welcomewelcome SSNAIK TNAU

CONTROLLED RELEASE FORMULATIONS AS A SMART CONTROLLED RELEASE FORMULATIONS AS A SMART DELIVERY SYSTEMS FOR THE ECO-FRIENDLY PESTICIDES DELIVERY SYSTEMS FOR THE ECO-FRIENDLY PESTICIDES

Credit seminar (0+1)

Student Sabhavat Srinivas NaikID.No:13-503-010

CHAIRMAN: Dr. M. Suganthy, Assistant Professor, Dept. of Medicinal & Aromatic Crops.ADVISORY COMMITTEE MEMBERS: Dr. S. Mohan Kumar, Professor, CPMB&B. Dr. V. Jegadeeswari, Assistant Professor, Dept. of Spices & Plantation Crops.

Introduction

Controlled release formulations (CRFs) Historical survey

Mechanisms of CRFs

CRFs for eco-friendly pesticides(case studies)

Conclusions Challenges

Nanotechnology Synthesis of the CRFs

Characterization of the CRFs

PART I

PART II

PART III

INDEX

How is the farmer struggling with Plants, Animals & Microorganisms ?

Rodents& others Insects-

Weeds-

(Animals)

(Plants)

(Animals)-

Diseases- (Microorganisms)

30%10%

45% 20%

INTRODUCTION

(Oerke,2005)

Consequences of the conventional pesticide usage

Bhopal tragedy–2000 people were died due to the MIC gas explosion.

Kasargod tragedy- 300 diseases identified - hydrocephalus

3 million cases of pesticide poisoning each year and up to 2,20,000 deaths, primarily in developing countries.

(Peterson,2009)

(Priyanka pulla, 2013)

(Katarina Lah, 2011)

1975-70 worker- kepone shakes - after 30 days of the exposure

Bhopal tragedy – 2000 people were died. MIC gas explosion.

Kasargod tragedy - 300 more diseases identified - hydrocephalus

Contd………

Environmental pollution.

Creating health hazards due to the presence of the pesticide residues in food, fiber and fodder. Development of resistance by the insects.

pesticide poisoning .

pesticides accumulating in soil and groundwater where they threaten the health of entire ecosystems.

Disadvantages of the conventional pesticides

- Nirmala devi (2011)

variable efficacy

Bio pesticides - drawbacks

Bio-pesticides are less harmfulNarrow broad spectrumBio-pesticides are effective in smaller quantities Decompose quicklyNo environmental pollution and health hazards Reduce the conventional pesticides and yield same

………………………………………………………………………………………………………………………………....

Advantages

Disadvantages

Variable efficacy - Easy degradation - Photo volatile

Less persistance

- Nirmala devi (2011)

PART II Controlled release formulations (CRFs)

Historical survey

Mechanisms of CRFs

CRFs for eco-friendly pesticides (case studies)

Nanotechnology Synthesis of the CRFs

Characterization of the CRFs

Controlled release formulations (CRFs)“Controlled release formulations are those smart

delivery systems which slowly and continuously release a toxic element into the environmental interface over a period of time measured in months and years”

(Cardarelli, 1976)

Hydrolysis

MicrobialDegradation

Volatilization

Photo degradation

a.i./conventional pesticide formulation

Encapsulated conventional pesticide

Hydrolysis Photo decomposition Microbial degradation Volatilization

x

Plant

Historical survey of CRFs

1930 - Bungenburg de Jong- coacervation Barrett Green-first microcapsules synthesis

1960 - Polar materials - encapsulated phase separation techniques

1950 - Many commercial products released using polymemers

1964 - Long-term release of antifouling agents realized by their incorporation in an elastomeric matrixControlled release larvicides Halogenated hydrocarbons Carbamates Organo phosphates.

1965 - Molluscicides based on organotins were developed.

1967 – Encapsulation niclosamide (molluscicide) in rubber.

1969 - First long-term controlled release herbicide- 2,4-D in natural rubber.

