Nanoencapsulation, Nano-guard for Pesticides: A ... - ACS Publications

Fabrication of a pH-Responsively Controlled-Release Pesticide Using an ... for Controlled 2,4-Dichlorophenoxy Acetic Acid Sodium Salt Release .... KON...
4 downloads 0 Views 7MB Size
Subscriber access provided by UNIV OF CALIFORNIA SAN DIEGO LIBRARIES

Review

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

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Journal of Agricultural and Food Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 149

1

Journal of Agricultural and Food Chemistry

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

2 3

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

9

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

Journal of Agricultural and Food Chemistry

Page 2 of 149

26

ABSTRACT

27

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

28

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.

45 46

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

47

environmental exposure

48 49

1. INTRODUCTION

2 ACS Paragon Plus Environment

Page 3 of 149

Journal of Agricultural and Food Chemistry

50

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

53

application of this technology in agriculture where multifunctional approaches were

54

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

55

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

56

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

62

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%

65

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

66

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

67

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

3 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 4 of 149

74

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

75

concentration.

76

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

77

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

78

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,

81

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

82

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

83

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

84

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

85

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

86

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

88

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

89

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

90

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

91

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

92

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

4 ACS Paragon Plus Environment

Page 5 of 149

Journal of Agricultural and Food Chemistry

99

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

100

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

101

amount of pesticide required for pest control.20

102

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

104

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

105

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

106

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

107

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

108

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

112

efficacy and environmental impact of nanoencapsulated pesticides.

113

2. NANOENCAPSULATION AND NANOENCAPSULATION MATERIALS

114

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

117

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

5 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 6 of 149

124

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

140

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

6 ACS Paragon Plus Environment

Page 7 of 149

Journal of Agricultural and Food Chemistry

149

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

7 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 8 of 149

174

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 nano- emulsions 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

51 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 52 of 149

1266

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,

52 ACS Paragon Plus Environment

Page 53 of 149

Journal of Agricultural and Food Chemistry

1291

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

53 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 54 of 149

1316

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

54 ACS Paragon Plus Environment

Page 55 of 149

Journal of Agricultural and Food Chemistry

1341

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

55 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 56 of 149

1366

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

56 ACS Paragon Plus Environment

Page 57 of 149

Journal of Agricultural and Food Chemistry

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

57 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

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.

70 ACS Paragon Plus Environment

Page 71 of 149

Journal of Agricultural and Food Chemistry

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

71 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

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

72 ACS Paragon Plus Environment

Page 73 of 149

Journal of Agricultural and Food Chemistry

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

References

1799

(1)

Nanoparticulate material delivery to plants. Plant Sci. 2010, 179, 154-163.

1800 1801

Nair, R.; Varghese, S. H.; Nair, B. G.; Maekawa, T.; Yoshida, Y.; Kumar, D. S.

(2)

Scott, N.; Chen, H.; Rutzke, C. J. Nanoscale Science and Engineering for Agriculture

1802

and Food Systems: A Report Submitted to Cooperative State Research, Education and

1803

Extension Service, the United States Department of Agriculture: National Planning

1804

Workshop, November 18-19, 2002, Washington, DC. USDA: 2003.

1805

(3)

Ghormade, V.; Deshpande, M. V.; Paknikar, K. M. Perspectives for nano-

1806

biotechnology enabled protection and nutrition of plants. Biotechnol. Adv. 2011, 29,

1807

792-803.

1808

(4)

Gogos, A.; Knauer, K.; Bucheli, T. D., Nanomaterials in plant protection and

1809

fertilization: Current state, foreseen applications, and research priorities. J. Agric.

1810

Food Chem. 2012, 60, 9781-9792.

73 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

1811

(5)

Goswami, A.; Bandyopadh, A. Contribution of Nanobiotechnology in Indian Agriculture: Future Prospects. J. Indian Inst. Sci. 2012, 92, 219-232.

1812 1813

Page 74 of 149

(6)

Khot, L. R.; Sankaran, S.; Maja, J. M.; Ehsani, R.; Schuster, E. W. Applications of

1814

nanomaterials in agricultural production and crop protection: A review. Crop Prot.

1815

2012, 35, 64-70.

1816

(7)

management of insect pests. Appl. Microbiol. Biotechnol. 2012, 94, 287-93.

1817 1818

(8)

(9)

Roco, M. C. Nanotechnology: convergence with modern biology and medicine. Curr. Opin. Biotech. 2003, 14, 337-346.

1821 1822

Sekhon, B. S. Nanotechnology in agri-food production: an overview. Nanotechnol. Sci. Appl. 2014, 7, 31-53.

1819 1820

Rai, M.; Ingle, A. Role of nanotechnology in agriculture with special reference to

(10)

Perlatti, B.; Bergo, P. L. d. S.; Silva, M. F. d. G. F. d.; Fernandes, J. B.; Forim, M. R.

1823

Polymeric Nanoparticle-Based Insecticides: A Controlled Release Purpose for

1824

Agrochemicals. In Insecticides - Development of Safer and More Effective

1825

Technologies, Prof. Stanislav Trdan (Ed.), INTECH Open Access Publisher, 2013, pp.

1826

523-550.

1827

development-of-safer-and-more-effective-technologies/polymeric-nanoparticle-based-

1828

insecticides-a-controlled-release-purpose-for-agrochemicals

1829

(11)

Available

from:

http://www.intechopen.com/books/insecticides-

van den Berg, F.; Kubiak, R.; Benjey, W. G.; Majewski, M. S.; Yates, S. R.; Reeves,

1830

G. L.; Smelt, J. H.; van der Linden, A. M. A. Emission of pesticides into the Air.

1831

Water Air Soil Poll. 1999, 115, 195-218.

1832 1833

(12)

Bedos, C.; Cellier, P.; Calvet, R.; Barriuso, E. Occurrence of pesticides in the atmosphere in France. Agronomie 2002, 22, 35-49.

74 ACS Paragon Plus Environment

Page 75 of 149

1834

Journal of Agricultural and Food Chemistry

(13)

Mogul, M. G.; Akin, H.; Hasirci, N.; Trantolo, D. J.; Gresser, J. D.; Wise, D. L.

1835

Controlled release of biologically active agents for purposes of agricultural crop

1836

management. Resour. Conserv. Recy. 1996, 16, 289-320.

1837

(14)

sustainability and intensive production practices. Nature 2002, 418, 671-677.

1838 1839

Tilman, D.; Cassman, K. G.; Matson, P. A.; Naylor, R.; Polasky, S. Agricultural

(15)

Copping, L. G., European MEP Majority Supports Pesticide Legislation: Industry

1840

Looks Forward to More Science and Less Fiction during Implementation. Outlooks

1841

Pest Manag. 2009, 20, 6-7.

1842

(16)

Kah, M.; Beulke, S.; Tiede, K.; Hofmann, T. Nanopesticides: State of Knowledge,

1843

Environmental Fate, and Exposure Modeling. Crit. Rev. Environ. Sci. Technol. 2013,

1844

43, 1823-1867.

1845

(17)

P.;

Pollet,

E.;

Avérous,

L.

Nano-biocomposites:

Biodegradable

polyester/nanoclay systems. Prog. Polym. Sci. 2009, 34, 125-155.

1846 1847

Bordes,

(18)

Athanassiou, C. G.; Kavallieratos, N. G.; Meletsis, C. M. Insecticidal effect of three

1848

diatomaceous earth formulations, applied alone or in combination, against three

1849

stored-product beetle species on wheat and maize. J. Stored Prod. Res. 2007, 43, 330-

1850

334.

1851

(19)

entomotoxic silica nanoparticle. Toxicol. Environ. Chem. 2012, 94, 944-951.

1852 1853

(20)

1856

Yan, J.; Huang, K.; Wang, Y.; Liu, S. Study on anti-pollution nano-preparation of dimethomorph and its performance. Chin. Sci. Bull. 2005, 50, 108-112.

1854 1855

Debnath, N.; Das, S.; Patra, P.; Mitra, S.; Goswami, A. Toxicological evaluation of

(21)

Kah, M.; Hofmann, T. Nanopesticide research: Current trends and future priorities. Environ. Int. 2014, 63, 224-235.

75 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

1857

(22)

Page 76 of 149

Auffan, M.; Rose, J.; Bottero, J.-Y.; Lowry, G. V.; Jolivet, J.-P.; Wiesner, M. R.

1858

Towards a definition of inorganic nanoparticles from an environmental, health and

1859

safety perspective. Nat. Nano 2009, 4, 634-641.

1860

(23)

Grillo, R.; dos Santos, N. Z. P.; Maruyama, C. R.; Rosa, A. H.; de Lima, R.; Fraceto,

1861

L. F. Poly(ɛ-caprolactone)nanocapsules as carrier systems for herbicides: Physico-

1862

chemical characterization and genotoxicity evaluation. J. Hazard. Mater. 2012, 231–

1863

232, 1-9.

1864

(24)

Qian, K.; Shi, T.; He, S.; Luo, L.; liu, X.; Cao, Y. Release kinetics of tebuconazole

1865

from porous hollow silica nanospheres prepared by miniemulsion method. Micropor.

1866

Mesopor. Mat. 2013, 169, 1-6.

1867

(25)

drug delivery systems. Colloid. Surface. B 2010, 75, 1-18.

1868 1869

(26)

Mora-Huertas, C. E.; Fessi, H.; Elaissari, A. Polymer-based nanocapsules for drug delivery. Int. J. Pharm. 2010, 385, 113-142.

1870 1871

Kumari, A.; Yadav, S. K.; Yadav, S. C., Biodegradable polymeric nanoparticles based

(27)

Pinto Reis, C.; Neufeld, R. J.; Ribeiro, A. J.; Veiga, F. Nanoencapsulation I. Methods

1872

for preparation of drug-loaded polymeric nanoparticles. Nanomed. Nanotechnol.

