The effects of temperature on the first and second acid dissociation constants of 8-hydroquinoline (oxine) have been measured and the following thermodynamic values assigned to solutions of 0.1M strength. For the process, H₂Ox⁺ ⇋ H⁺ + HOx at 25°C., pK₁ = 5.103, ΔH = 5.7 kcal/mole, and ΔS° = -4 e.u. For the second acid dissociation constant, HOx ⇋ H⁺ + Ox⁻ at 25°C., pK₂ = 9.76, ΔH = 6.3 kcal/mole, and ΔS° = -23 e.u. The values for the second acid dissociation constant agree with those previously published. The values for the first dissociation constant have not been previously determined but are consistent with the result expected for reactions of this charge and chemical type. The partition of 8-hydroxyquinoline was determined as a function of temperature for the following systems: water-benzene, water-nitrobenzene, water-toluene, and water-chloroform. The pertinent thermodynamic values for the partitions are as follows: a. Water-benzene: log P = 2.44; ΔH = -2.0 kcal/mole; ΔS° = 4.5 e.u. b. Water-nitrobenzene: log P = 2.67; ΔH = -1.7 kcal/mole; ΔS° = 6.6 e.u. c. Water-toluene: log P = 2.33; ΔH = -1.3 kcal/mole; ΔS° = 6.2 e.u. d. Water-chloroform log P = 2.703 ΔH = -2.5 kcal/mole; ΔS° = 3.9 e.u. The values obtained for the water-chloroform system agree well with tho literature and serve as a check on the rest of the data. The effect of temperature on the overall extraction constant of nickel oxinate and ferric oxinate was measured for the system water-chloroform. The thermodynamic values found for the process Me⁺ⁿ + nHOx ⇌ MeOx_n + nH⁺ are the following at 25°C. and an ionic strength of 0.1M: a. Nickel oxinate log Kₑ = -2.73; ΔH = -40.4 kcal/mole; ΔS° = -148 e.u. b. Ferric oxinate log Kₑ = -3.97; ΔH = -14.1 kcal/mole; ΔS° = -29 e.u. The effect of ionic strength on the partition of S-hydroxyquinoline between water and benzene was determined for four different uni-univalent salts: potassium chloride, sodium chloride, potassium nitrate and sodium perchlorate. The “salting out” of oxine observed is typical of non-electrolytes. / Doctor of Philosophy

Call number: LD2668 .T4 1965 M36 / Master of Science

Digitized by Kansas Correctional Industries

by Cheng Pui Shan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.iv / Table of Contents --- p.v / List of Compounds --- p.viii / Abbreviations --- p.xi / Chapter Chapter 1. --- A General introduction to Metal amides / Chapter 1.1 --- introduction / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- Metal Complexes with 2-Pyridyl Amido Ligands --- p.2 / Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.4 / Chapter 1.3 --- references for chapter1 --- p.5 / Chapter Chapter 2. --- Group 13 metal Amides / Chapter 2.1 --- GENERAL BACKGROUND --- p.8 / Chapter 2.1.1 --- Common Methods for the Preparation of Group 13 Metal Amides --- p.8 / Chapter 2.1.2 --- "An Overview on Aluminum(III), Gallium(III) and Indium(III) Amides" --- p.9 / Chapter 2.1.3 --- An Overview on Aluminum(III) Aryloxides --- p.15 / Chapter 2.2 --- aims of our studies --- p.18 / Chapter 2.3 --- results and discussion --- p.19 / Chapter 2.3.1 --- Preparation of [HN(SiButMe2)(2-C5H3N-6-Me)] (HL1) and Its Lithium Derivative [LiL1(TMEDA)] --- p.19 / Chapter 2.3.2 --- "Synthesis and Structures of Aluminum(III), Gallium(III) and Indium(III) Amides" / Chapter 2.3.2.1 --- "Synthesis of [MCl(L1)2] (M = Al 3, Ga 4) and [In(L1)3] (5)" --- p.20 / Chapter 2.3.2.2 --- Physical Characterization of Compounds 3-5 --- p.21 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 3-5 --- p.24 / Chapter 2.3.3 --- Reactivity Studies --- p.35 / Chapter 2.3.3.1 --- Physical Characterization of Compounds 6 and7 --- p.38 / Chapter 2.3.3.2 --- Molecular Structures of Compounds 6 and7 --- p.39 / Chapter 2.4 --- EXPERIMENTALS FOR CHAPTER2 --- p.47 / Chapter 2.5 --- REFERENCES FOR CHAPTER2 --- p.52 / Chapter Chapter 3. --- A Silyl´ؤlinked diamine compound and its metal complexes / Chapter 3.1 --- A GENERAL INTRODUCTION TO DIAMINE COMPOUNDS --- p.59 / Chapter 3.2 --- A GENERAL INTRODUCTION TO MIXED ALKALI METAL AMIDES --- p.65 / Chapter 3.3 --- AIMS OF OUR STUDIES --- p.67 / Chapter 3.4 --- SYNTHESIS AND STRUCTURES OF [Me2Si{NH(2-Py)}2] AND THE CORRESPONDING ALKALI METAL AMIDES / Chapter 3.4.1 --- Synthesis and Structure of [Me2Si{NH(2-Py)}2] (HL2) (8) --- p.68 / Chapter 3.4.2 --- Synthesis and Structures of Alkali Metal Amides / Chapter i. --- Synthesis of Sodium Derivatives of8 --- p.74 / Chapter ii. --- Synthesis of a Mixed Alkali Metal Derivative of8 --- p.75 / Chapter iii. --- Attempted Metallation of 8 with KBun --- p.75 / Chapter iv. --- Physical Characterization --- p.77 / Chapter v. --- Molecular Structures --- p.80 / Chapter 3.5 --- synthesis and structure of the iron(ii) derivative [Fe(L2)Cl]2 / Chapter 3.5.1 --- An Overview on Iron(II) Amides --- p.95 / Chapter 3.5.2 --- Aims of Our Studies --- p.97 / Chapter 3.5.3 --- Synthesis and Structure of [FeCl(L2)]2 (14) / Chapter i. --- Synthesis and Characterization --- p.98 / Chapter ii. --- Molecular Structure --- p.99 / Chapter 3.6 --- EXPERIMENTALS FOR CHAPTER 3 --- p.102 / Chapter 3.7 --- REFERENCES FOR CHAPTER 3 --- p.106 / APPENDIX 1 / General Procedures and Physical Measurements --- p.110 / X-Ray Crystallography --- p.110 / APPENDIX 2 / Table A-1. Selected crystallographic data for compounds 3-5. --- p.113 / Table A-2. Selected crystallographic data for compounds 6´ؤ7. --- p.114 / Table A-3. Selected crystallographic data for compounds 8，10-11. --- p.115 / Table A-4. Selected crystallographic data for compounds 12-14. --- p.116

