Essential Oils II

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the Grand Vizier of King Djoser (2780 – 2720 B.C.). Imhotep is often. Fig. ...... Huignard, J., Lapied, B., Dugravot, S., Magnin-Robert, M. and Ketoh, G.K. (2008).
Recent Progress in Medicinal Plants Vol. 37

RPMP Vol. 37

Essential Oils II ABOUT THE VOLUME The objective of the volume 37 of Recent Progress in Medicinal Plants is to bring together the scientific material relating to essential oils of contemporary pharmaceutical importance. In general, essential oils are important not only as perfuming and flavouring agent, but also in terms of their putative medicinal or pharmacological properties. This volume aims to describe those important essential oils in a comprehensive and organized manner. Its contributors are from 14 countries namely Argentina, Bulgaria, Egypt, India, Iran, Italy, Korea, Romania, Slovak Republic, Tanzania, Turkey, USA, Venezuela and Yemen.

Essential Oils II

Essential Oils II

This volume is divided into 18 chapters. The first chapter details the applications of essential oils in aromatherapy. The second chapter gives an account on the promise of essential oils in veterinary medicine. The different neuropharmacological properties of essential oils are explained in the third chapter. The fourth chapter describes the recent updates in essential oils with antimicrobial activities. The fifth chapter deals with the effects on essential oils on insects. The activities of essential oils as green pesticides are explicated in the sixth chapter. The seventh chapter deals with the role of essential oils in protection of crops. The next chapters individually elaborate the biological and therapeutic properties of 10 important essential oils. The facts and findings presented in the present volume would serve as basic as well as applied scientific material for further work in developing newer and effective therapeutic agents, flavouring agents, cosmetics and insecticides from essential oils.

Volume 37

This special volume is designed for professionals of interdisciplinary health sciences, food technology, pharmaceutical sciences, pharmacognosy, pharmacology, agriculture, botany, medicine, therapeutics, traditional medicine, complementary and alternative medicine, aromatherapy, herbalism, medical and public health sciences, healthcare professionals of other various disciplines, policy-makers and marketing and economic strategists. It is addressed to undergraduates, post-graduates, teachers and researchers.

Studium Press LLC P.O. Box 722200, Houston TX 77072 - U.S.A. Tel: (281) 776-8950, Fax: (281) 776-8951 E-mail: [email protected] Website: http://www.studiumpress.in

SERIES ISBN: 0–9656038–5–7 ISBN 1-933699-97-3

J N GOVIL Foreword to the Series

9 781933 699974

PROF. M S SWAMINATHAN

S ANJIB BHATTACHARYA Foreword to the Volume

DR. S AYYAPPAN

ISBN : 1-933699-97-3

Table of Contents About the Series Foreword to the Series Foreword to the Volume Preface

vii ix xi xiii

1.

Essential Oils and Aromatherapy GEORGE DAN MOGOSANU, ALEXANDRU MIHAI GRUMEZESCU, ION ANGHEL AND MARIANA CARMEN CHIFIRIUC (ROMANIA)

2.

Essential Oils in Veterinary Medicine SANJIB BHATTACHARYA (INDIA)

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3.

Neuropharmacological Effects of Essential Oils S. JEON AND B.S. KOO (REPUBLIC OF KOREA)

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4.

Essential Oils and Antimicrobial Activity JANNE ROJAS AND ALEXIS BUITRAGO (VENEZUELA)

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5.

Biological Activities of Essential Oils on Insects JALAL JALALI SENDI AND ASGAR EBADOLLAHI (IRAN)

6.

Bioactivity of Essential Oils as Green Biopesticides: Recent Global Scenario HANEM FATHY KHATER (EGYPT)

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Essential Oils for Crop Protection and Healthier Food and Feed VALERIA TERZI, GIORGIO TUMINO, ELISA RATTOTTI, ANTONIO MICHELE STANCA AND CATERINA MORCIA (ITALY)

8.

Lemongrass (Cymbopogon flexuosus Steud.) Wats Essential Oil: Overview and Biological Activities DEEPAK GANJEWALA AND ASHISH KUMAR GUPTA (INDIA)

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Public Health Importance of Lemon Grass Essential Oil ELININGAYA J. KWEKA, HUMPHREY D. MAZIGO AND MARGARET MOLLEL (TANZANIA)

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Pharmacological Activities of Basil Oil: A Review NASSER A. AWADAH ALI AND WILLIAM N. SETZER (YEMEN, USA)

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10.

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11.

Rose Oil: Overview and Pharmacological Effects KRASIMIR RUSANOV, NATASHA KOVACHEVA AND IVAN ATANASSOV (BULGARIA)

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12.

Biological Effects of Rosemary (Rosmarinus officinalis L.) Essential Oil ZITA FAIXOVÁ (THE SLOVAK REPUBLIC)

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13.

Eucalyptus Oil: Overview and Biological Effects HASSAN SERESHTI (IRAN)

355

14.

Medicinal Properties of Tea Tree Oil, Melaleuca alternifolia: A Review BRIANT BURKE MD, MS (USA)

15.

The Mystery of Lemon Oil RANABIR CHANDA (INDIA)

417

16.

Composition and Importance of Sage Essential Oil HASAN YALCIN AND HATICE KAVUNCUOGLU (TURKEY)

455

17.

The Role of Essential oil of Minthostachys verticillata (Griseb.) Epling, (Lamiaceae) and its Active Metabolites in Immediate-Type Hypersensitivity Responses LAURA NOELIA CARIDDI (ARGENTINA)

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Biological Effects of Cinnamon (Cinnamomum zeylanicum Ness.) Essential Oil ZITA FAIXOVÁ (THE SLOVAK REPUBLIC)

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Subject Index

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6 Bioactivity of Essential Oils as Green Biopesticides: Recent Global Scenario

HANEM FATHY KHATER1*

ABSTRACT Plant essential oils (EOs) are produced commercially from several botanical sources, mainly form members of the mint family. Some EOs have been recognized as a natural source of pesticides as they have many compounds that adversely affect growth and development and alter feeding, mating and oviposition behaviors. EO- based pesticides find their way to the market and their stability can be influenced through microencapsulation or nanoencapsulation. EOs are advantageous due to their low mammalian toxicity, eco-safety, no development of resistance, low cost of the active ingredients, reduced number of applications, higher popularity with organic growers and environmentally conscious consumers, and suitability for urban areas, homes and other sensitive areas such as schools, restaurants and hospitals. EOs can be used as alternative to synthetic insecticides or along with other insecticides under integrated pest control management for pests of medical, veterinary and agriculture importance. Thus, essential oils could make their way from the traditional into the modern insecticidal domain. Key words: Pest control, Green pesticides, Commercialization, Mode of action, Microencapsulation, Nanoencapsulation

Department of Parasitology, Faculty of Veterinary Medicine, Benha University, Moshtohor 13736, Egypt. * Corresponding author: E-mail: [email protected]

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INTRODUCTION With a greater awareness of the hazards associated with the use of synthetic organic insecticides, (Sanchez-Bayo, 2011; Sheikh, 2011), essential oils (EOs) could be suitable alternative products for pest control. EOs are extracted from various aromatic plants generally localized in Mediterranean and tropical countries where they represent an important part of the traditional pharmacopoeia. They are usually obtained by steam or hydro-distillation. The ancient Egyptians may have been the first to discover the potential of fragrance.  They created various aromatic blends, both for personal use and for ceremonies performed in the temples and pyramids. The Egyptians were masters in using essential oils and other aromatics in the embalming process.  Historical records indicate that one of the founders of “pharaonic” medicine was the architect Imhotep, who was the Grand Vizier of King Djoser (2780 – 2720 B.C.). Imhotep is often

Fig. 1: Global scenario on the Bioactivity of Essential Oils as Green Pesticides, designed by Eslam Afify, Different, Benha, Egypt

Fig. 2: Nefertiti offering essential oils to Isis

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given credit for ushering in the use of oils, herbs and aromatic plants for medicinal purposes. EOs also developed in the middle Ages by Arabs. EOs are known for their antiseptic, medicinal properties and their fragrance. In addition, they are used in embalmment, preservation of foods and as antimicrobial, analgesic, sedative, anti-inflammatory, spasmolytic and locally anesthetic remedies. In recent times, approximately 3000 volatile oils are known, 300 of which are produced commercially for pharmaceutical, sanitary, cosmetic, perfume, agricultural and food industries (as food preservers and additives) and their mechanisms of action have been revealed, particularly at the antimicrobial and insecticidal levels. Botanicals have been traditionally used for protection of stored commodities in the Mediterranean region and in southern Asia, but interest in EOs was renewed with emerging demonstration of their fumigant and contact insecticidal activities to a wide range of pests in the 1990s. More particulars about EOs and their constituents as green insecticides will be highlighted in the present work. CHEMICAL CONSTITUENTS EOs are volatile with strong odor found in several plant families, such as Myrtaceae, Lauraceae, Rutaceae, Lamiaceae, Asteraceae, Apiaceae, Cupressaceae, Poaceae, Zingiberaceae and Piperaceae. EOs can be synthesized by all plant organs, such as buds, flowers, leaves, stems, twigs, seeds, fruits, roots, wood or bark. They are liquid, volatile, limpid and rarely cultured, lipid soluble and soluble in organic solvents with a generally lower density than that of water. The oils are generally composed of complex mixtures of monoterpenes, biogenetically related phenols, and sesquiterpenes, for instance, 1,8-cineole, the major constituent of oils from rosemary, Rosmarinus officinale (Rs. officinale) and eucalyptus, Eucalyptus globus (Eu. globules); eugenol from clove oil, Syzygium aromaticum (Sy. aromaticum); thymol from garden thyme, Thymus vulgaris (Th. vulgaris); and menthol from various species of mint (Mentha species) (Isman, 1999). The chemical composition and broad spectrum of biological activities for EOs can vary with plant age, the plant tissues, geographical origin of the plant, the organ used in the distillation process, the type of distillation, and the species and age of a targeted pest organism (Chiasson et al., 2001). The variety of types and levels of active constituents in each oil may be responsible for the variability in

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their potential against pests. Valuable reviews on the chemical constituents of EOs are those of Edris (2007), Ebadollahi (2011) and Khater (2012). MODE OF ACTION Essential oils protect plants as they act as antibacterials, antivirals, antifungals, insecticides and also against herbivores by reducing their appetite for such plants. EOs interfere with basic physiological, behavioral, metabolic, and biochemical functions of insects as insects inhale, ingest or skin absorb EOs. EOs provoke rapid action against some pests indicating a neurotoxic mode of action. EOs disturb the function of octopamine which generate a total breakdown of the nervous system in insects. Octopamine is a biogenic amine found in insects and acts as a neur otransmitter, neurohor mone and circulating neurohormone–neuromodulator. Octopamine exerts its effects through interacting with at least two classes of receptors, octopamine-1 and octopamine-2 (Evans, 1980). Studies on cultured cells of the American cockroach, Periplaneta americana (Pr. americana) and brains of Drosophila melanogaster (Drs. melanogaster) demonstrated that eugenol mimics the action of octopamine and increases intracellular calcium levels. The role of the octopaminergic system in the cytotoxicity of EOs was also demonstrated in cultures of epidermal cells of Helicoverpa armigera. Tyramine (a precursor of octopamine) receptors are also involved in the recognition of monoterpenes such as thymol, carvacrol, and -terpineol in Drs. melanogaster. These monoterpenes influence the production of cyclic AMP (cAMP) and calcium at the cellular level. (See Regnault-Roger et al. (2012) for more details). Investigation of the formamidine insecticides revealed sublethal behavioral and physiological effects, probably mediated by the octopaminergic nervous system (Matsumura & Beeman, 1982). Sublethal effects, ex. feeding deterrence, repellency, were observed with some of the EO compounds may be consistent with this mode-ofaction. The lack of octopamine receptors in vertebrates likely accounts for the profound mammalian selectivity of EOs as insecticides (i.e., EOs are toxic to insects but not to mammals); therefore, the octopaminergic system of insects represents a biorational target for insect control strategies (Enan et al., 1998).

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In addition to octopamine receptors, Huignard et al. (2008) describe several different types of receptors, including gamma aminobutyric acid, GABA-gated neurons, which are target sites of the compounds. Thymol binds to GABA receptors associated with chloride channels located on the neurotransmitter analogous to the vertebrate noradrenaline membrane of postsynaptic neurons and disrupts the functioning of GABA synapses (Priestley et al., 2003). Monoterpenoids also inhibit acetylcholinesterase enzyme activity as the major site of action in insects (Rajendran & Sriranjini, 2008). Volatile oils reduce egg hatchability as oil vapors are toxic to eggs (Moawad & Ebadah, 2007; Khater et al., 2009) or as a result of chemical ingredients which may diffuse into eggs, thus affecting vital processes associated with embryonic development (Schmidt et al., 1991). The ovicidal and deterrent effects of EOs could be utilized in prophylaxis against insect infestation especially against myiasis infestations (Khater & Khater, 2009; Khater et al., 2011) and stored product pests (Khater, 2011; 2012). Some of the EOs and their components induce chemosterilant activity, making the insect pests sterile. The compound -asarone extracted from rhizomes of Acorus calamus (Ac. Calamus), possesses antigonadial activity causing the complete inhibition of ovarian development of different insects (Varma & Dubey, 1999). In addition to direct toxicity and chemosterilant activity, EOs induce oviposition and feeding deterrence, repellence and attraction, fumigant and sterilizing effects. Moreover, some oils cause larvicidal effect and the capacity to delay development and suppress emergence of adults (Khater, 2003; Shalaby & Khater, 2005; Khater & Shalaby, 2008; Khater & Khater, 2009; Khater et al., 2009, 2011; Khater, 2011; 2012). Some EOs are useful against pests that are resistant towards synthetic pesticides because EOs are a complex mixture of components including minor constituents, whereas synthetic pesticides are based on single products. Components of Eos act synergistically within the plant as a defense strategy. Hence, it is likely that they are more durable towards pests evolving resistance (Feng & Isman, 1995). The mode of actions of EOs have been reviewed in details by Bakkali et al. (2008), Khater (2011, 2012), and Regnault-Roger et al. (2012). BEHAVIORAL INSECT CONTROL Some plants contain chemicals which alter the behavior and life cycle of insect pests without killing them. Such chemicals are termed as

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“semio-chemicals” by the organization for Economic Cooperation and Development. Plants with strong smells act as repellents and can protect the crops nearby and called “companion plants” such as French marigold and coriander. Behavioral insect control is based on repellents and attractants, whereby a given species is either repelled from a host plant by a repulsive agent or attracted to a bait or pheromone. A Push–Pull or stimulo–deterrent diversionary strategy has been developed in South Africa for minimizing damage due to maize stem borer insects (Cook et al., 2006). This strategy involves the selection of plant species employed as trap crops to attract stem borer insects away from maize crops, or some plant species are used as intercrops to repel insects. Pennisetum purpureum and Sorghum vulgare attract the stem borer insect, while Milinis minutiflra, Desmodium uncinatum and Desmodium intorium are the repellent plants. Moreover, the Push– Pull strategy is also employed in the control of Heliothis sp. in cotton fields. Such strategy exploiting the chemical ecology of plants would prove an interesting, indigenous and readily available concept in the management of insect population in field crops. Repellent Effect Insect repellents are an alternative way to the use of insecticides through application to the skin for protection of an individual from the bites of mosquitoes, mites, ticks and lice. Moreover, repellents may be used to exclude insects from an area, such as in packaging to prevent infestation of stored products. The first use of repellents goes back into the mists of time. Herodotus reported the use of strong smelling substances on the skin amongst the ancient Egyptians. The use of repellents by civilian and military travellers may reduce the occurrence of local disease incidences in temperate areas. One of the widely used synthetic insect repellents is DEET, N, Ndiethyl-m toluamide which is generally considered the “gold standard” repellent, providing long-lasting protection of up to 8 hours from time of application. Unfortunately, it may cause environmental and human health risks, which have been reviewed in details by Khater (2012). There are some rare reports of severe reactions in people, besides DEET melts plastics causing spoilage of equipment, such as glasses and mobile phones, and many consumers find the odor and sensation on the skin unpleasant (Logan et al., 2010). Accordingly, natural repellents attracted the attention of researches as safe and ecofriendly alternatives to synthetic chemicals.