1873

2006, 2, 8-21.

1874

(28)

Kango, S.; Kalia, S.; Celli, A.; Njuguna, J.; Habibi, Y.; Kumar, R. Surface

1875

modification of inorganic nanoparticles for development of organic–inorganic

1876

nanocomposites—A review. Prog. Polym. Sci. 2013, 38, 1232-1261.

1877

(29)

Liu, D. Synthesis of Hollow Inorganic Nanospheres Templated by Polymeric Micelles Core-Shell-Corona

Architecture.

2009.

1878

with

1879

http://portal.dl.saga-u.ac.jp/handle/123456789/117867 viewed on 11th March, 2015.

PhD

diss.

Available

at

76 ACS Paragon Plus Environment

Page 77 of 149

1880

Journal of Agricultural and Food Chemistry

(30)

Ezhilarasi,

P.

N.;

Karthik,

P.;

Chhanwal,

N.;

Anandharamakrishnan,

C.

1881

Nanoencapsulation Techniques for Food Bioactive Components: A Review. Food

1882

Bioprocess Technol. 2013, 6, 628-647.

1883

(31)

Meier, W. Polymer nanocapsules. Chem. Soc. Rev. 2000, 29, 295-303.

1884

(32)

Yang, F.-L.; Li, X.-G.; Zhu, F.; Lei, C.-L., Structural characterization of nanoparticles

1885

loaded with garlic essential oil and their insecticidal activity against Tribolium

1886

castaneum (Herbst) (Coleoptera: Tenebrionidae). J. Agric. Food Chem. 2009, 57,

1887

10156-10162.

1888

(33)

acephate nano-encapsulated complex. Nanosci. Methods. 2012, 1, 9-15.

1889 1890

Choudhury, S. R.; Pradhan, S.; Goswami, A., Preparation and characterisation of

(34)

Yin, Y-h.; Guo, Q-m.; Han, Y.; Wang, L-j.; Wan, S-q. Preparation, characterization

1891

and nematicidal activity of lansiumamide B nano-capsules. J. Integr. Agric. 2012, 11,

1892

1151-1158.

1893

(35)

Wu, J.; Zhou, Y-f.; Chen, J.; NIE, W-y.; SHI, R. Preparation of natural pyrethrum

1894

nanocapsule by means of microemulsion polymerization. Polym. Mater. Sci. Eng.

1895

2008, 24, 38.

1896

(36)

microspheres and nanospheres: an overview. Int. J. Pharm. 2004, 278, 1-23.

1897 1898

Sinha, V. R.; Bansal, K.; Kaushik, R.; Kumria, R.; Trehan, A. Poly-ϵ-caprolactone

(37)

Pereira, A. E. S.; Grillo, R.; Mello, N. F. S.; Rosa, A. H.; Fraceto, L. F. Application of

1899

poly(epsilon-caprolactone) nanoparticles containing atrazine herbicide as an

1900

alternative technique to control weeds and reduce damage to the environment. J.

1901

Hazard. Mater. 2014, 268, 207-215.

1902 1903

(38)

Campos, E. V. R.; de Oliveira, J. L.; Fraceto, L. F.; Singh, B. Polysaccharides as safer release systems for agrochemicals. Agron. Sustain. Dev. 2015, 35, 47-66.

77 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

1904

(39)

Page 78 of 149

Kumar, S.; Bhanjana, G.; Sharma, A.; Sidhu, M. C.; Dilbaghi, N. Synthesis,

1905

characterization and on field evaluation of pesticide loaded sodium alginate

1906

nanoparticles. Carbohydr. Polym. 2014, 101, 1061-1067.

1907

(40)

Guan, H.; Chi, D.; Yu, J.; Li, X. A novel photodegradable insecticide: Preparation,

1908

characterization and properties evaluation of nano-Imidacloprid. Pestic. Biochem.

1909

Physiol. 2008, 92, 83-91.

1910

(41)

Applications of Semiconductor Photocatalysis. Chem. Rev. 1995, 95, 69-96.

1911 1912

Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W. Environmental

(42)

Sun, C.; Shu, K.; Wang, W.; Ye, Z.; Liu, T.; Gao, Y.; Zheng, H.; He, G.; Yin, Y.

1913

Encapsulation and controlled release of hydrophilic pesticide in shell cross-linked

1914

nanocapsules containing aqueous core. Int. J. Pharm. 2014, 463, 108-114.

1915

(43)

Yin, Y.; Xu, S.; Chang, D.; Zheng, H.; Li, J.; Liu, X.; Xu, P.; Xiong, F. One-pot

1916

synthesis of biopolymeric hollow nanospheres by photocrosslinking. Chem. Commun.

1917

2010, 46, 8222-8224.

1918

(44)

Wu, Y.; Zheng, Y.; Yang, W.; Wang, C.; Hu, J.; Fu, S., Synthesis and

1919

characterization of a novel amphiphilic chitosan–polylactide graft copolymer.

1920

Carbohydr. Polym. 2005, 59, 165-171.

1921

(45)

submicron particles as imidacloprid carriers. Pest Manag. Sci. 2011, 67, 831-836.

1922 1923

Li, M.; Huang, Q.; Wu, Y. A novel chitosan-poly(lactide) copolymer and its

(46)

Zhang, J.; Li, M.; Fan, T.; Xu, Q.; Wu, Y.; Chen, C.; Huang, Q. Construction of novel

1924

amphiphilic chitosan copolymer nanoparticles for chlorpyrifos delivery. J. Polym.

1925

Res. 2013, 20, 1-11.

1926

(47)

Valletta, A.; Chronopoulou, L.; Palocci, C.; Baldan, B.; Donati, L.; Pasqua, G.

1927

Poly(lactic-co-glycolic) acid nanoparticles uptake by Vitis vinifera and grapevine-

1928

pathogenic fungi. J. Nanopart. Res. 2014, 16, 1-14.

78 ACS Paragon Plus Environment

Page 79 of 149

1929

Journal of Agricultural and Food Chemistry

(48)

Anand, P.; Nair, H. B.; Sung, B.; Kunnumakkara, A. B.; Yadav, V. R.; Tekmal, R. R.;

1930

Aggarwal, B. B. Design of curcumin-loaded PLGA nanoparticles formulation with

1931

enhanced cellular uptake, and increased bioactivity in vitro and superior

1932

bioavailability in vivo. Biochem. Pharmacol. 2010, 79, 330-338.

1933

(49)

Memarizadeh,

N.;

Ghadamyari,

M.;

Adeli,

M.;

Talebi,

K.

Preparation,

1934

characterization and efficiency of nanoencapsulated imidacloprid under laboratory

1935

conditions. Ecotox. Environ. Safe. 2014, 107, 77-83.

1936

(50)

Onopordon leptolepis DC. Ind. Crop. Prod. 2012, 37, 259-263.

1937 1938

Esmaeili, A.; Saremnia, B. Preparation of extract-loaded nanocapsules from

(51)

Forim, M. R.; Silva M. F. d. G. F. d.; Fernandes, J. B. Secondary Metabolism as a

1939

Measurement of Efficacy of Botanical Extracts: The Use of Azadirachta indica

1940

(Neem) as a Model, Insecticides. In Advances in Integrated Pest Management, Dr.

1941

Farzana

1942

10.5772/27961.

1943

advances-in-integrated-pest-management/secondary-metabolism-as-a-measurement-

1944

of-efficacy-of-botanical-extracts-the-use-of-azadirachta-indica. Viewed on 13 April,

1945

2015.

1946

(52)

Perveen

InTech,

2012.

(Ed.),

ISBN:

978-953-307-780-2,

DOI:

Available

from:

http://www.intechopen.com/books/insecticides-

Boehm, A. L. L. R.; Zerrouk, R.; Fessi, H. Poly epsilon-caprolactone nanoparticles

1947

containing a poorly soluble pesticide: formulation and stability study. J.

1948

Microencapsul. 2000, 17, 195-205.

1949

(53)

strategies and underlying principles. Nanomed-UK. 2010, 5, 485-505.

1950 1951

Trivedi, R.; Kompella, U. B., Nanomicellar formulations for sustained drug delivery:

(54)

Letchford, K.; Burt, H. A review of the formation and classification of amphiphilic

1952

block copolymer nanoparticulate structures: micelles, nanospheres, nanocapsules and

1953

polymersomes. Eur. J. Pharm. Biopharm. 2007, 65, 259-269.

79 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

1954

(55)

Page 80 of 149

Adak, T.; Kumar, J.; Shakil, N. A.; Walia, S. Development of controlled release

1955

formulations of imidacloprid employing novel nano-ranged amphiphilic polymers. J.

1956

Environ. Sci. Health, B 2012, 47, 217-225.

1957

(56)

Kaushik, P.; Shakil, N. A.; Kumar, J.; Singh, M. K.; Singh, M. K.; Yadav, S. K.

1958

Development of controlled release formulations of thiram employing amphiphilic

1959

polymers and their bioefficacy evaluation in seed quality enhancement studies. J.

1960

Environ. Sci. Health, B 2013, 48, 677-85.

1961

(57)

Kumar, J.; Shakil, N. A.; Singh, M. K.; Singh, M. K.; Pandey, A.; Pandey, R. P.

1962

Development of controlled release formulations of azadirachtin-A employing

1963

poly(ethylene glycol) based amphiphilic copolymers. J. Environ. Sci. Health, B 2010,

1964

45, 310-4.

1965

(58)

Loha, K. M.; Shakil, N. A.; Kumar, J.; Singh, M. K.; Adak, T.; Jain, S. Release

1966

kinetics of beta-cyfluthrin from its encapsulated formulations in water. J. Environ.

