Nanoencapsulation, Nano-guard for Pesticides: A New Window for

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Nanoencapsulation, Nano-Guard for Pesticides: A New Window for Safe Application Md. Nuruzzaman, Mohammad Mahmudur Rahman, Yanju Liu, and Ravi Naidu J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.5b05214 • Publication Date (Web): 05 Jan 2016 Downloaded from http://pubs.acs.org on January 10, 2016

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Journal of Agricultural and Food Chemistry

Nanoencapsulation, Nano-Guard for Pesticides: A New Window for Safe Application

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Md Nuruzzaman1 ,2, Mohammad Mahmudur Rahman1,2, Yanju Liu1,2, Ravi Naidu1,2*

4 5

1

6

The University of Newcastle, University Drive, Callaghan, NSW 2308, Australia

7

2

8

Environment (CRC CARE), ATC building, The University of Newcastle, Callaghan, NSW

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2308, Australia

Global Centre for Environmental Remediation (GCER), Faculty of Science and Technology,

Cooperative Research Centre for Contamination Assessment and Remediation of the

10 11 12

Corresponding Author

13

Tel: +61 2 4913 8705. E-mail: [email protected].

14 15 16 17 18 19 20 21 22 23 24 25

1 ACS Paragon Plus Environment


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ABSTRACT

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The application of nanotechnology in pesticide delivery is relatively new and in the early

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stages of development. This technology aims to reduce the indiscriminate use of conventional

29

pesticides and ensure their safe application. This critical review investigated the potential of

30

nanotechnology especially the nanoencapsulation process for pesticide delivery. In-depth

31

investigation of various nanoencapsulation materials and techniques, efficacy of application

32

and current research trends were also presented. The focus of ongoing research was on the

33

development of nanoencapsulated pesticide formulation which has slow releasing properties

34

with enhanced solubility, permeability and stability. These properties are mainly achieved

35

through either protecting the encapsulated active ingredients from premature degradation or

36

increasing their pest control efficacy for a longer period. Nanoencapsulated pesticide

37

formulation is able to reduce the dosage of pesticides and human exposure to them, which is

38

environmental friendly for crop protection. However, lack of knowledge of the mechanism of

39

synthesis and not having undertaken a cost-benefit analysis of nanoencapsulation materials

40

hindered their application in pesticide delivery. Further investigation of these materials

41

behavior and their ultimate fate in environment will help the establishment of a regulatory

42

framework for their commercialization. The review provided fundamental and critical

43

information for researchers and engineers in the field of nanotechnology, and specially using

44

nanoencapsulation techniques to deliver pesticides.

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KEYWORDS: nanoencapsulation, nanotechnology, agriculture, pesticide, pest control,

47

environmental exposure

48 49

1. INTRODUCTION


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Nanotechnology is an emerging phenomenon that occupies an increasingly important position

51

in the latest range of technologies.1 Over the last decade, it has emerged as having the

52

potential to revolutionize agricultural practices.2 To date, various reports have reviewed the

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application of this technology in agriculture where multifunctional approaches were

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observed.1-8 The potential applications of this technology in agricultural scenarios include

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seed treatment, germination, plant growth and development, pest control, pesticides delivery,

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fertilizer delivery, genetic material delivery, toxic agro-chemicals detection, pathogen

57

detection, etc.1-8 In terms of agrochemical (pesticides, fertilizers, growth hormones, etc.)

58

delivery, nanoscale particles have novel properties which can increase the agrochemicals’

59

efficiency and make the delivery system ‘smart’.1 Through a smart delivery system,

60

chemicals can be delivered in a controlled and targeted manner that is similar to nano-drug

61

delivery to humans.9

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Using this technology in pesticide delivery has created many opportunities for safe

63

application of conventional pesticides. Commonly used pesticides are greatly limited in their

64

application due to a number of problems associated with them. For example, more than 90%

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of applied pesticides are either lost in the environment or unable to reach the target area

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required for effective pest control.3,10 Around 20-30% of pesticides are lost through emissions

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but this can potentially increase to 50% of the total amount applied.11 A number of factors

68

including application technique, physicochemical properties of the pesticides and

69

environmental conditions (e.g. wind speed, humidity, and temperature) influence the extent

70

of loss during application.11,12 The remaining losses are the result of leaching, evaporation,

71

deposition, being washed away and degradation by photolysis, hydrolysis and microbial

72

activity.13 The major pathways of pesticide loss are represented in Figure 1. Given these

73

losses, the active ingredients (AIs) in the pesticide are removed prior to their application, and



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therefore, the concentration at the target area is well below the minimum effective

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concentration.

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Consequently, achieving the desired biological response in terms of pest control

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within a given period, the precise amount which influences non-specific and periodic

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application of the active ingredients is required.1 The repeated and indiscriminate application

79

of pesticides results in using them in quantities greatly exceeding the amount actually

80

required to control the target pests.3 Not only does the cost of treatment increase as a result,

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but such usage ends in unfavorable outcomes either to plants or to the environment including

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soil and water pollution,1 which ultimately poses dangers to public health.13 Such usage of

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pesticides increases pest and pathogen resistance, reduces soil biodiversity and nitrogen

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fixation, raises the bioaccumulation of pesticides, kills predators and pollinators.14 It also

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destroys the habitats and food sources of birds.14 In spite of these side effects, their utilization

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is essential if agricultural productivity is to be maximized. However, more knowledge

87

concerning the problems caused by agrochemicals pesticides for public health and wildlife

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has resulted in increasingly stringent controls of their use by different regulatory bodies.15

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In agriculture, the development of new plant protection formulations has long been a

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very active field of research because such problems associated with commercial pesticides

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must be overcome.16 Researchers are currently designing formulations similar to

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conventional formulations, but with improved features, i.e. more soluble, slower releasing,

93

and not prematurely degradable using the benefits of materials at nanoscale. Nanomaterials

94

used as a pesticide or as a carrier material have exhibited useful properties such as stiffness,