1973 -1980- Inorganic copper salts had been successfully formulated in slow release matrices and evaluated as molluscicides.

Contd……

2000- 2011– Electro spinning techniques & SPLAT-ISCA

2000- Sol-gel technique , PHSNp.(Cardarelli,1985)

(Rameash,2012)

What is the difference between the microparticle, microsphere and microcapsule ?

Micro particle Micro sphere Micro capsule

Nano particle Nano sphereNano capsule

Macro particle (> 1000µm)

(3-800µm)

(<0.1µm)

(Fatima Sopena, 2009)

.

Polymer Matrix

Active ingredient Polymer coat Entrapped Drug

(Reservoir system) (Monolithic system)

Difference between the microsphere and microcapsule

Spherical Spherical / Non spherical

Microspheres

Microcapsules

(Kataria Sahil,2011)

Microparticle

Solid core Non solid core Micro domains Non solid micro domains

Microcapsule/ Nanocapsule“Microencapsulation is the coating of small solid particles, liquid

droplets, or gas bubbles with a thin film of coating or shell materials. The product so obtained is termed as microcapsules. Microcapsules are small particles that contain an active agent or core material surrounded by a coating or shell”

(Fatima Sopena, 2009)

How is it possible ?

Nano technology

1. 1700-Industrial Revolution2. 1940-Nuclear Energy Revolution 3. 1960-The Green Revolution4. 1980s-Information Technology Revolution 5. 1990s-Biotechnology Revolution 6. Present era-Nanotechnology - sixth revolutionary

technology.

“Nanotechnology refers to controlling, building, and restructuring materials and devices on the scale of atoms and molecules”. A nanometer (nm) is one-billionth of a meter

(Tarafdar, 2013)

Nano form zeolites

Nano sensors Nano magnets

Nanoparticles, Nanoemulsions, Nano suspensions and Nanocapsules

Nanotechnology

Slow release and efficient dosage of water, fertilizersDrugs for livestock

Insecticides, insect repellentsHerbicide Antifouling agents

Soil quality for plant health monitoringPests detection

Removal of soil contaminants

Applications of nanotechnology in agriculture

(Tarafdar, 2013)

Synthesis of CRFs- Chemical bonding method

(Ragaei,2014)

Synthesis of CRFs-physical method

(Ragaei,2014)

Micro / Nanoencapsulation techniques

Physical Chemical Physico-chemical1.Extrusion 1.Interfacial

polymerization1.Emulsion

2.Spray drying 2.Molecular inclusion 2.Coacervation

3.Freeze drying 3.Emulsion-solvent evaporation

4.Emulsion crystallization/ solidification

5.Diffusion-controlled emulsion

6.Liposome entrapment

ii

RELEASE MECHANISMS OF THE CRFs

1. Dissolution2. Diffusion 3. Swelling 4. Osmosis5. Erosion

Nirmala devi and Majji (2011)

I. Physical mechanisms II.Chemical mechanisms

I.Physical Mechanisms

1.Dissolution

2.Diffusion

3.Osmosis

5.Erosion A.Reservoir system B.Monolithic system

B. Monolithic DevicesMonolithic Solution

Monolithic Dispersion

Nonporous Membrane

Microporous Membrane

Nonporous Matrix

A. Reservoir Devices

Microporous MatrixMonolithic Solution

Monolithic Dispersion

4.Swelling

Nirmala devi and Majji (2011)

1.Dissolution

Reservoir system Monolithic system

Dissolution –membrane Dissolution-matrix

Active ingredient

a.i. dispersed/dissolved

(Lewis,1977) Nirmala devi and Majji (2011)

2.Diffusion

Reservoir system

Non porous porous

Monolithic system

Non porous Porous

(Lewis,1977)

Osmotic force is the driving force in osmosis-controlled systems. Such systems generally consist of a solid and water-soluble active agent, which is enclosed by a water-permeable, but active agent impermeable polymer membrane with a small opening. Water is transported into the core by permeation and hydrostatic pressure will be built up in the core and subsequently, the dissolved active agent comes out.

