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Development strategies and prospects of nano-based smart pesticide formulation Xiang Zhao, Haixin Cui, Yan Wang, Changjiao Sun, Bo Cui, and Zhanghua Zeng J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b02004 • Publication Date (Web): 27 Jun 2017 Downloaded from http://pubs.acs.org on June 28, 2017

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Journal of Agricultural and Food Chemistry

1

Development strategies and prospects of nano-based smart

2

pesticide formulation

3

Xiang Zhao,1,2 Haixin Cui,1,2,* Yan Wang,1 Changjiao Sun,1 Bo Cui,1 and Zhanghua

4

Zeng1

5 6

1. Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of

7

Agricultural Sciences

8

12 South Zhongguancun Street, Haidian District, Beijing, 100081, P. R. China

9

2. Nanobiotechnology Research Centre, Chinese Academy of Agricultural Sciences

10

12 South Zhongguancun Street, Haidian District, Beijing, 100081, P. R. China

11

E-mail: [email protected]

12 13

ABSTRACT:

14

Pesticides are important inputs for enhancing crop productivity and preventing major

15

biological disasters. However, more than 90% of pesticides run off into the

16

environment and residue in agricultural products in process of application, due to the

17

disadvantages of conventional pesticide formulation such as use of harmful solvent,

18

poor dispersion, dust drift, etc. In recent years, using nanotechnology to create novel

19

formulations has shown great potential in improving the efficacy and safety of

20

pesticides. The development of nano-based pesticide formulation aims at precise

21

release of necessary and sufficient amounts of their active ingredients, in responding

22

to environmental triggers and biological demands through controlled release

23

mechanisms. This paper discusses several scientific issues and strategies regarding

24

development of nano-based pesticide formulations: (i) Construction of water-based

25

dispersion pesticide nanoformulation; (ii) Mechanism on leaf-targeted deposition and

26

dose transfer of pesticide nano-delivery system; (iii) Mechanism on increased

ACS Paragon Plus Environment


of

nano-based

pesticide

formulation;

and

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bioavailability

(iv)

Impacts of

28

nanoformulation on natural degradation and bio-safety of pesticide residues.

29 30

KEYWORDS:

31

nano-delivery system

nanoformulation,

pesticide,

nanotechnology,

agriculture,

32 33

1. Introduction

34

Pesticides play an important role in defensing of biological disasters, ensuring

35

the crop productivity and promoting the sustained steady growth of agricultural

36

production1. According to the Food and Agriculture Organization of the United

37

Nations (FAO) statistics, pest and pathogen control with pesticides has restored 30%

38

of total output of agricultural products all over the world2,3. However, indiscriminate

39

pesticide usage also brings a serious threat to the environment and human health. The

40

annual input amounts of pesticides have reached 4.6 million tons worldwide, 90% of

41

which run off into the environment, residue in agricultural products and redistribute in

42

ecological cycle during application4-10. Inefficient use of pesticides causes a series of

43

ecological environment problems, such as pathogen and pest resistance, non-point

44

pollution, water eutrophication, soil degradation, bioaccumulation in food chain, and

45

loss of biodiversity (Figure 1).

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Figure 1. Inefficient use of pesticides caused a series of environment problems

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Most of the pesticide active ingredients (AIs) are water-insoluble organic

51

compounds, which need to be added with carrier, solvent, emulsifier, dispersant and

52

other auxiliary ingredients, and processed into a suitable formulation in order to

53

facilitate the spray application in field11. The loss and decomposition rate of pesticide

54

on crop foliar is typically up to 70%, caused by run-off, spray drift and rolling down

55

during field application12,13. The actual utilization of biological target uptake is only

56

less than 0.1% after dust drift and rainwater leaching14,15 (Figure 2). The off-target

57

loss is the crucial problem for inefficient usage of conventional pesticide

58

formulations13,16. Wettable powder (WP) and emulsifiable concentrate (EC) are two

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major conventional pesticide formulations. WP is a crushed powder pesticide

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formulation composed of pesticide AIs, inert fillers and other additives. The inorganic

61

fillers in WP easily drift and run off into the environment, and the loaded AIs cannot

62

be completely released. In addition, the residual pesticides are difficult to be degraded.