95

permeability, crystallinity, thermal stability and biodegradability over commonly used

96

pesticides.17 The nano-carrier materials with AIs spread uniformly over the leaves and onto

97

the soil surface; thus, they are easily taken up by chewing insects.7 They are also absorbed

98

into the cuticular wax (lipid) layers of insects via a physio-sorption process and break down


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the water protection barrier, resulting in insect death from desiccation.18,19 The large surface

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area of nano-pesticides increases the affinity to the target species/groups and reduces the

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amount of pesticide required for pest control.20

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Nano-carrier materials also protect the AIs from premature degradation and allow

103

them to be released in a controlled way.1 In this way pesticides can be deliberately applied

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using nano-devices through adsorption on nanoparticles, attachment on nanoparticles,

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encapsulated with nanomaterials or trapped in nanomaterials.3 Recent reviews have already

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concentrated on the pesticidal efficacy of nanomaterials and their potentialas a carrier

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material.4,16,21 The available literature also suggests that of all the delivery techniques,

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nanoencapsulation technology is the most promising because it is much more efficient than

109

any other. Due to the wide range of potential, progress and possibilities of nanoencapsulation

110

technique, this review paper considers their utilization in pesticide delivery and their goals. It

111

is based on the available nanoencapsulation materials and formulations as well as pest control

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efficacy and environmental impact of nanoencapsulated pesticides.

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2. NANOENCAPSULATION AND NANOENCAPSULATION MATERIALS

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Nanoencapsulation is the coating of various substances within another material at various

115

sizes in the nano-range. The encapsulated material is commonly referred to as the internal

116

phase, the core material, the filler or the fill, for instance pesticides. The encapsulation

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material is known as the external phase, shell, coating or membrane, for example nano-

118

capsules. Attempts have been made to encapsulate commercial pesticides as well as biocides

119

using nano-materials in order to improve their physical properties and control the widespread

120

use of pesticides. Nanoencapsulation of pesticides involves the formation of pesticide loaded

121

or entrapped particles having a diameter within the nano-range. According to the definition of

122

nanoparticle, this size range should be 1 to 100 nm in at least one dimension.22 There is still

123

some debate about the particle size in a colloidal system such as pesticide formulations.16



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Recently, Kah et al.16 reviewed nano-pesticides as having a size ranging between 1 and 1000

125

nm. Conversely, in the literature, much evidence was found that the term ‘nano’ for

126

encapsulated pesticides referred to a particle size of more than 100 nm. This may be due to

127

the efficacy of their novel small-sized particulate. Grillo et al.23 reported that the definition of

128

nanoparticles can be considered not only based on their size (below 100 nm) but also their

129

application in medicine or agriculture where their size may be more than 100 nm. However,

130

in this review paper the size of nanoencapsulated materials has been considered up to 1000

131

nm. Various nanomaterials have already been used to encapsulate pesticides such as polymer-

132

based nanomaterials, solid lipid nanoparticles, inorganic porous nanomaterials, nano-clays

133

and

134

nanoencapsulation materials and encapsulate the pesticide forming different types of

135

nanomaterials, for example nanocapsules, nanospheres, micelles, nanogels, liposomes,

136

inorganic nano-cages, etc. (Figure 2). During encapsulation, a multi-stage delivery pattern

137

can be observed as some pesticides are absorbed and attached to the outer surface of the

138

shell.24

139

2.1. Polymer-based Nanoencapsulation Materials

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Polymers and polymeric materials have a wide range of applications in different fields. For

141

example, intense research has been dedicated to the production of nano-sized controlled

142

release drug formulations using different biodegradable polymers.25-27 Employing polymeric

143

nanomaterial for pesticide delivery is a recently developed approach.10 Generally, the active

144

ingredients are encapsulated with polymer, as polymer nano-composites (PNC) consist of a

145

polymer which has nanoparticles or nano-fillers dispersed within the polymer matrix.28

146

Polymers produced by natural sources are environmentally friendly, biodegradable, do not

147

produce any degradation by-products and are comparatively low cost.10 As a result of these

148

properties, they have proved to be suitable encapsulation materials for active ingredients.

layered

double

hydroxides

(LDHs),

etc.3

These

materials are

known

as


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Recently, amphiphilic block copolymers have drawn researchers’ attention in terms of their

150

ability to form various types of nanoparticles along with polymers. Generally, block

151

copolymers are obtained by the polymerization of more than one type of monomer.

152

Typically, the polymers should be contrasting in nature, i.e. one hydrophilic and another

153

hydrophobic. In this way, the block copolymers sustain their amphiphilic properties in

154

aqueous solution. Depending on the number of blocks the copolymers are known as bi-block

155

and tri-block copolymers (Figure 3). Various synthetic and natural polymers, such as

156

polyethylene glycol, poly-ε-caprolactone, chitosan, sodium alginate, etc., as well as the block

157

copolymers have served to encapsulate a wide range of pesticides through the formation of

158

different nano range materials (Figure 4).

159

2.1.1. Nanocapsules

160

Nanocapsules are vesicular systems that are made up of a polymeric membrane encapsulating

161

the active compounds as an inner liquid core at the nanoscale level.26,30 The nanocapsule

162

structure consists of a core-shell arrangement in which the shell is comprised of a polymeric

163

membrane or coating (Figure 5). The active substances are usually dissolved in the inner

164

liquid core. The inner core can also consist of pesticide formulations or polymeric matrix and

165

active ingredients may be absorbed by the polymeric shell. In this way the active substances

166

are encapsulated by nanocapsules spontaneously during the formation of nanocapsules.

167

Recently, Ezhilarasi et al.28 documented several nanoencapsulation techniques for

168

encapsulating food bioactive components through the formation of polymeric nanocapsules.

169

It was notable, however, that the techniques are similar to the synthesis of nanocapsules

170

required for encapsulating pesticides.