1967

Sci. Health, B 2011, 46, 201-6.

1968

(59)

Pankaj; Shakil, N. A.; Kumar, J.; Singh, M. K.; Singh, K. Bioefficacy evaluation of

1969

controlled release formulations based on amphiphilic nano-polymer of carbofuran

1970

against Meloidogyne incognita infecting tomato. J. Environ. Sci. Health, B 2012, 47,

1971

520-528.

1972

(60)

Sarkar, D. J.; Kumar, J.; Shakil, N. A.; Walia, S. Release kinetics of controlled release

1973

formulations of thiamethoxam employing nano-ranged amphiphilic PEG and diacid

1974

based block polymers in soil. J. Environ. Sci. Health, A 2012, 47, 1701-1712.

1975

(61)

Shakil, N. A.; Singh, M. K.; Pandey, A.; Kumar, J.; Pankaj; Parmar, V. S.; Singh, M.

1976

K.; Pandey, R. P.; Watterson, A. C. Development of Poly(ethylene glycol) Based

1977

Amphiphilic Copolymers for Controlled Release Delivery of Carbofuran. J.

1978

Macromol. Sci., A 2010, 47, 241-247.

80 ACS Paragon Plus Environment

Page 81 of 149

1979

Journal of Agricultural and Food Chemistry

(62)

Adak, T.; Kumar, J.; Shakil, N. A.; Walia, S.; Kumar, A.; Watterson, A. C. Synthesis

1980

and Characterization of Novel Surfactant Molecules Based on Amphiphilic Polymers.

1981

J. Macromol. Sci., A 2011, 48, 767-775.

1982

(63)

Koli, P.; Shakil, N. A.; Kumar, J.; Singh, B. B.; Watterson, A. C. Synthesis and

1983

Characterization of Novel Encapsulating Materials Based on Functionalized

1984

Amphiphilic Block Copolymers. J. Macromol. Sci., A. 2014, 51, 729-736.

1985

(64)

Lao, S.-B.; Zhang, Z.-X.; Xu, H.-H.; Jiang, G.-B. Novel amphiphilic chitosan

1986

derivatives: Synthesis, characterization and micellar solubilization of rotenone.

1987

Carbohydr. Polym. 2010, 82, 1136-1142.

1988

(65)

Feng, B.-H.; Peng, L.-F. Synthesis and characterization of carboxymethyl chitosan

1989

carrying ricinoleic functions as an emulsifier for azadirachtin. Carbohydr. Polym.

1990

2012, 88, 576-582.

1991

(66)

Networks of Infinite Capabilities. Angew. Chem. Int. Ed. 2009, 48, 5418-5429.

1992 1993

(67)

Ferreira, S. A.; Gama, F. M.; Vilanova, M. Polymeric nanogels as vaccine delivery systems. Nanomed. Technol. 2013, 9, 159-173.

1994 1995

Kabanov, A. V.; Vinogradov, S. V. Nanogels as Pharmaceutical Carriers: Finite

(68)

Soni, G.; Yadav, K. S. Nanogels as potential nanomedicine carrier for treatment of

1996

cancer: A mini review of the state of the art. Saudi Pharmaceutical Journal, 2014,

1997

http://dx.doi.org/10.1016/j.jsps.2014.04.001

1998

(69)

Akiyoshi, K.; Kobayashi, S.; Shichibe, S.; Mix, D.; Baudys, M.; Wan Kim, S.;

1999

Sunamoto, J. Self-assembled hydrogel nanoparticle of cholesterol-bearing pullulan as

2000

a carrier of protein drugs: Complexation and stabilization of insulin. J. Control.

2001

Release. 1998, 54, 313-320.

2002 2003

(70)

Daoud-Mahammed, S.; Couvreur, P.; Gref, R. Novel self-assembling nanogels: Stability and lyophilisation studies. Int. J. Pharm. 2007, 332, 185-191.

81 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

2004

(71)

Page 82 of 149

Rigogliuso, S.; Sabatino, M. A.; Adamo, G.; Grimaldi, N.; Dispenza, C.; Ghersi, G.

2005

Polymeric nanogels: nanocarriers for drug delivery application. Chemical

2006

Engineering Transactions 2012, 27, 247-252.

2007

(72)

Abreu, F. O. M. S.; Oliveira, E. F.; Paula, H. C. B.; de Paula, R. C. M.

2008

Chitosan/cashew gum nanogels for essential oil encapsulation. Carbohydr. Polym.

2009

2012, 89, 1277-1282.

2010

(73)

Ziaee, M.; Moharramipour, S.; Mohsenifar, A. Toxicity of Carum copticum essential

2011

oil-loaded nanogel against Sitophilus granarius and Tribolium confusum. J. Appl.

2012

Entomol. 2014, 138, 763-771.

2013

(74)

Pheromone Nanogels. Sci. Rep. 2013, 3, 1294 DOI: 10.1038/srep01294

2014 2015

Bhagat, D.; Samanta, S. K.; Bhattacharya, S. Efficient Management of Fruit Pests by

(75)

Tamjidi, F.; Shahedi, M.; Varshosaz, J.; Nasirpour, A. Nanostructured lipid carriers

2016

(NLC): A potential delivery system for bioactive food molecules. Innov. Food Sci.

2017

Emerg. Technol. 2013, 19, 29-43.

2018

(76)

using lipid based delivery systems. Trends Food Sci. Tech. 2012, 23, 13-27.

2019 2020

(77)

(78)

(79)

2027

Mozafari, M. R. Nanocarrier technologies: frontiers of nanotherapy. Mozafari, M. R. (Ed.). Dordrecht, The Netherlands, Springer: 2006, pp 225

2025 2026

Taylor, T. M.; Weiss, J.; Davidson, P. M.; Bruce, B. D. Liposomal Nanocapsules in Food Science and Agriculture. Crit. Rev. Food. Sci. 2005, 45, 587-605.

2023 2024

Mozafari, M. Nanoliposomes: preparation and analysis. In Liposomes, Springer 2010, 605, pp 29-50.

2021 2022

Fathi, M.; Mozafari, M. R.; Mohebbi, M., Nanoencapsulation of food ingredients

(80)

Mozafari, M. R.; Johnson, C.; Hatziantoniou, S.; Demetzos, C. Nanoliposomes and their applications in food nanotechnology. J. Liposome Res. 2008, 18, 309-327.

82 ACS Paragon Plus Environment

Page 83 of 149

2028

Journal of Agricultural and Food Chemistry

(81)

vesiculation. Adv. Colloid Interfac. 2001, 89–90, 337-349.

2029 2030

(82)

(83)

(84)

Grit, M.; Crommelin, D. J. A. Chemical stability of liposomes: implications for their physical stability. Chem. Phys. Lipids. 1993, 64, 3-18.

2035 2036

Natarajan, J. V.; Nugraha, C.; Ng, X. W.; Venkatraman, S. Sustained-release from nanocarriers: a review. J. Control. Release. 2014, 193, 122-138.

2033 2034

Mozafari, M. R. Liposomes: an overview of manufacturing techniques. Cell. Mol. Biol. Lett. 2005, 10, 711-719.

2031 2032

Lasic, D. D.; Joannic, R.; Keller, B. C.; Frederik, P. M.; Auvray, L. Spontaneous

(85)

Samuni, A. M.; Lipman, A.; Barenholz, Y. Damage to liposomal lipids: protection by

2037

antioxidants and cholesterol-mediated dehydration. Chem. Phys. Lipids. 2000, 105,

2038

121-134.

2039

(86)

Lo, Y.-l.; Tsai, J.-c.; Kuo, J.-h., Liposomes and disaccharides as carriers in spray-

2040

dried powder formulations of superoxide dismutase. J. Control. Release. 2004, 94,

2041

259-272.

2042

(87)

supercritical fluid and dense gas. Adv. Drug Deliver. Rev. 2008, 60, 411-432.

2043 2044

Mishima, K. Biodegradable particle formation for drug and gene delivery using

(88)

Sankar Kadimi, U.; Balasubramanian, D. R.; Ganni, U. R.; Balaraman, M.;

2045

Govindarajulu, V. In vitro studies on liposomal amphotericin B obtained by

2046

supercritical carbon dioxide–mediated process. Nanomed. Technol. 2007, 3, 273-280.

2047

(89)

Stark, B.; Pabst, G.; Prassl, R. Long-term stability of sterically stabilized liposomes

2048

by freezing and freeze-drying: Effects of cryoprotectants on structure. Eur. J. Pharm.

2049

Sci. 2010, 41, 546-555.

2050 2051

(90)

Chen, C.; Han, D.; Cai, C.; Tang, X. An overview of liposome lyophilization and its future potential. J. Control. Release. 2010, 142, 299-311.

83 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

2052

(91)

Page 84 of 149

Kawai, K.; Suzuki, T. Stabilizing Effect of Four Types of Disaccharide on the

2053

Enzymatic Activity of Freeze-dried Lactate Dehydrogenase: Step by Step Evaluation

2054

from Freezing to Storage. Pharm. Res. 2007, 24, 1883-1890.

2055

(92)

carrier systems by self-assembly. J. Microencapsul. 2009, 26, 722-33.

2056 2057

Bang, S. H.; Yu, Y. M.; Hwang, I. C.; Park, H. J. Formation of size-controlled nano

(93)

Hwang, I. C.; Kim, T. H.; Bang, S. H.; Kim, K. S.; Kwon, H. R.; Seo, M. J.; Youn, Y.

2058

N.; Park, H. J.; Yasunaga-Aoki, C.; Yu, Y. M. Insecticidal Effect of Controlled

2059

Release Formulations of Etofenprox Based on Nano-bio Technique. J. Fac. Agric.

2060

Kyushu Univ. 2011, 56, 33-40.