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Background: Thalassaemia is a genetic disorder disease, one of the most clinically relevant haemoglobinopathies in paediatric population. It interferes with the synthesis of haemoglobin chain. For the sake of maintaining the serum haemoglobin at a normal level, regular blood cell transfusion is required to the patients with thalassaemia. In general, patients with thalassaemia are often diagnosed at an early age and need to take a life-long iron chelating therapy to prevent the multi-organ failure caused by iron-overload. The safety issue is considered a very importance aspect in the treatment among paediatric population and young people. In the past decades, numerous randomised controlled trials (RCTs) and meta-analysis regarding the efficacy and safety of iron chelating agents including deferoxamine, deferiprone, deferasirox, in reducing iron accumulation among patients with thalassaemia had been published, yet limited meta-analysis reveal the same issue among paediatric population and young adults. Further evidence and understanding are therefore needed to confirm whether or not the iron chelating agents are safe among young patients with thalassaemia. Objective: To conduct a meta-analysis to evaluate the safety of iron chelating agents in paediatric population and young adults with thalassaemia. Methods: Literature search was carried out in PubMed, EMBASE, BIOSIS Previews, Science Citation Index Expanded and Cochrane Library databases. This meta-analysis of observational studies was conducted following the PRISMA and MOOSE statements. Selection Criteria All prospective uncontrolled cohort studies were eligible to include. Articles were assessed according to the age range of its participants and the quality of the reported adverse effects. All enrolled studies should record countable cases of adverse effects of paediatric population and young patients up to 25 years of age, diagnosed with alpha/beta thalassaemia or sickle cell disease and under the treatment of iron chelating agents. Data Collection and analysis Two reviewers independently retrieved the data and conducted the quality assessment for each of the included studies. Agency for healthcare research and quality assessment tool was used to evaluate the general risk of bias, whilst the quality of harms was assessed with the Mcharm question criterions. Meta-analysis was carried out for detecting the entire proportion value of six adverse effects including liver abnormality, renal abnormality, rash, abdominal pain/discomfort, nausea and neutropenia, and the forest plot was generated accordingly. The I2 was estimated to assess the methodological quality of each outcome. Random or fixed model was used for the analysis. The sensitivity analysis was conducted to assess the robust of the result. Results A total of 8199 articles were identified in the initial database search. After removal of duplications, update from other sources and exclusion based on the exclusion criteria, 25 full articles were retrieved and 14 uncontrolled cohort studies were included in this review. Eight hundred and fifty-four patients up to 25 years of age were included in the analysis. The general quality of the studies was moderate while the quality of adverse effects was low to moderate. Out of the 14 included studies, nine were under the deferasirox treatment; five for deferiprone therapy. No study included deferoxamine. Most adverse effects were observed among the paediatric patients under deferasirox treatment. The meta-analysis of pooled proportion under deferasirox were 17.23% (95%CI, 8.78-25.68%) for liver abnormality, 11.58% (95%CI, 5.91-17.25%) for renal abnormality, 5.41% (95%CI, 3.23-7.58%) for rash, 11.03% (95%CI, 1.83-20.22%) for abdominal pain/discomfort and 5.77% (95%CI, 1,50-10.03%) for nausea. Only one study reported case of neutropenia in the patients under deferasirox, whereas more cases were recorded within the paediatric patients with deferiprone, estimated proportion of 5.98% (95%CI, 2.79-9.16%). However, the meta-analysis of estimated proportion for liver abnormality in paediatric patients with deferiprone was 10.08% (95%CI, 2.67-17.49%), abdominal pain/discomfort was 4.31% (95%CI, 1.65-6.98%). Only one study reported case of renal abnormality, rash and nausea respectively in the patients with deferasirox, which a meta-analysis could not be conducted. Conclusions Among paediatric population and young patients with thalassaemia disease, most drug-related adverse effects were liver injury among patients under both deferasirox and deferiprone. For patients under deferasirox, the proportions of the risk of abdominal pain/discomfort and renal abnormality were in a secondary high-level, whereas the proportions of the risk of rash and nausea were comparatively very low. Few adverse effects were detected among young patients with deferiprone. In addition, the proportion of liver abnormality and abdominal pain/discomfort were lower for deferiprone than deferasirox. Further investigation is needed to assess the safety and efficacy between different dosage of iron chelating agents and the risk of other adverse effects among paediatric population, which are necessary to guide the clinical practice in the treatment of paediatric patients with thalassaemia. / published_or_final_version / Pharmacology and Pharmacy / Master / Master of Medical Sciences

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