PHOTOSTABILIZATION OF PYRETHRINS (Thesis Proposal Sample)

STUDIES ON PHOTO STABILIZATION OF NATURAL PYRETHRUM EXTRACTS USING CLAY NANOPARTICLES FOR DEVELOPMENT OF AN ENVIRONMENTAL FRIENDLY PESTICIDE MAINA ESTHER WAMAITHA A Research Proposal Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry of Jomo Kenyatta University of Agriculture and Technology 2014 DECLARATION This research proposal is my original work and has not been presented for a degree in any other university. Maina Esther Wamaitha (SC 331-2710/2013) Signature………………………………… Date……………………… This research proposal has been submitted for examination with our approval as university supervisors. Dr. Harrison Wanyika Chemistry Department, JKUAT, Kenya Signature………………………………… Date……………………… Prof. Anthony Gachanja Chemistry Department, JKUAT, Kenya Signature………………………………… Date……………………… TABLE OF CONTENTS TOC \o "1-3" \h \z \u DECLARATION PAGEREF _Toc390862198 \h i TABLE OF CONTENTS PAGEREF _Toc390862199 \h ii LIST OF FIGURES PAGEREF _Toc390862200 \h v ABBREVIATIONS AND ACRONYMS PAGEREF _Toc390862201 \h vii ABSTRACT PAGEREF _Toc390862205 \h viii 1.0 INTRODUCTION AND LITERATURE REVIEW PAGEREF _Toc390862206 \h 1 1.1Background PAGEREF _Toc390862207 \h 1 1.2 Pyrethrum Extracts PAGEREF _Toc390862208 \h 2 1.3 Clay PAGEREF _Toc390862209 \h 5 1.3.1 Organo Clays Synthesis PAGEREF _Toc390862210 \h 6 1.4 Adsorption Isotherms PAGEREF _Toc390862211 \h 9 1.4.1 Langmuir Kinetic Model PAGEREF _Toc390862212 \h 10 1.4.2 Freundlich Adsorption Kinetic Model PAGEREF _Toc390862213 \h 11 1.4.3 Temkin Adsorption Isotherm PAGEREF _Toc390862214 \h 11 1.5 Sorption Kinetics PAGEREF _Toc390862216 \h 12 1.5.1 Pseudo-first Order Equation PAGEREF _Toc390862217 \h 12 1.5.2 Pseudo-second Order Equation PAGEREF _Toc390862218 \h 13 1.6 Thermodynamics of Adsorption PAGEREF _Toc390862219 \h 13 1.7 Pesticide Formulation PAGEREF _Toc390862220 \h 14 1.7.1 Surfactants PAGEREF _Toc390862221 \h 15 1.7.2 Wetting Agents PAGEREF _Toc390862223 \h 15 1.7.3 Penetrants PAGEREF _Toc390862225 \h 15 1.7.4 Thickeners PAGEREF _Toc390862226 \h 15 1.7.5 Emulsifiers Agent PAGEREF _Toc390862227 \h 16 1.7.6 Spreaders and Stickers PAGEREF _Toc390862229 \h 16 1.8 Analytical Techniques PAGEREF _Toc390862230 \h 16 1.8.1 Fourier Transform Infrared Spectroscopy (F.T.I.R) PAGEREF _Toc390862231 \h 16 1.8.2 Column Bed Technique PAGEREF _Toc390862232 \h 17 1.8.3 High Performance Liquid Chromatography (HPLC) PAGEREF _Toc390862233 \h 17 1.8.4 UV-Visible Spectroscopy PAGEREF _Toc390862234 \h 18 1.8.5 X-ray Diffractometer PAGEREF _Toc390862235 \h 18 1.9 Statement of the Problem PAGEREF _Toc390862236 \h 19 1.10 Justification PAGEREF _Toc390862237 \h 19 1.11 Hypothesis PAGEREF _Toc390862238 \h 19 1.12 Objectives PAGEREF _Toc390862239 \h 20 1.12.1 Overall Objective PAGEREF _Toc390862240 \h 20 1.12.2 Specific Objectives PAGEREF _Toc390862241 \h 20 2.0 MATERIALS AND METHODS PAGEREF _Toc390862242 \h 21 2.1 Materials and Reagents PAGEREF _Toc390862243 \h 21 2.2 Sampling and Sample Collection PAGEREF _Toc390862244 \h 21 2.3 Clay Purification Process PAGEREF _Toc390862245 \h 22 2.4 Isolation of Nano Clays PAGEREF _Toc390862246 \h 23 2.5 Characterization of Nano Clay PAGEREF _Toc390862247 \h 23 2.5.1 Characterization Using F.T.I.R PAGEREF _Toc390862248 \h 23 2.5.2 Characterization Using XRD PAGEREF _Toc390862249 \h 24 2.6 Clay Modification PAGEREF _Toc390862250 \h 24 2.7 Characterization of Organo Clay PAGEREF _Toc390862251 \h 25 2.7.1 Characterization Using F.T.I.R PAGEREF _Toc390862252 \h 25 2.7.2 Characterization Using XRD PAGEREF _Toc390862253 \h 25 2.8 Adsorption- desorption Experiment PAGEREF _Toc390862254 \h 26 2.8.1 Effect of Temperature PAGEREF _Toc390862255 \h 26 2.8.2 Effect of Time PAGEREF _Toc390862256 \h 27 2.8.3 Effect of pH PAGEREF _Toc390862257 \h 27 2.8.4 Desorption PAGEREF _Toc390862258 \h 28 2.9 Kinetic Adsorption PAGEREF _Toc390862259 \h 28 2.10 Intercalation of Pyrethrum Extracts into Clay Gallery Spaces PAGEREF _Toc390862260 \h 29 2.10.1 Simple Immersion Technique PAGEREF _Toc390862261 \h 29 2.10.2 Column Bed Technique PAGEREF _Toc390862262 \h 30 2.10.3 Rotor Evaporator Technique PAGEREF _Toc390862263 \h 30 2.11 Characterization of Pyrethrum Extracts Loaded Nano Clay/Modified Nano clay PAGEREF _Toc390862264 \h 30 2.12 Accelerated Stability Tests PAGEREF _Toc390862265 \h 31 2.13 