63

EC is a liquid pesticide formulation. Pesticide AIs are dissolved in the solvent, added

64

with emulsifier, and then diluted into water to form a stable emulsion. The organic



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solvents and toxic ingredients directly leach and leak into the environment while

66

pesticide spraying, resulting serious pollutants in soil and water system, chemical

67

residues in crops and food products, and potential threat to human health17. These

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environmental problems and health risks has aroused the universal concerns.

69

70 71

Figure 2. Low efficiency of conventional pesticide formulations

72 73

Nanotechnology represents a new impetus for sustainable agriculture

74

development, thus using nanotechnology to formulate nano-based smart formulation

75

for pesticides and nutrients by virtue of nanomaterials related properties has shown a

76

great potential for alleviation of these problems18-20. Nano-based smart formulation

77

could release their AIs in responding to environmental triggers and biological

78

demands more precisely through targeted delivery or controlled release mechanisms.

79

Developing new advanced nano-based formulations that remain stable and active in

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the spray condition (sun, heat, rain), penetrate and delivery to the target, prolong the

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effective duration, and reduce the run-off in environment, is one of the hotspots in the

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field of nano-technical agriculture applications11,21,22. In 2003, United States

83

Department of Agriculture (USDA) firstly launched the Nanoscale Science and

84

Engineering for Agriculture and Food Systems Research Program, smart delivery

85

systems of agricultural chemicals was one of the key research directions23. In 2009,


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Food and Agriculture Organization (FAO) held the International Conference on Food

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and Agriculture Applications of Nanotechnologies, and published a strategic research

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report on the prospects of nanotechnologies in agriculture24. Recent years, United

89

States Environmental Protection Agency (EPA) and European Commission have

90

successively enacted rules on the management and usage of nanopesticides25,26. Bayer,

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DuPont, Syngenta and other agrochemical enterprises also pay great attention to the

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development of nano-based pesticide formulations, and some products has been

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applied to crop production or plant protection24.

94 95

2. Nano-based pesticide formulation: properties and advantages

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Nanotechnology involves manufacture, manipulation, and application of

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ultrafine materials that have at least one size dimension in the order of 1-100nm27.

98

Particles

99

surface-to-volume ratio and unique optical properties at a critical length scale of less

100

than 100 nm11. However, because other phenomena (transparency, turbidity, stable

101

dispersion, etc.) that extend the upper limit are occasionally considered, a broader

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definition of nano-based pesticide formulations is accepted as systems with

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dimensions smaller than 500 nm, exhibit novel properties associated with their small

104

size19,28-30.

have

unique

properties

such

as

size-dependent

qualities,

high

105

Nanomaterials held great promise regarding their application in nano-based

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pesticide formulation due to their small size, big surface area and target modified

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properties. Nano-based formulation may bring beneficial improvements in properties

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and behaviors of pesticides, such as solubility, dispersion, stability, mobility and

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targeting delivery. Furthermore, it might significantly improve the efficacy, safety and

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economic effects of traditional pesticides by increasing efficacy, extending effect



111

duration, reducing dose required, providing capability to controlled release of active

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ingredients, and improving stability of payloads from the environment; subsequently

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diminishing run-off and environmental residuals (Figure 3).