171

Polymeric nanocapsules are widely applied and subsequently, intensified research

172

studies have been conducted for their effective synthesis. The availability of different

173

polymers and their inherent properties have given researchers the option for synthesizing



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nanocapsules through different methods. The most commonly developed strategies are

175

nanoprecipitation,

176

emulsification-coacervation and layer-by-layer deposition (Figure 6). Nevertheless, various

177

other methods were found in the literature along with modifications of the above mentioned

178

methods, for example melt dispersion, emulsion polymerization, interfacial polymerization,

179

interfacial deposition method, solvent displacement technique, emulsion-evaporation, etc.27

180

However, various synthesizing methods of nanocapsules have been described elsewhere.26, 27,

181

30, 31

emulsion-diffusion,

solvent

evaporation,

double-emulsification,

182

So far, nanocapsules synthesized using various polymers have demonstrated their

183

potential as an effective encapsulation material for pesticides and biocides. A polymer such

184

as polyethylene glycol (PEG) has been utilized as shell material for the synthesis of

185

nanocapsules. Using a melt-dispersion method, Yang et al.32

186

nanocapsules of polyethylene glycol (PEG) loaded with garlic essential oil (Figure 7a). The

187

loading efficiency was influenced by the optimal ratio of essential oil to PEG and the loading

188

efficiency reached 80% at the essential oil to PEG ratio of 10%. The nanocapsules retained

189

with good dispersion have an average diameter >1), the exponential term needs to be much smaller than 1. This occurs

1248

only with a particle size in the nano-range. This aforementioned phenomenon is another

1249

demonstration for the transformation of the physicochemical properties of materials on the

1250

nanoscale. Similarly, other nano-encapsulated pesticide formulations such as microemulsion

1251

and nanoemulsion have also been prepared to avoid the disadvantages of available

1252

commercial pesticides. Micro- or nanoemulsions can also improve the pesticides’ solubility

1253

and bioavailability.6 Furthermore, it was suggested the nano-sized aqueous dispersion

1254

formulation enhanced the solubility of pesticides. Nano-sized aqueous dispersions or

1255

nanosuspensions eliminated the need for organic solvents and provided a process for

1256

stabilizing formulations of two or more immiscible pesticides. The superficial solubility of

1257

poorly water soluble pesticides can be increased through encapsulation with additives such as

1258

surfactants, polymers, etc., or by means of nano-particulate formation with changing solid

1259

structures.235 Lipid-based nanoencapsulation materials can also be used to solubilize water

1260

insoluble lipophilic active compounds.76

1261

4.3. Protection against Premature Degradation

1262

During their application conventional pesticides enter the environment in several ways such

1263

as degradation, volatilization or evaporation and leaching.236 Yet a modern pesticide should

1264

have the ability to survive in the spray environment.202 At present, several pesticides are

1265

sensitive to UV light and have a very short life, for example avermectin (6h)221 is volatile in



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nature or tends to be leached down. To protect liable pesticides from photo-degradation, the

1267

microencapsulation technique was introduced.237 The shell of the microcapsules is usually

1268

very thick and compact, which inhibits the proper release of AIs from capsules. Consequently

1269

the nano-encapsulation technique was introduced to solve the disadvantages of the micro-

1270

encapsulation technique. Nano-capsulation is such an effective technology that it has the

1271

ability to protect pesticides from premature degradation, maintaining their effective

1272

release.221

1273

PHSNs were reported as acting like a shield that protected the photosensitive pesticide

1274

avermectin as well as maintaining its apposite release.169,221 Besides other factors (pH,

1275

temperature) shell thickness of PHSNs significantly affected the loading efficiency, UV-

1276

shielding property and controlled release of avermectin from PHSNs.169 UV shielding

1277

efficiency rose and the release property slowed down with increasing shell thickness. PHSNs

1278

with a shell thickness of ~15 nm and a pore diameter of 4-5 nm increased the shelf life of

1279

avermectin up to 30 days.221 Generally, most biocides are essential oils extracted from

1280

different plant parts which are volatile in nature. Nanoencapsulation materials were found to

1281

be effective for reducing volatilization and releasing the active components in a controlled

1282

way. Lai et al.110 investigated the ability of SLN to prevent the rapid evaporation of the

1283

incorporated Artemisia arborescens L essential oil. They reported that at 35°C, the

1284

cumulative release of AIs from emulsion formulations were double the formulations of SLN

1285

after 48 hours. In another analysis, polymeric nanocapsules of PEG loaded with garlic

1286

essential oil reduced the volatility of active components and retained their availability for a

1287

longer time.32

1288

Clay materials can serve as an effective tool for protecting the unstable pesticides

1289

against volatilization and photo-degradation.125 In an earlier study, organo-clay formulations

1290

exhibited their potential to protect herbicides from photo-degradation and volatilization,


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while maintaining their herbicidal activity.238 It has been suggested that the reversible binding

1292

of the pesticide on clay minerals is a feasible solution for reducing their leaching into the

1293

environment via air and water.125 Leaching of AIs was significantly reduced with fungicides,

1294

namely tebuconazole, encapsulated in core/shell nanoparticles prepared from amphiphilic

1295

copolymers of gelatin grafted with methyl methacrylate.239

1296

4.4. Increased Stability

1297

Nanoencapsulation materials can support AIs to achieve both physical and environmental

1298

stability. The physical stability of AIs is required for long-term storage and their successful

1299

application whereas environmental stability is required for effective pest control. The

1300

nanoencapsulated pesticide formulations exhibited better stability over time due to steric and

1301

electrostatic interaction of different phases in the colloidal system. Conventional pesticide

1302

formulations showed poor stability and disintegrated during storage. The nano-based

1303

pesticide formulations have exhibited their potential to remain stable for a longer storage

1304

period. Wang et al.192 prepared nanoemulsion formulations of β-cypermethrin stabilized by

1305

polymeric surfactants. The formulations exhibited good stability, even after 24 hours of

1306

dilution in comparison to commercial microemulsion, due to the steric interaction between

1307

the polymeric inner surfaces with pesticides. The electrostatic interaction between several

1308

polymers showed better efficiency in stabilizing the nanoemulsion formulation than the

1309

single polymers.222 Storm et al.194 used milling technologies in the presence of grinding

1310

media (polymer beads) and surface active agents to obtain stable nanosuspensions of various

1311

fungicides and insecticides with particle sizes of around 148-314 nm.