2061

(94)

Natarajan, J. V.; Darwitan, A.; Barathi, V. A.; Ang, M.; Htoon, H. M.; Boey, F.; Tam,

2062

K. C.; Wong, T. T.; Venkatraman, S. S. Sustained Drug Release in Nanomedicine: A

2063

Long-Acting Nanocarrier-Based Formulation for Glaucoma. ACS Nano 2014, 8, 419-

2064

429.

2065

(95)

Müller, R. H.; Mäder, K.; Gohla, S. Solid lipid nanoparticles (SLN) for controlled

2066

drug delivery – a review of the state of the art. Eur. J. Pharm. Biopharm. 2000, 50,

2067

161-177.

2068

(96)

applications. Adv. Drug Deliver. Rev. 2001, 47, 165-196.

2069 2070

Mehnert, W.; Mäder, K. Solid lipid nanoparticles: Production, characterization and

(97)

Müller, R. H.; Radtke, M.; Wissing, S. A. Solid lipid nanoparticles (SLN) and

2071

nanostructured lipid carriers (NLC) in cosmetic and dermatological preparations. Adv.

2072

Drug Deliver. Rev. 2002, 54, Supplement, S131-S155.

2073 2074

(98)

Saupe, A.; Rades, T. Solid lipid nanoparticles. In Nanocarrier Technologies, Springer: 2006; pp 41-50.

84 ACS Paragon Plus Environment

Page 85 of 149

2075

Journal of Agricultural and Food Chemistry

(99)

Potta, S. G.; Minemi, S.; Nukala, R. K.; Peinado, C.; Lamprou, D. A.; Urquhart, A.;

2076

Douroumis, D. Preparation and characterization of ibuprofen solid lipid nanoparticles

2077

with enhanced solubility. J Microencapsul. 2011, 28, 74-81.

2078 2079

(100) Utreja, S.; Jain, N. Solid lipid nanoparticles. In Advances in controlled and novel drug delivery. New Delhi, India: CBS Publishers 2001, pp. 408-425.

2080

(101) Pardeshi, C.; Rajput, P.; Belgamwar, V.; Tekade, A.; Patil, G.; Chaudhary, K.; Sonje,

2081

A. Solid lipid based nanocarriers: An overview/Nanonosači na bazi čvrstih lipida:

2082

Pregled. Acta Pharmaceut. 2012, 62, 433-472.

2083 2084

(102) Ekambaram, P.; Sathali, A. A. H.; Priyanka, K. Solid lipid nanoparticles: a review. Sci. Rev. Chem. Commun. 2012, 2, 80-102.

2085

(103) Miiller, R.; Dingier, A.; Schneppe, T.; Gohla, S. Large-scale production of solid lipid

2086

nanoparticles (SLN) and nanosuspensions (DissoCubes). Handbook of pharmaceutical

2087

controlled release technology 2000, 359.

2088 2089

(104) Himawan, C.; Starov, V. M.; Stapley, A. G. F. Thermodynamic and kinetic aspects of fat crystallization. Adv. Colloid Interfac. 2006, 122, 3-33.

2090

(105) Bunjes, H.; Koch, M. H. J. Saturated phospholipids promote crystallization but slow

2091

down polymorphic transitions in triglyceride nanoparticles. J. Control. Release. 2005,

2092

107, 229-243.

2093

(106) Golemanov, K.; Tcholakova, S.; Denkov, N. D.; Gurkov, T. Selection of Surfactants

2094

for Stable Paraffin-in-Water Dispersions, undergoing Solid−Liquid Transition of the

2095

Dispersed Particles. Langmuir. 2006, 22, 3560-3569.

2096 2097

(107) Awad, T. S. Ultrasonic studies of the crystallization behavior of two palm fats O/W emulsions and its modification. Food Res. Int. 2004, 37, 579-586.

2098

(108) Awad, T.; Helgason, T.; Kristbergsson, K.; Decker, E.; Weiss, J.; McClements, D. J.

2099

Effect of cooling and heating rates on polymorphic transformations and gelation of

85 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 86 of 149

2100

tripalmitin solid lipid nanoparticle (SLN) suspensions. Food Biophys. 2008, 3, 155-

2101

162.

2102

(109) Helgason, T.; Awad, T. S.; Kristbergsson, K.; McClements, D. J.; Weiss, J. Effect of

2103

surfactant surface coverage on formation of solid lipid nanoparticles (SLN). J. Colloid

2104

Interf. Sci. 2009, 334, 75-81.

2105

(110) Lai, F.; Wissing, S.; Müller, R.; Fadda, A. Artemisia arborescens L essential oil-

2106

loaded solid lipid nanoparticles for potential agricultural application: Preparation and

2107

characterization. AAPS Pharm. Sci. Tech. 2006, 7, E10-E18.

2108

(111) Ao, M.; Zhu, Y.; He, S.; Li, D.; Li, P.; Li, J.; Cao, Y. Preparation and characterization

2109

of 1-naphthylacetic acid-silica conjugated nanospheres for enhancement of controlled-

2110

release performance. Nanotechnology. 2013, 24, 035601.

2111 2112

(112) Wen, J.; Kim, G. J. A.; Leong, K. W. Poly(d-lactide–co-ethyl ethylene phosphate)s as new drug carriers. J. Control. Release. 2003, 92, 39-48.

2113

(113) Radin, S.; El-Bassyouni, G.; Vresilovic, E. J.; Schepers, E.; Ducheyne, P. In vivo

2114

tissue response to resorbable silica xerogels as controlled-release materials.

2115

Biomaterials 2005, 26, 1043-1052.

2116

(114) Popat, A.; Liu, J.; Hu, Q.; Kennedy, M.; Peters, B.; Lu, G. Q.; Qiao, S. Z. Adsorption

2117

and release of biocides with mesoporous silica nanoparticles. Nanoscale. 2012, 4,

2118

970-5.

2119

(115) Polshettiwar, V.; Cha, D.; Zhang, X.; Basset, J. M. High-Surface-Area Silica

2120

Nanospheres (KCC-1) with a Fibrous Morphology. Angew. Chem. Int. Ed. 2010, 49,

2121

9652-9656.

2122 2123

(116) Wanyika, H. Sustained release of fungicide metalaxyl by mesoporous silica nanospheres. J. Nanopart. Res. 2013, 15, 1831.

86 ACS Paragon Plus Environment

Page 87 of 149

2124 2125 2126 2127 2128 2129

Journal of Agricultural and Food Chemistry

(117) He, D.; Wang, S.; Lei, L.; Hou, Z.; Shang, P.; He, X.; Nie, H. Core–shell particles for controllable release of drug. Chem. Eng. Sci. 2015, 125, 108-120. (118) Wu, S.-H.; Mou, C.-Y.; Lin, H.-P. Synthesis of mesoporous silica nanoparticles. Chem. Soc. Rev. 2013, 42, 3862-3875. (119) Tang, F.; Li, L.; Chen, D. Mesoporous Silica Nanoparticles: Synthesis, Biocompatibility and Drug Delivery. Adv. Mater. 2012, 24, 1504-1534.

2130

(120) Wen, L.-X.; Li, Z.-Z.; Zou, H.-K.; Liu, A.-Q.; Chen, J.-F. Controlled release of

2131

avermectin from porous hollow silica nanoparticles. Pest Manag. Sci. 2005, 61, 583-

2132

590.

2133

(121) Chen, J.-F.; Wang, J.-X.; Liu, R.-J.; Shao, L.; Wen, L.-X. Synthesis of porous silica

2134

structures with hollow interiors by templating nanosized calcium carbonate. Inorg.

2135

Chem. Commun. 2004, 7, 447-449.

2136

(122) Liu, F.; Wen, L.-X.; Li, Z.-Z.; Yu, W.; Sun, H.-Y.; Chen, J.-F. Porous hollow silica

2137

nanoparticles as controlled delivery system for water-soluble pesticide. Mater. Res.

2138

Bull. 2006, 41, 2268-2275.

2139

(123) Domingo, C.; Garcıá -Carmona, J.; Fanovich, M. A.; Saurina, J. Study of adsorption

2140

processes of model drugs at supercritical conditions using partial least squares

2141

regression. Anal. Chim. Acta. 2002, 452, 311-319.

2142

(124) Sasidharan, M.; Zenibana, H.; Nandi, M.; Bhaumik, A.; Nakashima, K. Synthesis of

2143

mesoporous hollow silica nanospheres using polymeric micelles as template and their

2144

application as a drug-delivery carrier. Dalton Trans. 2013, 42, 13381-13389.

2145

(125) Choy, J.-H.; Choi, S.-J.; Oh, J.-M.; Park, T. Clay minerals and layered double

2146

hydroxides for novel biological applications. Appl. Clay Sci. 2007, 36, 122-132.

87 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 88 of 149

2147

(126) Lee, W.-F.; Fu, Y.-T. Effect of montmorillonite on the swelling behavior and drug-

2148

release behavior of nanocomposite hydrogels. J. Appl. Polym. Sci. 2003, 89, 3652-

2149

3660.

2150

(127) Majeed, K.; Jawaid, M.; Hassan, A.; Abu Bakar, A.; Abdul Khalil, H. P. S.; Salema,

2151

A. A.; Inuwa, I. Potential materials for food packaging from nanoclay/natural fibres

2152

filled hybrid composites. Mater. Des. 2013, 46, 391-410.

2153 2154 2155 2156 2157 2158

(128) Yuan, G.; Wu, L. Allophane nanoclay for the removal of phosphorus in water and wastewater. Sci. Tech. Adv. Mater. 2007, 8, 60-62. (129) Schoonheydt, R. A. Smectite-type clay minerals as nanomaterials. Clays Clay Miner. 2002, 50, 411-420. (130) Uddin, F. Clays, Nanoclays, and Montmorillonite Minerals. Metall. Mat. Trans. A 2008, 39, 2804-2814.

