Synthesis and Technology of Nanoemulsion-Based Pesticide Formulation

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Synthesis and Technology of Nanoemulsion-Based Pesticide Formulation nanomaterials Review Synthesis and Technology of Nanoemulsion-Based Pesticide Formulation Isshadiba Faikah Mustafa and Mohd Zobir Hussein * Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, Seri Kembangan 43400, Selangor, Malaysia; [email protected] * Correspondence: [email protected] Received: 6 July 2020; Accepted: 13 August 2020; Published: 17 August 2020 Abstract: Declines in crop yield due to pests and diseases require the development of safe, green and eco-friendly pesticide formulations. A major problem faced by the agricultural industry is the use of conventional agrochemicals that contribute broad-spectrum effects towards the environment and organisms. As a result of this issue, researchers are currently developing various pesticide formulations using different nanotechnology approaches. The progress and opportunities in developing nanoemulsions as carriers for plant protection or nanodelivery systems for agrochemicals in agricultural practice have been the subject of intense research. New unique chemical and biologic properties have resulted in a promising pesticide nanoformulations for crop protection. These innovations—particularly the nanoemulsion-based agrochemicals—are capable of enhancing the solubility of active ingredients, improving agrochemical bioavailability, and improving stability and wettability properties during the application, thus resulting in better efficacy for pest control and treatment. All of these—together with various preparation methods towards a greener and environmentally friendly agrochemicals—are also discussed and summarized in this review. Keywords: nanoemulsion; agrochemical; properties; pesticide; agriculture 1. Introduction Colloidal nanoformulations have remarkable properties that have attracted much attention for use in various applications. These advanced nanoformulation systems bring many improvements in the agricultural sector for better efficacy towards antifungal activities [1,2] and pesticide delivery systems [3,4]. The incorporation of colloid nanoformulations into cosmetic products has enabled the modification of the drug permeation and allowing optimum efficiency on the skin [5,6]. This nanoformulation system also used for the food industry [7] to extend the shelf life of food [8] and improve food protection from the biodeterioration process [9]. Recently, the advantages of colloidal nanoformulation have opened up some alluring possibilities for enhancing technology in the agricultural sector. Industrial agriculture estimates that more than 70% of traditional pesticides are not efficient due to repetitive use at a higher dose in achieving optimal bio-efficiency thus leading to environmental fate through some process including runoff, leaching and volatilization [10]. Some of the conventional agrochemicals that are usually in emulsifiable concentrate or wettable powder forms are embedded in soil or groundwater for years. The long degradation period has resulted in its accumulation in the food chain and hazardous to the human and animal health and the environment. These pesticides have been banned through strict pesticide regulations in developed countries, but unfortunately, it is still widely used in many developing countries [11]. Hence, water-based pesticide formulations using colloidal systems can be a good alternative in replacing the existing formulation [12]. Nanomaterials 2020, 10, 1608; doi:10.3390/nano10081608 www.mdpi.com/journal/nanomaterials Nanomaterials 2020, 10, x FOR PEER REVIEW 2 of 26 Hence, water-based pesticide formulations using colloidal systems can be a good alternative in Nanomaterials 2020, 10, 1608 2 of 26 replacing the existing formulation [12]. Figure 1 displays the type of colloidal systems: micelle, liposome and nanoemulsion which were developedFigure 1to displays overcome the typethe ofdrawback colloidal of systems: the conv micelle,entional liposome agrochemicals. and nanoemulsion Micelle whichis the wereterm developedfrequently toused overcome when theemulsions drawback are of discussed. the conventional Microemulsion agrochemicals. requires Micelle a high is the concentration term frequently of usedsurfactant when of emulsions 20% or more are discussed. compared Microemulsion to only 3%–10% requires for nanoemulsion a high concentration [13]. The of surfactantdevelopment of 20% of ornanoemulsion more compared has tomany only significant 3%–10% for advantages nanoemulsion as it [reduces13]. The the development use of organic of nanoemulsion solvents [12] has or manybioactive significant oil concentration advantages and as it increases reduces thethe use solubi of organiclization solvents of active [12 ingredients] or bioactive