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Ticks detect repellents on the tarsi of the first pair of legs (Haller’s organ) and insects detect the same substances on the antennae. These structures are thought to be serially homologous between the two classes. Furthermore, the differences in sensitivity to repellents between different classes, orders and families are differences of degree only; no fundamental differences in the type of response are observed (Rutledge et al., 1997). Repellent metabolites

Over the centuries, more plant extracts, particularly essential oils, have been described as insect repellents. The best known repellent is citronella oil, which is obtained from various Cymbopogon species (Gramineae), e.g. Cymbopogon nardus (Cy. nardus). Citronella oil consists mainly of citronellal ((3,7-dimethyl-oct-6-enal) and geraniol (3,7dimethyl- octa-2,6(2,7)-dien-1-ol) (Büchel, 1970). Both components are also effective alone (citronella, e.g. Cockcroft et al., 1998; geraniol, e.g. Mumcuoglu et al., 1996). Structure-activity relationships of repellents indicate that when an insect repellent incorporates a ring structure, there is often a carbonyl group immediately removed from the ring. Most insect repellents are volatile terpenoids, such as terpenen-4-ol. Other terpenoids can act as attractants. In some cases, the same terpenoid can repel certain undesirable insects while attracting more beneficial insects to favor the dispersion of pollens and seeds, ex., geraniol repels house flies while attracting honey bees (Duke, 1990). Acyclic or monocyclic monoterpenes are small-volatile molecules. They are therefore involved in the transmission of airborne signals from plants to insects. In the sensilla of insects, specialized odorant binding proteins (OBPs) respond to volatile monoterpenes. For example, trichoid sensilla of the female silkworm, Bombyx mori, respond to linalool (Picimbon et al., 2008). Most of the arthropod-repellent compounds are oxygenated, having the hydroxyl group linked to a primary, secondary or aromatic carbon. More importantly, some metabolites with the hydroxyl group linked to a tertiary carbon (linalool, -terpineol and limonene), such activity is suppressed against Anopheles gambiae (An. gambiae), suggesting the possibility that the type of carbon where the hydroxyl substitution is present modulates repellency. Some metabolites are responsible for the repellent activity of EOs such as -pinene, isolated from the EO of Dianthus caryophyllum, against ticks, Ixodes ricinus (Ix. ricinus), monoterpenes (-pinene,

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cineole, eugenol, limonene, terpinolene, citronellol, citronellal, camphor, and thymol) against mosquitoes; and sesquiterpenes, -caryophyllene, repellent against Aedes aegypti (Ae. aegypti); phytol, a linear diterpene alcohol, against An. gambiae; phenylethyl alcohol, -citronellol, cinnamyl alcohol, geraniol. Patterns of sensitivity were similar among some chemicals of unrelated structure, but some differences existed between the sensitivity to compounds of similar structure. Observed non-correlation of structure with activity suggests that repellent tolerances may be non-adaptive; i.e. evolved by random drift of selectively neutral mutations (Rutledge et al., 1997). For reviews, see Peterson & Coats (2001), Nentwig (2003), Nerio et al. (2010); Dubey et al. (2011); Khater (2011, 2012), and Regnault-Roger et al. (2012). SYNERGISTIC PHENOMENA In the context of synergism between the components of EOs, they are complex mixtures of numerous molecules and the activity of the main components is modulated by other minor molecules. It is expected that several components of the EO take part in defining the fragrance, the density, the texture, the color, cell penetration, lipophilic or hydrophilic attraction, fixation on cell walls and membranes, and cellular distribution. This last trait is very important because the distribution of the oil in the cell determines the different types of radical reactions produced, depending on their compartmentation in the cell. As a result, it is more useful to study an entire oil rather than some of its main components, e.g., terpineol, eugenol, thymol, carvacrol, carvone, geraniol, linalool, citronellol, nerol, safrole, eucalyptol, limonene, cinnamaldehyde. It is worthy to mention that an insecticide developed with essential oils does not need to be restricted to just one essential oil or even essential oils only. It may be possible to combine patchouli and thyme oils with lower cost essential oils which showed moderate toxicity, for instance, peppermint or clove oils. Alternately, essential oils could be added to other insecticides such as pyrethrum based insecticides, to enhance their toxicity. The concept of synergism appears to be more meaningful for reducing the dose of applied substances and the risk of developing resistance. It is important to note that negative synergism can occur between EOs or their components and the other ingredients present in the total formulation. For more info about synergistic phenomena of EOs, see Bakkali et al. (2008), Nerio et al. (2010) and Khater (2011,2012).

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SAFETY AND ADVANTAGES Some of the purified terpenoid ingredients of EOs are moderately toxic to mammals. With few exceptions, the oils themselves or products based on them are mostly nontoxic to mammals, birds, and fish ((Stroh et al., 1998: Isman, 2000). Many of the commercial products that include EOs are on the ‘Generally Recognized as Safe’ (GRAS) list fully approved by the Food and Drug Administration (FDA) and Environmental Protection Agency (EPA) in USA for food and beverage consumption. Eugenol is completely broken down to common organic acids by soilborne Pseudomonas bacteria (Rabenhorst, 1996). Some EO constituents acquired through the diet are actually beneficial to human health; consequently, there is no concern for residues of EO pesticides on food crops (Huang et al., 1994). As broad-spectrum insecticides, both pollinators and natural enemies are vulnerable to poisoning via direct contact by products based on EOs. Because of their volatility, EOs have limited persistence under field conditions; consequently, predators and parasitoids reinvade a treated crop one or more days after treatment and they are unlikely to be poisoned by residue contact as often occurs with conventional insecticides. Farmers in developing countries, especially in tropical and subtropical regions, get the benefits of botanical insecticides. Mosquito management/abatement, is done through large-scale urban fogging, or for individual property ‘‘perimeter’’ treatments, using controlled-release timers (‘‘puffers’’). Treatment of waterways and standing water using essential oil as larvicides and repellents has been a very recent field of investigation. They are used for home and garden use for flying and crawling insects and related pests; management of turfgrass and landscape pests; for ectoparasite control on dogs and cats; and as personal repellents for application to the skin and/or clothing to prevent/ limit attack by blood-feeding flies and ticks. The cytotoxic capacity of the essential oils, based on a prooxidant activity, can make them outstanding antiseptic and antimicrobial agents for personal uses, i.e. for purifying air, personal hygiene, or even internal use via oral consumption, and for insecticidal use for the preservation of crops or food stocks. Moreover, EOs are usually devoid of long-term genotoxic risks and some of them show a very clear antimutagenic capacity which could be linked to an anticarcinogenic activity. The prooxidant activity of essential oils or some of their constituents, like that of some polyphenols, is capable in reducing local tumor volume or tumor cell proliferation by apoptotic and/or necrotic effects (Buhagiar

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et al., 1999; Salim & Fukushima, 2003; Manosroi et al., 2006). Due to the capacity of EOs to interfere with mitochondrial functions, they may add prooxidant effects and thus become genuine antitumor agents. The previously mentioned safety and advantages designate that EOs could find their way from the traditional into the modern medical and insecticidal domain. For more particulars about safety and advantages of EOs, see Isman (2000, 2006, 2008, 2010), Tripathi et al. (2009), Nerio et al. (2010), Isman et al. (2011), Khater (2011, 2012) and RegnaultRoger et al. (2012). COMMERCIALIZAION The most important aspect of using EOs and/or their constituents is their favorable mammalian toxicity and the relatively low cost of the active ingredients, a result of their extensive worldwide use as fragrances and flavoring. In contrary, pyrethrum and neem are used predominantly for insecticide production. For valuable information about neem as source of bioinsecticides, see Ahmed et al. (1984) Forim et al. (2011) and Nicoletti et al. (2011). Owing to their safety, EO based products are generally exempted from toxicity data requirements by the Environmental Protection Agency (EPA), USA and some American companies have been able to produce essential- oil-based pesticides to market. With over a dozen registered products by the end of 1999, EcoSMART Technologies, Inc., United States) is aiming to become a world leader in EO-based pesticides. Such company currently produce aerosol and dust formulations containing proprietary mixtures of EO compounds, including eugenol and 2-phenethyl propionate for controlling domestic pests (cockroaches, ants, fleas, flies, wasps, etc.). These are marketed to pest control professionals under the brand name EcoPCOR, with less concentrated formulations for sale to the consumer under the name BioganicTM. EcoSMART Technologies also produce several products, such as Mosquito & Tick Control which kills and repels mosquitoes, ticks, fleas, gnats, crickets, millipedes, mites and other crawling and flying insects and the product holds eugenol, peppermint, rosemary, thyme and sesame oils; Flying Insect Killer which kills flies, gnats, mosquitoes, moths, wasps and other flying insect pests on contact and includes peppermint, cinnamon, sesame, wintergreen and canola oils; Bed Bug Killer and Repellent contains peppermint, rosemary, wintergreen oil and white mineral oils; Home Pest Control which kills and repels over 100 home invading pests, such as ants, beetles, centipedes, cockroaches,

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crickets, earwigs, fleas, millipedes, pantry pests, pillbugs, silverfish, spiders, sowbugs, ticks and other crawling insect pests; and Garden Insect Killer for many common insect garden pests including aphids, mites, thrips, whiteflies, beetles, and caterpillars. The latest two products contain peppermint, rosemary, thyme, and clove oils. Mycotech Corporation produces CinnamiteTM, an aphidicide/ miticide/fungicide for glasshouse and horticultural crops and ValeroTM, a miticide/ fungicide for use in grapes, berry crops, citrus and nuts. Both products are based on cinnamon oil, with cinnamaldehyde (30% in EC formulations) as the active ingredient. Many commercial products such as Buzz Away (containing oils of citronella, cedarwood, eucalyptus and lemongrass), Green Ban (containing oils of citronella, cajuput, lavender, safrole from sassafrass, peppermint and bergaptene from bergamot oil) and Sin-So-SoftR (containing various oils) are in use as insect repellents (Chou et al., 1997). Several EO constituents are already in use as an alternative to conventional insecticides. For example, pulegone and citronellal are used as mosquito repellents. A patented natural repellent is based on nepetalactone and dihydronepetalactone obtained from Nepeta cataria (N. cataria) that is effective against cockroaches, mosquitoes, mites, ticks and other household insects (Scialdone, 2006; Hallahan, 2007). Nootkatone from vetiver oil and its derivatives, tetrahydronootkatone and 1,10dihydronootkatone have been patented as repellent against mosquitoes, cockroaches, termites, and ants (Henderson et al., 2005 a,b: Zhu et al., 2005). For more information about patent literature on mosquito repellent inventions which contain plant essential oils, see Pohlit et al., (2011). Several smaller companies in the U.S. and the U.K. have developed garlic-oil based pest control products. There are consumer insecticides for home and garden, in U.S.A, using mint oil as the active ingredient. Menthol has been approved for use in North America for control of tracheal mites in beehives. A product produced in Italy (Apilife VARTM) containing thymol and lesser amounts of cineole, menthol and camphor is used to control varroa mites in honeybees (Canadian Honey Council; http://www.saskatchewanbeekeepers.ca/users/folder.asp@FolderID =5317.htm). Neem is widely used as insecticide and repellent. The biological compound MiteStop® based on a neem seed extract has a very high and broad efficacy against a wide spectrum of insects, ticks and mites that

