of the environment makes the utilization of issue of food poisons and increase in death of
pesticides counterproductive. This might cause a many families [10]. Another typical challenge is the
long-term or short-term effect that entails issue of increase in human infertility and birth
contamination of groundwater or drinking water. defects [11].
Some pesticides also have adverse effect on 8. The continual utilization of pesticides has
nontarget plant which results to the bio- increased the issue of environmental pollution
accumulation of the pesticide’s residues [6]. whenever pesticides are used for the management
2. Many pesticides have been shown to exhibit a of pests. This has resulted to pesticide applications
nontarget effect on beneficial microorganism, soil that contribute significantly to pollution of the
quality soil enzymes as well as other beneficial environment. This happens whenever pesticides
aquatic microorganisms and algae [7]. are introduced into the environment that normally
3. The continuous use of pesticides has led to the leads to run-off into water body, leakage of pol-
development of resistance by target organism as lutants and irrigation water into groundwater, and
well as cross-resistance to other vigorous constitu- drift of pesticides through wind and soil erosion.
ents from some pesticides. This later on might lead All these have led to systemic introduction of pes-
to the development of more enhanced vicious ticides into the ecosystem that has increased the
populaces of pests or target organisms. number of killing among the wildlife while some
4. Severe usage of pesticides has made the farmers to grieve impairment to vital roles such as reproduc-
depend and ignore other available alternatives tive failure.
32 PART I Green Approach to Pest and Disease Control

9. The continual utilization of pesticides has led to absence of formulation control, and pesticide res-
high level of soil impoverishment by affecting the idue investigative amenities and competencies [13].
water retention, soil structure, physicochemical 14. Inadequate safety measures has led to several issues
properties, and porosity that normally results into of contaminations and poisoning in the field. For
less water permeation and more run-offs thereby, example, most farmers in the rural area are ignorant
leading to flooding down streams. about some safety measures that are necessary
10. The incessant application of pesticides has resulted whenever they apply pesticides on their farm, that is,
into pollution of water bodies. This has led to the protective clothing and gloves as well as other pro-
continual washing of pesticides into the water tecting gears wear in the course of spraying of pes-
bodies by irrigation water and rainwater. The non- ticides. Other preventive actions are barely observed
biodegradability of pesticides that easily build-up in by these farmers as the farmers have been several
the bodies of plant and animal causes a great times without number to be eating, or drinking in-
instability along the food chain and high level of between smoking spraying actions. Mostly, these
imbalance in the ecosystem, and causes biodiversity farmers utilize all or some of these pesticide con-
collapse. A typical example is the percolation or tainers for domestic purposes that make some
leakages of pesticide residues into water bodies, pesticide residues to cause a lot of hazards.
which consequently led to the killing of aquatic 15. The challenges of poor extension services from staffs
invertebrates and fishes whenever pesticides are involved in the extension services have shown
applied, that is, application of DDT for the killing of considerable effect on rural farmers that dwells most
fishes. especially in the rural areas. This might be linked to
11. The continual usage of pesticides has increased the reduced staffing and mobility. Extensionists in
rate of attenuation of soil fertility. Most especially it general are deprived of necessary support, poorly
also affects the activity of soil microorganism that educated in the area of pesticide administration,
perform decomposition of organic matters, soil lack incentive, and are scarcely any supplement
aeration, and most especially these microorgan- arrangement to educate farmers most especially
isms that are involved in the biodegradation of soil from developing country on safety protections as
nutrient (nitrogen cycles, carbon cycle, phosphorus well as overall understanding on pesticide utiliza-
cycle), that is, free-living nitrogen-fixing bacteria, tion. Moreover, lack of close intimacy between the
nitrogen-fixing blue-green algae, blue-green algae, farmers and the extension officer has increased the
and arbuscular mycorrhizal fungus. reliability and overreliance of the extension officer
12. The erroneous dosage of pesticide has been identi- on pesticide vendors. Mismanagement and main-
fied as one of the major problems affecting agri- tenance of equipment used for the application of
cultural produce. This might be linked to the large pesticides due to high level of illiteracy of the
financial losses experienced by primitive farmers farmers henceforth indulge in severe misuses of
most especially in the developing countries. They pesticide usage such as incorrect timing of applica-
normally experience high level of phytotoxicity, tion and dearth of awareness on the time required
which will normally reduce yield of agricultural for complete degradation of pesticides, inappro-
produce because the rate of photosynthesis has been priate utilization of use of nozzles, incompetent to
affected. In addition, there is a large tendency for the differentiate one pest from the other, use of incor-
pests to cultivate resistance against pesticides, which rect doses and formulations, and mingling together
normally have devastating effect on the large-scale of various types of pesticides [14].
production of agricultural produce [12].
13. The problem of low government intervention has
greatly affected the pesticide regulatory role of the CLASSIFICATION OF PESTICIDES
government most especially in most developing A pesticide varies in identity (physical and chemical
country. This might be linked to the inadequate of properties). According to Drum [15], pesticides can
staffs in pesticide regulatory events, absence of be broadly classified in different ways depending on
appropriate legislative expert, shortage of infra- their origin (Table 3.1) and target pest species
structure, equipment and materials, transportation, (Table 3.2). They can also be classified based on func-
reduced budget provision on operating money, tion (Table 3.3).
CHAPTER 3 Pesticides, History, and Classification 33