2159

(131) Bhattacharyya, K. G.; Gupta, S. S. Adsorption of a few heavy metals on natural and

2160

modified kaolinite and montmorillonite: A review. Adv. Colloid Interfac. 2008, 140,

2161

114-131.

2162

(132) Khajeh, M.; Laurent, S.; Dastafkan, K. Nanoadsorbents: Classification, Preparation,

2163

and Applications (with Emphasis on Aqueous Media). Chem. Rev. 2013, 113, 7728-

2164

7768.

2165 2166 2167 2168

(133) Aguzzi, C.; Cerezo, P.; Viseras, C.; Caramella, C. Use of clays as drug delivery systems: Possibilities and limitations. Appl. Clay Sci. 2007, 36, 22-36. (134) Annabi-Bergaya, F. Layered clay minerals. Basic research and innovative composite applications. Micropor. Mesopor. Mat. 2008, 107, 141-148.

2169

(135) Ruiz-Hitzky, E.; Aranda, P.; Darder, M.; Rytwo, G. Hybrid materials based on clays

2170

for environmental and biomedical applications. J. Mater. Chem. 2010, 20, 9306-9321.

88 ACS Paragon Plus Environment

Page 89 of 149

Journal of Agricultural and Food Chemistry

2171

(136) Ruiz-Hitzky, E.; Van Meerbeek, A. Chapter 10.3 Clay Mineral– and Organoclay–

2172

Polymer Nanocomposite. In Developments in Clay Science, Faïza Bergaya, B. K. G.

2173

T.; Gerhard, L., Eds. Elsevier: 2006; 1, pp 583-621.

2174

(137) Fu, Y.-T.; Heinz, H. Cleavage Energy of Alkylammonium-Modified Montmorillonite

2175

and Relation to Exfoliation in Nanocomposites: Influence of Cation Density, Head

2176

Group Structure, and Chain Length. Chem. Mater. 2010, 22, 1595-1605.

2177

(138) Patel, H.; Somani, R.; Bajaj, H.; Jasra, R. Nanoclays for polymer nanocomposites,

2178

paints, inks, greases and cosmetics formulations, drug delivery vehicle and waste

2179

water treatment. Bull. Mater. Sci. 2006, 29, 133-145.

2180

(139) Chen, B.; Evans, J. R. G.; Greenwell, H. C.; Boulet, P.; Coveney, P. V.; Bowden, A.

2181

A.; Whiting, A. A critical appraisal of polymer-clay nanocomposites. Chem. Soc. Rev.

2182

2008, 37, 568-594.

2183

(140) Vaia, R. A.; Ishii, H.; Giannelis, E. P. Synthesis and properties of two-dimensional

2184

nanostructures by direct intercalation of polymer melts in layered silicates. Chem.

2185

Mater. 1993, 5, 1694-1696.

2186

(141) Chevillard, A.; Angellier-Coussy, H.; Guillard, V.; Gontard, N.; Gastaldi, E.

2187

Controlling pesticide release via structuring agropolymer and nanoclays based

2188

materials. J. Hazard. Mater. 2012, 205–206, 32-39.

2189 2190 2191 2192

(142) Gerstl, Z.; Nasser, A.; Mingelgrin, U. Controlled Release of Pesticides into Soils from Clay−Polymer Formulations. J. Agric. Food Chem. 1998, 46, 3797-3802. (143) Bojemueller, E.; Nennemann, A.; Lagaly, G. Enhanced pesticide adsorption by thermally modified bentonites. Appl. Clay Sci. 2001, 18, 277-284.

2193

(144) Fernández-Pérez, M.; Villafranca-Sánchez, M.; González-Pradas, E.; Flores-

2194

Céspedes, F. Controlled Release of Diuron from an Alginate−Bentonite Formulation: 

89 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 90 of 149

2195

Water Release Kinetics and Soil Mobility Study. J. Agric. Food Chem. 1999, 47, 791-

2196

798.

2197

(145) Fernández-Pérez, M.; Villafranca-Sánchez, M.; González-Pradas, E.; Martinez-López,

2198

F.; Flores-Céspedes, F. Controlled Release of Carbofuran from an Alginate−Bentonite

2199

Formulation:  Water Release Kinetics and Soil Mobility. J. Agric. Food Chem. 2000,

2200

48, 938-943.

2201 2202

(146) Lvov, Y. M.; Shchukin, D. G.; Möhwald, H.; Price, R. R. Halloysite Clay Nanotubes for Controlled Release of Protective Agents. ACS Nano. 2008, 2, 814-820.

2203

(147) Lvov, Y.; Price, R.; Gaber, B.; Ichinose, I. Thin film nanofabrication via layer-by-

2204

layer adsorption of tubule halloysite, spherical silica, proteins and polycations.

2205

Colloids Surf. A 2002, 198–200, 375-382.

2206 2207 2208 2209 2210 2211 2212 2213 2214 2215 2216 2217

(148) Zhang, D.; Zhou, C.-H.; Lin, C.-X.; Tong, D.-S.; Yu, W.-H. Synthesis of clay minerals. Appl. Clay Sci. 2010, 50, 1-11. (149) Nalawade, P.; Aware, B.; Kadam, V.; Hirlekar, R., Layered double hydroxides: A review. J. Sci. Ind. Res. 2009, 68, 267-272. (150) Bi, X.; Zhang, H.; Dou, L. Layered Double Hydroxide-Based Nanocarriers for Drug Delivery. Pharmaceutics 2014, 6, 298-332. (151) Wang, Q.; O’Hare, D. Recent Advances in the Synthesis and Application of Layered Double Hydroxide (LDH) Nanosheets. Chem. Rev. 2012, 112, 4124-4155. (152) Oh, J.-M.; Biswick, T. T.; Choy, J.-H. Layered nanomaterials for green materials. J. Mater. Chem. 2009, 19, 2553-2563. (153) Zümreoglu-Karan, B.; Ay, A. Layered double hydroxides — multifunctional nanomaterials. Chem. Pap. 2012, 66, 1-10.

90 ACS Paragon Plus Environment

Page 91 of 149

Journal of Agricultural and Food Chemistry

2218

(154) Evans, D. G.; Duan, X. Preparation of layered double hydroxides and their

2219

applications as additives in polymers, as precursors to magnetic materials and in

2220

biology and medicine. Chem. Commun. 2006, 485-496.

2221 2222

(155) Ladewig, K.; Xu, Z. P.; Lu, G. Q. Layered double hydroxide nanoparticles in gene and drug delivery. Expert Opin. Drug Del. 2009, 6, 907-922.

2223

(156) Kuang, Y.; Zhao, L.; Zhang, S.; Zhang, F.; Dong, M.; Xu, S. Morphologies,

2224

Preparations and Applications of Layered Double Hydroxide Micro-/Nanostructures.

2225

Materials 2010, 3, 5220-5235.

2226

(157) Pan, D.; Zhang, H.; Zhang, T.; Duan, X. A novel organic–inorganic microhybrids

2227

containing anticancer agent doxifluridine and layered double hydroxides: Structure

2228

and controlled release properties. Chem. Eng. Sci. 2010, 65, 3762-3771.

2229

(158) Cardoso, L. P.; Celis, R.; Cornejo, J.; Valim, J. B. Layered double hydroxides as

2230

supports for the slow release of acid herbicides. J. Agric. Food Chem. 2006, 54, 5968-

2231

5975.

2232

(159) Park, M.; Lee, C. I.; Seo, Y. J.; Woo, S. R.; Shin, D.; Choi, J. Hybridization of the

2233

natural antibiotic, cinnamic acid, with layered double hydroxides (LDH) as green

2234

pesticide. Environ. Sci. Pollut. Res. Int. 2010, 17, 203-9.

2235

(160) Sarlak, N.; Taherifar, A.; Salehi, F. Synthesis of nanopesticides by encapsulating

2236

pesticide nanoparticles using functionalized carbon nanotubes and application of new

2237

nanocomposite for plant disease treatment. J. Agric. Food Chem. 2014, 62, 4833-

2238

4838.

2239 2240 2241 2242

(161) Lee, J. S.; Feijen, J. Polymersomes for drug delivery: Design, formation and characterization. J. Control. Release. 2012, 161, 473-483. (162) Soussan, E.; Cassel, S.; Blanzat, M.; Rico‐Lattes, I. Drug delivery by soft matter: matrix and vesicular carriers. Angew. Chem. Int. Ed. 2009, 48, 274-288.

91 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

2243 2244

Page 92 of 149

(163) Kesharwani, P.; Jain, K.; Jain, N. K. Dendrimer as nanocarrier for drug delivery. Prog. Polym. Sci. 2014, 39, 268-307.

2245

(164) Watanabe, H.; Mizuno, Y.; Endo, T.; Wang, X.; Fuji, M.; Takahashi, M. Effect of

2246

initial pH on formation of hollow calcium carbonate particles by continuous CO2 gas

2247

bubbling into CaCl2 aqueous solution. Adv. Powder Technol. 2009, 20, 89-93.

2248

(165) Wei, W.; Ma, G.-H.; Hu, G.; Yu, D.; McLeish, T.; Su, Z.-G.; Shen, Z.-Y. Preparation

2249

of Hierarchical Hollow CaCO3 Particles and the Application as Anticancer Drug

2250

Carrier. J. Am. Chem. Soc. 2008, 130, 15808-15810.

2251

(166) Lehman, S. E.; Larsen, S. C. Zeolite and mesoporous silica nanomaterials: greener

2252

syntheses, environmental applications and biological toxicity. Environ. Sci. Nano

2253

2014, 1, 200-213.