114

115 116

Figure 3. Nano-based formulation brings beneficial improvements in pesticides properties

117 118

The size, shape, surface charge, crystal phase and the presence of different

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modified functional groups of nanoparticles are critical factors in their application31. A

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broad variety of natural or synthesized materials are used in construction of pesticide

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nanoformulations, such as metal, metal oxides, non-metal oxides, carbon, silicates,

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ceramics, clays, layered double hydroxides, polymers, lipids, dendrimers, proteins,

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quantum dots, and so on32-36. Nano-pesticides may be developed by two pathways,

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directly processing into nanoparticles (nanosized pesticides), and loading pesticides

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with nano-carriers in delivery systems11. In nano-carrier systems, pesticides are

126

loaded through: encapsulation inside the nanoparticulate polymeric shell, absorption

127

onto the nanoparticle surface, attachment on the nanoparticle core via ligands, or

128

entrapment within the polymeric matrix (Figure 4).

129

A variety of nanoformulation types have been developed, including

130

nanoemulsions, nanocapsules, nanospheres, nanosuspensions, solid lipid nanoparticles,


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nanoparticles,

and

nanoclays37-41.

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mesoporous

Aqueous

nanoemulsion

and

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nanosuspension of pesticides increase solubility of water insoluble AIs, eliminate the

133

toxic organic solvents, and would gradually substitute the conventionally EC

134

products42-44. Nanocapsule and nanosphere are suggested as vehicles for the

135

environmentally sensitive pesticides, due to their capability to slow release of AIs,

136

improve stability of formulation, prevent early degradation, and extend the longevity

137

of pesticides45-48. Mesoporous nanoparticles, such as nanoclay, activated carbon and

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porous hollow silica are also verified to be suitable for the controlled release and

139

delivery systems for the water-soluble and fat-dispersible pesticides which possess

140

high drug-loading capacity, good biocompatibility, low toxicity and multistage release

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pattern49,50.

142 143

Figure 4. Schematic diagram of nano-based pesticide formulation

144 145

3. Challenges and scientific issues

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The mode of pesticide application influences their efficiency and environmental

147

impact51-53. Insect pests and pathogens are the targets of pesticides. However, it is



148

extremely difficult to directly spray the pesticides on pests or pathogens. As a result,

149

the pesticides are sprayed on the crop foliage to form an effective toxic zone,

150

maintaining the toxic stress on the pests or pathogens. Currently spraying system of

151

pesticide application needs to focus on efficacy enhancement and spray drift

152

management11.

153

Most of the pesticide AIs are poorly soluble, or even insoluble in water. One of

154

the challenges associated with pesticide formulation is increasing their solubility and

155

dispersion in aqueous solution. In addition, the most of crop leaf surfaces are highly

156

hydrophobic which inhibits liquid deposition54,55. Thus another challenge is reducing

157

the spray drift and run-off loss on the hydrophobic foliage. As shown in Figure5,

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size-down of pesticide particles benefit to significantly improve their water-dispersion,

159

targeting coverage and insecticidal activity due to smaller particle size and higher

160

surface area. In addition, Pesticide nanoformulations increase adhesion and deposition

161

of droplets on the leaves through leaf-affinity modification.

162

163 164

Figure 5. Size-down of pesticides increase bioavailability and efficiency

165 166

After spraying on the foliage, the pesticide droplets spread and adhere on the leaf


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surfaces, and then the AIs deposite, release and transfer from the foliage to the pest or

168

pathogen targets, finally kill the insects or pathogens before degradation (Figure 6).

169

Therefore, water-dispersion, leaf-affinity, bio-availability and residues degradation are

170

the most critical factors regarding development of nano-based pesticide formulations.

171

Four key scientific issues for improvement of pesticide efficacy and safety are

172

proposed: (i) Construction of water-based dispersion pesticide nanoformulation; (ii)

173

Mechanism on leaf-targeted deposition and dose transfer of pesticide nano-delivery

174

system; (iii) Mechanism on increased bioavailability of nano-based pesticide

175

formulation; and (iv) Impacts of nanoformulation on natural degradation and

176

bio-safety of pesticide residues.