TABLE 3.1 TABLE 3.3


Classification of Pesticides Based on Origin. Classification of Pesticides Based on Function.
Based on Origin Sources and Examples Action Function Examples
Organic sources Naturaldplant phytochemical Feeding Prevent an insect or (Azadirachta
(essential oil, plant extracts, leftover deterrents other pest from Indica A. Juss)
oilseed cakes) feeding
Syntheticdproduced by chemical Ovipositor Prevent egg laying by Azadirachta
synthesis e.g., Pyrethroids, deterrent gravid female indica
organophosphates, carbamates,
organochlorine Repellents Deters pest from Plant essential
approaching toward oil
Inorganic Inorganicdmixture of inorganic salts crops
sources [1]
Bordeaux mixture Cu (OH)2.CaSO4 Attractants A chemical that lures Gossyplure
Malachite Cu (HO)2.CuCO3 and pests
sulfur Fumigants Kills the target pests Phosphine
Biological Biological: microbial pesticide by producing vapor
(bacteria, virus, and fungi) Insect A substance that Diflubenzuron
growth works by disrupting
regulator the growth or
development of an
insect
Synergist A chemical that Piperonyl
TABLE 3.2
enhances the toxicity butoxide
Classifications of Pesticides Based on Target
of a pesticide but not
Pest Species. by itself toxic to pest
Pesticide
Class Target Pests Example
Acaricides Mites Bifonazole Natural Organic Pesticides
Algaecides Algae Copper Natural organic pesticides include class of pesticides
sulfate such as the phytochemicals present in plants; alka-
Avicides Birds Avitrol loids, terpenes, and phenolic compounds, which
Bactericides Bacteria Copper have proven pesticidal potential [16]. Plant-derived
complexes essential oil, plant extracts, and leftover oilseed cakes
are found to be active against varieties of pests [17].
Fungicides Fungi Azoxystrobin
These are particularly attractive on the grounds of
Herbicides Weeds Atrazine low mammalian toxicity, short environmental persis-
Insecticides Insects Aldicarb tence, and complex chemistry that do not develop
Larvicides Larvae Methoprene resistance in pest [18].
Molluscicides Snail Metaldehyde
Inorganic Pesticides
Nematicides Nematodes Aldicarb Inorganic pesticides include inorganic salts such as cop-
Ovicides Egg- prevents hatching Benzoxazine per sulfate, ferrous sulfate and lime, and sulfur [19]. The
of egg in insects and chemicals in inorganic pesticides tend to be simpler and
mites are soluble in water than those of organic pesticides.
Piscicides Fishes Rotenone Many of them work by causing stomach poisoning in
Repellents Insects Methiocarb insects [20].
Rodenticides Rodents Warfarin
Synthetic Pesticides
Termiticides Kills termites Fipronil The major classes of synthetic pesticides are organo-
Viricides Viruses Scytovirin chlorines, organophosphates, carbamates, and
pyrethroides.
34 PART I Green Approach to Pest and Disease Control

