Ng, Tsz Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 86-98). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vii / List of Figures --- p.xiii / List of Plates --- p.XV / List of Tables --- p.xxi / Abbreviations --- p.xxii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- "Pollution, toxicity and environmental impact of azo dye" --- p.1 / Chapter 1.2 --- Common treatment methods for dyeing effluent --- p.2 / Chapter 1.2.1 --- Physicochemical methods --- p.2 / Chapter 1.2.1.1 --- Coagulation/ flocculation --- p.2 / Chapter 1.2.1.2 --- Adsorption --- p.3 / Chapter 1.2.1.3 --- Membrane filtration --- p.4 / Chapter 1.2.1.4 --- Fenton reaction --- p.4 / Chapter 1.2.1.5 --- Ozonation --- p.5 / Chapter 1.2.1.6 --- Photocatalytic oxidation --- p.6 / Chapter 1.2.2 --- Biological treatments --- p.7 / Chapter 1.2.2.1 --- Degradation of azo dyes by bacteria --- p.8 / Chapter 1.2.2.1.1 --- Anaerobic conditions --- p.8 / Chapter 1.2.2.1.2 --- Aerobic conditions --- p.9 / Chapter 1.2.2.1.3 --- Combined anaerobic and aerobic conditions --- p.10 / Chapter 1.2.2.2 --- Decolourization of azo dyes by fungi --- p.11 / Chapter 1.2.2.3 --- Mechanisms of azo dye reduction by microorganisms --- p.12 / Chapter 1.3 --- "Chromium species, toxicity and their impacts on environment" --- p.14 / Chapter 1.4 --- Common treatment methods for chromium --- p.16 / Chapter 1.4.1 --- Chemical and physical methods --- p.16 / Chapter 1.4.2 --- Biological methods --- p.17 / Chapter 1.4.2.1 --- Chromium reduction by aerobic bacteria --- p.17 / Chapter 1.4.2.2 --- Chromium reduction by anaerobic bacteria --- p.18 / Chapter 1.5 --- Studies concerning azo dye and Cr(VI) co-treatment --- p.19 / Chapter 1.6 --- Response surface methodology --- p.21 / Chapter 1.6.1 --- Response surface methodology against one-factor-at-a-time design --- p.22 / Chapter 1.6.2 --- Phases of response surface methodology --- p.25 / Chapter 1.6.3 --- 2 - level factorial design --- p.26 / Chapter 1.6.4 --- Path of steepest ascent --- p.27 / Chapter 1.6.5 --- Central composite design --- p.28 / Chapter 2. --- Objectives --- p.30 / Chapter 3. --- Materials and Methods --- p.31 / Chapter 3.1 --- Isolation of bacterial strains --- p.31 / Chapter 3.1.2 --- Azo dye decolourization --- p.33 / Chapter 3.1.3 --- Chromate reduction --- p.34 / Chapter 3.2 --- Identification of selected bacterial strains --- p.35 / Chapter 3.2.1 --- Gram stain --- p.35 / Chapter 3.2.2 --- Sherlock® Microbial Identification System --- p.35 / Chapter 3.2.3 --- 16S ribosomal RNA sequencing --- p.37 / Chapter 3.3 --- Optimization of dye decolourization and chromate reduction efficiency with response surface methodology --- p.38 / Chapter 3.3.1 --- Minimal-run resolution V design --- p.38 / Chapter 3.3.2 --- Path of steepest ascent --- p.40 / Chapter 3.3.3 --- Central composite design --- p.41 / Chapter 3.3.4 --- Statistical analysis --- p.43 / Chapter 3.3.5 --- Experimental validation of the optimized conditions --- p.43 / Chapter 3.4 --- Determination of the performance of the selected bacterium in different conditions --- p.43 / Chapter 3.5 --- Determination of azoreductase and chromate reductase activities --- p.44 / Chapter 3.5.1 --- Preparation of cell free extract --- p.44 / Chapter 3.5.2 --- Azoreductase and chromate reductase assay --- p.45 / Chapter 3.6 --- Determination and characterization of degradation intermediates --- p.45 / Chapter 3.6.1 --- Isolation and concentration of the purple colour degradation intermediate --- p.45 / Chapter 3.6.2 --- Mass spectrometry analysis --- p.47 / Chapter 3.6.3 --- Atomic absorption spectrometry analysis --- p.48 / Chapter 4. --- Results --- p.49 / Chapter 4.1 --- Azo dye decolourizing and chromate reducing ability of the isolated bacterial strain --- p.49 / Chapter 4.2 --- Identification of selected bacterium --- p.50 / Chapter 4.3 --- Optimization of dye decolourization and chromate reduction efficiency with response surface methodology --- p.50 / Chapter 4.3.1 --- Minimal-run resolution V design --- p.50 / Chapter 4.3.2 --- Path of the steepest ascend --- p.54 / Chapter 4.3.3 --- Central composite design --- p.55 / Chapter 4.3.4 --- Validation of the predicted model --- p.62 / Chapter 4.4 --- Performance of the selected bacterium in different conditions --- p.62 / Chapter 4.4.1 --- Chromate and dichromate --- p.62 / Chapter 4.4.2 --- Initial pH --- p.63 / Chapter 4.4.3 --- Low and high salt concentration --- p.63 / Chapter 4.4.4 --- Initial K2CrO4 concentration --- p.63 / Chapter 4.4.5 --- Initial Acid Orange 7 concentration --- p.63 / Chapter 4.4.6 --- Nutrients limitation --- p.64 / Chapter 4.5 --- Chromate reductase and azoreductase activities --- p.67 / Chapter 4.6 --- Determination of degradation intermediates --- p.67 / Chapter 4.6.1 --- Mass spectrum of the degradation intermediate --- p.68 / Chapter 4.6.2 --- Chromium content of the degradation intermediate --- p.70 / Chapter 5. --- Discussion --- p.71 / Chapter 5.1 --- Characteristic of Brevibacterium linens --- p.71 / Chapter 5.2 --- Optimization of dye decolourization and chromate reduction with response surface methodology --- p.72 / Chapter 5.3 --- Performance of Brevibacterium linens under different culture conditions --- p.75 / Chapter 5.4 --- Postulation of mechanisms --- p.76 / Chapter 5.4.1 --- Possible reasons of unexpected results of the effect of initial Acid Orange 7 and K2CrO4 concentration --- p.76 / Chapter 5.4.2 --- Properties of the purple colour degradation intermediate --- p.78 / Chapter 5.4.3 --- Mechanisms likely responsible for the chromate reduction --- p.80 / Chapter 5.4.4 --- Explanation of the unexpected results --- p.80 / Chapter 6. --- Conclusions --- p.83 / Chapter 7. --- References --- p.86 / Chapter 8. --- Appendices --- p.99 / Chapter 8.1 --- Definition and calculation of different terms in 2-level factorial design --- p.99 / Chapter 8.2 --- Definition and calculation of different terms in ANOVA table --- p.100 / Chapter 8.3 --- Aliases of terms and resolution --- p.103 / Chapter 8.4 --- Moving of factors in path of steepest ascent --- p.105 / Chapter 8.5 --- Estimation of the parameters in linear regression models --- p.106 / Chapter 8.6 --- Definition and calculation of different terms in test of fitness --- p.109

Cai, Qinhong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 142-166). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of contents --- p.viii / List of figures --- p.xv / List of plates --- p.xix / List of tables --- p.xxi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Pollution generated from dyeing industry --- p.1 / Chapter 1.2 --- Occurrence and pollution of chromium azo dyes --- p.2 / Chapter 1.3 --- Common treatment methods for dyeing effluents --- p.7 / Chapter 1.3.1 --- Physicochemical methods --- p.7 / Chapter 1.3.2 --- Chemical methods --- p.9 / Chapter 1.3.2.1 --- Ozonation --- p.10 / Chapter 1.3.2.2 --- Fenton reaction --- p.11 / Chapter 1.3.2.3 --- Sodium hypochlorite (NaOCl) --- p.12 / Chapter 1.3.2.4 --- Photocatalytic oxidation (PCO) --- p.13 / Chapter 1.3.3 --- Physical methods --- p.14 / Chapter 1.3.3.1 --- Adsorption --- p.14 / Chapter 1.3.3.2 --- Membrane filtration --- p.15 / Chapter 1.3.4 --- Biological treatments --- p.16 / Chapter 1.3.4.1 --- Decolorization of azo dyes by bacteria --- p.16 / Chapter 1.3.4.1.1 --- Under anaerobic conditions --- p.18 / Chapter 1.3.4.1.2 --- Under anoxic conditions --- p.19 / Chapter 1.3.4.1.3 --- Under aerobic conditions --- p.21 / Chapter 1.3.4.2 --- Mechanisms of azo dye reduction by bacteria --- p.23 / Chapter 1.3.4.3 --- Decolorization of azo dyes by fungi and algae --- p.27 / Chapter 1.4 --- Chromium species and their impacts on environment --- p.27 / Chapter 1.4.1 --- Chromium toxicology and speciation --- p.28 / Chapter 1.4.2 --- Common treatment methods for chromium --- p.31 / Chapter 1.5 --- Studies concerning treatment of chromium azo dyes --- p.32 / Chapter 1.6 --- Response surface methodology (RSM) --- p.33 / Chapter 1.6.1 --- RSM vs. one factor-at-a-time (OFAT) design --- p.36 / Chapter 