while oil concentration maintaining andbiologic increases activity. the Along solubilization with the offormation active ingredients of nanoemulsion, while maintaining spontaneous biologic formation activity. of micelle Along or with the theso-called formation micellization of nanoemulsion, has also spontaneousoccurred, which formation indicates of micellethat micelle or the formation so-called micellizationis to exist in hasthe alsonanoemulsion. occurred, which indicates that micelle formation is to exist in the nanoemulsion. Figure 1. Composition of the micelle, liposome and nanoemulsion droplet (micelles with a hydrophobic Figure 1. Composition of the micelle, liposome and nanoemulsion droplet (micelles with a core which is formed by the tails of the surfactant molecules. Liposomes with an aqueous core hydrophobic core which is formed by the tails of the surfactant molecules. Liposomes with an surrounded by a double phospholipid layer. Nanoemulsions droplets with a hydrophobic liquid core aqueous core surrounded by a double phospholipid layer. Nanoemulsions droplets with a composed of the oil that is dispersed in the water and stabilized by a surfactant monolayer) Reproduced hydrophobic liquid core composed of the oil that is dispersed in the water and stabilized by a with permission from [14]. surfactant monolayer) Reproduced with permission from [14]. Here, we discuss the synthesis, physicochemical and biologic characterizations and the technology of nanoemulsion-basedHere, we discuss pesticide the synthesis, formulation physicochemi for agriculturalcal and use. biologic The role ofcharacterizations each component and used the for thetechnology formulation of nanoemulsion-based is described in detail. Additionally,pesticide formul studiesation of thefor useagricultural of the nanoemulsion use. The role for pesticideof each deliverycomponentin vitrousedand for inthe vivo formulationapplications is described also are reviewed. in detail. Moreover,Additionally, the penetrationstudies of the pathways use of the of nanoemulsion-basednanoemulsion for pesticide agrochemicals delivery and in theirvitro activeand in release vivo applications into the living also organism are reviewed. also are Moreover, explained. Thethe penetration environmental pathways risk assessment of nanoemulsion-based is also briefly indicated agrochemicals in this review. and their active release into the living organism also are explained. The environmental risk assessment is also briefly indicated in this 2.review. Nanoemulsion as A Colloidal System Nanoemulsion is also known as a miniemulsion, sub-micron emulsion or ultrafine emulsion, in 2. Nanoemulsion as a Colloidal System which the size is between 20–500 nm [15]. The nanoemulsion structure can be custom-made to meet the needsNanoemulsion of various is applications. also known Thereas a miniemulsion, are three types sub-micron of nanoemulsion: emulsion oil or inultrafine water (O emulsion,/W), water in inwhich oil (W the/O) size and is bi-continuous.between 20–500 In nm the [15]. later, The the na systemnoemulsion is obtained structure when can the be oil custom-made and aqueous to phase meet arethe separatedneeds of various by the surfactantapplications. layer. There Nanoemulsions are three types consist of nanoemulsion: of three main oil parts: in water oil, surfactant (O/W), water and water.in oil (W/O) Twoimmiscible and bi-continuous. phases—oil In the or later, organic the and system water is phaseobtained that when are present the oil and in a aqueous nanoemulsion phase system—areare separated separated by the surfactant by interfacial layer. tension Nanoemulsions induces by consist surfactants of three [16 main]. parts: oil, surfactant and water. Two immiscible phases—oil or organic and water phase that are present in a nanoemulsion 2.1.system—are Surfactant separated as an Emulsifier by interfacial in Nanoemulsion tension induces by surfactants [16]. One of the important components in nanoemulsions are surfactants, also called emulsifiers. There2.1. Surfactant are four as types an Emulsifier of surfactants: in Nanoemulsion cationic, anionic, amphoteric and nonionic. In formulating nanoemulsion-basedOne of the important for pesticide components applications, in nanoemulsi nonionicons surfactants are surfactants, are usually also encapsulated called emulsifiers. into the nanoemulsion,There are four astypes they areof surfactants: less affected cationic, by the pH anionic, and ionic amphoteric strength. Thisand additionalnonionic. componentIn formulating can alternanoemulsion-based the stability and sizefor pesticide of the nanoemulsion, applications, as nonionic a result ofsurfactants cohesion betweenare usually the encapsulated anionic surfactant into and the solution. The selection of surfactants also can be related to its
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