Organochlorines chemicals [21], which control broad range of pests,


Organochlorine pesticides (also called chlorinated hy- weeds, or plant diseases because of their multiple func-
drocarbons) are organic compounds attached to five tions. They are acetylcholine cholinesterase inhibitors,
or more than five chlorine atoms. They represent one disturbing neurotransmitter across a synapse [22]. As
of the first categories of pesticides ever synthesized a result, nervous impulses fail to move across the syn-
and are used in agriculture. Most of them are usually apse causing a rapid twitching of voluntary muscles,
used as insecticides for the control of a broad range of hence, leading to paralysis, which is associated to death.
insects, and have a long-term residual effect in the envi- Some of the widely used organophosphorus insecti-
ronment. These insecticides may alter the proper func- cides include parathion, malathion, dichlorvos, diaz-
tion of the nervous system of the insects leading to inon, and glyphosate (Fig. 3.2). The compounds in
disorders such as convulsions and paralysis followed this group are characterized by a covalent binding of
by eventual death [1]. Common examples of these pes- carbon to phosphate (CeP) bond replaced by one of
ticides include DDT, lindane, endosulfan, aldrin, diel- its four carbon to oxygen to phosphorus bonds of phos-
drin, heptachlor, toxaphene, and chlordane (Fig. 3.1). phate ester [23]. The CeP direct linkage is described to
Although, the production and usage of DDT has been be chemically and thermally inert, making organo-
banned in most developed countries including the phosphonate compounds resistant to some drastic con-
United States many years back, it is still produced and ditions such as chemical hydrolysis, photolysis
being used in most tropical developing countries for compared and thermal decomposition with analogous
the control of vector. compounds characterized with more reactive NeP,
SeP, or OeP linkages.
Organophosphorus Organophosphate pesticides have contributed dras-
Organophosphorus are phosphoric acid-derived pesti- tically to improved agricultural productivity as well as
cides (Fig. 3.2), considered to be one of the wide spec- effective crop yields [24]. Developing countries are
trum pesticides consisting of a heterogeneous group of increasingly adapting to its use. For example, Iran

FIG. 3.1 Chemical structures of some organochlorine compounds.


CHAPTER 3 Pesticides, History, and Classification 35

FIG. 3.2 Chemical structures of some organophosphate compounds.

agriculturists use pistachios for orchards to pest control (Chrysanthemum Coccineum and Chrysanthemum cine-
being the largest producer [25]. These pesticides are also rariaefolium) [1]. The insecticidal properties of pyre-
biodegradable, also cause minimum environmental thrins are due to pyrethroic acids. Pyrethroides affect
pollution, and may be classified as slow pest resistance the sodium channels and lead to paralysis of the or-
compounds. ganism. The most widely used synthetic pyrethroids
includes permethrin, cypermethrin, deltamethrin,
Carbamates lethrin, furethrin, fenevelerate, and alphcyperameth-
Carbamates are organic pesticides derived from carba- rin. The synthetic pyrethroids also belong to this group
mic acid. These include carbaryl, carbofuran, and ami- of pesticide, which can be synthesized by duplicating
nocarb [1]. They are similar in structure to the structure of natural occurring pyrethrins. Rela-
organophosphates. However, they differ from their tively, they are more stable and effective than natural
origin. Organophosphates are derivatives of phosphoric pyrethrins. The major active components are pyrethrin
acid, while carbamates are derived from carbamic acid. I and pyrethrin II plus smaller amounts of the related
The principle behind the use of carbamate pesticides is cinerins and jasmolins. Synthetic-pyrethroid pesti-
similar to that of organophosphate pesticides by cides are highly neurotoxic to insects and fish but
affecting the transmission of nerve signals resulting in less toxic to mammals and birds. Most of synthetic in-
the death of the pest through poisoning [26]. Some- secticides are nonpersistent, and can be broken easily
times, they are also used as stomach and contact poi- on exposure to light. They are considered the safest in-
sons as well as fumigant. This pesticide can be easily secticides for use in food. Modern pyrethroids slightly
be degraded under natural environment with minimum resemble their pyrethrin I (progenitor) and exert
environmental pollution. different mode of action from the original natural
products. The commonly used synthetic-pyrethroid
Pyrethroides pesticides are cypermethrin, fenvalerate, fluvalinate,
Pyrethroids are organic compounds isolated from deltamethrin, lethrin, furethrin, and permethrin
the naturally occurring flowers of pyrethrums (Fig. 3.3).
36 PART I Green Approach to Pest and Disease Control

FIG. 3.3 Chemical structures of some synthetic pyrethroids.