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molest birds, animals and humans (Abdel-Ghaffar et al., 2008a, b; AbdelGhaffar & Semmler, 2007; Abdel-Ghaffar et al., 2009; Locher et al., 2010a; b). More products based on neem and other botanical resources will be discussed later on in this chapter. See Khater (2012) for more information in relation to resource availability, production and barriers to commercialization of botanicals. Standardization The chemical profile of the essential oil products differs not only in the number of molecules but also in the stereo chemical types of molecules extracted, according to the type of extraction, which chosen according to the purpose of the use. The extracted product can vary in quantity, quality, and in composition according to plant organ, age, vegetative cycle stage, climate, and soil composition (Masotti et al., 2003; Angioni et al., 2006). As with many herbal products, herbal repellents have a problem of standardization. For example, the oil obtained from Cy. nardus, which is used against mosquitoes, has a considerably more lasting effect than the oil from Cymbopogon commutatus, Cymbopogon martinii or Cymbopogon pendulus (Tyagi et al., 1998). In order to obtain essential oils of constant composition, they have to be extracted under the same conditions from the same organ of the plant which has been growing on the same soil, under the same climate and has been picked in the same season. Most of the commercialized essential oils are chemotyped by gas chromatography and mass spectrometry analysis published (European pharmacopoeia, ISO, WHO, Council of Europe) to ensure good quality of essential oils. For more information about standar dization, regulatory approval and commercialization, see Tripathi et al. (2009), Isman (2006, 2010), Dubey et al. (2011), and Khater (2012). IMPROVING THE EFFICACY EOs are good penetrants which increase their own bioavailability and that of coadministered products. These properties are related to the disruption of lipid bilayers in cells. Coconut oils, which have some repellent effect themselves, are used for preference as carriers, particularly for neem, Azadirachta indica (Az. indica) oil (e.g. Sharma et al., 1993). Some EOs have specific modes of action that make them good synergists. In particular, a number of compounds are well-established inhibitors of insect P450 cytochromes responsible for phase I metabolism

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of xenobiotics, including insecticides. These include phytochemicals containing methylene dioxy rings such as dillapiole in dill (Anthema sowa, Ant. sowa) oil, piperamides from Pipe r spp. oils, and furanocoumarins from oil of bergamot (Citrus bergamia). Dillapiole and semisynthetic derivatives have a synergistic factor of two- to six fold when combined with botanical insecticides (Belzile et al., 2000), but piperamides have a remarkable synergism factor of 11 when combined with pyrethrin (Jensen et al., 2006) and they have profound effects on the cytochrome P450 transcriptome of treated insects. It worth to mention that some oils are mosquito repellents such as coconut, palm nut and andiroba oils, although all of these three oils are far less effective than DEET, they may be useful as carriers for other repellent actives as they are cheap and contain unsaturated fatty acids and emulsifiers that improve repellent coverage and slow evaporation of volatile repellent molecules (see Maia & Moore (2011) and Khater (2011, 2012) for more details). Attractant adhesive films with EOs are used for controlling insects in agriculture and horticulture (Klerk’s Plastic Industries B.V., 1990). EOs can also be incorporated with polymers into sheets. The stability of essential oil formulations can also be influenced by the use of specific agents known to maintain essential oil stability or by using techniques such as microencapsulation or nanoencapsulation during the manufacturing process. Smart delivery systems will allow real-time monitoring and regulation of delivery of constituents (nutraceuticals, nutrients, drug, insecticides, pesticides, fertilizers, vaccines, etc.) to people, animals, plants, insects, microorganisms, soils and the environment. MICROENCAPSULATION Encapsulation reduces the loss of the active agents and offers the possibility of a controlled release of oil vapors. Therefore, it is a suitable technology for the formulation of EO- based pesticides. Encapsulated product from Syngenta, one of the world’s largest agrochemical corporations, delivers a broad control spectrum on primary and secondary insect pests of cotton, rice, peanuts, and soybeans. Marketed under the name Karate® ZEON, a quick release microencapsulated product contains the active compound lambda-cyhalothrin (a synthetic insecticide based on the structure of natural pyrethrins) which breaks open on contact with leaves. The encapsulated product “gutbuster” only breaks open to release its contents when it comes into contact with alkaline environments, such as the stomach of certain insects.

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Microcapsules containing the most promising oils such as Rs. officinalis and Thymus herba-barona induce larvicidal effects against gypsy moth, Limantria dispar, larvae, one of the most serious pests of cork oak forests. The microcapsules had toxic effects at a concentration similar to that usually employed for localized treatments with microgranular synthetic pesticides. Toxicity appeared to be maximized when the microparticles adhered to the typical hair structures of several defoliator families (Moretti et al., 2002). See Nerio et al. (2010), Khater (2012), and Regnault-Roger et al. (2012) for more innovative ideas about improving the efficacy of EOs. NANOTECHNOLOGY The potential uses of nanotechnology are immeasurable. These include enhancement involving nanocapsules for vector and pest management and nanosensors for pest detection. Nanoparticles are 1-100 nm in diameter. Such particles are agglomerated atom by atom. Nanotechnology is used widely in Agriculture and Food (Joseph & Morrison, 2006). Such technology improves pesticide delivery systems which can take action to environmental changes in a controlled manner in response to different signals e.g. heat, moisture, ultrasound, magnetic fields, etc. Nanosilica, a novel nanobiopesticide, surface charged modified hydrophobic nanosilica (~3-5 nm) could be successfully used to control a range of agricultural insect pests and animal ectoparasites of veterinary importance (Ulrichs et al., 2005, 2006 a, b, c, d, e). Using oil-in-water microemulsions as a nano-pesticide delivery system to replace the traditional emulsifiable concentrates (oil), in order to reduce the dosage of pesticides and the use of organic solvent and increase the disparity, wettability and penetration properties of the droplets is being developed. These microemulsions would be a useful strategy in green pesticide technology. Green synthesis of nanoparticles (NPs), such as silver or gold NPs, has been attracting increasing attention in recent years. The pediculicide and larvicidal activity of synthesized Ag NPs using an aqueous leaf extract of Tinospora cordifolia (sizes measuring 54–80 nm) showed maximum mortality against the human head louse, Pediculus humanus capitis (P.h. capitis) and fourth instar larvae of Anopheles subpictus (An. subpictus) and Culex quinquefasciatus (Cx. quinquefasciatus) (the medin lethal concetraion, LC 50 = 12.46, 6.43 and 6.96 mg l”1), respectively (Jayaseelan et al., 2011). The methanol, aqueous leaf extracts and synthesized Ag NPs of Euphorbia prostrata (E. prostrate) possessed high acaricidal activity against the adult cattle tick,

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Haemaphysalis bispinosa (Hm. bispinosa) and the haematophagous fly, Hippobosca maculata (Hip. maculata) infesting cattle in India (Zahir & Rahuman, 2012). The first report on the activity of synthesized Ag NPs using leaf aqueous extract of Manilkara zapota (Mn. zapota) against the housefly, Musca domestica (Mu. domestica) had been provided by Kamaraj et al. (2012). Adult flies were exposed to different concentrations of the aqueous extract of synthesized Ag NPs, 1 mM silver nitrate (AgNO3) solution and aqueous extract of Mn. zapota. AgNPs showed 72% mortality in 1 h, 89% mortality was found in 2 h, and 100% mortality was found in 3 h exposure at the concentration of 10 mg/mL; whereas, the leaf aqueous extract showed 32% mortality in 1 h, 48% mortality was found in 2 h, and 83% mortality was found in 3 h exposure at concentration of 50 mg/mL. The most efficient activity was observed in synthesized Ag NPs against Mu. domestica (LD50 = 3.64 mg/mL; LD90 = 7.74 mg/mL), the moderate activity reported in the aqueous extract of Mn. zapota (LD50 = 28.35 mg/mL; LD90 = 89.19 mg/mL) and nil activity were observed in AgNO3 solution at 3 h exposure time at 10 mg/mL. The acaricidal and larvicidal activity of synthesized silver nanoparticles (AgNPs) utilizing aqueous leaf extract from Musa paradisiaca L (Ms. paradisiaca). were evaluated against the larvae of Hm. bispinosa and larvae of hematophagous fly Hip. maculata and against the fourth-instar larvae of malaria vector, Anopheles stephensi (An. stephe nsi) Liston, Japan ese encephalitis vector , Culex tritaeniorhynchus (Cx. tritaeniorhynchus). The parasite larvae were exposed to varying concentrations of aqueous extract of Ms. paradisiaca and synthesized AgNPs for 24 h. The maximum efficacy was observed in the aqueous extract of Ms. paradisiaca against Hm. bispinosa, Hip. maculata, and the larvae of An. stephensi, Cx. tritaeniorhynchus with LC50 values of 28.96, 31.02, 26.32, and 20.10 mg/lm, respectively. The synthesized AgNPs of Ms. paradisiaca showed the LC50 against Hm. bispinosa, (1.87 mg/l), Hip. maculata (2.02 mg/l), and larvae of An. stephensi (1.39), against Cx. tritaeniorhynchus (1.63 mg/l), respectively (Jayaseelan et al., 2012). Anti-parasitic activities of synthesized zinc oxide nanoparticles (ZnO NPs) against the larvae of cattle tick Rhipicephalus (Boophilus) microplus (R. microplus), P.h. capitis, larvae of malaria vector, An. subpictus, and filariasis vector, Cx. quinquefasciatus were evaluated through exposure to filter paper envelopes impregnated with different ZnO NP concentrations. The mortality effects of synthesized ZnO NPs were 43% at 1 h, 64% at 3 h, 78% at 6 h, and 100% after 12 h against R. microplus

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activity. In pediculocidal activity, the results showed that the optimal times for measuring mortality effects of synthesized ZnO NPs were 38% at 10 min, 71% at 30 min, 83% at 1 h, and 100% after 6 h against P.h. capitis. One hundred percent lice mortality was observed at 10 mg/L treated for 6 h. The mortality was confirmed after 24 h of observation period. The larval mortality effects of synthesized ZnO NPs were 37%, 72%, 100% and 43%, 78% and 100% at 6, 12, and 24 h against An. subpictus and Cx. quinquefasciatus, respectively. The maximum efficacy was observed in zinc oxide against R. microplus, P.h. capitis, and the larvae of An. subpictus, Cx. quinquefasciatus with LC50 values of 29.14, 11.80, 11.14, and 12.39 mg/L, respectively. The synthesized ZnO NPs showed the LC50 against R. microplus (13.41 mg/L), P.h. capitis (11.80 mg/L), and the larvae of An. subpictus (0.945 mg/L), against Cx. quinquefasciatus (4.87 mg/L), respectively ( Kirthi et al., 2011). Synthesized silver nanoparticles Ag NPs using leaf aqueous extract of Lawsonia inermis possess excellent anti-lousicidal activity against the human head louse, P.h. capitis, and sheep- biting louse, Bovicola ovis (B. ovis) through direct contact method. The average percent mortality for synthesized Ag NPs was 33, 84, 91, and 100 at 10, 15, 20, and 35 min, respectively against B. ovis. The maximum activity was observed in the aqueous leaf extract of L. inermis, 1 mM AgNO3 solution, and synthesized Ag NPs against P.h. capitis with LC50 values of 18.26, 7.77, and 1.33 mg l1 , respectively, and against B. ovis showed with LC50 values of 21.19, 8.49, and 1.41 mg l-, respectively (Marimuthu et al., 2011). Zahir et al. (2012) evaluated the efficacies of aqueous leave extracts of E. prostrata, silver nitrate (AgNO 3) solution (1mM) and silver nanoparticles, synthesized Ag NPs against the adult of Sitophilus oryzae L (S. oryzae). The LD50 values were 213.32, 247.90, 44.69 mg/kg –1; LD90=1648.08, 2675.13, 168.28 mg/kg –1, respectively, which indicate that the leave aqueous extracts of E. prostrata, and synthesized Ag NPs have the potential to be used as an ideal eco-friendly approach for the control of the S. oryzae. Nanoparticles loaded with garlic essential oil are efficacious against the red flour beetle, Tribolium castaneum (T. castaneum) Herbst (Yang et al., 2009). Aluminosilicate filled nanotube can stick to plant surfaces while nano ingredients of nanotube have the ability to stick to the surface hair of insect pests and ultimately enters the body and influences certain physiological functions (Patil, 2009). DNA tagged gold nanoparticles are effective against the major polyphagous pest, Spodoptera litura (S. litura), 2nd instar larvae. The LC50 (216.91 to 938.95 conc. at 95% CI) increased as the larval age increased (Chakravarthy et al., 2012). Encapsulated citronella oil

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nanoemulsion is prepared by high-pressure homogenization of 2.5% surfactant and 100% glycerol, to create stable droplets that increase the retention of the oil and slow down release. The release rate relates well to the protection time so that a decrease in release rate can prolong mosquito protection time (Sakulku et al., 2009). Innovative alternative approach had been conducted to control the hematophagous fly and sheep-biting louse by synthesized titanium dioxide nanoparticles (TiO2 NPs) utilizing leaf aqueous extract of Catharanthus roseus (C. roseus) against the adults of hematophagous fly, Hip. maculata, and B. ovis. Adulticidal parasitic activity was observed in varying concentrations of aqueous leaf extract of C. roseus, TiO2 solution, and synthesized TiO2 NPs for 24 h. The maximum parasitic activity was observed in aqueous crude leaf extracts of C. roseus against the adults of Hip. maculata and B. ovis with LD50 values of 36.17 and 30.35 mg/L, respectively. The highest efficacy was reported in 5 mM TiO2 solution against Hip. maculata and B. ovis (LD50 = 33.40 and 34.74 mg/L), respectively, and the maximum activity was observed in the synthesized TiO2 NPs against Hip. maculata and B. ovis with LD50 values of LD50 = 7.09 and 6.56 mg/L, respectively (Velayutham et al., 2012). Likewise, nanoencapsulation of garlic oil using polyethylene glycol coated nanoparticles dramatically improved the stability of garlic oil in the control of the stored product pest, T. castaneum. The nanoencapuslated garlic oil was 80% as toxic at 5 months as the first day, while non-encapusalted garlic oil caused only 11% toxicity. In addition, the chemical composition of the nanoencapsulated garlic oil was still similar to the original composition, even after 5 months had passed (Yang et al., 2009). Nanoparticles are simple, non-toxic, ecofriendly green material and widely acceptable publicly. For more in rank about usages of nanoparticles, see Torney (2009), Omara et al. (2009), Yang et al. (2009), Bhattacharyya et al. (2008, 2010), Ahmed et al. (2011), Hashim (2011), and Khater (2011, 2012). ESSENTIAL OILS FOR CONTROLLING SERIOUS PESTS Insects of Medical and Veterinary Importance Mosquitoes

Mosquitoes are one of the most important insect pests that affect the health and well being of humans and domestic animals worldwide. Female mosquitoes require a blood meal for egg production, and they

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produce a painful bite as they feed. They act as vectors for many tropical and subtropical diseases such as dengue fever, yellow fever, malaria, filariasis and encephalitis of different types. Mosquito control is an important component in the strategies to manage mosquito-borne diseases. In the past few years, several authors have investigated various plant compounds with anti-mosquito potential that included larvicidal, adulticidal and repellent activities. Culex species