Quantification of Pyrethrum Extracts PAGEREF _Toc390862266 \h 31 2.14 Pesticide Formulation PAGEREF _Toc390862267 \h 32 2.15 Bioassay Tests PAGEREF _Toc390862268 \h 32 2.15.1 Tomato Growing, Insect Source and Rearing PAGEREF _Toc390862269 \h 32 2.15.2 Laboratory Bioassay on Tomato Plant PAGEREF _Toc390862270 \h 33 2.15.3 Field Bioassay in the Green House PAGEREF _Toc390862271 \h 34 2.15.4 Bioassay on Stored Maize Grain PAGEREF _Toc390862272 \h 35 2.16 Statistical Analysis PAGEREF _Toc390862273 \h 36 2.17 Facilities PAGEREF _Toc390862274 \h 36 WORK PLAN PAGEREF _Toc390862275 \h 37 BUDGET PAGEREF _Toc390862276 \h 38 REFERENCES PAGEREF _Toc390862277 \h 39 LIST OF FIGURES TOC \h \z \c "Figure" Figure 1.1: Pyrethrins I PAGEREF _Toc390850403 \h 3 Figure1.2: Pyrethrins II PAGEREF _Toc390850404 \h 3 Figure1.3: Cinerin I PAGEREF _Toc390850405 \h 3 Figure1.4: Cinerin II PAGEREF _Toc390850406 \h 4 Figure1.5: Jasmolin I PAGEREF _Toc390850407 \h 4 Figure1.6: Jasmolin II PAGEREF _Toc390850408 \h 4 Figure1.7: Structure of dodecyltrimethylammonium bromide PAGEREF _Toc390850409 \h 8 Figure1.8: Map of Kenya showing sampling sites PAGEREF _Toc390850410 \h 21 ABBREVIATIONS AND ACRONYMS CEC Cation Exchange Capacity ceq Pyrethrum extracts concentration at equilibrium (mg/L) Co Initial pyrethrum extract concentration EtOH Ethanol F.T.I.R Fourier Transform Infrared Spectroscopy HCl Hydrochloric acid H2O Water HPLC High Performance Liquid Chromatography JKUAT Jomo Kenyatta University of Agriculture and Technology MMT Montmorillonite NaOH Sodium hydroxide Qe Uptake capacity Qmax Langmuir maximum uptake capacity (mg/g) Qt Uptake capacity at time t (s) rpm revolutions per minute UV Ultraviolet light ABSTRACT Pyrethrum extracts are natural organic insecticides composed of six natural chemicals: pyrethrins I & II, Jasmolin I & II, Cinerin I & II extracted from pyrethrum flowers Chrysanthemum cinerariaefolium and Chrysanthemum cineum. Pyrethrum extracts have better insecticidal properties, are biodegradable and have low toxicity to humans and birds. They degrade on exposure to UV light and are thus limited to indoor application. This study aims to photo-stabilize the pyrethrum extracts using clay and then formulate an efficacious and environmental-friendly pyrethrum-extracts clay pesticide. Clay samples will be collected from J.K.U.A.T farm, Juja, air dried and stored in polyethylene bags. It will then be purified through grinding, sieving and reacting with hydrogen peroxide, followed by isolation of nanoclay through sedimentation and centrifugation processes and later will be characterized using F.T.I.R. and XRD techniques. Functionalization process using organic cations will follow. The adsorption influencing factors such as pH, time and temperature will be optimized through adsorption study and experimental data will be fitted into the adsorption isotherms. Rotary evaporation and column bed techniques will be used to intercalate pyrethrum extracts into the montmorillonite clay and accelerated stability tests will follow using artificial UV lamp at 254nm and 366nm. The photo stabilized pyrethrum-extracts based pesticide will be formulated by addition of adjuvants and bioassay tests will be carried out on stored cereals and tomato plants to confirm the enhanced efficacy. The anticipated outcome is a photo stabilized pyrethrum-extracts clay product for the stored maize grains and horticultural crops. Establishment of an effective and eco-friendly pesticide will be a major positive step to the agricultural sector due to utilization of natural resource, resulting to food security, reduced environmental pollution, raised income levels for pyrethrum farmers and consequently this would result in boosting Kenya’s economy. 1.0 INTRODUCTION AND LITERATURE REVIEW 1.1Background Synthetic pesticides use in the world agricultural sector has resulted to severe environmental pollution. Moreover, due to the processes like pesticide degradation, these results to only small percentage reaching the target site (Carrizosa et al., 2003). The risk of these chemicals is that they ultimately find their way into the human food via drinking water through leaching giving a need for extensive research. For instance, pyrethroid synthetic pesticide was developed for outdoor use in agriculture, forestry, termite control and it is t...