Biorationals for diverse biological activities [29]. The secondary me-


Biorational pesticides (biopesticides) represent a spe- tabolites are not directly involved in reproduction,
cific group of compounds that are considered relatively growth, or development but are useful as sources of vi-
safe to the environment and nontoxic to humans. Bio- tal compounds with diverse biochemical activities
rational pesticides are derived from natural materials [29e31]. Natural pesticides are found in terpenoids,
including plants, animals, bacteria, and certain mineral phenolics, and alkaloids. Research evidences have
elements. They can be subdivided into two major shown that over hundreds of isolated compounds
groups, the biochemically derived ones which include from plants have demonstrated bioactivities. However,
hormones, enzymes, pheromones and the microbial rather than killing the insects, more of the compounds
derived which are viruses, bacteria, fungi, protozoa, are active as feed deterrents or growth inhibitors [32].
and nematodes. Biochemical pesticides are less selective Some of the identified natural pesticides were reviewed
compared to microbial pesticides. In arthropods, the below.
mechanism of action is based on the interruption of
their natural growth processes. Diflubenzuron, metho- Terpenoids
prene, and Bacillus thuringiensis serotype israelensis Terpenoids are secondary metabolites which have hy-
(Bti) are specific examples in biorational class of pesti- drocarbon isoprene (C5H8) as their simplest unit
cides. Another notable microbial pesticide is those [29,33]. Volatile isoprene produced in large quantities
derived from fungus, Trichoderma [27]. In addition, during the process of photosynthesis protects plants’
some insect viruses found in nature such as those of cell membrane from damages caused by light radia-
Baculovirus family (Baculoviridae) are considered as bio- tions and high temperature [33]. The protective roles
pesticides [27,28]. of terpenoids are attributed to their bitter taste, pre-
venting plants containing them from being eaten by
Pesticides of Plant Origin animals [34]. Chrysanthemum plants have monoter-
Natural plant defense systems are found useful in the pene ester (Pyrethroids) in their leaves and flowers,
prevention of insects and other arthropods. Plant chem- which are strong insecticides and protect the
ical constituents are subdivided into two categories plant from insects. Monoterpenoids are neurotoxic
namely secondary and primary metabolites derived to insects and to mites after significant contact with
from distinct biochemical pathways and are responsible them.
CHAPTER 3 Pesticides, History, and Classification 37