1312

The effects of different stabilizing polymers have been investigated during

1313

nanosuspension formulation preparation of the poorly water soluble pesticide Bifenthrin

1314

using a flash nano-precipitation process.220 It was reported that pesticide formulations

1315

encapsulated with PAA-b-PBA, PVP and PVOH were most stable over time, having an



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average particle radius distribution of 97-171 nm and the concentration and type of stabilizers

1317

significantly affected the size and stability of formulations.220 On the other hand, although the

1318

average particle radius distribution was 70-80 nm with pluronic, PS-b-PEO and PEG-b-PCL,

1319

macro-phase separation was observed after 7 days.220 Although not focusing on agriculture,

1320

Anjali et al.240 reported the nanoemulsion formulation of the artificial polymer-free nano-

1321

permethrin served as an effective larvicide that was stabilized by plant extracted natural

1322

surfactants.

1323

Controlled release properties and protection against premature degradation ultimately

1324

enhance the environmental stability of AIs. For example, the stability of avermectin increased

1325

from 6 h to 30 days through encapsulation with PHSNs. The encapsulation materials

1326

permitted a controlled release of AIs and protected them from UV light.221 Phytochemicals

1327

such as secondary metabolites and essential oils have already shown their efficacy in pest

1328

control but they are non-persistent in water and soil. Essential oils are usually unstable in

1329

nature and evaporate as well as degrade rapidly in the presence of air, light, moisture and

1330

high temperature. Nanoencapsulation of such essential oils has enhanced their stability while

1331

maintaining their pest control efficacy for a long period of time. In order to improve

1332

environmental stability, effective maintenance and bioavailability of lanssiumamide B was

1333

encapsulated in the form of nanocapsules.34 The nanocapsule suspensions were kept at 54°C

1334

and 0°C and, after 14 days, encapsulation efficiency declined slightly at 54°C but did not

1335

change at 0°C, indicating their good stability.34 Other studies of nanoencapsulation

1336

discovered it was significantly related to increasing pesticides’ effectiveness. Boehm et al.208

1337

investigated the encapsulation efficacy of Eudragit S100 polymer. They concluded that the

1338

nanosphere formulation prepared by Eudragit S100 polymer was not effective in terms of

1339

controlled release of active ingredients because the encapsulation rate was only 3.5%.

1340

However, their penetration in the plant was enhanced due to the particle size (135 nm) being


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smaller than the classical suspension.208 In their review paper, Tadros et al.191 stated that

1342

nanoemulsions enhance the wetting and spreading and penetration ability of the droplets due

1343

to their low surface tension of the whole system as well as low interfacial tension of emulsion

1344

droplets. In another study, Song et al.187 observed that the hydrolysis of organophosphorous

1345

insecticides like triazophos is pH-dependent and easily hydrolyzed in basic solutions. To

1346

protect the insecticide from being hydrolyzed, a nanoemulsion formulation was prepared

1347

where the effect of surfactants was prominent in basic conditions to prevent the hydrolysis

1348

compared to acidic or neutral pH.

1349

5. PEST CONTROL EFFICACY OF NANOENCAPSULATED PESTICIDES

1350

It is expected that the nanoencapsulated pesticides should have better pest control efficacy

1351

over commercially available pesticides, non-encapsulated pesticides or micro-encapsulated

1352

pesticides. Judging by the available literature, nanoencapsulated pesticides have already

1353

exhibited better pest control efficacy than commercially available pesticides or those without

1354

encapsulated active compounds. Pest control efficacy refers to different aspects based on the

1355

nano-guard properties of nanoencapsulated materials. Nanoencapsulation materials allow the

1356

release of active ingredients in a controlled way, resulting in the retention of pest control

1357

efficacy over a longer period than commercial formulations. Various controlled release

1358

formulations have already been prepared using different nanoencapsulation materials and

1359

their release behavior has been described in the previous section. On the other hand, several

1360

investigations have observed the pest control efficacies of those nanoencapsulated CRFs.

1361

For controlling stored grain pests, repeated application of pesticides or biocides is

1362

required due to their fast releasing characters as well as shorter POA. Nanoencapsulated

1363

CRFs were found to be an effective tool to control stored grain pests. Loha et al.206 evaluated

1364

the pest control efficacy of nanoencapsulated CRFs of β-cyfluthrin on the mortality of

1365

Callosobruchus maculatus. They developed CRFs by encapsulating β-cyfluthrin with PEG



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originated amphiphilic copolymers in the form of nano-micelles. The bio-efficacy data of

1367

these CRFs with commercial 025 SC indicated that on the 1st day of application the EC50

1368

(effective concentration for 50% mortality) of commercial β-cyfluthrin (0.51 mg L-1) was

1369

much lower than the CFRs (97.24 mg L-1, 85.46 mg L-1, 59.89 mg L-1 and 37.32 mg L-1 for

1370

polymers having PEG 600, PEG 1000, PEG 1500 and PEG 2000, respectively). After that the

1371

EC50 of commercial β-cyfluthrin increased rapidly. Interesting features were noticed among

1372

the different CRFs. The lowest EC50 of CRFs having PEG 600 and PEG 1000 (1.89 mg L-1

1373

and 1.03 mg L-1, respectively) were observed on the 7th day of application whereas for CRFs

1374

having PEG 1500 and PEG 2000 (2.20 mg L-1 and 1.1.58 mg L-1, respectively) were observed

1375

on the14th day of application. The EC50 of commercial β-cyfluthrin on the 7th and 14th days

1376

of applications were 43.24 mg L-1 and 129.21 mg L-1, respectively.206 Another study

1377

examined the release pattern of β-cyfluthrin from these formulations in water.58 It emerged

1378

that the releasing rate of commercial β-cyfluthrin was higher than the CRFs and resulted in

1379

the lowest POA. Of the CRFs, the POA increased with increasing carbon chain of PEG, i.e.