Some Egyptian essential oils provided an excellent potential for controlling Culex pipiens (Cx. pipiens). The LC50 values were 32.42, 47.17, 71.37, 83.36, 86.06, and 152.94 ppm for fenugreek (Trigonella foenum-grecum), earth almond (Cyperus esculentus), mustard (Brassica compestris), olibanum (Boswellia serrata), rocket (Eruca sativa), and parsley (Carum ptroselinum), respectively. The tested oils altered some biological aspects of Cx. pipiens, for instance, developmental periods, pupation rates, and adult emergences. The lowest concentrations of olibanum and fenugreek oils (7.81 ppm for both oils) caused remarkable prolongation of larval (14.90 and 9.75 days, respectively) and pupal (8.25 and 5.85 days, respectively) durations. Data also showed that the increase of concentrations was directly proportional to reduction in pupation rates and adult emergences. Remarkable reduction in pupation rate (1.67 %) was achieved by mustard oil at 1000 ppm. Adult emergence was suppressed by earth almond and fenugreek oils at 125 ppm. In addition, the tested plant oils exhibited various morphological abnormalities on larvae, pupae, and adults. Consequently, fenugreek was the most potent oil and the major cause of malformation of both larval and pupal stages (Khater & Shalaby, 2008). Ginger, Zingiber officinale (Zn. officinale), yield volatile oil ranges from 1 to 3% which contains mainly mono and sesquiterpenoids (Ali et al., 2008). The essential oil was found to have larvicidal activity against the late insetars of the filarial mosquito Cx. quinquefasciatus with LC50 of 50.78 ppm after 24 h of treatment (Pushpanathan et al., 2008). The hydrolates of four plants, Zanthoxylum limonella (Z. limonella), Zn. officinale, Curcuma longa (Cr. longa), and Cymbopogon citratus (Cy. citratus) induced larvicidal activity against laboratory reared Cx. quinquefasciatus. Z. limonella was the most effective hydrolate of against Cx. quinquefasciatus with LC50 15.5 (%v/v). The larvicidal activity of hydrolates of Zn. officinale, Cr. longa and Cy. citratus were also found promising with LC50 of 21.8, 35.5 and 38.8 (%v/v) (Rabha et al., 2012).

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An insecticide containing azadirachtin form neem (Az. indica) extract was effective against larvae and pupae of Cx. pipiens. After treatment of larval stage, LC50 and LC90 values for azadirachtin were 0.35 and 1.28 mg/L in direct effect and 0.3-0.99 mg/l in indirect effect, respectively. Second, after treatment of the pupal stage, the LC50 and LC90 in direct effect were measured as 0.42 -1.24mg/l and in indirect effect was 0.39mg/l-1.14mg/l, respectively. Mosquito adult fecundity was markedly decreased and sterility was increased by the azadirachtin after treatment of the fourth instar and pupal stage. The treatment also prolonged the duration of the larval stage (Alouani et al., 2009). It worth to mention that rosemary controlled Cx. pipines effectively (Shalaby & Khater, 2005). The essential oils of spices/aromatic medicinal plants particularly Foeniculum vulgare and Tagetes patula carry huge potential as a mosquito larvicide (Rana & Rana, 2012). Moreover, EOs of Cy. citratus induced larvicidal effect against Cx. quinquefasciatus. The LC50 values calculated after 24 hours treatment for the 2nd, 3rd and 4th larval instar

Fig. 3: . Morphological abnormalities induced by some essential oils against mosquitoes treated as 4th larval instars. A. Normal larva. B-D. Malformed larvae. B. Larvae with deformed cuticles. C. Larva with an opaque swelling on the thorax and black coloration at the posterior end. D. Pharate pupa. E. Normal Pupa. F, G. Elephantoid pupa, with enlarged cephalic region and extended abdomen. H. Black cephalothorax (lower arro ws) and extended abdomen with transparent posterior end (upper arrow) and no anal gills. I. Normal adult. J. flaiur of adult eclosion. K. malformed adult, deformed wing and legs. Adapted form Khater (2003)

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were 144.54, 165.70 and 184.18 ppm, respectively (Pushpanathan et al., 2006). Sesame, Sesamum indicum, nigella, Nigella sativa, and onion, Allium cepa (Al. cepa), oils induced larvicidal effect and adversely affect pupation and adult emergence rates of Cx. pipiens, Fig. 3 (Khater, 2003). In addition, Ansari et al. (2000) found that application of peppermint, Mentha piperita L. (M. piperita) oil at 3 ml/m2 of water surface area resulted in 100% mortality within 24 h for Cx. quinquefasciatus. Anopheles species

It was proved by Ajaiyeoba et al. (2008) that essential rhizome oil from Cr. longa was most potent larvicide against the An. gambiae with an LC50 of 0.017 mg/ml. The plant-based compounds from neem oil such as limonoids may be an effective alternative to conventional synthetic insecticides for the control of An. stephensi (Senthil-Nathan et al., 2005) M. piperita oil at 3 ml/m2 of water surface area resulted in 85% for An. stephensi (Ansari et al., 2000). Alkaloids isolated from Annona squamosa have shown larvicidal growth-regulating and chemosterilant activities against An. stephensi at concentrations of 50 to 200 ppm (Saxena et al., 1993). Four essential oil of basil accessions conferred complete mosquito repellency against Anopheles mosquito (assayed by the human-bait technique) lasting for 1.5 to 2.5 h per one application of 0.1 mL to a volunteer’s arm (Nour et al., 2009). Aedes sepcies

The larvicidal activity of hydrodistillate extracts from peppermint, M. piperita, Ocimum basilicum L. (Oc. basilicum), Cr. longa L. and Zn. officinale L. had been proved against the dengue vector Ae. aegypti. The results indicated that the mortality rates at 80, 100, 200 and 400 ppm of M. piperita, Zn. officinale, Cr. longa and Oc. basilicum concentrations were highest amongst all of the crude extracts tested against all the larval instars and pupae of Ae. aegypti. LC90 values were 47.54 and 86.54 ppm for M. piperita, 40.5 and 85.53 ppm for Zn. officinale, 115.6 and 193.3 ppm for Cr. longa and 148.5 and 325.7 ppm for Oc. basilicum, respectively. All of the tested oils proved to have strong larvicidal activity (doses from 5 to 350 ppm) against Ae. aegypti fourth instars, with the most potent oil being M. piperita extract, followed by Zn. officinale, Cr. longa and Oc. basilicum. In general, early instars were more susceptible than the late instars and pupae (Kalaivani et al., 2012).

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The oil of Carapa guianensis (Ca. guianensis), extracted from andiroba seed kernels, occurs not only in southern Central America but also in Colombia, Venezuela, Suriname, French Guiana, Brazil, Peru, Paraguay, and the Caribbean islands (Pennington et al., 1981). Studies demonstrating the larvicidal activity of Ca. guianensis were firstly described by Silva et al. (2004) for wild populations of Aedes albopictus (Ae. albopictus). After that, Mendonça et al. (2005) evaluated the oil of this plant for laboratory populations of Ae. aegypti. Oils of Ca. guianensis and Copaifera spp. are well known in the Amazonian region as natural insect repellent. Both oils brought on larvicidal in wild populations of Ae. aegypti with a history of exposure to organophosphate. The wild populations of Ae. aegypti, transmitting the dengue virus in the environment, were also susceptible to Ca. guianensis and Copaifera sp. oils. The lethal concentrations for Copaifera sp. ranged from LC50 47 to LC90 91 (milligrams per liter), and for Ca. guianensis, they were LC50 136 to LC90 551 mg/L (Prophiro et al., 2012). The essential oil of leaves of Hyptis martiusii Benth and 1,8-cineole showed pronounced insecticidal effect against Ae. aegypti larvae (Araújo et al., 2003). Essential oil from Eucalyptus globulus (Eu. globulus) is toxic to Ae. aegypti larvae and showed LC50 of 32.4 ppm (Lucia et al., 2007). The essential oils obtained from the inflorescence of Piper marginatum, though proved to be effective larvicides, did not interfere significantly in the oviposition activity of Ae. aegypti (Autran et al., 2009). The hydrolates of four plants, Z. limonella, Zn. officinale, Cr. longa, and Cy. citratus induced larvicidal activity against laboratory reared Ae. albopictus .The hydrolate of Z. limonella was most effective against both Ae. albopictus with LC50 11 (%v/v). The larvicidal activity of hydrolates of Zn. officinale, Cr. longa and Cy. citratus were also found promising with LC50 at 15.8, 24.7 and 33.7 (%v/v) respectively against Ae. albopictus (Rabha et al., 2012). M. piperita oil at 3 ml/m2 of water surface area resulted in 90% for Ae. aegypti larvae (Ansari et al. 2000) and the essential oil of Cy. citratus was observed to have an LC50 of 69 ppm (Cavalcanti et al., 2004). Mosquito control and temperature variation

In relation to different temperature, the effectiveness of the oils on larval mortality was directly related to the increase of temperature, and better results were observed for a temperature at 25°C (Prophiro et al., 2012). At temperatures under 25°C, the mortality decreased significantly. These results were expected, since mosquitoes decrease their movements or even their metabolism when temperatures are lower or higher than

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optimal. Therefore, the direct influence of low temperatures on larval mortality of Ae. aegypti indicates the necessity of a larger quantity of oil estimated for effective control. Likewise, Patil et al. (2011) evaluated larvicidal activity of extracts of medicinal plants Plumbago zeylanica L. and Cestrum nocturnum L. against Ae. aegypti; the LC50 values of both plants were less than 50 ppm. The larvicidal stability of the extracts at five constant temperatures (19°C, 22°C, 25°C, 28°C and 31°C) evaluated against fourth instar larvae revealed that toxicity of both plant extracts increases with increase in temperature. Eggs and larval stages are the weakest link in mosquito life cycle and effective mosquito control must include successful ovicidal and larvicidal programs. The larvicidal mode of action of essential oils could be explained as the susceptibility of mosquito larvae and pupae to surface materials entering their tracheal system, observing that essential oils increased the tendency to tracheal flooding and chemical toxicity (Corbet et al., 1995). Mosquito repellents

The World Health Organization also recommends repellents for protection against malaria, because of the increasing resistance of Plasmodium falciparum to anti-malarial drugs such as chloroquine (Anonymous, 1988). Several reports are available about the repellent properties of essential oils against adult mosquitoes. Botanical, herbal or natural-based repellents include one or several plant essential oils. These oils are considered safe by the EPA at the low concentrations used, but provide a limited duration of protection against mosquitoes (< 3 hours). Citronella is the principal and sometimes only active ingredient in many plant-based insect repellents. (See Stafford (2007) for more details). Regarding the use of eucalyptus, burning of leaves of Eucalyptus citriodora (Eu. citriodora) provides a cost-effective method of household protection against mosquitoes in Africa (Seyoum et al., 2003). A variety of eucalyptus oils are reported to be very good repellents to mosquitoes, but they are attractive to other biting flies. Eucalyptus oil has been used as an antifeedant, particularly against biting insects as eucalyptus based products used on humans as insect repellent can protect from biting insects up to 8 h depending upon the concentration of the essential oil (Trigg, 1996a,b). Moreover, the insect-repellent activity could be extended up to 8-days, when eucalyptus essential oils are applied on the clothes (Mumcuoglu et al., 1996). Eucalyptus oil (30%) can prevent mosquito bite for 2 h; however, the oil must have at least 70% cineole content (Fradin & Day, 2002).

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Recently, a plant derived repellent, para-methane 3–8, diol (PMD) naturally found in the oil of the lemon eucalyptus plant. The compound was isolated from waste distillate of lemon eucalyptus oil extract, but the synthetic compound was used. PMD is the only plant-based repellent that has been encouraged for use in disease endemic areas by the CDC (Centres for Disease Control). It has been proven to be suitably efficacious and safe to compete with DEET in the field of disease prevention, and repellents have been recognized by WHO as a useful disease prevention tool to complement insecticide based means of vector control. It is safe for both children and adults as its the toxicity of PMD is very low. However, the label indicates it should not be used on children under the age of three (A 2% soybean oil-based repellent has been reported to provide an average of 1.5 hours of protection against mosquito bites, while other botanical repellents tested provided only short-term protection with a mean protection time of only 3 to 20 minutes. (See Stafford (2007); Khater (2012) for more particulars). Oil of lemon eucalyptus, soybean oil or geraniol is the sole active ingredients in some products. Available in several brands or formulations, oil of lemon eucalyptus provides protection against mosquitoes similar to low concentrations of DEET. Two products containing oil of eucalyptus or its primary compound provided the most protection against mosquitoes with protection ranging from 60 to 217 minutes, better than 7-15% DEET. Other essential oils used in naturalproduct based repellents include peppermint, lemongrass, lavender, cedar, canola, rosemary, pennyroyal, geranium and cajeput, see Stafford (2007). The oil of lemon eucalyptus or PMD were listed as active ingredients in only four products of 88 U.S. products examined by Arnason et al. (2011). Inappropriately, many of these products suffer from a short period of efficacy compared to DEET, because they are volatile or quickly absorbed and are lost from the skin surface. An exception is catnip EO, which contains the highly oxygenated compound, nepetalactone. Such compound is heavier than water and has an efficacy up to 4 h against Aedes sp., when properly formulated, compared to 6 h for DEET. Even though catnip oils are attractive to some species of felines, the attraction of domesticated cats has not been a problem so far. See Regnault-Roger et al. (2012) for more details. Oil of lemon eucalyptus, soybean oil or geraniol is the sole active ingredients in some products. Available in several brands or formulations, oil of lemon eucalyptus provides protection against mosquitoes similar to low concentrations of DEET. Two products

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containing oil of eucalyptus or its primary compound provided the most protection against mosquitoes with protection ranging from 60 to 217 minutes, better than 7-15% DEET. Other essential oils used in naturalproduct based repellents include peppermint, lemongrass, lavender, cedar, canola, rosemary, pennyroyal, geranium, and cajeput among others (see Stafford (2007). Concerning geraniol, it is effective in repelling mosquitoes (Omolo et al., 2004). Therefore, geraniol-based products are available commercially as natural repellents. Geraniol candles were found to be more effective than citronella and linalool candles in protecting a person from being bitten indoors by mosquitoes and sand flies (Müller et al., 2008). In a comparative study between three botanical natural repellents, a lemongrass extract in combination with 25% geraniol oil exhibited the longest protection time against mosquitoes (Qualls & Xue, 2009). Müller et al. (2009) determined the degree of personal protection provided by commercial citronella, linalool and geraniol candles or diffusers. Indoors, the repellency rate of geraniol candles was 50%, while the diffusers provided a repellency rate of 97%. Outdoors, geraniol diffusers placed 6 m from mosquito traps repelled female mosquitoes by 75%. Geraniol had significantly more repellent activity than citronella or linalool in both indoor and outdoor settings. Geraniol also affected the activation and orientation stages of the blood-feeding behavior; after 48 h of exposure to 0.250 µg/ml geraniol, almost 100% of Ae. albopictus lost their host-seeking ability (Hao et al., 2008). Oils of soybean, lemongrass, cinnamon and PMD (from lemon eucalyptus), citronellal (from lemongrass) and 2-phenethylpropionate (from groundnut), are effective against mosquitoes based on short-term tests with humans, although their duration is a very controversial issue (Fradin & Day, 2002). Essential oils of six plants growing in Kenya proved repellent activities against An. gambiae sensu stricto. The oils of Conyza newii and Plectranthus marrubioides were the most repellent (RD50 = 8.9 × 10"5 mg cm”2, 95% CI) followed by Lippia javanica, Lippia ukambensis, Tetradenia riparia, Iboza multiflora and Tarchonanthus camphoratus. Eight constituents of the different oils (perillyl alcohol, cis-verbenol, cis-carveol, geraniol, citronellal, perillaldehyde, caryophyllene oxide and a sesquiterpene alcohol) exhibited relatively high repellency. Four synthetic blends of the major components (present in ~*1.5%) of the essential oils were found to exhibit comparable repellent activity to the parent oils (Omolo et al., 2004).