177

178 179

Figure 6. Four critical factors regarding development of nano-based pesticide formulations

180 181

4. Construction of water-based dispersion pesticide nanoformulation

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The fundamental limitation with the use of current pesticides is that they are

183

generally comprised of virtually insoluble compounds57. This lack of solubility

184

requires the addition of large amounts of organic solvents for dissolution and spraying

185

application in field, which increases costs, applicators' exposures and environmental



186

pollutants58. Water-based dispersion pesticide nanoformulations improve the solubility

187

and dispersion in water, uniform leaf coverage, biological efficacy and environmental

188

compatibility, due to the small particle size, high surface area and elimination of

189

organic solvents in comparison to conventionally formulations58-60.

190

Synthesis of nano-based formulations involve size reduction by top-down

191

methods such as milling, high pressure homogenization and sonication, while

192

bottom-up processes involve meltdispersion, solvent displacement, complex

193

coacervation, interfacial polymerization, and emulsion diffusion13, 61. Nanocapsules,

194

nanoemulsions, nanospheres, nanomicelles, and nanosuspensions show great potential

195

for improving formulation properties, such as water-dispersion, chemical stability,

196

targeting adhesion, permeability and controlled release (Figure 7).

197

198 199

Figure 7. Schematic representation of water-based dispersion pesticide nanoformulation

200 201

Nanocapsules are core−shell structural vesicular systems, encapsulating the

202

pesticide AIs in the inner core. The shell is usually composed of biodegradable

203

polymeric, including poly-ε-caprolactone (PCL), polylactic acid (PLA), polyglycolic

204

acid (PGA), poly (lactic-co-glycolic) acid (PLGA), polyethylene glycol (PEG),

205

chitosan, and etc62-69. The polymeric shell degrades slowly in the environment, thus


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improves chemical stability for environment-sensitive compounds (i.e., UV

207

degradation and soil degradation). In addition, nanocapsules can increase the targeting

208

delivery efficiency with membranal polymeric leaf-affinity modification, improving

209

the behaviors of wetting, spreading and absorbing of droplets on leaves.

210

Nanoemulsions are oil-in-water (O/W) emulsions where the pesticides are dis-

211

persed as nanosized droplets in water, and the surfactant molecules localized at the

212

pesticide-water interface71-73. Nanoemulsions improve the efficacy and safety effects

213

of traditional pesticides, due to the small size effect, high dissolution rate and

214

elimination of toxic organic solvents.

215

Nanospheres are solid sphere vesicular systems where the pesticides are

216

uniformly distributed through adsorption or entrapment inside the nano-matrix74-77.

217

Nanospheres are composed of organic polymer materials or inorganic mesoporous

218

materials, such as activated carbon, non-metal oxides and porous hollow silica.

219

Nanospheres possess high drug-loading capacity, good biocompatibility and

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slow/controlled release pattern, showing great potential in soil infection disease and

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soil pest control78-80.

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Nanomicelles are ideal bioactive smart nano delivery systems for encapsulating

223

pesticides. Nanomicelles can be induced by the external environment, and thus make

224

the corresponding changes in physical and chemical properties. For example, based

225

on the hydrogen bonding cross-linked nanomicelle, an environment-responsive

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controlled release system was constructed. Under high temperature and high humidity

227

conditions, the hydrogen bonding fractured, the nanomicelle swelled and the

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pesticides were released. The pesticides were blocked under low temperature and low

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humidity conditions the other way round81.

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Naonosuspensions are pesticide nanoparticles uniformly suspended in water. The



231

aqueous colloid dispersion systems render higher solubility and dispersion for

232

insoluble or fat-dispersible compounds in solution, improve the pesticide

233

bioavailability, and reduce the costs due to the ease to large-scale manufacture.