1380

the order of POA is PEG 2000 (20.5 days) > PEG 1500 (18.0 day) > PEG 1000 (15.8 days) >

1381

PEG 600(14 days) > commercial 025 SC (1.4 days).58 However, the function of hydrophilic

1382

segment of PEGs was not clearly stated. Basically, β-cyfluthrin is not persistent because once

1383

it is in the water it disappears rapidly since it has poor water solubility and extremely high

1384

adsorption affinity to organic material. That is why commercial β-cyfluthrin degrades rapidly

1385

in water and minimum POA was observed. On the 3rd day EC50 of CRFs having PEG 600

1386

and PEG 1000 were higher than the CRFs having PEG 1500 and PEG 2000, which indicates

1387

longer polymeric chain absorbed more β-cyfluthrin within the shell of micelles. This caused

1388

faster release that was initially responsible for lower EC50. On the other hand, a longer

1389

polymeric chain enhanced shell thickness and reduced the diffusion release rate, resulting in

1390

delayed EC50 as well as increased POA. These results suggest that depending on the polymer


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1391

matrix used, the application rate of β-cyfluthrin can be optimized to achieve insect control at

1392

the desired level and period, as the hydrophilic segment influences the active compound’s

1393

release. Overall, the developed formulations retained their efficacy for longer periods than the

1394

commercial β-cyfluthrin. Similar results were also observed during the bio-efficacy

1395

investigation of CRFs of carbofuran against the root-knot nematode (Meloidogyne incognita)

1396

infecting tomato plant (cv.PusaRuby).59 In both pot and field conditions, the developed

1397

formulations with PEG 600 and PEG 900 showed better response at different concentrations

1398

than commercial carbofuran in controlling the penetration as well as further development of

1399

second stage juveniles (J2s) of M. incognita on tomato root system. In contrast developed

1400

formulations with PEG 900 exhibited better efficacy than the formulation with PEG 600.59

1401

In a study, Choudhary et al.216 evaluated the bio-efficacy CRFs of carbofuran against

1402

Meloidogyne incognita. The CRFs were prepared by encapsulating carbofuran with

1403

commercially available rosin and sodium carboxymethylcellulose (CMC). Release of

1404

carbofuran was faster from commercial formulations than with new CR formulations. In

1405

addition the rate of release declined due to the introduction of clay (bentonite, kaolinite, and

1406

Fuller’s earth) materials to the biodegradable clay materials. The half-release (t1/2) values of

1407

different CRFs along with commercial formulations ranged between 4.79 and 25.11 days, and

1408

the POA of carbofuran ranged from 15.10 to 43.97 days where the lowest value was observed

1409

in commercial formulations. The order of release of rate, t1/2 values and POA of different

1410

formulations were as follows:

1411 1412 1413 1414

Release rate: commercial granule 3G > rosin-yellow > CMC > CMC-kaolinite > CMC-bentonite > rosin-black > CMC-Fuller’s earth Half-release (t1/2) values: commercial granule 3G < rosin-yellow < CMC < CMCkaolinite < CMC-bentonite < CMC-Fuller’s earth < rosin-black



1415

Page 58 of 149

POA: commercial 3G < CMC < rosin-black < CMC-Fuller’s earth < CMC-kaolinite
5000 mg kg-1 whereas its half-life is approximately 20 h.265 It explains

1724

why plant derivatives such as essential oils, extracts and isolated active compounds (bio-

1725

chemicals) having pest control efficacy can be termed green pesticides or botanical

1726

pesticides. However, some botanical pesticides have been deemed toxic to humans and

1727

subsequently their utilization has been drastically reduced. For instance, nicotine - an alkaloid

1728

obtained from leaf extracts of Nicotiana tabacum - is a well-known insecticide but its

1729

utilization has declined due to extreme toxicity (acute oral LD50 to rat is 50 mg kg-1) and

1730

rapid dermal absorption in humans.266 Some promising botanical pesticides and their modes

1731

of action are listed in Table 4. Such pesticides constitute a major aspect of bio-pesticides.265

1732

Although such types of plant products are considered safe for humans, generally, they are

1733

either unstable or suffer from premature degradation, for instance high volatility, thermal

1734

decomposition, etc.268 Because of such properties, until now, their application is not up to the

1735

level of commercial synthetic pesticides. Considering the benefits of botanical pesticides to

1736

humans and the environment, new formulations with improved features in potency and

1737

stability constitute a major research area in the pest management industry.


Page 71 of 149


1738

The utilization of nanotechnology and especially the widespread application of

1739

nanoencapsulation materials in a drug delivery system has drawn attention to the selection of

1740

safe materials for enhancing botanical pesticide formulations. Recently, de Oliveira et al.268

1741

reviewed an application of nanotechnology for encapsulating botanical insecticides. They

1742

noted that except for a few botanical active compounds their utilization is limited to

1743

entomological concerns. Bio-chemicals derived from other types of bio-pesticides can also be

1744

used for strengthening the safe application of pesticides. In their review paper, Copping and

1745

Menn267 mentioned other sources of bio-pesticides such as micro-organisms derived

1746

compounds, insect derived compounds, etc.

1747

So far, a number of investigations have commented on the improved features of

1748

nanoencapsulated bio-pesticides (Table 3). More importantly, the development of less

1749

harmful plant protection products through nanoencapsulation was the focus of most research.