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MiteStop®, based on a neem seed extract, had a considerable repellent effect on bloodsucking, mosquitoes, tabanids, ceratopogonids, simuliids, as well as on licking flies. This repellency effect was noted to last for up to 7 days if the horses were not washed (Al-Quraishy et al., 2012a). Against An. stephensi, the repellency of botanical repellents was lower than that of DEET as a synthetic repellent. The protection time of 50% essential oils of marigold (Calendula officinalis) and myrtle, (Myrtus communis) were respectively 2.15 and 4.36 hours compared to 6.23 hours for DEET 25%. The median effective dose (ED50) of 50% essential oils was 0.1105 and 0.6034 mg/cm2, respectively, in myrtle and marigold. The figure for DEET was 0.0023 mg/cm2 (Tavassoli et al., 2011). Skin repellent test at 1.0, 2.5 and 5.0 mg/cm2 concentration of Cy. citratus gave 100% protection against Cx. quinquefasciatus up to 3.00, 4.00 and 5.00 hours, respectively. The total percentage of protection of this essential oil was 49.64% at 1.0 mg/cm2, 62.19% at 2.5 mg/cm2 and 74.03% at 5.0 mg/cm2 for 12 hours (Pushpanathan et al., 2006).. The use of the essential oils of Oc. basilicum as promising new natural repellents at 0.1% concentration against the Anopheles and Aedes mosquitoes has been suggested by Nour et al. (2009). The five most effective oils which induced 100% repellency against An. aegypti, An. stephensi, and Cx. quinquefasciatus were those of litsea, Litsea cubeba (Lt. cubeba), cajeput (Melaleuca leucadendron), niaouli (Melaleuca quinquenervia), violet (Viola odorata), and catnip (N. cataria) (Amer & Mehlhorn, 2006). The repellency of Zanthoxylum armatum seed oil (ZA-SO), alone or in combination with vanillin (VA), its six major constituents, and another four major previously known Zanthoxylum piperitum fruit oil constituents, as well as aerosol products containing 5 or 10% ZA-SO and 5% VA, was proved against female Ae. aegypti in laboratory and field studies (Kwon et al., 2011). The essential oil of catmint, N. cataria, was hydrogenated to yield an oil enriched in dihydronepetalactone (DHN) diastereomers. This material was used for the preparation of liquid alcohol–based and lotion formulations. The efficacy of these formulations as repellents was tested after application to human test subjects at two locations in the United States: Maine and Florida. In Maine, data on repellency of the hydrogenated catmint oil formulations toward black flies (Simulium decorum Walker) and mosquitoes (primarily Aedes intrudens Dyar) were obtained. In these tests, protection from black flies was conferred for 6

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h or more with all formulations, and both liquid and lotion formulations at 15 wt% active ingredient gave complete protection for 7.5 h. All formulations conferred protection from mosquitoes for >4 h, with the best (15 wt% lotion) giving >8 h of complete protection. In Florida, data on repellency toward a mixed population of mosquitoes indicated that all formulations conferred protection for >4 h, with the 15 wt% lotion giving >6 h complete protection from bites (Spero et al., 2008). Oviposition deterrence and ovicidal potential

The mosquito oviposition behavior has been investigated as one of the prospective parameters for their control improved (Bassolé et al., 2003). Some essential oils, peppermint oil (M. piperita), basil oil (Oc. basilicum), rosemary oil (Rs. officinalis), citronella oil (Cy. nardus) and celery seed oil (Apium graveolens, Ap. graveolens), induce oviposition deterrence and ovicidal potential against female adults of Ae. Aegypti (Warikoo et al., 2011). Oils of Cinnamomum zeylanicum (Cn. zeylanicum), Zn. officinale, and Rs.officinalis expressed oviposition deterrent, ovicidal, and repellent activities against An. stephensi, Ae. aegypti, and Cx. quinquefasciatus (Prajapati et al., 2005). Similar oviposition deterrent potential of the EO of Cn. zeylanicum against the previously mentioned three mosquito spp. has been reported (Prajapati et al., 2005). Likewise, relative high oviposition deterrence of the essential oils obtained from Cr. longa (94.7%), Schefflera leucantha (91.6%), Zn. officinale (90.1%), Vitex trifolia (89.1%), Melaleuca cajuputi (87.9%), Hedychium coronarium (87.5%), Psidium guajava (87.1%), Manglietia garrettii (86.1%), and Houttuynia cordata (85%) against Ae. aegypti. Furthermore, the essential oils of Pip nigr um (82% ), Lt. cube ba (80.6%), and Eleutherococcus trifoliatus (80.2%) exhibited moderate degrees of deterrence (Tawatsin et al., 2006). The EOs of three plants, Cymbopogon proximus, Lippia multiflora, and Ocimum canum (Oc. canum) have ovicidal activity against Ae. aegypti and An. gambiae. The ovicidal potential of all the oils against these mosquitoes, the essential oil from Oc. canum being the least effective among the three (Bassolé et al., 2003). Cy. citratus oil at 300 ppm induced 100% ovicidal activity against Cx. quinquefasciatus (Pushpanathan et al., 2006). Mosquitoes can sense and detect various chemical signals by sensory receptors present on their antennae and select or reject their specific oviposition sites. Mosquito oviposition behavior could allow the

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formulation of effective oviposition deterrents for the reduction of mosquito populations in the future. Because they are vectors of several serious diseases, mosquitoes must be controlled safely and effciently. Using of botanicals as mosquito control agents can be efficient due to their eco-safety, negligible resistance, reduced number of applications, higher acceptability, and suitability for rural areas. Flies House flies

The house fly, (Ms. domestica), is a well-known cosmopolitan pest from both farm and home environment. Excessive fly populations are not only an irritant to farm workers but also a public health problem which may occur, when human habitations are located in the nearby surroundings. Microorganisms are picked up by flies from garbage, sewage and from other sources of filth, and carried on their mouthparts,

Fig. 4: Morphological malformations of house flies treated as larvae (3rd stage larvae) with some essential oils. A. Normal larva. B-D. Malformed larva, showing signs of pigmentation. B. Curved larva with tow central dark spots. C. Macerated larva with week transparent cuticle. D. Larviform puparium. E. Normal pupa. F-I. Malformed pupae. F. Pupa with week puparium, G. Larviform pupa, pigmented with small dark spots at the intersegmental regions. H. C- shaped pupa with anterior constriction and small patches of black pigments (arrow heads). I. Failure of adult eclosion.J. Normal adult. K. Malformed adult, adult with poorly developed wings and legs. Adapted form Khater (2003

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Fig. 5: Repellent effect of essential oils applied to water buffaloes, with an average body weight of 400 kg, were treated. Buffaloes were grouped into six groups, 8 animals per group, and doses of each compound (2.5 L of each DD) were poured on along the backline of the animal, 1.4, 2.9, 3.6, 3.4, and 0.6 ml/kg b.w. for camphor, onion, peppermint, chamomile, d- phenothrin, respectively. In the untreated control group, animals were treated with distilled water and few drops of tween 80. The repellent effect and protection time of the applied materials toward flies, Musca domestica, Stomoxys calcitrans, Haematobia irritans, and Hippobosca equia, were checked daily for 10 days post-treatment, Flies were counted from a distance of 2 m away from the animals. Adapted from Khater et al. (2009)

through their vomitus, feces and contaminated external body parts to human and animal food. Mu. domestica is ubiquitous insect that has the potential to spread a variety of pathogens to humans and livestock. They are mechanical carriers of more than hundred human and animal intestinal diseases and are responsible for protozoan, bacterial, helminthic, and viral infections (West, 1951). Sesame, nigella and onion oils induced larvicidal effect and adversely affect pupation and adult emergence rates of the housefly, Fig. 4 (Khater, 2003). Add details Camphor, onion, peppermint, and chamomile oils repelled flies (Mu. domestica, Stomoxys calcitrans, Haematobia irritans, and Hippobosca equina infecting buffaloes in Egypt for almost 6 days post-treatment, Fig. 5. No adverse effects were noted on either animals or on operators after exposure to the applied oils, (Khater et al., 2009). Kumar et al. (2011) investigated the insecticidal efficacy of six essential oils [peppermint, M. piperita; bergamot mint, Mentha citrata; blue gum, Eu. globulus; lemongrass, Cy. citratus, and khus grass, Vetiver zizanoides, and turmeric, Cr. longa] for repellent, larvicidal and

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pupicidal activities against the housefly, Mu. domestica. Subsequently, emulsifiable concentrate (EC) formulations of the two most effective oils were prepared and tested in the laboratory as well as in the field. In repellency bioassays, M. piperita (RC84, 61.0 µg/cm2) was found to be most effective, followed by Eu. globulus (RC84, 214.5 µg/cm2) and Cy. citratus (RC84, 289.2 µg/cm2). Formulated M. piperita and E. globulus showed RC84values of 1.6 µg/cm2and 4.1 µg/cm2, respectively. Formulated M. piperita and Eu. globulus achieved larval mortality (LC50) in 72 h at 5.12 µg/cm2and 6.09 µg/cm2, respectively. In pupicidal bioassays, crude oils of M. piperita and Eu. globulus suppressed the emergence of adult flies by 100%. Field experiments with the M. piperita formulation showed reductions in fly density (number of flies/h) of 96% on treated cattle and 98% on treated plots. The insecticidal activity of 34 essential oils, extracted from plants, was screened against the house fly, Mu. domestica L. under laboratory conditions. Essential oils from Pogostemon cablin proved to be the most efficient at a lethal dose of 3 µ µg/fly after topical application (Pavela, 2008). Plant EOs possess diversified insecticidal properties. Under screening programme of survey of bioactive agents for insect control, 31 essential oils from different botanicals (2% in acetone), were studied by Singh and Singh (1991) for repellency and direct toxicity (insecticidal effect) against laboratory bred Mu. domestica. the authors found that the EOs obtained from Ocimum gratissimum L., Thymus serpyllum L. (Th. serpyllum), Illicium verum Hooks, f. (Il. verum), Myristica fragrans Houtt., Curcuma amada Roxb. showed 100% repellent activity, and Ac. calamus and Th. serpyllum. showed about 40% insecticidal activity. Shalaby et al. (1998) found that lethal doses of citrus oils, applied to mature house flies, reduced the number of eggs delivered in a ratio of 50% per single female. In addition, repellency has been noted for more essential oils against the housefly (Maganga et al., 1996). These secondary impacts may play a main role in the total decrease in the population of insects. Blow flies

Myiasis, infestation of tissues with dipterous fly larvae, is a significant medical and veterinary problem that affects human and animal welfare and national economies. Larvae of the green blowfly, Lucilia sericata (L. sericata) are facultative ectoparasites that infest suppurative wounds. Khater and Khater (2009) assessed the toxicity of some Egyptian oils against L. sericata la rvae. The LC50 values were 2.81, 4.60, 6.93, and 7.92% for (Trigonella foenum-graecum),

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Fig. 6: Morphological abnormalities after treatment with essential plant oils. Larval abnormalities include: (1) a small, shrunken larva with diffuse brown pigment; (2) a weak cuticle with ulceration (arrow); (3) a weak cuticle with ulceration (arrows) and patches of brown pigment; and (4) a twisted larva with diffuse brown pigment. Pupal deformations include: (1) a puparium with an abnormal eclosion fissure; (2) a larviform puparium; (3) a small cracked puparium with a central groove (arrow); and (4) a small and distorted puparium. Adult anomalies include: (1) a deformed wing; (2) a deformed wing and legs; (3) a crumpled wing and deformed legs; and (4) a small, crumpled, poorly developed adult, Adapted from Khater et al. (2011)

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celery (Ap. graveolens), radish (Raphanus sativus), and mustard (Brassica compestris), respectively. The adverse effects on larval treatment also included the survival of pupae and adults. The pupation rate was strongly decreased after treatment with 16% fenugreek and celery. Moreover, adult emergence was suppressed after treatment of larvae with 8% mustard, 12% radish, and 16% fenugreek and celery oils. The number of emerged males exceeded the number of females, which could lead to population decline. Morphologic abnormalities of larvae, pupae, and adults were recorded after treatment with all tested oils (Fig. 6). In the same regard, some other Egyptian oils were highly toxic to L. sericata larvae, with LC50 of 0.57%, 0.85%, 2.74%, and 6.77% for lettuce (Lactuca sativa), chamomile (Matricaria chamomilla, Ma. chamomilla), anise (Pimpinella anisum, Pm. anisum), and rosemary (Rs. officinalis) oils, respectively. Pupation rates were markedly decreased after treatment with 8% lettuce oil, and adult emergence was suppressed by 2% lettuce and chamomile oils. Morphological abnormalities were recorded after treatment with all tested oils, and lettuce was the major cause of deformation. There was a predominance of males over females (4:1) after treatment with lower concentrations of chamomile and rosemary; such a skew toward males would lead to a population decline (Khater et al., 2011). Low concentrations of some extracts, such as American wormseed, Chenopodium ambrosiodes, and thyme, Th. vulgaris (Morsy et al., 1998) are effective against L. sericata. The volatile oils of dill, Anthem graveolens, and burnoof, Conyza dioscoridis, effectively controlled L. sericata (Mazyad et al., 1999); moreover, the same oils induced great retardation of larval development of Parasarcophaga aegyptiaca (LC50 were 70 and 150 ppm, respectively) (Hussien, 1995). House hold and structural pests

Putting red cedar blocks or sachets in closets to repel clothing moths is a common practice. Therefore, many hope chests are made of red cedar for protection of heirloom clothing. Pioneers in the American West placed the ripe fruit of the osage orange (hedgeapple) (Maclura pomifera) in cupboards to repel cockroaches and other insects. The fruit has a compound irritating to the feet of an insect that will cause that insect to spend less time in a treated area. Its oil contain numerous sesquiterpenoids many of them were repellent to the German cockroach, Blattella germanica L. (Peterson & Coats, 2001). In addition, cineole, geraniol and piperidine found in bay leaves, Laurus nobilis, possess repellent properties towards cockroaches (Verma & Meloan, 1981).