Primary components of essential oils include mono- Other insecticidal compounds from the family include
terpenoids and sesquiterpenoids, which are high vola- conocarpan (P. decurrens) and dillapiol (P. aduncum) [32].
tile compounds that contribute to plant fragrances. Essential oils obtained from plants through various
These essential oils can act as insect toxins and protect methods from aromatic medicinal plants have shown
plants against the attack of bacterial and fungal. Exam- great potentials as insecticidal compounds or as insect
ples of plants with terpenoids insecticidal properties repellants. They have been commercialized as natural
include Cinnamomum spp., Laurus spp., Mentha spp., oils for their use as insect repellants or insecticidal pur-
Ocimum spp., Origanum spp., Piper spp., Rosmarinus poses [32]. The activities vary with structure, amount of
spp., Salvia spp., Satureja spp. and Thymus spp. among saturation, and functional groups of the oils [46].
others. Thymol a typical ovicidal compound from this class
Diterpenoids (C20) synthesized from sesquiterpe- of compounds is toxic to housefly [46]. Thymol was
noids (C15) [29] similarly exhibit insecticide activities. more active compared with its derivatives that were
Diterpenoids from Gossypium hirsutum (cotton) are evaluated. The enhanced fumicidal and ovicidal activ-
strong antibacterial and antifungal compounds. ities are attributed to increase volatility and lipophilicity
Triterpenoids (C30) are secondary metabolites whose of the new acylated derivative [46].
biosynthesis is a complex one [29]. They have similar
structural identification with animal steroids and other Saponins
steroid hormones. Because of this structural relationship, Saponins belong to the group of nonnitrogenous plant
phytoecdysones, which mimic insect molting hormones, secondary metabolites commonly found in plants [29].
can disrupt larvicidal development and increase mortal- They are glycosylated triterpenoids with detergent prop-
ity of insects. Phytoecdysones are found in plants such as erties, and they disrupt the cell membranes of invading
Spinacia oleracea. Limonoids are also examples of triterpe- microbial organism. Avenacins (triterpenoid saponins)
noids, which are found in Azadirachta indica (neem trees) contained in wheat prevent the invasion of Gaeumanno-
seed as azadirachtin [35,36]. Azadirachtin are strong myces graminis, the pathogen for wheat.
limonoid with insect repelling properties at low concen- Trilactone terpenes extracted from Ginkgo biloba fo-
trations (Fig. 3.4). The mechanism by which azadirachtin liages are potent insecticides on brown planthopper
exact its insecticidal effects is through the interference of (Nilaparvata lugens) rice pest. The array of promising
insect neuroendocrine system, disrupting moulting, compounds in Ginkgo has paved way for their cultiva-
metamorphosis, and reproduction process in the insects. tion and use for the preparation of several pharmaceu-
Cymbopogon citratus (lemon grass) is another example of ticals and natural insecticidal compounds [32].
plant with high limonoid levels. Grayanoid diterpenes from Rhododendron molle are
Melia volkensii is a source of insecticidal compounds strong grayanotoxins, which are strong neurotoxic com-
that can be obtained from its large fruit extract [37]. The pounds in invertebrates and mammals [32].
active principles are identified to be limonoids, pre-
dominantly volkensin triterpene that is closely related Phenolics
to nimbilin from A. indica [32]. Phenolics are a class of secondary metabolites with hy-
Rocaglamides are Aglaia compounds obtained from droxyl group [29]. They are synthesized in plants as part
the family of Meliaceae [38,39] among interested bio- of their host defense mechanism against pathogens.
logical compounds such as lignans [40] and triterpenes Phenolics have large and complex chemical structure
[41]. Rocaglamides occurs in nature with over 50 iden- [47]. Flavonoids are the largest class of phenolics. Phy-
tified compounds [39]. They are aromatic with cyclo- toalexins are isoflavonoids that present antibiotic and
pentatetrahydrobenzofuran skeleton, and are strong antifungal properties in response to invading pathogen
insecticidal compounds with broad-spectrum activities attacks. They are toxic molecules that disrupt pathogen
against neonate larvae of Spodoptera littoralis, Ostrinia biochemical process or the cellular structure. Specific ex-
sp. and Helicoverpa armigera [36,42,43]. The mode of ac- amples of phytoalexin include rishitin obtained from
tions of rocaglamides is derived from their ability to tomatoes and potatoes (Solanaceae), camalexin from
inhibit protein synthesis, which also account for their Arabidopsis thaliana and medicarpin obtained from Med-
potential anticancer activity [44]. icago sativa (Fig. 3.5).
Isobutylamides from Piper nigrum (black pepper) such Furanocoumarin is another example of phenolics
as its pipericide have been known with acute insecticidal synthesized by a wide variety of plants as response to her-
properties. The Piperaceae from which pipericide are rich bivore attack or invading pathogen. Furanocoumarins
with numerous potentials of natural insecticides [45]. are highly toxic to some vertebrate and invertebrate
38 PART I Green Approach to Pest and Disease Control

FIG. 3.4 Chemical structures of some terpenoids derived pesticides.

Lignins are strong components of plant cell walls,


which confer them with rigidity, insolubility, and indi-
gestibility making them excellent barriers against the
attack of various pathogen attacks.