3.Osmosis

H2O

Solid –active ingradient-water soluble

Water permeable membrane

Medium

Soluble a.i. released into the medium

Impermeable pore size for a.i.

- (Fan & Singh, 1989).

Swelling controlled systems Here, the dispersed or dissolved active agent in polymer matrix is unable to diffuse to any considerable extent. The active agent is released out slowly when the polymer system gets into contact with a compatible solvent or fluid in the environment and swelling takes place. Examples used in such systems are Poly(hydroxyl methyl methacrylate), polyacrylamide and poly(ethylene glycols) etc.

4.Swelling

Solvent / fluid in the medium

+

Swelling

Matrix type device

Medium

Active ingradient

(Ragaei,2014)

The release of the active agent occurs here by erosion of the polymer. The active agent is physically immobilized in the polymer matrix. Active agent release rate is generally proportional to the erosion rate of the polymer matrix which undergoes surface erosion. A zero order release can be achieved in these systems if the erosion rate is constant and matrix dimension remains unchanged.

5. Erosion

a.i.

Matrix

Erosion of the matrix

a.i. released in to the medium

(Scher,1977)

II.Chemical MechanismsActive agent is released only when the polymer active agent bond

is cleaved or the polymer is degraded. A zero order release profile may be obtained when the active agent is a co-monomeric unit in polymer backbone and release occur by polymer degradation. Polymer

Chemical bond

Active ingredient

(Scher,1977)

CHARACTERIZATION OF THE CRFS

1.Scanning electron microscope2.Transmission electron microscope 3.Fourier transform infrared spectroscopy 4.Particle size analyser

(Chinnamuthu and Natarajan,2007)

1. Scanning Electron Microscope

SEM

(Jayakumar Jerobin,2012)

Surface morphology features of the nano materials and biological samples

Topography of any sample Elemental composition – EDAX

Morphology of encapsulated neem oil emulsion

(Zhu-Zhu Li, 2006)

Avermectin PHSNs

2.Transmission Electron Microscope

TEM

Internal feature of the sample Elemental composition – EDAX

3.PARTICLE SIZE ANALYZER CUM ZETA POTENTIAL

To know the stability of the nanoparticle For good stability above +/- 30.

5.FOURIER TRANSMISSION INFRARED SPECTROSCOPY

Based on the polarization effect To know the reaction between the polymer and the active

ingredient

Applications of the CRFs (Case studies)

CASE STUDY 1 : PHEROMONECASE STUDY 2 : ENTOMOPATHOGENIC BATERIA CASE STUDY 3 : ENTOMOPATHOGENIC FUNGI CASE STUDY 4 : RECENT TECHNOLOGY IN CRF

Case study 1 Efficient Management of Fruit Pests by Pheromone Nanogels

Scientist Deepa Bhagat and co workersYear 2013 Place Indian Institute of Science, Bangalore.

Department of Science and Technology, New Delhi. Objective To study the efficacy of the controlled release nanogel

formulation

(Deepa Bhagat,2013)

Slope magnitude comparison

(Deepa Bhagat,2013)

(Deepa Bhagat,2013)

30 days after storage

Fruit flies attracted towards the thin film nanogel

1 2

3 4Nanogel

Fruit fly counting

Establishment

(Deepa Bhagat,2013)

Field experiment

Num

ber o

f cat

ches

Number of days (Deepa Bhagat,2013)

Number of days of catches for the ME and Nano ME gel

(Deepa Bhagat,2013)

Trap catches from the Methyl Eugenol (ME) and Nano ME gel

Assessment of Microencapsulated Formulations for Improved Residual Activity of Bacillus thuringiensis

Objective :To evaluate best polymer combination for encapsulating Bt and for resistant against the rain, sunlight