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Some essential oils of Chinese medicinal herbs repel the Germane cockroach such as Angelica sinensis, Curuma aeruginosa, Cyperus rotundus, Eucalyptus robusta, Il. verum Lindera aggregate, Oc. basilicum, and Zanthoxylum bungeanum (Liu et al., 2011). Manzoor et al. (2012) evaluated the toxicity, repellency and fumigant activity of three essential oils that is, Cy.citratus, Mentha arvensis (M. arvensis), Eu. citriodora against Pr. americana under laboratory conditions. Cy. citratus showed the maximum toxicity (20 to 100%) between 2 to 24 h intervals, repellency (100%) and 70 to 100% fumigation after 24 h exposure. Eucalyptus (Eu. citrodora) oil was found to have least toxicity, repellency and fumigant activity. Percentage mortality (0 to 80%) between 2 to 24 h, 40 to 60% fumigant activity was observed after 24 h at different concentrations. oils were arranged according to the following order of preference that is, Cy. citratus, M. arvensis and Eu. citriodora. d-Limonene is used mainly for controlling structural pests as termite in California, and other plant oils (clove, peppermint, etc.) are used in the USA by professional pest control operators as ‘flushing agents’ for cockroach control and for ‘perimeter treatments’ of homes against ants and termites, suggesting that repellence makes a strong contribution to the efficacy of these products (Isman et al., 2011). The mechanism of the insecticidal property ascribed to geraniol was investigated by testing its neurophysiological effect in Pr. americana (the American cockroach) and Blaberus discoidalis (discoids).Geraniol suppressed spontaneous and stimulus-evoked impulses recorded extracellularly in the abdominal nerve cord, but increased spontaneous firing at lower doses (threshold 2.5 × 10–4 M). Geraniol produced dose-related biphasic effects on dorsal unpaired median neurons. Low doses of geraniol (threshold ca. 10–4 M) reversibly increased the frequency of spontaneous foregut contractions and abolished these at 2 × 10–3 M (together with response to electrical stimulation) (Price & Berry, 2006). The essential oil extracts of six Malaysian plants, i.e. Cr. longa, Zn. officinale, Pandanus odorus, Cn. zeylanicum, Sy. aromaticum and Cy. citratus, were evaluated for repellent activity against Pr. americana using a modification of the ‘two-cylinders’ method. Dose-dependent repellency ranging from 57.1 to 100% was exhibited by all six extracts at the lowest concentration tested (12 ppm) (Ahmed et al., 1995). Vetiver (Vetiveria zizanioides) essential oil obtained by steam distillation of aromatic roots contains a large number of oxygenated

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sesquiterpenes. This oil is known to protect clothes and other valuable materials from insect attack when placed inclosets, drawers, and chests, see koul et al. (2008).  Regarding termite control, EOs act as a wood preservative solution by mixing eucalyptus essential oils with pyrethroids and borax (Urabe, 1992). A series of experiments to assess the repellency and toxicity of patchouli oil and its main constituent, patchouli alcohol, against the Formosan subterranean termite, Coptotermes formosanus Shiraki (Cp. formosanus) recealed the repellency and that paper filters treated with patchouli oil were less consumed by worker termites (Zhu et al.,2003). Sand treated with vetiver oil, Cp. formosanus Shiraki, or its component, nootkatone, at 100 µg/g substrate were effective barriers to termites as they disrupted tunneling behavior of termites. As a consequence, after 21 d, wood consumption and termite survival were significantly lowered compared with cedrene-treated or untreated sand treatments (Maistrello et al., 2001). Repellency and toxicity of 8 essential oils (vetiver grass, cassia leaf, clove bud, cedarwood, Eu. globules, Eu. citrodora, lemongrass and geranium) were evaluated against the Formosan subterranean termite, Cp. formosanus. Vetiver oil proved the most effective repellent because of its long-lasting activity. Clove bud was the most toxic, killing 100% of termites in 2 days at 50 ¹g/cm2. Vetiver oil decreased termite tunneling activity at concentrations as low as 5 ¹g/g sand. Tunneling and paper consumption were not observed when vetiver oil concentrations were higher than 25 ¹g/g sand. Bioactivity of the 8 oils against termites and chemical volatility were inversely associated. Listed in decreasing order of volatility, the major constituents of the 8 oils were: eucalyptol, citronellal, citral, citronellol, cinnamaldehyde, eugenol, thujopsene, and both ®- and vetivone. Consequently, vetiver oil is a promising novel termiticide with reduced environmental impact for use against subterranean termites (Zhu et al., 2001). Park and Shin (2005) evaluated essential oils from herbaceous and woody plants as potential fumigants against Japanese termites and reported that clove bud and garlic oils showed the most potent antitermitic activity among the plant EOs. The termiticidal properties of decanal, cinnamic acid, and its derivatives on Cp. formosanus have been proven (Kartal et al., 2006). The anti-termitic activities of 11 essential oils from three species of coniferous tree against Cp. formosanus were investigated using direct

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contact application. At the dosage of 10mg/g, the heartwood and sapwood essential oils of Calocedrus macrolepis var. formosana (C.m. formosana) and Cryptomeria japonica and the leaf essential oil of Chamaecyparis obtusa var. formosana had 100% mortality after 5 d of test. Among the tested essential oils, the heartwood essential oil of C.m. formosana killed all termites after 1 d of test, with an LC50 value of 2.6mg/g, exhibiting the strongest termiticidal property. The termiticidal eVect of heartwood essential oil was due to its toxicity and its repellent action (Cheng et al., 2007). For more information about control of structural pests, see Ashley et al. (2006) and Brown (2012). Lice Human lice

Control of human lice, several studies have demonstrated the in vitro pediculicidal efficacy of some essential oils towards head lice, P.h. capitis. Eucalyptus (Eu. globules), rosemary and pennyroyal (Mentha pulegium , M. pulegium), a member of the mint genus, oils were found to be least, if not more, effective than d-phenothrin and pyrethrum, two commonly used pediculicides (Yang et al., 2004a). Essential oils from Eu. globulus and its major monoterpene 1,8cineole showed toxicity against human head lice, P.h. capitis more than that of commercially used pediculides—delta-phenothrin or pyrethrum. The LT50 value of essential oil was 0.125 mg/ cm2 compared to 0.25 mg/ cm2 of commercial pediculides (Yang et al., 2004b). The fumigant toxicity/ repellent activity of essential oil eucalyptus from Eu. cinerea, Eu. viminalis and Eu. saligna, against permethrin-resistant human head lice with KT50 (time for 50% knockdown) values of 12.0, 14.9 and 17.4 min, respectively (Ceferino et al., 2006). Essential oils, in particular, pennyroyal, tea tree and anise, have potent insecticidal activity for killing head lice and their eggs (Williamson, 2007). Citronellal, cotronellol, citronellyl or a mixture of these have been patented as pest treatment composition against human louse (Ping, 2007). Studies have demonstrated the in vitro pediculicidal efficacy of some essential oils against female head lice. Eucalyptus (Eu. globules), rosemary, and pennyroyal (M. pulegium, a member of the mint genus) oils were found to be at least as effective, if not more so, against P. h. capitis than d-phenothrin and pyrethrum, two commonly used pediculicides (Priestley et al., 2006). Essential oils, in particular, pennyroyal, tea tree and anise, have potent insecticidal activity against

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head lice and their eggs. Eu. globulus leaf oil-derived monoterpenoids are highly toxic to eggs and females of the human head louse (Gurusubramanian & Krishna, 1996). Pennyroyal and its benzyl component are effective repellents against P. h. capitis (Yang et al., 2004b). Ovicidal efficacy against P. h. capitis were 68.3%, 44.4%, and 3.3% for the “suffocation” pediculicide, the melaleuca oil and lavender oil pediculicide (TTO/LO), eucalyptus oil and lemon tea tree oil pediculicide (EO/LTTO) (Barker & Altman, 2011). Anise oil demonstrated repellent effects against a wide range of insects, such as the human head louse, P.h. capitis (Whitledge, 2002). Some essential oils, Artemisia species, Ant. sowa, Cr. longa, and Lippia alba (Li. Alba). Clove, rosemary, thyme, eucalyptus and various mint species, have demonstrated contact and fumigant toxicity to a wide spectrum of insects, including human head lice (Toloza et al., 2008). It worth to mention that Artemisia is a well-known deworming plant (Seddiek, et al. 2011). A neem seed extract contained in a fine shampoo formulation (Wash Away® Louse) blocked the aeropyles of the eggs (nits) of head and body lice, P.h. capitis and Pediculus humanus corporis, thus preventing the embryos of both races of lice from accessing oxygen and from releasing carbon dioxide. Thus, this product offers a complete cure from head lice upon a single treatment, if the lice (motile stages and eggs) are fully covered for about 10 min (Mehlhorn et al., 2011). It was shown that the active compound in MiteStop® eliminates P.h. capitis (Abdel-Ghaffar et al., 2010). EOs contain monoterpenoids, which have lousicidal and ovicidal effects against clothing lice, Pediculus humanus (P. humanus) (Priestley et al., 2006); peppermint and rosemary oils were reported to control such louse (Veal, 1996). Furthermore, peppermint and rosemary oils are reported to control such lice (Palevitch & Craker, 1994). Animal and bird lice

Some Egyptian oils have pronounced pediculicidal activity against the buffalo louse, Haematopinus tuberculatus (H. tuberculatus), Four minutes post-treatment, the median lethal concentration, LC50, values were 2.74, 7.28, 12.35, 18.67 and 22.79% for camphor (Cinnamomum camphora, Cn. camphora), onion (Al. cepa), peppermint (M. piperita), chamomile (Ma. chamomilla) and rosemary oils (Rs. officinalis), respectively, whereas for d-phenothrin, it was 1.17%.The lethal time (50) (LT50) values were 0.89, 2.75, 15.39, 21.32, 11.60 and 1.94 min

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In vivo pediculicidal activity of some oils against buffalo louce. Fortyeight water buffaloes, with an average body weight of 400 kg, were treated. Buffaloes were grouped into six groups, 8 animals per group, and doses of each compound (2.5 L of each diagnostic dose) were poured on along the backline of the animal, 1.4, 2.9, 3.6, 3.4, and 0.6 ml/kg b.w. for camphor, onion, peppermint, chamomile, and dphenothrin, respectively. In the untreated control group, animals were treated with distilled water and few drops of tween 80. Adapted form Khater et al. (2009).

after treatment with 7.5% camphor, onion, peppermint, chamomile, rosemary and dphenothrin, respectively. All the materials used except rosemary, which was not applied, were ovicidal to the eggs of H. tuberculatus. Essential oils have pronounced in vivo pediculicidal activity as the number of lice infesting water buffaloes in Egypt was significantly reduced 3, 6, 4, and 6 days after treatment with the essential oils of camphor, peppermint, chamomile, and onion, respectively, Fig. 7 (Khater et al., 2009). Tobacco (Nicotiana tobaccum), tubli (Derris philippinensis), makabuhay (Tinosphor a rumphi) and neem (Az. indica) at concentrations of 10%, 20% and 40% in oil emulsion induced more than 90% mortality in Carabao louse, H. tuberculatus in vitro, whereas in vivo experimentation showed that only tobacco and makabuhay induced

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45.91% and 79.67% reduction in louse infestations, respectively (Robles, 2004). A single treatment of dogs with neem seed preparations, MiteStop® or Wash Away Dog, killed motile stages and eggs of the chewing lice, Trichodectes canis, and the bloodsucking lice, Linognathus setosus. In both cases, the product had been left for 20 min. onto the hair before it was washed away just with normal tap water (Mehlhorn et al., 2012).The previous product (diluted 1:20 with tap water) usefully controlled chewing lice, Werneckiella spp. infesting horses belonging to short hair and long hair races. A hidden infestation with these biting lice had existed, which became visible when the product was brushed onto the hair. Furthermore, this treatment of horses stopped the forming of dandruff of the skin of the horses, which, in case of heavy mallophage infestations, had looked like being powdered (Al-Quraishy et al., 2012a). When dipping (just in–out) the infested birds completely into the 1:33 tap water-diluted MiteStop® solution, it was noted that after drying (1 h) the feathers, all motile stages (nymphs and adults) of the “shaft louse” Menopon gallinae, the elongate feather louse Lipeurus caponis, or Columbicola sp. were dead. Also, the same product induced ovicidal and repellent effects. When treating in vitro cutoff feathers contaminated with the bird louse, Lipeurus caponis, it was seen under the stereomicroscope, that the mallophages tried to run away from the 1:33 water-diluted active compound indicating that there is a repellent effect of the neem seed extract, MiteStop® (Al-Quraishy et al., 2012b). Other insects