1750

The types of nanoencapsulation materials used were similar to those employed for drug

1751

delivery in humans. Considering the environmental risk factors, the nanoencapsulation

1752

materials that originated from biodegradable polymers were quite promising in the

1753

formulation of less harmful bio-pesticides. In recent years, biologically originated

1754

biodegradable materials (beeswax, corn oil, lecithin, cashew gum, etc.) were also used to

1755

prepare less harmful bio-pesticides by encapsulating bioactive compounds forming various

1756

nanomaterials.72,212,213 On the other hand, nanoencapsulation materials such as amorphous

1757

silica nanoparticles were declared safe for humans by the World Health Organization (WHO)

1758

and US Department of Agriculture269, whereas nano-clays already exist in the earth. It is

1759

expected that the wide range of nanoencapsulation materials and encapsulation approaches

1760

are able to simplify the synthesis of nanoencapsulated bio-pesticides. The widespread

1761

application of dangerous bio-pesticides can be overcome through nanoencapsulation which



Page 72 of 149

1762

may begin a new era where pesticides required for effective pest control in agriculture are

1763

environmentally safe.

1764

7. SUMMARY AND FUTURE TRENDS

1765

The indiscriminate usage of agrochemicals especially pesticides has drawn scholarly attention

1766

as they pollute the environment and pose a danger to living beings. Nanotechnology is a

1767

recent approach that is becoming increasingly important for delivering pesticides and their

1768

safe application. Of all the various types of nanotechnology related to pesticide delivery, this

1769

review analyzed and presented the importance, efficacy and trends inherent in the

1770

nanoencapsulation technique. Different nanoencapsulation materials have already shown

1771

their potential, promising results and applications by encapsulating the available pesticides

1772

and biocides. Among them polymer, porous silica, clay and LDHs-based nanomaterials were

1773

found to be very important. Further studies are required to understand the compatibility

1774

between the pesticides and encapsulation materials as well as the encapsulation mechanism of

1775

pesticides formulations. Of the wide potential applications of nanoencapsulation techniques

1776

for pesticide delivery, developing a slow releasing property with enhanced solubility,

1777

permeability and stability is the main focus of current research. These properties will be

1778

achieved through either protection of the encapsulated active ingredients from premature

1779

degradation or increasing their pest control efficacy for a longer period.

1780

The controlled release properties of nanoencapsulation materials to release the AIs to

1781

the target area using autosensing power needs further investigation. Although complete

1782

features (e.g., synthesis, efficacy and their fate) related to these nanomaterials are rarely

1783

found and promising nanoencapsulated pesticides are at a very early stage of development, it

1784

is expected that this technology will reduce firstly, the dosage of pesticides needed for crop

1785

protection, and secondly, human exposure to pesticides. A major contribution that is expected

1786

to emerge from the auspicious results of green pesticides, is the application of nanoparticles


Page 73 of 149


1787

to encapsulate and stabilize bio-products, which will reduce environmental hazards.

1788

However, more studies will be required to establish common synthesis procedures for a

1789

particular group of pesticides and to assess the fate of nanoencapsulation materials. The main

1790

challenges associated with nanoencapsulated pesticides are whether they will be able to

1791

compete with existing formulations, in terms of both cost and performance or otherwise.

1792

ACKNOWLEDGEMENTS

1793

The first author is grateful, firstly, to the University of Newcastle for the University of

1794

Newcastle Postgraduate Research Scholarship (UNIPRS)and secondly, to the Cooperative

1795

Research Centre for Contamination Assessment and Remediation of the Environment (CRC-

1796

CARE) for scholarship funding. We also acknowledge the University of South Australia for

1797

the logistic and fellowship supports to the first author.

1798

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2541 2542 2543 2544 2545 2546 2547 2548 2549 2550 2551 2552 2553 2554


Table 1. Physicochemical characteristics of different types of mesoporous silica nanoparticles and their adsorption capacities of imidacloprid (Reprinted with permission from ref 114). Copyright © 2012 the Royal Society of Chemistry) Types of MSNs MCM-41 MCM-41-Imi SBA-15 SBA-15-Imi IBN-1 IBN-1-Imi MCM-48 MCM-48-Imi

SBET /m2g-1 1020 754 505 415 919 700 1250 650

DP/nm 2.4 2.0 6.5 5.1 11.0 10.2 2.0 1.8

VP/cm3g-1 1.03 0.50 0.84 0.75 0.86 0.70 1.35 0.50

Adsorption capacities/ mg g-1 3 4 7 16 -

2555 2556 2557 2558 2559 2560 2561 2562 2563 2564 2565 2566 2567 2568 2569 2570 2571 2572 2573 2574 2575 2576 2577 2578 2579 2580 2581 105 ACS Paragon Plus Environment


2582 2583 2584 2585 2586 2587 2588 2589 2590 2591 2592 2593 2594 2595 2596 2597 2598 2599

Page 106 of 149

Table 2. Basal spacing (Å) of LDH−herbicide complexes prepared with three different methods. (Reprinted with permission from ref 158. Copyright © 2006 American Chemical Society)

