اسم المؤلف:
رنا عباس رشيد
اسم المشرف:
زهير عبد الامير خماس
المستخلص:
In fact, the separation and extraction of trace amounts of medicaments in biological fluids, environmental samples and also in pharmaceuticals did not receive widespread attention by using the so - called cloud point extraction. In this regard, we believe that the current research work will contribute to open new horizons in the design and construction of analytical procedures relating to this subject and expand this methodology application of extraction in one of the important areas such as pharmacy and environmental sciences as well as in forensic analyses.This study focuses on the development of environmentally friendly methodology for the mutual determination of two selected medicaments, namely doxycycline HCl using iron (III) and chromium (VI) as mediated ions, trifluoperazine HCl using vanadium (V) as a mediated ion and their determination in real samples such as urine, blood serum, pharmaceutical and water. Also, the exploitation of these drugs in the chemical analysis as chelating agents to determine the content of Fe (III), Cr (VI) and V (V) iron in different samples via using the cloud point extraction methodology combined with molecular spectrophotometric technique. In general, these procedures include the use of one of non - ionic surfactant such as Triton - X - 114 as an extracting medium for the colored complexes resulting from the reaction between the above - mentioned drugs and metal ions in acidic medium as the reaction systems exploited in the design of various procedures in the point cloud extraction for this work.This piece of thesis included three main chapters : - As the first chapter in the its preamble refers to the comprehensive coverage of chemical structures, properties, pharmaceutical and bioactivity importance of two medicaments, doxycycline HCl and trifluoperazine HCl, and Abizaid in details about Fe (III), Cr (VI) and V (V) ions, along with a comprehensive review of the chemical literature to estimate these drugs and metallic ions under study using different analytical techniques. This chapter also deals with on the basic principles of the cloud point extraction method supported by adequate explanations about the experimental procedures and the factors affecting the extraction of metal ions and coupling this approach with different analytical techniques, and then Abizaid chapter the objectives of this current work.The Second chapter covers in details the instrumental techniques, general apparatus, chemicals used and their methods of preparations in the present work. Also it entered on the full details of the analytical procedures of extraction point planned to determine the selected medicaments and metal ions under the study, as well as the preparation of bio - samples and pharmaceutical preparations submitted for analysis.The Third chapter highlights the important part of this work, which deals with the results and discussion of two important issues in analytical chemistry is the extraction and detection processes. These results can be summarized as follows : First : obtaining chleting complexes through the reaction of a drug doxycycline HCl (DOXH) with Fe (III) ion in diluted sulfuric acid and also its reaction with the Cr (VI) ions as a mediated ion in diluted hydrochloric acid. As well as, this study included the reaction of trifluoperazine HCl (TFPH) with V (V) as a mediator inacidic medium acid. Each drug was individually determined in its complex spectrophotometrically at its respective absorption maximum after its extraction via the cloud point extraction under the established optimum parameters. Then the proposed methods were applied in the estimation of these drugs in the blood serum, urine, water and pharmaceutical samples after the application of the optimum experimental conditions. At first, a series of experimental studies were carried out to monitor the impact of factors affecting the extraction efficiency sequentially via classical optimization (OFAT) including pH, the concentration of the reagents and metal ions, the amount surfactant, equilibration temperature and incubation time of, as well as study the impact of interfering materials on the extraction efficiency of the metals under study. The optimum experimental conditions which have been obtained as follows : 1. It was shown that the best experimental conditions for determining the drug (DOXH) via the reaction with Fe (III) as a mediated ion are : pH = 4.0, Fe (III) concentration (4 ppm), (0.2 mL) Triton X - 114 (10%), temperature and time (65 °C at 15 min). As for the best experimental conditions for the determination of Fe (III) ions by its reaction with (DOXH) as ligand have not changed except drug concentration and found to be of (30 ppm).2. The best experimental conditions to estimate the drug (DOXH) via its reaction with Cr (VI) ions as a mediator are : pH=2.0, concentration of Cr (VI) (8 ppm), (0.5 mL) Triton X - 114 (10 %), temperature and time (80 °C at 30 min). The best experimental conditions to estimate Cr (VI) ions through