Neem oil repelled sand flies under laboratory and field conditions. Concentrations of 2% neem oil mixed in coconut or mustard oil provided 100% protection against Phlebotomus argentipes throughout the night under field conditions; against Phlebotomus papatasi it repelled sand flies for about 7 h in the laboratory. Neem oil is an indigenous product and a low-cost alternative for personal protection against sand fly bites (Sharma & Dhiman, 1993). Large number of essential oils repels arthropod species. A neem extract proprietary product, AG1000, has been shown to be repellent to the biting midge Culicoides imicola, which can spread cattle diseases (Braverman et al., 1999). Flea control products for companion animals based on d-limonene, a constituent of citrus peel oil, or oils of peppermint, cinnamon, clove, thyme and lemongrass, have been introduced recently. MiteStop®, a

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neem- based product, acts very specifically against beetles from the families Tenebrionidae and Dermestidae, the larvae of which may enter the plumage of poultry and feed on tiny feathers or on skin debris (Walldorf et al., 2012). Rue, Ruta graveolens L. (Rutaceae), is a traditional medicinal plant known to prevent the attacks by fleas and other noxious insects (see De Feo et al., 2002). Sfara et al. (2009) evaluate the fumigant and repellent activity of five essential oils (eucalyptus, geranium, lavender, mint, and orange oil) and seven monoterpenes (eucalyptol, geraniol, limonene, linalool, menthone, linalyl acetate, and menthyl acetate) on first-instar nymphs of the bloodsucking bug Rhodnius prolixus Stahl (vector of Chagas disease in several Latin American countries). Fumigant activity was evaluated by exposing the nymphs to the vapors emitted by 100 ×l of essential oil or monoterpene in a closed recipient. The knockdown time 50% (KT50) for eucalyptus essential oil was 215.6 min (seven times less toxic than dichlorvos, a volatile organophosphorus insecticide used as a positive control). The remaining essential oils showed a poor fumigant activity: 50% inhibited completely the reproduction of R. microplus females (Silva et al., 2011). It is worth to mention that peracetic acid (PPA), a safe and ecofriendly organic acid, had a great potential as acaricide against the cattle hard tick, R. annulatus, and the fowl tick, Argas persicus (Ar. persicus), In vitro (Khater & Ramadan, 2007). Ar. persicus is of veterinary importance as a parasite of poultry and wild birds. PAA (0.5 %) was highly efficient in in vitro and vivo against Ar. persicus larvae resulting 100 % mortality after 2 minutes. The lethal concentrations, LC50 and LC95 were 0.310 and 0.503 %, respectively. The lethal time values LT50 and LT95 were 5.34 and 40.00 minutes, respectively, after treatment with PAA (0.25 %). Seven days post dipping of infested laying chickens, the reduction percentages of Ar. persicus infesting laying hens was 99.15%. In addition, PAA inhibits molting effectively (28%) (Khater et al., 2012). For a review of tick control, see Kiss et al. (2012)

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Mites

The European and American house dust mites, Dermatophagoides (Dr) pteronyssinus and Dr. farinae, have a huge impact upon human health worldwide due to being the most important indoor trigger of atopic diseases such as asthma, rhinitis and atopic dermatitis. Eucalyptus oils rich in cineole have been shown to be effective against Dr. pteronyssinus (Saad et al., 2006). The study of Khan et al. (2012) showed, for the first time, that N. cataria, enriched in iridoid nepetalactones and (E)-(1R,9S)-caryophyllene, exhibited potent repellent activity for both species of house dust mites, and has the potential for deployment in control programs based on interference with normal house dust mite behavior. Also, Methyl eugenol and Asarum sieboldii Miq. essential oil controlled Dr. farinae and toxicity was largely due to the vapor phase (Wu et al., 2012). In the same regard, the acaricidal activity of clove (Eugenia caryophyllata) bud oil-derived eugenol and its congeners (acetyleugenol, isoeugenol, and methyleugenol) against adults of Dr. farinae and Dr. pteronyssinus was examined using direct contact application and fumigation methods and compared with those of benzyl benzoate and N,N-diethyl-m-toluamide (DEET). Responses varied according to compound, dose, and mite species. On the basis of LD50 values, the compound most toxic to Dr. farinae adults was methyleugenol (0.94 µg/ cm2) followed by isoeugenol (5.17 µg/cm2), eugenol (5.47 µg/cm2), benzyl benzoate (9.22 µg/cm2), and acetyleugenol (14.16 µg/cm2). Very low activity was observed with DEET (37.59 µg/cm 2). Against Dr. pteronyssinus adults, methyleugenol (0.67 µg/cm2) was much more effective than isoeugenol (1.55 µg/cm 2), eugenol (3.71 µg/cm 2), acetyleugenol (5.41 µg/cm2), and benzyl benzoate (6.59 µg/cm2). DEET (17.85 µg/cm 2) was least toxic. These results indicate that the lipophilicity of the four phenylpropenes plays a crucial role in dust mite toxicity. The typical poisoning symptom of eugenol and its congeners was a similar death symptom of the forelegs extended forward together, leading to death without knockdown, whereas benzyl benzoate and DEET caused death following uncoordinated behavior. In a fumigation test with both mite species, all four phenylpropenes were much more effective in closed containers than in open ones, indicating that the mode of delivery of these compounds was largely due to action in the vapor phase (Kim et al., 2003). Geraniol is an effective plant-based insect repellent. Geraniol is a common constituent of several EOs and occurs in Monarda fistulosa (N95%), ninde oil (66.0%), rose oil (44.4%), palmarosa oil (53.5%) and citronella oil (24.8%). Geraniol has characteristic rose-like odour and

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the taste (at 10 ppm) is described as sweet floral rose-like, citrus with fruity, waxy nuances. This monoterpene alcohol is a widely used fragrance material. It is present in 76% of deodorants on the European market, included in 41% of domestic and household products and in 33% of cosmetic formulations based on natural ingredients and its production exceeds 1000 metric tons per annum. In addition, geraniol exhibits various biochemical and pharmacological properties. See Chen and Viljoen (2010) for more details about geraniol. Geraniol (1%) showed a reduction in the mean number of ticks per animal of 98.4%, 97.3%and 91.3%at days 7, 14 and 21, respectively (Khallaayoune et al., 2009). The previous studies indicated that EOs and their constiutents are promising agents for controlling pest of medical and veterinary importance. Pesticides of agricultural importance Stored product pests

Food grain losses due to stored product pests during storage are a serious problem. Losses caused by insects include not only the direct ingestion of kernels, but also accumulation of exuviae, webbing, and cadavers. High levels of the insect detritus may afford grain that is unfit for human consumption and qualitative and quantitative losses of the food commodities. Insect infestation in the storage environment provide suitable conditions for storage fungi that cause further losses. It is estimated that more than 20,000 species of field and storage pests destroy approximately one-third of the world’s food production, valued annually at more than $100 billion among which the highest losses (43%) occurring in the developing world. The use of oils in stored-products pest control is also an ancient practice. Botanical insecticides such as pyrethrum, derris, nicotine, oil of citronella, and other plant extracts have been used for centuries (Rajapakse, 2006; Rajashekar et al., 2012). The currently used fumigants, phosphine, methyl bromide, and DDVP (2,2-dichlorovinyl dimethyl phosphate) provoke some safety concerns. Insect resistance to phosphine is a matter of serious concern. Phosphine is the major cause of suicidal deaths in India. Methyl bromide has ozone-depleting potential and DDVP has a possible human carcinogen potential. For more information about the side effects of fumigants, see Khater (2012). As a consequence, development of safe alternative that could replace the toxic fumigants against stored product pests is very important. EOs from aromatic plants have been assayed to address several crop protection problems in pre- and postharvest situations as many plant

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essential oils have fumigant action, such as those of Artemisia species, Ant. sowa, Cr. longa, and Li. alba. Isolates like d-limonene, carvones and 1,8-cineole have been well documented as fumigants. Some essential oils have bioactivity against stored product pests, such as oils of basil, citrus peel, eucalyptus, various mint species, lavender, and rosemary, but not all essential oils are active against all insect pests (Don-Pedro, 1996; Papachristos & Stamopoulos, 2002). Nutmeg oil has been determined to significantly impact both the maize weed, Sitophilus zeamais (St. zeamais) and the red-flour beetle, T. castaneum and demonstrates both repellent and fumigant properties (Huang et al., 1997). The exact mode of action of these oils as fumigant is unknown, but the oils mainly act in the vapor phase via respiratory system. For more details about fumigants, see Tripathi et al., (2009); Isman (2010), and Khater (2011, 2012). Turmeric, garlic, Vitex negundo, gliricidia, castor, Aristolochia, ginger, Agave americana, custard apple, Datura, Calotropis, Ipomoea and coriander are some of the other widely used botanicals to control and repel crop pests. The essential oil of Artemisia annua repels against T. castaneum and Callosobruchus maculates. Furthermore, two major constituents of the essential oil of garlic, Allium sativum, methyl allyl disulfide and diallyl trisulfide were to be potent toxicant and fumigants against St. zeamais and T. castaneum. The essential oil vapours distilled from anise, cumin, eucalyptus, oregano, and rosemary were also reported as fumigantants and caused 100% mortality of the eggs of Tribolium confusum and Ephestia kuehniella. Many species of the genus Ocimum oils, extracts, and their bioactive compounds have been reported to have insecticidal activities against various insect species. Coconut oil has been found effective against the Pulse Beetle, Callosobruchus chinensis (Cal. chinensis), for a storage period of six months, when applied to Vigna radiata (green gram) at 1%. Formulations of menthol were used as protection of pulse grain from attack of Cal. chinensis. (See Rajashekar et al. (2012) for more information). For the protection of stored products, the toxicity of EOs of patchouli (Pogostemon spp.) and of sweet basil (Oc. basilicum) to the coleopterans St. oryzae (rice weevil), Stegobium paniceum (drugstore beetle), T. castaneum, and Bruchus chinensis (Br. chinensis) pulse beetle and EOs of Eucalyptus or thyme to the lesser grain borer (Rhyzopertha dominica, Rh. dominica ) were determined. see Regnault-Roger et al. (2012) for more fine points. The neem oil and kernel powder gave effective grain protection against stored grain insect pests like St. oryzae, T. castaneum, Rh. dominica, and Cal. chinensis at the rate of 1 to 2% kernel powder or oil (Pereira

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&Wohlgemuth, 1982). The neem oil adhered to grain forms uniform coating around the grains against storage pests for a period of 180–330 days (Ahmed, 1994). The essential oils of plants Xylopia aethiopica, Vepris heterophylla, and Luppia rugosa are used for protection of stored grains from attack of stored grain insect pests (Ngamo et al., 2007). The essential oil derived from the flowering aerial parts of Schizonpeta multifida and its two main components, pulegone and menthone induced fumigants/ insecticides effect against two grain storage insects, maize weevil (St. zeamais) and T. castaneum (Liu et al., 2011). The repellent activity of the mixture of essential oils from Artemisia princeps and Cn. camphora against the adult weevils, St. oryzae and Bruchus rufimanus was significantly higher than that elicited by individual oils (Liu et al., 2006). Repellent activity may also underlie the use of these oils in the long-term protection of foods and food products through their incorporation into packaging materials. Cr. longa leaf oil possesses toxic, antifeedant, oviposition-deterrent and ovicidal activity against Rh. dominica (lesser grain borer), St. oryzae (rice weevil) and T. castaneum (Tripathi et al., 2002). Concerning chemosterilants, a compound 1, 3, 7-trimethylxanthine, was isolated from seed extract of Coffea arabica. It proved effective as a chemosterilant for Cal. chinensis, causing nearly 100% sterility at a concentration of 1.5%. At similar concentration the compound had no phytotoxic effect on the crop plant Vigna mungo. Using the compound for control of stored-grain pests is recommended (Rizvi et al., 1980). On the subject of the acaricidal effect, geraniol from the oil of Pelargonium graveolens was more effective using an impregnated fabric disc bioassay against the storage food mite, Tyrophagus putrescentiae than benzyl benzoate with the 50% lethal dose value being 1.95 µg/cm3 and 1.27 µg/ cm3, respectively (Jeon et al., 2009). Screening of several medicinal herbs showed that root bark of Dictamnus dasycarpus possessed significant feeding deterrence against two stored-product insects. For more information about control of stored product pests, see Rajashekar et al. (2012). Pests of agriculture importance

Extracts of locally available plants in Africa can be effective as crop protectants, either used alone or in mixtures with conventional insecticides at reduced rates, which indicate that indigenous knowledge and traditional practice can make valuable contributions to domestic food production in countries where strict enforcement of pesticide regulations is impractical.