Case study 2

Scientist : Patricia tamez-Guerra and co workers

Place : Bioactive Agents Research Unit. USDA -ARS-NCAUR

Year : 1997-1998

Ostrinia nubilalis % mortality 1.Only corn flour

Patricia tamez-Guerra (2000)

Laboratory bioassay

Lignin + corn flour & technical formulation

Patricia tamez-Guerra (2000)

Laboratory bioassay Ostrinia nubilalis % mortality

Ostrinia nubilalis % mortality

Patricia tamez-Guerra (2000)

Laboratory bioassay

Lignin + corn flour & Dipel 2x commercial formulation

Trichoplusia ni % mortality-August month

(Patricia tamez-Guerra, 2000)

Field experiment

Trichoplusia ni % mortality-October month

(Patricia tamez-Guerra, 2000)

Field experiment

Case study 3 Biocompatible Chitosan Nanoparticles Incorporated Pesticidal Protein Beauvericin (CSNp-BV) Preparation for the Improved

Pesticidal Activity Against Major Groundnut Defoliator Spodoptera Litura (Fab.) (Lepidoptera; Noctuidae)

Scientist Arvind Bharani and co workers

Year 2014 Place Department Of Biotechnology, Sathyabama

University, Chennai Objective To prepare the improved pesticides activity CSNp

for controlling the Spodoptera litura

Cumulative mortality (%) of S.litura treated with free beauvericin (F-BV) and chitosan nanoparticles incorporated beauvericin (CSNp-BV)

(Arvind Bharani, 2014)

Table 1.

Effect of free beauvericin (F-BV) and chitosan nanoparticles incorporated beauvericin (CSNp-BV) on pupal and adult emergence

(Arvind Bharani, 2014)

Recent technology in

CRFs

SPLAT ®

SPECIALIZED PHEROMONE AND LURE APPLICAION TECHNOLOGY

Dr. Agenor Mafra-NetoCEO OF ISCA TECHNOLOGIESUSA,CALIFORNIA.

SPLAT- A controlled release technology

It is an controlled release technology.

Chemical emulsion type CRF. Basically It Is Matrix type diffusion system.

Developed by ISCA technologies, USA, California.

Used for the Semiochemicals and other pesticides.

In September 2009, the first SPLAT mating disruption formulation, SPLAT LBAM HD-O, was approved by the EPA for National Organic Program for organic certified farms.Beginning in 2011, all SPLAT mating disruption products are certified for use for organic production.

(Mafra-Neto,2013)

Mechanism of pheromone release

SPLAT: Aqueous component + Active ingredient + Additives+ Matrix

(Mafra-Neto, 2013)

Aqueous component evaporation

(Mafra-Neto,2013)

Aerial Application Caulking Gun

SPLAT-o-GatorSPLAT Gator

(Mafra-Neto,2013)

Conclusions 3Rs & environmental pollution present pest management

Change -sustainable agriculture/precision /organic farming

CRFs Protected and long live eco friendly pesticides.

Nano science -important in the CRFs- smart delivery system

Select active compound, encapsulate, characterize and evaluate

Involved physics and chemistry for the designing in CRFs

Single attempt we cannot achieve the better results

Future challenges to the scientific community

Nanoparticle

Bio accumulation

Toxicity to soil biota

Toxicity to humans

Toxicity to pollinators

(Luiz de Oliveira, 2014)

MICROENCAPSULATION SPLAT

PLEASE KEEP WATCH………………………….

SPECIAL THANKS TO :

Dr. S. KUTTALAM (PROF. & HEAD - AGRI.ENTO) Dr. K.GUNASEKARAN (PROF.& HEAD - NS&T)Dr. P.JAYAKUMAR (JSS UNIVERSITY)Dr. T. GOWATAHAM RAJ (JSS UNIVERSITY)SRFs - BHARATHIAR UNIVERSITY

Keep the farmers smile…… because we are scientific

Thanks a lot