234 235

5. Mechanism on leaf-targeted deposition and dose transfer of pesticide

236

nano-delivery system

237

The pesticide spray application on foliage is inadequate due to the weak adhesion

238

to the crop foliage. For the spray pesticides, pesticides are firstly deposited on crop

239

foliage, and then they go to parts of the plant attacked by a pest through diffusion,

240

uptake and/or transfer processes, leading to pest poisoning or death by active or

241

passive contact13, 82. Consequently, leaf hydrophobicity and pesticide droplet retention

242

are key parameters affecting the effective utilization of pesticides. As shown in Figure

243

8, the pesticide droplet forms a spherical shape, minimizing contact with the

244

hydrophobic foliage, poorly wetting and spreading on the waxy layer, and resulting in

245

loss as rolling down and run-off. After water evaporation, the residual pesticide

246

particles easily drift or fall off from the leaves, since the particles are too large to

247

embed in the microstructured or nanostructured mastoids of leaf surfaces.

248

Nano-delivery systems form stable dispersions, increase the efficiency, and

249

improve the wetting and spreading behavior on leaf surface, due to the leaf-affinity

250

modification of pesticides. In addition, the pesticide nanoparticles deposite and adhere

251

favorably on the surface of foliage, leading to increased retention rate and decreased

252

spraying dosage (Figure 8). The adhesion properties of nano-based formulation were

253

achieved by the multimodal interactions between the nanoparticles and the crop

254

foliage, such as hydrogen bonding, electrostatic attraction and covalent bonding83.

255

The adhesion strength strongly depended on the size distribution of nanoparticles and


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the functional groups on the nanoparticle surface, and was easily regulated by size

257

controlling and varying functional groups82. Carboxyl-modified nanocapsules reduced

258

the surface tension of pesticide dispersions, decreased the contact angle of droplet on

259

hydrophobic foliage, and improved the retention rate84,85. Additionally, increased leaf

260

coverage, improved diffusion properties, and penetration into plants were

261

observed47,86.

262

263 264

Figure 8. Pesticide deposition efficiency and dose transfer mechanism

265 266

6. Mechanism on increased bioavailability of nano-based pesticide formulation

267

Compared with the traditional pesticide formulation, nano-based formulations

268

have smaller particle size and larger specific surface area, which can effectively

269

increase the coverage, adhesion and permeability of the pest. In addition, nano-based

270

formulations may affect the action modes and the transfer paths of conventional

271

pesticides by introducing insect-target modification and enhancing release of AIs

272

(Figure 9). Pesticides can be classified according to four distinctive functions:

273

stomach poisoning, the pesticide enters the body of pests via their mouthpart and

274

digestive system; inhalation poisoning, pesticides enters the body of pests via fluids



275

from a consumed host organism; contact poisoning, the pesticide enters the body of

276

pests via their epidermis upon contact; and fumigation, the pesticide in gas form

277

enters the body of pests via their respiration system. It was presumed that nano-based

278

formulation might enhance the stomach poisoning and contact poisoning functions,

279

since it significantly improve the dispersal and permeability, and thus increase the rate

280

of pesticide entering pest bodies87,88. Furthermore, the enhancement of the transport,

281

conduction and transformation efficiency of pesticide nanoparticles inside pests can

282

accelerate pests poisoning, further improve the efficacy, bioactivity and dose effect of

283

pesticides89.

284

285 286

Figure 9. Bioavailability of pesticide nano-delivery system

287 288

7. Impacts of nanoformulation on degradation and bio-safety

289

Inevitably, nanoparticles will be released into the plants and the environment system.