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Essential oil constituents such as thymol, citronellal and -terpineol are effective as feeding deterrent against tobacco cutworm, S. litura synergism, or additive effects of combination of monoterpenoids from essential oils have been reported against S. litura larvae. Carvone is a monoterpene of the essential oil of Carum carvi. It is a non-toxic botanical insecticide used under the trade name TALENT. It enhances the shelf life of stored fruits and vegetables and inhibits microbial deterioration without altering the taste and odor of the fruits after treatment (Varma & Dubey, 1999). The LD50 value of carvone (in mice) is reported to be 1640 mg/kg (Isman, 2006). Extracts of locally available plants in Africa can be effective as crop protectants, either used alone or in mixtures with conventional insecticides at reduced rates, which indicate that indigenous knowledge and traditional practice can make valuable contributions to domestic food production in countries where strict enforcement of pesticide regulations is impractical. The essential oil of leaves of Hyptis martiusii Benth and 1,8-cineole showed pronounced insecticidal effect against Bemisia argentifolii, the vectors of white fly fruit plague (Araújo et al., 2003). Nineteen essential oils, obtained by hydrodistillation from aromatic and medicinal plants of Moroccan origin, were tested for their insecticidal effects on Hessian fly (Cecidomyiidae) adults and eggs. This insect is the major pest of wheat in Morocco. Most of the aromatic plants belong to the family Labiatae. The species M. pulegium, Origanum compactum (O. compactum), and Origanum majorana were the most toxic to adults; Ammi-visnaga, Pistacia lentiscus, O. compactum, and M. pulegium were more efficient on eggs (Lamiri et al., 2001). Scott et al. (2004) recommended the use of Piper extracts be restricted to small-scale spot treatments in residential areas where insect pest outbreaks have occurred as they tested extracts from three species of the plant family Piperaceae, Pip. nigrum, Piper guineense (Schum & Thonn), and Piper tuberculatum (Jacq.) for efficacy against insects from five orders. All three species contain isobutyl amides, plant secondary compounds that act as neurotoxins in insects. When 24-h Pip. nigrum LC50 values were compared between common insect pests from eastern Canada and the northeastern United States, the most sensitive species in order of increasing lethal concentration were eastern tent caterpillar, Malacosoma americanum (F.) < European pine sawfly larvae, Neodiprion sertifer (Geoffroy) < spindle ermine

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moth larvae, Yponomeuta cagnagella [Hübner] < viburnum leaf beetle larvae, Pyrrhalta viburni [Paykull] < stripped cucumber beetle adults, Acalymma vittatum (F.) < Colorado potato beetle adults, Leptinotarsa decemlineata (Say) < Japanese beetle adults, Popillia japonica [Newman] < hairy chinch bug, Blissus leucopterus hirtis (Montandon). The life stage tested was the point at which each species causes the greatest amount of damage to the host plant and the point at which most gardeners would likely choose to treat with a conventional synthetic insecticide. Greenhouse trials revealed that the pepper formulations also had a repellent activity, thus protecting plant leaves from 1) herbivory (lily leaf beetle, Lilioceris lilii (Scopoli), adults and larvae and stripped cucumber beetle adults) and 2) oviposition [European corn borer, Ostrinia nubilalis (Hübner)]. Combinations with other botanical extracts were additive at best in toxicity and repellent trials. Nontarget toxicity to beneficial invertebrates is a possibility because the Pip. nigrum LC50 for beneficial ladybird beetles was 0.2%. Pip. nigrum extracts can provide a reasonable level of control against lepidopteran and European pine sawfly larvae and also will work as a short-term repellent and feeding deterrent. Machial et al. (2010) evaluated 17 essential oils against the oblique banded leafroller, Choristoneura rosaceana (Cho. rosaceana), and the rosy apple aphid, Dysaphis plantaginea (Dy. plantaginea) as are serious pests in apple orchards throughout North America, also the green peach aphid, Myzus persicae (My. persicae) and the cabbage looper, Trichoplusia ni (Tr. ni). The most toxic of these were further evaluated to determine their LC50 and LD50 values. Patchouli oil was found to be among the most toxic to all four species. Thyme oil was also toxic to both Cho. rosaceana larvae and Dy. plantaginea adults, while citronella oil demonstrated high toxicity to Dy. plantaginea. Garlic and lemongrass oils were also identified as potential candidates for Tr. ni control and lavender oil was identified as the second most toxic essential oil to My. persicae. Mixtures of plant compounds reduce the evolution of tolerance to natural insecticides, compared to a single compound, as exemplified with My. persicae. Eugenol, abundantin cloves (Eugenia caryophyllata), or cinnamaldehyde, abundant in cinnamon (Cinnamomumverum), exerts ovicidal, larvicidal, and adulticidal toxicity on the bean weevilAcanthoscelidesobtectus (Acn. obtectus)and inhibits its reproduction (Regnault-Roger & Hamraoui, 1995).

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Toxicity levels of EOs to the Mediterranean fruit fly, Ceratitis capitata (Cer. capitata), and the cereal aphids Rhopalosiphum padi and Metopolophium dirrhodum have been determined. The efficacy of EOs and their constituents varies according to the phytochemical profile of the plant extract and the entomological target. The bruchid Acn. obtectus is more sensitive to phenolic monoterpenes and the aphid R. padi to methoxylated monoterpenes, whereas the Mediterranean fruit fly, Cer. capitata, respond to both types of compounds. EOs such as oil of thyme, rosemary (Rs. officinalis), and eucalyptus have antifeedant or repellent activity. The oil of citronella repels mosquitoes and flies, and garlic oil is a deterrent to many insect herbivores. Such oils are currently marketed to horticulturists, greenhouses, and home gardens in the United States and the United Kingdom. (For more details, see RegnaultRoger et al., 2012). Park et al. (2006) carried out fumigant bioassays of an additional 40 plant species to determine their larvicidal activity against L. ingenua. The best fumigant activities were obtained with EOs of horseradish (Armorica rusticana), anise (Pm. anisum), and garlic oils. The toxicity of EOs of citrus peel, in which limonene is the most abundant ingredient, was observed on Cer. capitata. Larvae were administered diets in which the LC50 values of limonene ranged from 7 to 11 ml g-1. (Papachristos et al., 2009). Essential oils of cumin (Cuminum cyminum), anise (Pm. ansium), oregano (Origanum syriacum var. bevanii) and eucalyptus (Eucalyptus camaldulensis) were effective fumigants against the cotton aphid (Aphis gossypii) and the carmine spider mite (Tetranychus cinnabarinus), two greenhouse pests (Tuni & Sahinkaya, 1998). The potential of basil (Ocimum spp.) against garden pests has been reviewed (Quarles, 1999). Dietary effects of a number of monoterpenoids against the European corn borer (Ostrinia nubilalis) have been reported (Lee et al., 1999). The toxicity of a range of essential oil constituents to the western corn rootworm (Diabrotica virgifera), the two-spotted spider mite (Tetranychus urticae) (Lee et al.,1997). Mixtures of different monoterpenes produced a synergistic effect on mortality, and a proprietary monoterpene mixture was developed containing 0.9% active ingredient for use against foliar feeding pests (Hummelbrunner & Isman, 2001). Alghough limonene found in sour oranges (Citrus aurantium) is toxic to adult bean weevils (Callosobruchus phasecoli), it is highly attractive to male Mediterranean fruit flies (Jacobson, 1982). -Ocimene is repellent to the leaf cutter ant, Attacephalotis in both field and laboratory experiments (Harborne, 1987). Experiments with the aphid Carvariella

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aegopodii, which feeds on the aromatic Apiaceae (Apiales) species in summer, indicate that the aphid can be captured in traps baited with carvone, and repelled by linalool (Chapman et al. 1981; Harborne, 1987). Carvone occurs in the essential oils of several plants of the Apiaceae. Rosemary oil reduces the hatchability of eggs (62.65%) and adversely affects some biological aspects of the potato tuber moth, Phthorimaea operculella (Lepidoptera: Gelechiidae) (Moawad & Ebadah, 2007). Concerning mite control, the constituents of essential oils, carvone, carvacrol, cineole, cinnamaldehyde, cuminaldehyde, eugenol, geraniol, limonene, linalool, menthol, thymol are recognized as effective against spider mites (Miresmailli et al., 2006; Badawy et al., 2010; Lim et al., 2011). Examples of registered commercial formulations of acaricides aimed to control of plant-feeding mites include products based on cinnamaldehyde, eugenol, cottonseed, clove and canola oils, rosemary and peppermint oils, American wormseed oil (Copping & Menn, 2000; Miresmailli & Isman, 2006; Copping & Duke, 2007; Cloyd et al., 2009; Regnault- Roger et al., 2012). Products based on citronellol and farnesol act as attractants; they increase activity of mites which enhance their exposure to a co-applied synthetic acaricide (Copping & Menn, 2000; Tomlin, 2009; Chandler et al., 2011). Plant essential oils and their constituents are used as fumigants for beehives to manage economically important honey bee ectoparasites, the varroa mite, Varroa jacobsoni (V. jacobsoni) and the tracheal mite (Acarapis woodi). In North America, menthol (from peppermint) is widely used for this purpose (Delaplane, 1992), and in Europe thymol (from gardenthyme) is most often used (Floris et al., 2004). Tetranychus urticae (Te. urticae) and Phytoseiulus persimilis (Choi et al., 2004). EO-based pesticides or repellents may become complementary to more toxic chemicals and can be used in organic food production both in field and in controlled environment. For more details about Insect and mite control in field crops, see Hertel et al. (2011). For more information about using plant essential oils for pest and disease management, see Ahmed et al. (1984), Isman (2000), Regnault-Roger et al. (2012), Khater (2011, 2012) and Rajashekar et al. (2012). CONCLUSIONS The environmental problems caused by overuse of pesticides have attracted the attention of scientists in recent for development of safe, biodegradable and environmental friendly plant-based products that can be used to reduce synthetic pesticide use while maintaining crop

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yields. EOs are long used as fragrances and flavorings in the perfume and food industries, respectively. Essential oils demonstrate a wide range of bioactivities from direct toxicity to insects, to oviposition and feeding deterrence as well as repellence and attraction. Most insect repellents are volatile terpenoids, while other terpenoids can act as attractants. Repellents and attractants could be used efficiently for behavioral insect control. In recent years, the use of EOs as low-risk insecticides has increased considerably owing to their popularity with organic growers and environmentally conscious consumers. Natural pest controls using EOs are safer to the user because of their low mammalian toxicity and the environment because they break down into harmless compounds within hours or days in the presence of sunlight. They are also very close chemically to those plants from which they are derived, so they are easily decomposed by of the microbes common in most soils. Predator, parasitoid and pollinator insect populations will be less impacted on account of the minimal residual activity. Accordingly, the greatest beneûts from EOs might be achieved in industrialized countries in situations, where human and animal health are foremost – for pest control in and around homes and gardens, in commercial kitchens and food storage facilities and on companion animals, as well as in developing countries, where human pesticide poisonings are most prevalent. Several commercial insecticides based on plant essential oils intended for professional, agricultural, veterinary and consumer applications have been introduced to the market in the past decades. EOs are effective as ‘‘stand-alone’’ products under low pest pressure, e.g., early in a growing season. Outstandingly, they can be applied in rotation or in combination (tank-mixed) with other crop protectants, including conventional synthetic or microbial pesticide products. Pesticides based on plant EOs or their constituents have demonstrated efficacy against a range of stored product pests, domestic pests, blood feeding pests and certain soft-bodied agricultural pests, as well as against some plant pathogenic fungi. More importantly, resistance will develop more slowly to formulations based on EOs owing to the complex mixtures of constituents that characterize these oils. Commercial production of EO-based insecticides has been greatly facilitated by exemption from registration for certain oils, commonly used in processed foods and beverages, which favor development of such products for agricultural, industrial, and veterinary applications, and

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for the consumer market. Stability of EO- based products could be prolonged by several ways, such as encapsulated formulations, which seem to be able to protect the core material against environmental agents and could be considered for use in controlled release systems, as well as nanoparticles which have the potential to be used as an ideal eco-friendly approach for the control of insect pests. There are several challenges to the commercial application of plant essential-oil-based pesticides include resource availability with sufficient quantities. Even though many essential oils may be abundant and available year round due to their use in the perfume, food and beverage industries, large-scale commercial application of essential-oil-based pesticides could require greater production of certain oils. Biodiversity of plant sources is very important concern. Therefore, collection of wild plants must be properly managed, and it is preferable to select plant species with rapid turnover in the wild or that can be cultivated. Standardization is also a challenge as the chemical profile of plant species can vary naturally depending on genetic, geographic, climatic, annual or seasonal factors, and pesticide manufacturers have a duty to standardize their products will perform consistently. The other challenges include protection of technology (patents) and regulatory approval. This complete and eco-friendly approach would afford new methods of controlling insect pests and the diseases associated with them. Further investigations of the potential of these methods for effective pest control and the seeking of the various plants as control agents, are also required for making EO- based pesticides go well together with integrated pest management programs. However, further studies in this trend are needed to establish the shelf life, consistency and efficacy of these formulations in different settings and climatic conditions. The way will be open for EOs in case of endorsement of strong political will, consumer awareness, and market responses. These steps forward will guarantee an increasing position in the marketplace for the near future and help in preventing the disposal of thousands of tons of pesticides on the earth and provide residue-free food and a safe environment to live (Khater, 2011, 2012). Unquestionably, the number and quality of EO- based pesticides will increase and the costs will fall; accordingly, the unemployment rate will drop and the national income will increase for the welfare of developed and developing centuries. ACKNOWLEDGEMENTS The author is grateful to Dr. Aza Abdel Fattah Moustafa, Professor and consultant of Insecticides at the Research Institute of Medical

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Entomology, Egypt, for her interest on the subject, their precious advices and helpful discussions; Dr. Mohamed Hafez, Plant Pathology Department, Faculty of Agriculture, Benha University, Egypt, for his valuable advice and his help for the quality of the figures; and Eslam Afify, Different, Benha, Egypt, for his design for Fig. 1, Global Scenario on the Bioactivity of Essential Oils as Green Pesticides. LIST OF APPRECIATIONS A: Anocentor Ac: Acorus Acn: Acanthoscelides Ae: Aedes Al: Allium Am: Amblyomma An: Anopheles Ant:Anthema Ap: Apium Ar: Argas Az: Azadirachta B: Bovicola Br: Bruchuschinensis C. Catharanthus C.m: Calocedrusmacrolepis Ca: Carapa Cal: Callosobruchus Cer: Ceratitis Ch: Chamaecyparis Cho : Choristoneura Cn: Cinnamomum Cn: Cinnamomum Cp: Coptotermes Cr: Curcuma Cy: Cymbopogon D. Desmodium DEET: N, N-diethyl-m toluamide, synthetic insect repellent Dr: Dermatophagoides Drs: Drosophila Dy: Dysaphis E: Euphorbia EOs: essential oils Eu. Eucalyptus H: Haematopinus Hip: Hippobosca

Il: Illicium Ix: Ixodes L: Lucilia Li: Lippia Lt: Litsea M. Mentha Ma: Matricaria Mn: Manilkara Ms: Musa Mu: Musca My: Myzus N: Nepeta NPs: Nanoparticles O: Origanum Oc: Ocimum P.h.: Pediculus humanus P: Pediculus Pip: Piper Pm: Pimpinella PMD: a plant derived repellent, paramethane 3–8, diol Pr. Periplaneta R. Rhipicephalus (Boophilus) Rh: Rhyzopertha Rs: Rosmarinus S: Spodoptera St: Sitophilus Sy: Syzygium T: Tribolium Te:Tetranychus Th: Thymus Tr: Trichoplusia Tr:Trichoplusia Z: Zanthoxylum Zn: Zingiber

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