2254

(167) SMARTtrain Chemical notes 1, Agriculture pesticides formulations. 2007, available

2255

at

2256

Pesticide-Formulations.pdf viewed on 20th February, 2015

2257 2258

http://www.smarttrain.com.au/__data/assets/pdf_file/0007/351862/Agricultural-

(168) Seaman, D. Trends in the formulation of pesticides—an overview. Pestic. Sci. 1990, 29, 437-449.

2259

(169) Li, Z.-Z.; Xu, S.-A.; Wen, L.-X.; Liu, F.; Liu, A.-Q.; Wang, Q.; Sun, H.-Y.; Yu, W.;

2260

Chen, J.-F. Controlled release of avermectin from porous hollow silica nanoparticles:

2261

Influence of shell thickness on loading efficiency, UV-shielding property and release.

2262

J. Control. Release. 2006, 111, 81-88.

2263 2264 2265 2266

(170) Solans, C.; García-Celma, M. J. Surfactants for microemulsions. Curr. Opin. Colloid Interface Sci. 1997, 2, 464-471. (171) Langevin, D. Microemulsions - interfacial aspects. Adv. Colloid Interfac. 1991, 34, 583-595.

92 ACS Paragon Plus Environment

Page 93 of 149

Journal of Agricultural and Food Chemistry

2267

(172) Porras, M.; Solans, C.; González, C.; Gutiérrez, J. M. Properties of water-in-oil (W/O)

2268

nano-emulsions prepared by a low-energy emulsification method. Colloids Surf. A

2269

2008, 324, 181-188.

2270

(173) Huang, Q.; She, D.; Li, F.; Zhang, C.; Bu, X.; Li, G.; Zhang, W. Studies on the Phase

2271

Behavior of Beta‐cypermethrion Microemulsion. J. Dispersion Sci. Technol. 2006,

2272

27, 1065-1071.

2273 2274 2275 2276 2277 2278 2279 2280 2281 2282 2283 2284

(174) Green, J. M.; Beestman, G. B. Recently patented and commercialized formulation and adjuvant technology. Crop Prot. 2007, 26, 320-327. (175) Lawrence, M. J.; Rees, G. D. Microemulsion-based media as novel drug delivery systems. Adv. Drug Deliver. Rev. 2012, 64, Supplement, 175-193. (176) McClements, D. J. Nanoemulsions versus microemulsions: terminology, differences, and similarities. Soft Matter 2012, 8, 1719-1729. (177) Schubert, K. V.; Kaler, E. W. Nonionic Microemulsions. Berichte der Bunsengesellschaft für physikalische Chemie 1996, 100, 190-205. (178) Pratap, A. P.; Bhowmick, D. N. Pesticides as Microemulsion Formulations. J. Dispersion Sci. Technol. 2008, 29, 1325-1330. (179) Zhao, F.; Xia, H.-y.; He, J.-l. Formulation design of cyhalothrin pesticide microemulsión. Curr. Sci. 2009, 97, 1458-1462.

2285

(180) Rao, J.; McClements, D. J. Food-grade microemulsions and nanoemulsions: Role of

2286

oil phase composition on formation and stability. Food Hydrocolloid. 2012, 29, 326-

2287

334.

2288

(181) Anjali, C. H.; Sharma, Y.; Mukherjee, A.; Chandrasekaran, N. Neem oil (Azadirachta

2289

indica) nanoemulsion--a potent larvicidal agent against Culex quinquefasciatus. Pest

2290

Manag. Sci. 2012, 68, 158-63.

93 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 94 of 149

2291

(182) Xu, J.; Fan, Q.-J.; Yin, Z.-Q.; Li, X.-T.; Du, Y.-H.; Jia, R.-Y.; Wang, K.-Y.; Lv, C.;

2292

Ye, G.; Geng, Y.; Su, G.; Zhao, L.; Hu, T.-X.; Shi, F.; Zhang, L.; Wu, C.-L.; Tao, C.;

2293

Zhang, Y.-X.; Shi, D.-X. The preparation of neem oil microemulsion (Azadirachta

2294

indica) and the comparison of acaricidal time between neem oil microemulsion and

2295

other formulations in vitro. Vet. Parasitol. 2010, 169, 399-403.

2296 2297 2298 2299

(183) Feng, Z.; Shan, L.; Ying, X. H.; Ling, H. J. Formula design of pesticide microemulsion formulation. Tenside Surfact. Det. 2010, 47, 113-118. (184) Kogan, A.; Garti, N. Microemulsions as transdermal drug delivery vehicles." Adv. Colloid Interfac. 2006, 123, 369-385.

2300

(185) McClements, D. J.; Rao, J. Food-Grade Nanoemulsions: Formulation, Fabrication,

2301

Properties, Performance, Biological Fate, and Potential Toxicity. Crit. Rev. Food. Sci.

2302

2011, 51, 285-330.

2303

(186) Mason, T. G.; Wilking, J.; Meleson, K.; Chang, C.; Graves, S. Nanoemulsions:

2304

formation, structure, and physical properties. J. Phys. Condens. Matter 2006, 18,

2305

R635-R666.

2306 2307 2308 2309

(187) Song, S.; Liu, X.; Jiang, J.; Qian, Y.; Zhang, N.; Wu, Q. Stability of triazophos in self-nanoemulsifying pesticide delivery system. Colloids Surf. A 2009, 350, 57-62. (188) Koroleva, M. Y.; Yurtov, E. V. Nanoemulsions: the properties, methods of preparation and promising applications. Russian Chem. Rev. 2012, 81, 21.

2310

(189) Anton, N.; Benoit, J.-P.; Saulnier, P. Design and production of nanoparticles

2311

formulated from nano-emulsion templates—A review. J. Control. Release. 2008, 128,

2312

185-199.

2313 2314

(190) Solans, C.; Solé, I. Nano-emulsions: Formation by low-energy methods. Curr. Opin. Colloid Interface Sci. 2012, 17, 246-254.

94 ACS Paragon Plus Environment

Page 95 of 149

2315 2316 2317 2318 2319 2320

Journal of Agricultural and Food Chemistry

(191) Tadros, T.; Izquierdo, P.; Esquena, J.; Solans, C. Formation and stability of nanoemulsions. Adv. Colloid Interfac. 2004, 108–109, 303-318. (192) Wang, L.; Li, X.; Zhang, G.; Dong, J.; Eastoe, J. Oil-in-water nanoemulsions for pesticide formulations. J. Colloid Interf. Sci. 2007, 314, 230-235. (193) Porras, M.; Solans, C.; González, C.; Martínez, A.; Guinart, A.; Gutiérrez, J. M. Studies of formation of W/O nano-emulsions. Colloids Surf. A 2004, 249, 115-118.

2321

(194) Strom, R.; Price, D.; Lubetkin, S., A stable aqueous dispersion of pesticide has a

2322

water solubility of less than 0,1%, and melting point sufficiently high so as not to melt

2323

during milling, contains stabilizing amount of surfactant; dispersion has specific

2324

particle. US2001/0051175 A1

2325 2326

(195) Chingunpituk, J. Nanosuspension technology for drug delivery. WJST. 2011, 4, 139153.

2327

(196) Elek, N.; Hoffman, R.; Raviv, U.; Resh, R.; Ishaaya, I.; Magdassi, S. Novaluron

2328

nanoparticles: Formation and potential use in controlling agricultural insect pests.

2329

Colloids Surf. A 2010, 372, 66-72.

2330

(197) Zeng, H.; Li, X.; Zhang, G.; Dong, J., Preparation and Characterization of Beta

2331

Cypermethrin Nanosuspensions by Diluting O/W Microemulsions. J. Dispersion Sci.

2332

Technol. 2008, 29, 358-361.

2333

(198) Saini, P.; Gopal, M.; Kumar, R.; Srivastava, C. Development of pyridalyl nanocapsule

2334

suspension for efficient management of tomato fruit and shoot borer (Helicoverpa

2335

armigera). J. Environ. Sci. Health, B 2014, 49, 344-351.

2336

(199) Van Eerdenbrugh, B.; Van den Mooter, G.; Augustijns, P. Top-down production of

2337

drug nanocrystals: Nanosuspension stabilization, miniaturization and transformation

2338

into solid products. Int. J. Pharm. 2008, 364, 64-75.

95 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

2339 2340

Page 96 of 149

(200) Patel, V. R.; Agrawal, Y. Nanosuspension: An approach to enhance solubility of drugs. J. Adv. Pharm. Technol. Res. 2011, 2, 81-87.

2341

(201) Verma, S.; Kumar, S.; Gokhale, R.; Burgess, D. J. Physical stability of

2342

nanosuspensions: Investigation of the role of stabilizers on Ostwald ripening. Int. J.

2343

Pharm. 2011, 406, 145-152.

2344 2345

(202) Smith, K.; Evans, D. A.; El-Hiti, G. A. Role of modern chemistry in sustainable arable crop protection. Philos. T. Roy. Soc., B. 2008, 363, 623-637.

2346

(203) Sasson, Y.; Levy-Ruso, G.; Toledano, O.; Ishaaya, I. Nanosuspensions: Emerging

2347

Novel Agrochemical Formulations. In Insecticides Design Using Advanced

2348

Technologies, Ishaaya, I.; Horowitz, A. R.; Nauen, R., Eds. Springer Berlin

2349

Heidelberg; 2007; pp 1-39.

2350

(204) Kookana, R. S.; Boxall, A. B. A.; Reeves, P. T.; Ashauer, R.; Beulke, S.; Chaudhry,

2351

Q.; Cornelis, G.; Fernandes, T. F.; Gan, J.; Kah, M.; Lynch, I.; Ranville, J.; Sinclair,

2352

C.; Spurgeon, D.; Tiede, K.; Van den Brink, P. J. Nanopesticides: Guiding Principles

2353

for Regulatory Evaluation of Environmental Risks. J. Agric. Food Chem. 2014, 62,

2354

4227-4240.