Sample 2,4-D-LDH MCPA−LDH Picloram−LDH

direct synthesis (DS) 19.02 18.43 16.72

synthesis method regeneration (RE) 19.36 19.19 16.44

ion exchange (IE) 19.42 19.24 16.35

2600 2601


Page 107 of 149


Table 3. Improved properties of nanoencapsulated commercial pesticides and biocides Encapsulation Pesticides/ Nanoencapsulation Improved features achieved due to nanoencapsulation Sl. No. materials Biocides materials/ forms Commercial pesticides A. Synthetic Polymer/Polyesters 1. Poly-ethylene glycol Carbofuran Nano-micelles Applications of the a.i. can be optimized to achieve insect (PEG) originated control for the desired period depending on the matrix of the block copolymers polymer used Imidacloprid Nano-micelles In water, release of a.i. was faster in commercial formulation than the developed CR formulations Imidacloprid Nano-micelles CR formulations of imidacloprid exhibited significantly better control pests compared to its commercial formulations β-cyfluthrin Nano-micelles Slow release of the a.i. compared to commercial pesticide formulations and application rate of β-cyfluthrin can be optimized to achieve insect control at the desired level and period. Carbofuran Nano-micelles Under field conditions, developed CR formulations of carbofuran have exhibited greater potential for effective management of pests than the commercial formulation Thiram Nano-micelles Slow releasing properties have been achieved due to encapsulation and their applications can be optimized to achieve disease control for the desired period Thiamethoxa Nano-micelles More time is required for releasing 50% of the active m ingredients in sandy loam soil than commercial formulations Acephate Nanocapsules Nanoencapsulated acephate retained greater functional integrity over time and was more efficacious than commercial formulations 2. PCA–PEG–PCA Imidacloprid Nanocapsules Dosage of pesticide and environmental risk significantly triblock copolymers decreased due to nanoencapsulation of imidacloprid 3. Poly-(εAI Nanospheres Better stability of nanospheres was obtained in an aqueous caprolactone) (PCL) suspension over two months

References

61

55 205 206

59

56

60 207

49 208

107

ACS Paragon Plus Environment


4.

Polyacrylate (PAL)

Emamectin benzoate

B. Natural Polymer / polysaccharides 1. Chitosan -co-(D,LImidacloprid lactide) 2. Alginate/chitosan Paraquat

3.

Sodium alginate

Imidacloprid

4.

Biocopolymers of Methomyl azidobenzaldehyde and carboxymethyl chitosan C. Lipid-based nanomaterials 1. Compritol 888 Gamma(lipid) cyhalothrin

2. 3.

Chitosan coated lipid Chitosan coated beeswax (solid lipid) 4. Corn oil (liquid lipid) and beeswax (solid lipid) D. Porous nanomaterials 1. Silica

Page 108 of 149

Nanoparticle conjugation

Photostability and insecticidal effects of the novel emamectin 209 benzoate formulation increased, and were better than those of the commercial pesticide formulation

Nano-micelles

Sustained release of imidacloprid was achieved

Nanoparticles

The release profile of the herbicide was altered and its 210 interaction with the soil, indicating this system could effectively minimize the problems caused by paraquat. Exhibited less cytotoxicity but retained better pest efficacy 40 over plain imidacloprid The insecticidal activity of methomyl-loaded nanocapsules 43 against the armyworm larvae was significantly superior to the original, even 100% over 7 days

Nanocapsules Nanocapsules

Solid lipid nanoparticles (SLNs)

Entofenprox Deltamethrin

Liposomes SLNs

Deltamethrin

Nanostructured lipid carriers

Tebuconazol e 2,4-D and

Porous hollow silica nanospheres Mesoporous silica

Reduced toxicity to aquatic fish (Brachydanio rerio) and daphnia (Daphnia magna) by a factors of 10 and 63, respectively, compared to the traditional emulsifiable concentrate Better pest control efficacy was observed for a longer period Chitosan-SLNs demonstrated ability to protect deltamethrin against photodegradation Higher payload, slower release rate and higher photoprotection was obtained due to incorporation of corn oil compared to SLN

46

211

93 212 213,214

Slower release of the active ingredient was noticed in water 24 under different conditions Slower release of the active ingredient was achieved up to 26 215 108


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picloram Imidacloprid

nanospheres Mesoporous silica nanosparticles Mesoporous silica nanospheres

days for 2,4-D and 30 days for picloram Release of imidacloprid from these nanoparticles was found 114 to be controlled over 48 hours Slower release of metalaxyl was exhibited from mesoporous 116 silica nanospheres in soil than the free metalaxyl

Nanocomposites

Adding clay particles in the formulations reduced the release 216 of active ingredients

Ethofumesate Nanocomposites

Slow releasing properties were achieved due to clay/ pesticide 217 interactions

Novaluron

O/W microemulsions Microemulsion

Enhanced solubility was observed

196

Better pest control efficacy than commercial permethrin

218

O/W nanoemulsion

Sprayed solution of nanoemulsion formulation exhibited better stability than commercial microemulsion of βcypermethrin The stability of triazophos improved and was protected from hydrolysis by being incorporated into the nanoemulsion system Results of pot experiment indicated slightly better efficacy than the commercial formulation popularly known as ‘Roundup’

192

Enhanced penetration into the plant was observed; it was due to smaller particle size than the classical suspension Controlled and efficient release of bifenthrin was observed from polymeric stabilized suspension

208

Metalaxyl E. Clay and LDHs 1. Bentonite, kaolinite and fuller’s earth with polymer 2. Montmorillonites and wheat gluten F. Microemulsions 1. Oil phase, surfactants and water 2. Oil phase, surfactants and water G. Nanoemulsions 1. Oil phase, surfactants and water

Carbofuran

Permethrin βcypermethrin

2.

Oil phase, Triazophos surfactants and water

O/W nanoemulsion

3.

Oil phase, Glyphosate surfactants and water

O/W nanoemulsion

H. Nanosuspensions 1. Eudragit S100 (polymer) 2. PAA-b-PBA, PVP and PVOH

AI

Nanosuspension

Bifenthrin

Nanosuspension

187

219

220 109



3.

Microemulsion

βcypermethrin

Nanosuspension

Biocides A. Synthetic Polymer/Polyesters 1. Poly-ethylene glycol Garlic Nanocapsules (PEG) essential oil Azadirachtin- Nano-micelles A

Lansiumamid Nanocapsules eB B. Natural Polymer / polysaccharides 1. Amphiphilic Rotenone chitosan derivatives

Nano-micelles

Azadirachtin

Nano-micelles

2.

Chitosan and cashew gum

Lippia sidoides oil

Nanogels

3.

Gelator

Nanogels

4.