Alkaloids
FIG. 3.5 Chemical structures of some phenolic pesticides.
Alkaloids are a class of secondary metabolite with char-
acteristic bitter-tasting nitrogenous compound. They are
synthesized from aspartic acid, tyrosine, lysine, or tryp-
herbivores. They are usually inactive until exposed to tophan [29]. Alkaloids can be found in several vascular
ultraviolet light, and act by their integration into verte- plants: major classes are morphine, caffeine, nicotine,
brate DNA leading to the rapid death of cells. Furanocou- and cocaine. Caffeine are found in Camellia sinensis
marins are found in smaller quantities in grapefruits. (tea), Coffea arabica (coffee), and Theobroma cacao (co-
coa). Caffeine is toxic to insects and fungi as beneficial
Tannins to the host plant (Fig. 3.6). Atropine are products of
Tannins are a class of flavonoid polymers, which are Atropa belladonna also known as “deadly nightshade
water-soluble. They are stored in vacuoles after produc- plant.” They are neurotoxic and cardiac stimulant
tion by plants. Tannins binds to insect salivary proteins compounds.
and digestive enzymes (trypsin and chymotrypsin) Plant-derived compounds have been used in the
leading to the inactivation of the proteins. This action field and farms as traditional means for the control of
makes tannins toxic to insects. Tannins similarly pre- pest and vermifuges [48]. Specifically, acetogenins iso-
vent weight gains in insect herbivores who inject high lated from Asimina triloba, A. longifolia, and Annona
amount of tannins leading to their premature death. muricata have been evaluated for their pesticidal activity
CHAPTER 3 Pesticides, History, and Classification 39

FIG. 3.6 Chemical structures of some alkaloid pesticides.

[49]. Squamocin, a complex alkaloid, was among the


compound studied (Fig. 3.6). Rotenone is also from
this group of chemicals. They are commercial botanical
insecticide derived from the plant Derris elliptica. Aceto-
genins and rotenone exhibit similar mechanism of ac-
tion, which is the inhibition of mitochondrial NADH:
ubiquinone oxidoreductase enzyme [50].
Alkaloids from the Stemonaceae family contain use- FIG. 3.7 Chemical structures of some napthoquinone
ful biological compounds with insecticidal activities. pesticides.
They are the only source of stemona alkaloids [51],
that are structurally characterized due to the presence
of pyrrolo(1,2-a)azepine (5,7 bicyclic AB-ring system) been characterized as 2-acetoxy-3-(1,1-dimethylprop-2-
nucleus [52]. Japanese and Chinese traditional medi- enyl)-1,4-naphthoquinone and 2-(1,1-dimethylprop-2-
cine system for centuries have explored the use of plant enyl)- 3-hydroxy-1,4-naphthoquinone, respectively
extract from Croomia and Stemona for the manage- (Fig. 3.7). The compounds are effective against aphids,
ment of respiratory diseases, enteric helminths as well spider mite, and tobacco whitefly [58,59]. BTG 504 and
as ectoparasites of humans and cattle [53,54]. The insec- BTG 505 are good insecticidal and fungicidal when
ticidal activities of the plants have also been explored compared to dunnione. The compounds are potent
[55,56].The alkaloid stemofoline from crude extract of against Musca domestica (house fly), B. tabaci (whitefly),
Stemona cochinchinensis and S. curtisii roots are attrib- Phaedon cochleariae (beetle), and T. urticae (spider mite)
uted to the strong insecticidal activities against Spodop- unlike dunnione [60]. The mechanism of action for the
tera littoralis [56]. Similarly, the extract from S. collinsae compounds was found to be different. Although BTG
possesses insecticidal activities against S. littorallis. This 505 acts through the inhibition of mitochondrial com-
has been attributed to the presence in large quantities plex III, dunnione acts primarily by the initiation of
of didehydrostemofoline and smaller stemofoline. redox cycling [60].
The insect-toxic potencies of these two alkaloids are
higher than that of standard pyrethrum extract. The Defense proteins
mechanism of action of the stemofoline is by agonism Plant proteins can play protective roles against pest and
to insect nicotinic acetylcholine receptor [57]. pathogens in some plants producing them. These pro-
teins, which may be present in plants, or plant seeds
Napthoquinone specifically can inhibit pathogens and pest enzymes
Napthoquinone compounds (BTG 504 and BTG 505) through the formation of enzyme complexes, which
from Calceolaria andina, a Chilean plant from Scrophu- form complexes that block the active sites and may alter
lariaceae are important pesticides. The compounds have the conformation of enzymes, in turn reducing the
40 PART I Green Approach to Pest and Disease Control

functions of enzymes. They serve as defensins, lectins, [6] P.C. Struik, F. Bonciarelli, Resource use at the cropping
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