2355

(205) Adak, T.; Kumar, J.; Dey, D.; Shakil, N. A.; Walia, S. Residue and bio-efficacy

2356

evaluation of controlled release formulations of imidacloprid against pests in soybean

2357

(Glycine max). J. Environ. Sci. Health., B 2012, 47, 226-231.

2358

(206) Loha, K. M.; Shakil, N. A.; Kumar, J.; Singh, M. K.; Srivastava, C., Bio-efficacy

2359

evaluation of nanoformulations of beta-cyfluthrin against Callosobruchus maculatus

2360

(Coleoptera: Bruchidae). J. Environ. Sci. Heath., B. 2012, 47, 687-91.

2361

(207) Pradhan, S.; Roy, I.; Lodh, G.; Patra, P.; Choudhury, S. R.; Samanta, A.; Goswami,

2362

A. Entomotoxicity and biosafety assessment of PEGylated acephate nanoparticles: A

96 ACS Paragon Plus Environment

Page 97 of 149

Journal of Agricultural and Food Chemistry

2363

biologically safe alternative to neurotoxic pesticides. J. Environ. Sci. Health, B. 2013,

2364

48, 559-569.

2365

(208) Boehm, A. L.; Martinon, I.; Zerrouk, R.; Rump, E.; Fessi, H. Nanoprecipitation

2366

technique for the encapsulation of agrochemical active ingredients. J. Microencapsul.

2367

2003, 20, 433-441.

2368

(209) Shang, Q.; Shi, Y.; Zhang, Y.; Zheng, T.; Shi, H. Pesticide-conjugated polyacrylate

2369

nanoparticles: novel opportunities for improving the photostability of emamectin

2370

benzoate. Polym. Adv. Technol. 2013, 24, 137-143.

2371

(210) Silva, M. d. S.; Cocenza, D. S.; Grillo, R.; Melo, N. F. S. d.; Tonello, P. S.; Oliveira,

2372

L. C. d.; Cassimiro, D. L.; Rosa, A. H.; Fraceto, L. F. Paraquat-loaded

2373

alginate/chitosan nanoparticles: Preparation, characterization and soil sorption studies.

2374

J. Hazard. Mater. 2011, 190, 366-374.

2375

(211) Frederiksen, H. K.; Kristensen, H. G.; Pedersen, M. Solid lipid microparticle

2376

formulations of the pyrethroid gamma-cyhalothrin—incompatibility of the lipid and

2377

the pyrethroid and biological properties of the formulations. J. Control. Release.

2378

2003, 86, 243-252.

2379

(212) Nguyen, H. M.; Hwang, I.-C.; Park, J.-W.; Park, H.-J. Photoprotection for

2380

deltamethrin using chitosan-coated beeswax solid lipid nanoparticles. Pest Manag.

2381

Sci. 2012, 68, 1062-1068.

2382

(213) Nguyen, H. M.; Hwang, I. C.; Park, J. W.; Park, H. J. Enhanced payload and photo-

2383

protection for pesticides using nanostructured lipid carriers with corn oil as liquid

2384

lipid. J. Microencapsul. 2012, 29, 596-604.

2385

(214) Nguyen, M.-H.; Hwang, I.-C.; Park, H.-J. Enhanced photoprotection for photo-labile

2386

compounds using double-layer coated corn oil-nanoemulsions with chitosan and

2387

lignosulfonate. J. Photochem. Photobiol., B 2013, 125, 194-201.

97 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 98 of 149

2388

(215) Prado, A. G. S.; Moura, A. O.; Nunes, A. R. Nanosized silica modified with

2389

carboxylic acid as support for controlled release of herbicides. J. Agric. Food Chem.

2390

2011, 59, 8847-8852.

2391

(216) Choudhary, G.; Kumar, J.; Walia, S.; Parsad, R.; Parmar, B. S. Development of

2392

Controlled Release Formulations of Carbofuran and Evaluation of Their Efficacy

2393

against Meloidogyne incognita. J. Agric. Food Chem. 2006, 54, 4727-4733.

2394

(217) Chen, Y.; Chen, H.; Guo, L.; He, Q.; Chen, F.; Zhou, J.; Feng, J.; Shi, J.

2395

Hollow/Rattle-Type Mesoporous Nanostructures by a Structural Difference-Based

2396

Selective Etching Strategy. ACS Nano 2009, 4, 529-539.

2397

(218) Suresh Kumar, R. S.; Shiny, P. J.; Anjali, C. H.; Jerobin, J.; Goshen, K.; Magdassi, S.;

2398

Mukherjee, A.; Chandrasekaran, N. Distinctive effects of nano-sized permethrin in the

2399

environment. Environ. Sci. Pollut. Res. 2013, 20, 2593-2602.

2400

(219) Jiang, L. C.; Basri, M.; Omar, D.; Abdul Rahman, M. B.; Salleh, A. B.; Raja Abdul

2401

Rahman, R. N. Z.; Selamat, A. Green nano-emulsion intervention for water-soluble

2402

glyphosate isopropylamine (IPA) formulations in controlling Eleusine indica (E.

2403

indica). Pestic. Biochem. Physiol. 2012, 102, 19-29.

2404 2405

(220) Liu, Y.; Tong, Z.; Prud'homme, R. K. Stabilized polymeric nanoparticles for controlled and efficient release of bifenthrin. Pest Manag. Sci. 2008, 64, 808-812.

2406

(221) Li, Z. Z.; Chen, J. F.; Liu, F.; Liu, A. Q.; Wang, Q.; Sun, H. Y.; Wen, L. X. Study of

2407

UV-shielding properties of novel porous hollow silica nanoparticle carriers for

2408

avermectin. Pest Manag. Sci. 2007, 63, 241-6.

2409

(222) Choi, A.-J.; Kim, C.-J.; Cho, Y.-J.; Hwang, J.-K.; Kim, C.-T. Characterization of

2410

capsaicin-loaded nanoemulsions stabilized with alginate and chitosan by self-

2411

assembly. Food Bioprocess Technol. 2011, 4, 1119-1126.

98 ACS Paragon Plus Environment

Page 99 of 149

Journal of Agricultural and Food Chemistry

2412

(223) Sugumar, S.; Clarke, S. K.; Nirmala, M. J.; Tyagi, B. K.; Mukherjee, A.;

2413

Chandrasekaran, N. Nanoemulsion of eucalyptus oil and its larvicidal activity against

2414

Culex quinquefasciatus. Bull. Entomol. Res. 2014, 104, 393-402.

2415 2416

(224) Tsuji, K. Microencapsulation of pesticides and their improved handling safety. J. Microencapsul. 2001, 18, 137-147.

2417

(225) Ritger, P. L.; Peppas, N. A. A simple equation for description of solute release I.

2418

Fickian and non-fickian release from non-swellable devices in the form of slabs,

2419

spheres, cylinders or discs. J. Control. Release 1987, 5, 23-36.

2420

(226) Needham, D.; Dewhirst, M. W. The development and testing of a new temperature-

2421

sensitive drug delivery system for the treatment of solid tumors. Adv. Drug Deliver.

2422

Rev. 2001, 53, 285-305.

2423

(227) Kono, K.; Nakai, R.; Morimoto, K.; Takagishi, T. Thermosensitive polymer-modified

2424

liposomes

that

release

contents

2425

Biomembranes. 1999, 1416, 239-250.

around

physiological

temperature.

BBA-

2426

(228) Kono, K.; Igawa, T.; Takagishi, T. Cytoplasmic delivery of calcein mediated by

2427

liposomes modified with a pH-sensitive poly(ethylene glycol) derivative. BBA-

2428

Biomembranes. 1997, 1325, 143-154.

2429

(229) Cho, E. C.; Lim, H. J.; Kim, H. J.; Son, E. D.; Choi, H. J.; Park, J. H.; Kim, J.-W.;

2430

Kim, J. Role of pH-sensitive polymer–liposome complex in enhancing cellular uptake

2431

of biologically active drugs. Mater. Sci. Eng., C 2009, 29, 774-778.

2432

(230) bin Hussein, M. Z.; Zainal, Z.; Yahaya, A. H.; Foo, D. W. V. Controlled release of a

2433

plant growth regulator, α-naphthaleneacetate from the lamella of Zn–Al-layered

2434

double hydroxide nanocomposite. J. Control. Release 2002, 82, 417-427.

2435

(231) Hussein, M. Z.; Jaafar, A. M.; Yahaya, A. H.; Zainal, Z. The Effect of Single, Binary

2436

and Ternary Anions of Chloride, Carbonate and Phosphate on the Release of 2,4-

99 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 100 of 149

2437

Dichlorophenoxyacetate Intercalated into the Zn-Al-layered Double Hydroxide

2438

Nanohybrid. Nanoscale Res. Lett. 2009, 4, 1351-1357.

2439

(232) Qiu, D.; Li, Y.; Fu, X.; Jiang, Z.; Zhao, X.; Wang, T.; Hou, W. Controlled-release of

2440

Avermectin from Organically Modified Hydrotalcite-like Compound Nanohybrids.

2441

Chin. J. Chem. 2009, 27, 445-451.

2442 2443 2444 2445 2446 2447

(233) Knowles, A. Recent developments of safer formulations of agrochemicals. Environmentalist. 2008, 28, 35-44. (234) Rabinow, B. E. Nanosuspensions in drug delivery. Nat. Rev. Drug Discov. 2004, 3, 785-96. (235) Horn, D.; Rieger, J. Organic Nanoparticles in the Aqueous Phase-Theory, Experiment, and Use. Angew. Chem. Int. Ed. 2001, 40, 4330-4361.