reaction with (DOXH) have not changed except the concentration of this drug and found to be (20 ppm).3. The optimum experimental conditions to estimate the drug (TFPH) via its reaction with V (V) ion as a mediator are : pH = 1.5, V (V) concentration (20 ppm), (0.2 mL) Triton X - 114 (10%), temperature and time (75 °C at 30 min.). As the best experimental conditions to estimate the content of V(V) ion through its reaction with the drug (TFPH) have been not changed except for the concentration of this drug and found to be (60 ppm).Second : the application of the optimum conditions that obtained in the above were used in the construction of calibration curves for drugs and metals ions under study followed their determination by Spectro - photometry. The obtained results can be summarized as follows : 1. The analytical figures of merit that were obtained by the proposed method for a drug (DOXH) by reacting with Fe(III) ions as a mediator were : the linear range (0.2 - 8.0 μg mL - 1), the detection limit (0.07 μg mL - 1) , enrichment factor (97.4) time, molar absorptivity (5.85x104 L mol - 1 cm - 1), extraction efficiency (96.00%), mean recovery percentage (98.33 ± 0.56%) in aqueous solution and (95.95%±1.09%) in the urine sample. The proposed method was applied to estimate the drug (DOXH) in the selected samples such as vital (urine) and environmental (river water) as well as the pharmaceutical preparation of Cyprus origin (Medomycin) to identify the extent of reliability and validity of the proposed method by applying the statistic tools required.2. The analytical figures of merit that were obtained by the proposed method for a drug (DOXH) by reacting with Cr(VI) ions as a mediator were : : the linear range (8 - 0.5 μg mL - 1), detection limit (0.29 μg mL - 1), enrichment plants (44) folds , molar absorptivity(2.6x104 L mol - 1 cm - 1), extraction efficiency (96.00%) and mean percent recovery (101.47±1.36%) in river water. The proposed method was applied to estimate (DOXH) in the selected samples such as vital (urine) and environmental (river water) as well as the pharmaceutical preparation of Cyprus origin (Medomycin) to identify the extent of reliability and validity of the proposed method by applying the statistic tools required.3. The analytical figures of merit that were obtained by the proposed method for a drug (TFPH) reacting with V(V) ions as a mediator were : the linear range (0.2 - 80 μg mL - 1), the detection limit (4.04 μg mL - 1), enrichment factor (54.2) fold, molar absorptivity (6.4 x103 L mol - 1 cm - 1), extraction efficiency (94.00%) and the mean percent recoveries (99.93±2.88%) and (99.33±3.45%) in tap water and river, respectively. The proposed method was applied to estimate the drug (TFPH) in commercial tablets medicine of Egyptian origin (Stelazine), blood serum and river water.Third, the determination of Fe (III), Cr (VI) and V (V) ions at sub - ng mL - 1 levels were conducted via the use of the drugs under study as chelating agents (ligands) in a variety of samples such as drug formulations, water and food sample. These determinations were based on the same above reaction systems in the presence of excess concentration of the drugs mentioned above after extracting of their complexes by micelles generated with cloud point extraction method and then estimated at wavelength absorption maxima. The obtained results can be summarized as follows : 1. Analytical figures of merit obtained by the proposed method for Fe(III) ions using a drug (DOXH) as ligand were : linearity (200 - 20) ng mL - 1, detection limit (9.57) ng mL - 1, quantitation limit(31.90) ng ml - 1, molar absorptivity (1.33x105 L mol - 1 cm - 1) mean percent recovery (97.0±3.26 %) in the aqueous solution and (101.55 ± 0.77%) in the water of the river. The proposed method was applied to estimate Fe (III) ions in iron supplement pharmaceuticals imported as tablets.2. The analytical figures of merit obtained by the proposed method for Cr(VI) ions using the drug (DOXH) as ligand were : linearity (30 - 140) ng mL - 1, detection limit (6.87) ng mL - 1, quantitation limit (22.94) ng mL - 1, molar absorptivity (1.8x104 L mol - 1 cm - 1) and percent recovery ranged between (95.5%) and (98.5%) in river water samples. The proposed method was applied to estimate Cr (VI) in the discharge resulting from leather tanning processes before and after chemical treatment and the data were compared statistically with the results of flame atomic absorption spectrometry.3. The analytical figures of merit were obtained in the proposed method for V(V) ions using the drug (TFPH) as ligand were : linearity (0.5 - 10) μg mL - 1, detection limit (0.113) μg mL - 1, a quantitation limit (0.38) μg mL - 1, molar absorpitivity (1.78x104 L mol - 1 cm - 1) and the average percent recovery (99.43±1.40 %) in tap water. The proposed method has been applied to determine vanadium in the selected samples of domestic and imported black pepper powders and the results were statistically compared with the results of the analysis by electrothermal atomic absorption spectro
