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العنوان
Study on Pesticide Residues in Food using Molecular Imprinting Technique /
المؤلف
Shable, Nashwa Shable Abdalla.
هيئة الاعداد
باحث / نشوى شبل عبدالله شبل
مشرف / أيمن حلمى كامل
مشرف / عمرو على محمد
تاريخ النشر
2021.
عدد الصفحات
150 p. :
اللغة
الإنجليزية
الدرجة
الدكتوراه
التخصص
Analytical Chemistry
تاريخ الإجازة
12/1/2021
مكان الإجازة
جامعة عين شمس - كلية العلوم - قسم الكيمياء
الفهرس
Only 14 pages are availabe for public view

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from 150

Abstract

This thesis entitled with ”Study on Pesticide Residues in Food using Molecular Imprinting Technique” includes five chapters.
Chapter one:
This chapter is included three parts: Part (Ⅰ) contains Background on pesticides residues in food, Part (Ⅱ) Background on Potentiometric Sensors and Part (Ⅲ) Background on Molecularly Imprinted Polymers (MIPs.
Chapter two:
All-solid-state potentiometric sensors were prepared by using polyaniline (PANI) as the solid contact material. A film of PANI (thickness approximately being 0.25 µm) was deposited on a solid substrate (carbon screen printed platform). The PANI layer was subsequently coated with an ion-selective membrane (ISM) containing uniform-sized molecularly imprinted nanoparticles to produce a solid-contact ion-selective electrode (SC/ISE) for bispyribac herbicide (sensor I). In addition, aliquat 336 was also used as an ion exchanger in plasticized PVC membrane (sensor II). The proposed sensors revealed a remarkably improved sensitivity towards bispyribac ions with anionic slopes of -47.8 ± 1.1 (r2 = 0.9995) and -44.4 ± 1.4 (r2 = 0.9997) mV/decade over a linear range 1.0 × 10-2–8.6 × 10-6 M, 1.0 × 10-2–9.0 × 10-6 M and detection limits of 1.33 and 1.81 µg/mL for sensors I and II, respectively. selectivity of both sensors is significantly high for different common pesticides and inorganic anions. The potential stability of the SC/ISEs was studied using chronopotentiometry. Electrochemical impedance spectrometry was used to understand the charge-transfer mechanisms of the different types of ion-selective electrodes studied. The impedance response of the electrodes was modelled by using equivalent electrical circuits. The sensors were used for a direct measurement of the bispyribac content in commercial herbicide formulations and soil samples collected from agricultural lands planted with rice and sprayed with bispyribac herbicide. The results agree fairly well with data obtained using HPLC method.
Chapter three:
Screen-printed ion-selective electrodes were designed and characterized for the assessment of cyromazine (CYR) pesticide. A novel approach is to design tailor-made specific recognition sites in polymeric membranes using molecularly imprinted polymers for cyromazine (CR) determination (sensor I). Another sensor (sensor II) is the plasticized PVC membrane incorporating cyromazine/tetraphenyl borate ion association complex. The charge-transfer resistance and water layer reached its minimal by incorporating Polyaniline (PANI) solid-contact ISE. The designed electrodes demonstrated Nernstain response over a linear range 1.0 × 10-2–5.2 × 10-6 and 1.0 × 10-2–5.7 × 10-5 M with a detection limit 2.2 × 10-6 and 8.1 × 10-6 M for sensors I and II, respectively. The obtained slopes were 28.1 ± 2.1 (r2 = 0.9999) and 36.4 ± 1.6 (r2 = 0.9991) mV/decade, respectively. The results showed that the proposed electrodes have a fast and stable response, good reproducibility, and applicability for direct measurement of CYR content in commercial pesticide preparations and soil samples sprayed with CYR pesticide. The results obtained from the proposed method are fairly in accordance with those using the standard official method.
Chapter four:
Novel potentiometric solid-contact ion-selective electrodes (SC/ISEs) based on molecularly imprinted polymers (MIPs) as sensory carriers (MIP/PANI/ISE) were prepared andcharacterized as potentiometric sensors for flucarbazone herbicide anion. However, aliquat S 336 was also studied as a charged carrier in the fabrication of Aliquat/PANI/ISEs for flucarbazone monitoring. The polyaniline (PANI) film was inserted between the ion-sensing membrane (ISM) and the electronic conductor glassy carbon substrate (GC). The sensors showed a noticeable response towards flucarbazone anions with slopes of -45.5 ± 1.3 (r2 = 0.9998) and -56.3 ± 1.5 (r2 = 0.9977) mV/decade over the range of 10-2–10-5, 10-2–10-4 M and detection limits of 5.8 × 10-6 and 8.5 × 10-6 M for MIP/PANI/ISE and Aliguat/PANI/ISE, respectively. The selectivity and long-term potential stability of all presented ISEs were investigated. The short-term potential and electrode capacitances were studied and evaluated using chronopotentiometry and electrochemical impedance spectrometry (EIS). The proposed ISEs were introduced for the direct measurement of flucarbazone herbicide in different soil samples sprayed with flucarbazone herbicide. The results agree well with the results obtained using the standard liquid chromatographic method (HPLC).
Chapter five:
Screen‐printed platforms integrated with molecularly imprinted polymers (MIP) were fabricated and characterized as potentiometric sensors for diquat (DQ). The synthesized MIP beads were studied as sensory carriers in plasticized poly (vinyl chloride) membranes. The sensors were constructed by using poly (3, 4‐ethylenedioxythiophene) (PEDOT) as solid‐contact material to diminish charge‐transfer resistance and water layer potential. Conventional ion‐selective electrodes (ISEs) with internal filling solution were used for comparison. The designed electrodes showed near Nernstian slopes of 28.2 ± 0.7 (r² = 0.999) over the concentration range of 1.0 × 10-6–1.0 × 10-2 M with the limit of detection 0.026 μg/mL over the pH range 4.2–9.0. The electrode exhibited good selectivity for diquat cations over a large number of organic and inorganic cations. The sensor was successfully introduced for direct measurement of diquat content in commercial pesticide preparations and different spiked potato samples. The results showed that the proposed electrode has a fast and stable response, good reproducibility, and applicability for direct assessment of diquat content. The proposed potentiometric method is simple and accurate in comparison with the reported HPLC methods. Besides, it is applicable to turbid and colored sample solutions.