2448

(236) Ravier, I.; Haouisee, E.; Clement, M.; Seux, R.; Briand, O. Field experiments for the

2449

evaluation of pesticide spray-drift on arable crops. Pest. Manag. Sci. 2005, 61, 728-

2450

36.

2451 2452

(237) Jenning, V.; Gohla, S. H. Encapsulation of retinoids in solid lipid nanoparticles (SLN). J. Microencapsul. 2001, 18, 149-158.

2453

(238) El-Nahhal, Y.; Nir, S.; Margulies, L.; Rubin, B. Reduction of photodegradation and

2454

volatilization of herbicides in organo-clay formulations. Appl. Clay Sci. 1999, 14,

2455

105-119.

2456

(239) Salma, U.; Chen, N.; Richter, D. L.; Filson, P. B.; Dawson-Andoh, B.; Matuana, L.;

2457

Heiden, P. Amphiphilic Core/Shell Nanoparticles to Reduce Biocide Leaching From

2458

Treated Wood, 1 – Leaching and Biological Efficacy. Macromol. Mater. Eng. 2010,

2459

295, 442-450.

100 ACS Paragon Plus Environment

Page 101 of 149

Journal of Agricultural and Food Chemistry

2460

(240) Anjali, C. H.; Sudheer Khan, S.; Margulis-Goshen, K.; Magdassi, S.; Mukherjee, A.;

2461

Chandrasekaran, N. Formulation of water-dispersible nanopermethrin for larvicidal

2462

applications. Ecotox. Environ. Safe. 2010, 73, 1932-1936.

2463

(241) Kang, M. A.; Seo, M. J.; Hwang, I. C.; Jang, C.; Park, H. J.; Yu, Y. M.; Youn, Y. N.

2464

Insecticidal activity and feeding behavior of the green peach aphid, Myzus persicae,

2465

after treatment with nano types of pyrifluquinazon. J. Asia Pac. Entomol. 2012, 15,

2466

533-541.

2467

(242) Wu, J.; Chen, J.; Zhou, Y.; NIE, W. Y; CHENG, X. M. Structure characterization and

2468

insecticidal activity tests of natural pyrethrin and abermectin nanocapsules.

2469

Pesticides-Shenyang. 2007, 46, 672.

2470 2471 2472 2473

(243) Casanova, H.; Araque, P.; Ortiz, C. Nicotine carboxylate insecticide emulsions:  effect of the fatty acid chain length. J. Agric. Food Chem. 2005, 53, 9949-9953. (244) Ragaei, M.; Sabry, Al-k. H. Nanotechnology for insect pest control. Int. J. Sci. Environ. Technol. 2014, 3, 528 – 545

2474

(245) Damalas, C. A.; Eleftherohorinos, I. G. Pesticide exposure, safety issues, and risk

2475

assessment indicators. Int. J. Environ. Res. Public Health 2011, 8, 1402-1419.

2476

(246) Fenske, R. A.; Day, E. W. Assessment of Exposure for Pesticide Handlers in

2477

Agricultural, Residential and Institutional Environments. In Occupational and

2478

Residential Exposure Assessment for Pesticides, C. A. Franklin and J. P. Worgan;

2479

John Wiley & Sons, Ltd, Chichester, UK., 2005; pp.11-43.

2480 2481 2482 2483

(247) Davis, J. R.; Brownson, R. C.; Garcia, R. Family pesticide use in the home, garden, orchard, and yard. Arch. Environ. Contam. Toxicol. 1992, 22, 260-266. (248) Jaga, K.; Dharmani, C. Sources of exposure to and public health implications of organophosphate pesticides. Rev. Panam. Salud Publica. 2003, 14, 171-85.

101 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

Page 102 of 149

2484

(249) Mortensen, L. J.; Oberdorster, G.; Pentland, A. P.; Delouise, L. A. In vivo skin

2485

penetration of quantum dot nanoparticles in the murine model: the effect of UVR.

2486

Nano Lett. 2008, 8, 2779-87.

2487

(250) When

particles

are

so

small

that

they

seep

right

2488

http://www.urmc.rochester.edu/news/story/index.cfm?id=2138,

2489

March 2015.

2490 2491 2492 2493 2494

through

Viewed

skin. 10th

on

(251) Hillyer, J. F.; Albrecht, R. M. Gastrointestinal persorption and tissue distribution of differently sized colloidal gold nanoparticles. J. Pharm. Sci. 2001, 90, 1927-1936. (252) Alvarez-Román, R.; Naik, A.; Kalia, Y. N.; Guy, R. H.; Fessi, H. Skin penetration and distribution of polymeric nanoparticles. J. Control. Release. 2004, 99, 53-62. (253) New

study

says

nanoparticles

don’t

penetrate

the

skin.

2495

http://www.bath.ac.uk/news/2012/10/01/nanoparticles-skin/, Viewed on 15th March

2496

2015.

2497

(254) Campbell, C. S. J.; Contreras-Rojas, L. R.; Delgado-Charro, M. B.; Guy, R. H.

2498

Objective assessment of nanoparticle disposition in mammalian skin after topical

2499

exposure. J. Control. Release. 2012, 162, 201-207.

2500 2501

(255) El Maghraby, G. M.; Barry, B. W.; Williams, A. C. Liposomes and skin: From drug delivery to model membranes. Eur. J. Pharm. Sci. 2008, 34, 203-222.

2502

(256) Kalayou H. G.; Amare A. A. Assessment of pesticide use, practice and environmental

2503

effects on the small holder farmers in the North Shoa Zone of Amhara National

2504

Regional State of Ethiopia. Res. J.Agr. Env. Sci. 2015, 2, 16-24.

2505

(257) Gil, Y.; Sinfort, C.; Brunet, Y.; Polveche, V.; Bonicelli, B. Atmospheric loss of

2506

pesticides above an artificial vineyard during air-assisted spraying. Atmos. Environ.

2507

2007, 41, 2945-2957.

102 ACS Paragon Plus Environment

Page 103 of 149

Journal of Agricultural and Food Chemistry

2508

(258) Juhasz, A. L.; Smith, E.; Weber, J.; Rees, M.; Rofe, A.; Kuchel, T.; Sansom, L.;

2509

Naidu, R. In Vivo assessment of arsenic bioavailability in rice and its significance for

2510

human health risk assessment. Environ. Health Persp. 2006, 114, 1826–1831.

2511

(259) Rahman, M. M.; Ng, J. C.; Naidu, R. Chronic exposure of arsenic via drinking water

2512

and its adverse health impacts on humans. Environ Geochem Health. 2009, 31, 189-

2513

200.

2514 2515

(260) Guan, H.; Chi, D.; Yu, J.; Li, H. Dynamics of residues from a novel nanoimidacloprid formulation in soyabean fields. Crop Prot. 2010, 29, 942-946.

2516

(261) Grillo, R.; Pereira, A. E. S.; Nishisaka, C. S.; de Lima, R.; Oehlke, K.; Greiner, R.;

2517

Fraceto, L. F. Chitosan/tripolyphosphate nanoparticles loaded with paraquat

2518

herbicide: An environmentally safer alternative for weed control. J. Hazard. Mater.

2519

2014, 278, 163-171.

2520 2521

(262) Pérez-de-Luque, A.; Rubiales, D. Nanotechnology for parasitic plant control. Pest Manag. Sci. 2009, 65, 540-545.

2522

(263) Scrinis, G.; Lyons, K. The emerging nano-corporate paradigm: nanotechnology and

2523

the transformation of nature, food and agri-food systems. Int. J. Sociol. Food Agric.

2524

2007, 15, 22-44.

2525 2526 2527 2528

(264) El-Wakeil, N. E. Botanical pesticides and their mode of action. Gesunde Pflanzen. 2013, 65, 125-149. (265) Isman, M. B. Botanical insecticides, deterrents, and repellents in modern agriculture and an increasingly regulated world. Annu. Rev. Entomol. 2006, 51, 45-66.

2529

(266) Casanova, H.; Ortiz, C.; Pelaez, C.; Vallejo, A.; Moreno, M. E.; Acevedo, M.

2530

Insecticide formulations based on nicotine oleate stabilized by sodium caseinate. J.

2531

Agric. Food Chem. 2002, 50, 6389-94.

103 ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

2532 2533

Page 104 of 149

(267) Copping, L. G.; Menn, J. J. Biopesticides: a review of their action, applications and efficacy. Pest Manag. Sci. 2000, 56, 651-676.

2534

(268) de Oliveira, J. L.; Campos, E. V. R.; Bakshi, M.; Abhilash, P. C.; Fraceto, L. F.

2535

Application of nanotechnology for the encapsulation of botanical insecticides for

2536

sustainable agriculture: Prospects and promises. Biotechnol. Adv. 2014, 32, 1550-

2537

1561.

2538 2539

(269) Barik, T. K.; Sahu, B.; Swain, V. Nanosilica-from medicine to pest control. Parasitol. Res. 2008, 103, 253-258.

2540

104 ACS Paragon Plus Environment

Page 105 of 149

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

Journal of Agricultural and Food Chemistry

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

Journal of Agricultural and Food Chemistry

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

106 ACS Paragon Plus Environment

Page 107 of 149

Journal of Agricultural and Food Chemistry

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

Journal of Agricultural and Food Chemistry

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

ACS Paragon Plus Environment

Page 109 of 149

Journal of Agricultural and Food Chemistry

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

ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

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 nano- micellar 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

ACS Paragon Plus Environment

Page 111 of 149

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

D. Porous nanomaterials 1. Silica

Journal of Agricultural and Food Chemistry

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

ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

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

ACS Paragon Plus Environment

Page 113 of 149

Journal of Agricultural and Food Chemistry

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

ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

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