Myristic acid and chitosan

Methyl eugenol (Pheromone) Carum copticum oil

Nanogels

Particle size was increased but no influence over composition was observed

Page 110 of 149

197

The encapsulation materials reduced volatilization of essential 32 oils and retained 80% pest control efficacy over 5 months In water, the rate of release of encapsulated azadirachtin-A 57 from nanomicellar aggregates was reduced by increasing the molecular weight of PEG which controlled half release time (t1/2) of 3.05 to 42.80 days In pot experiment, nanoencapsulated lansiumamide B showed 34 higher nematicidal activity compared to only lansiumamide B where LC50 values were observed 2.1407 mg L-1 and 19.3608 mg L-1, respectively, after 24 h treatment The solubility of rotenone increased (up to 26.0 mg mL-1) which was about 13000 times greater than free rotenone in water (about 0.002 mg mL-1) Azadirachtin was protected by the carriers from rapid degradation and released over the course of 11 days into the environment Slower and sustained release of Lippia sidoides oil was noticed in vitro release profiles while more effective larvicidal efficacies were obtained compared to the pure L. sidoides oil. The evaporation of pheromone significantly slowed down and remained stable in open ambient conditions Nanogels exhibited more fumigant toxicity than the free oil over a longer period of time to control store grain pest

64

65

72

74

73

110


Page 111 of 149

C. Lipid-based NPs 1. Compritol 888 ATO (lipid)

D. Porous nanomaterials 1. Silica


Artemisia arborescens L essential oil

Solid lipid nanoparticles (SLNs)

Physical stability was obtained as the solid lipid nanoparticles reduced the rapid evaporation of essential oils

110

Avermectin

Porous hollow silica nanoparticles (PHSNs) PHSNs

Release of avermectin can be controlled by adjusting pH and temperature; UV-shielding properties were improved when shell thickness was adjusted Controlled release formulations were prepared

120,221

Cinnamate

Nanohybrid of CLDHs

Considered to be a green pesticide due to its controlled release and nature compatibility properties

159

Neem oil

Microemulsion

The acaricidal activity demonstrated by neem oil microemulsion was effective against Sarcoptes scabie var. cuniculi larvae in vitro.

182

Capcicin

Nanoemulsion

Neem oil

Nanoemulsion

Better stability of capcicin loaded nanoemulsion was obtained 222 due to electrostatic interactions of the polymers Larvicidal efficacy increased when droplet size decreased 181

Eucalyptus oil

Nanoemulsion

Superior larvicidal efficacy compared to bulk oil

Validamycin E. Clay and LDHs 1. LDHs F. Microemulsions 1. Tween-80 and the SDBS G. Nanoemulsions 1. Sodium alginate & chitosan 2. Non-ionic surfactant Tween20 and water 3. Tween 80 and water

122

223

111



Page 112 of 149

Table 4. Some promising botanical pesticides and their mode of action (reproduced from refs. 265-268) Sources Seed and leaf extracts of Azadirachta indica

Bioactive compounds Azadirachtin (C35H44O16)

Function Insecticide & fungicide

Mode of action Blocks the synthesis and release of moulting hormones (ecdysone). Disrupts the normal mating behaviour and results in reduced fecundity. Anti-feedant / repellent effect on many insects.

Properties Photo-degradable Half-life 20 h Acute oral LD50 to rat is >5000 mg kg-1

Dried flowers of Chrysanthemum cinerariaefolium

Pyrethrins

Insecticide & acaricide

Disrupts the sodium and potassium ion exchange process in nerve axons. Rapid knockdown effect on flying insects.

Photo-degradable Acute oral LD50 to rat is 350-2000 mg kg-1 (depends on purity)

Roots and rhizome extracts of Derris sp., Lonchocarpus sp. & Tephrosia sp.

Rotenone(C23H22O6)

Insecticide, acaricide & piscicide

Inhibits cellular respiration (at site I) Highly toxic to fish within electron transport chain and Acute oral LD50 to rat is prevents energy production. 132 mg kg-1

Stem extracts of Ryania speciosa

Ryanodine (C25H35NO9)

Insecticide

Affects muscles by binding to the More effective on selected calcium channels in the sarcoplasmic species 112


Page 113 of 149


reticulum.

Acute oral LD50 to rat is 1200 mg kg-1

Leaf extracts of Nicotiana tabacum

Nicotine (C10H14N2)

Insecticide

Causes continuous uncontrolled nerve firing by binding with acetylcholine receptors at nerve synapses. Act as fumigant against sucking pests

More effective on selected species Acute oral LD50 to rat is 50 mg kg-1 Dermal adsorption in human

Essential oil of Thymus vulgaris

Thymol (C10H14O)

Fungicide, bactericide & insecticide

Inhibits bacterial growth, lactate production and decreases cellular glucose uptake. Alters the hyphal morphology and causes hyphal aggregates, resulting in reduced hyphal diameters and lyses of hyphal wall.

Minimal potential toxicity and poses minimal risk. Degrades rapidly (DT50 16 days in water, 5 days in soil).

Essential oil of Origanum vulgare Thymus sp., Origanum majorana,

Carvacrol (C10H14O)

Bactericide

Disrupts cell membrane of bacteria, e.g. In rats, carvacrol is Pseudomonas aeruginosa. metabolized and excreted Inhibits the growth of several bacteria within 24 h. strains, e.g. Escherichia coli and Bacillus cereus

Fruit extracts of Citrus sp.

Limonene (C10H16)

Insecticide

Used as repellent

Non-toxic to humans, birds and animals

113



Bud and leaf extracted essential oils of Syzygium aromaticum,

Eugenol (C10H12O2)

Insecticide

Used in bait to attract and collect insects Causes hepatotoxicity in humans

Essential oil of Eucalyptus globulus

Eucalyptol (C10H18O)

Insecticide

Used as repellent Acute oral LD50 to rat is Used in bait to attract and collect insects 2480 mg kg-1

Seed extracts of Annona sp.

Annonin I(C37H66O7)

Insecticide

Inhibitory effect on the NADH- In pure form is toxic to cytochrome c-reductase and complex I mammals (LD50 is

Nanoencapsulation, Nano-guard for Pesticides: A New Window for

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