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The unique physical and chemical properties of nanoparticles might cause some

291

unpredictable adverse effects on crops, agricultural products and ecosystem90-93. In

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addition, these materials will accumulate over time in soils and rates may vary in

293

response to unknown parameters94,95. The general concern is that some nanoparticles or


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294

nanostructured materials may flow into the environmental systems and food chain, which

295

may become a new class of pollutant resources that threaten human health and ecosystem

296

balance. However, because farmland is an open complicated system with many

297

influencing factors of complicated functions, actual data measuring environmental

298

concentration of nanoformulations in various media is scarce96-98. The environmental fate

299

and

300

nanoformulations is also unclear99. Therefore, avoiding risk research should be conducted

301

on safety and risk assessments of nanopesticides according to the methodologies

302

established in nanotoxicology and nanomedicine. Investigating the toxicological effect,

303

environmental behavior, and pharmacokinetics of nanoparticles, studying the interaction

304

mechanism between nanoparticles and plants, and evaluating their potential impact on the

305

quality and safety of agricultural products can provide a theoretical basis for the

306

development of nanopesticides and the sustainable implementation of nanotechnology in

307

agriculture (Figure 10). On the other hand, nano-based pesticide formulation can

308

accelerate the catalytic degradation of toxic residues and reduce the pesticide residues in

309

environment by introducing bio-degradable material carriers and photocatalysts100.

potential

bio-safety

problem

of

nanomaterials

or

nanoparticles

310

311 312

Figure 10. Catalytic degradation and bio-safety of pesticide residues

313


from


314

8. Conclusion and prospects

315

Clearly, nano-based pesticide formulations have many advantages over the

316

conventional equivalents such as high efficiency, environment friendliness,

317

high-targeting delivery and smart controlled release. Due to the technological

318

advancement, large scale applications of nanopesticides in crop production have just

319

become possible. These are the desired properties and research objectives of

320

nano-based pesticide formulations as summarized in Table 1.

321 322

Table 1. Desired properties and research objectives of nano-based pesticide

323

formulations Desirable Properties

Research objectives of Nanopesticieds-Enabled Technologies Increasing targeted delivery efficiency of pesticide into action

Targeted delivery

targets, such as plants, insects, pathogen16,17,24,27,30 . Controlling release of pesticide at least effective concentration for

Controlled release

killing pests and pathogens30,37,46-50,84,85,101,102. Increasing solubility and dispersion for fat-soluble chemicals in

Water dispersion

aqueous solution40,43-4556,59,70-73. Improving chemical stability for light-sensitive compounds by

Chemical stability

Bioavailability

restricting photo-degradation46,70-83,86. Increasing bioavailability for saving pesticides89,99. Reducing pesticides application and treatment frequency by

Lasting validity period

Lower toxicity

extended lasting validity period80,82,83,86. Protecting biodiversity in ecosystem16,17,24. Reducing food residues and non-point source pollution due to the

Environmental friendliness minimum pesticide loss29,30,41,53. 324 325

In conclusion, nano-based pesticide formulations bring beneficial improvements


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326

in properties and behaviour of traditional pesticides such as solubility, dispersion,

327

stability, and targeting delivery, controlled release of active ingredients. Additionally,

328

it might not only significantly improve the bioavailability and the duration of drug

329

efficacy, but also reduce the toxicity of non-target wildlife, the food and

330

environmental residual. On the other hand, some toxic nanoparticles from pesticides

331

may flow into the environment and food systems threaten human health and

332

ecosystem balance. Avoiding risk research should be conducted on safety and risk

333

assessments of nanopesticides according to the methodologies established in

334

nanotoxicology and nanomedicine. Safer and bio-degradable nanomaterials should be

335

developed for nanopesticides production. As a most promising and attractive field of

336

nanotechnology application in agriculture, these novel agrochemical products will

337

provide multiple benefits such as reduced use of chemicals and subsequently reduced

338

water pollution and food product residual contamination, efficient use of agricultural

339

resources, increased soil and environmental qualities.

340 341



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ACKNOWLEDGMENTS

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This paper was supported by the Major National Scientific Research Program of

622

China (2014CB932200), the National Key Research and Development Program of

623

China (2017YFD0500900, 2016YFD0200500), and the Agricultural Science and

624

Technology Innovation Program (CAAS-XTCX2016004).

625



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Graphic for table of contents

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