1.6.2 --- Phases of RSM --- p.39 / Chapter 1.6.3 --- Two level factorial design --- p.40 / Chapter 1.6.4 --- Path of steepest ascent (PSA) --- p.43 / Chapter 1.6.5 --- Central composite design (CCD) --- p.44 / Chapter 1.6.6 --- Estimation of the parameters in linear regression models --- p.45 / Chapter 1.6.7 --- Test of fitness --- p.47 / Chapter 2. --- Objectives and significance of the project --- p.49 / Chapter 3. --- Materials and methods --- p.50 / Chapter 3.1 --- Chemicals --- p.50 / Chapter 3.1.1 --- Chemicals for preparation of bacterial culture media --- p.50 / Chapter 3.1.2 --- Chemicals for identification of bacteria --- p.50 / Chapter 3.1.3 --- Chemicals for chromium speciation --- p.51 / Chapter 3.1.4 --- Chemicals for immobilization of bacterial cells --- p.52 / Chapter 3.2 --- Sludge samples --- p.53 / Chapter 3.3 --- Characterization of Acid Yellow 99 --- p.54 / Chapter 3.4 --- Monitor of azo dye decolorization --- p.55 / Chapter 3.5 --- "Isolation of bacterial strains, which can degrade Acid Yellow 99" --- p.55 / Chapter 3.6 --- Identification of selected bacterial strains --- p.58 / Chapter 3.6.1 --- Gram stain --- p.58 / Chapter 3.6.2 --- Sherlock® microbial identification system --- p.58 / Chapter 3.6.3 --- Biolog® microstation system --- p.59 / Chapter 3.6.4 --- Selection of the most effective bacterial strains --- p.59 / Chapter 3.6.5 --- 16S ribosomal RNA sequencing --- p.60 / Chapter 3.7 --- Chromium speciation with interferences of chromium organic complexes --- p.60 / Chapter 3.7.1 --- Instrumentation --- p.60 / Chapter 3.7.2 --- Column preparation --- p.61 / Chapter 3.7.3 --- Determination of percentage retained and recovery --- p.62 / Chapter 3.7.4 --- "Speciation of Cr(VI), ionic Cr(III) and chromium azo dye" --- p.63 / Chapter 3.7.4 --- Preparation of Cr(III)-organic complexes --- p.65 / Chapter 3.7.5 --- Preparation of a microbial degraded chromium azo dye sample --- p.65 / Chapter 3.8 --- Chromium distribution in a treated solution --- p.66 / Chapter 3.9 --- Distribution of AY99 in a treated solution --- p.68 / Chapter 3.10 --- Optimization of decolorization process with response surface methodology (RSM) --- p.70 / Chapter 3.10.1 --- Correlation of cell mass and cell density of selected bacteria --- p.70 / Chapter 3.10.2 --- Preliminary investigation of the optimum conditions --- p.70 / Chapter 3.10.3 --- Minimal run resolution V (MR5) design --- p.71 / Chapter 3.10.4 --- Path of steepest ascent (PSA) --- p.74 / Chapter 3.10.5 --- Central composite design (CCD) and RSM --- p.75 / Chapter 3.10.6 --- Statistical analysis --- p.76 / Chapter 3.10.7 --- Experimental validation of the optimized conditions --- p.77 / Chapter 3.11 --- Immobilization of bacterial cells --- p.77 / Chapter 3.11.1 --- Immobilization by polyvinyl alcohol (PVA) gels --- p.77 / Chapter 3.11.2 --- Immobilization by polyacrylamide gels --- p.78 / Chapter 3.11.3 --- Performance of immobilized cells and free cells --- p.79 / Chapter 3.11.5 --- Storage stabilities of immobilized cells and free cells --- p.80 / Chapter 3.12 --- Performance of a laboratory scale bioreactor --- p.80 / Chapter 3.12.1 --- Chromium distribution in the bioreactor --- p.82 / Chapter 3.12.2 --- Distribution of AY99 in the bioreactor --- p.82 / Chapter 3.12.3 --- Fourier transform infrared spectroscopy (FT-IR) analysis of suspended particles in the treated solution --- p.84 / Chapter 4. --- Results --- p.85 / Chapter 4.1 --- Characterization of AY99 --- p.85 / Chapter 4.2 --- Identification of isolated bacterial strains --- p.86 / Chapter 4.3 --- Selection of the most effective bacterial strains --- p.89 / Chapter 4.4 --- Chromium speciation with interferences of chromium organic complexes --- p.91 / Chapter 4.4.1 --- Effect of pH --- p.91 / Chapter 4.4.2 --- Speciation of Cr(VI)，ionic Cr(III) and chromium azo dye --- p.92 / Chapter 4.4.3 --- Effect of other Cr(III)-organic complexes --- p.93 / Chapter 4.4.4 --- Limit of detection --- p.94 / Chapter 4.4.5 --- Capacity of Amberlite XAD-4 resin --- p.94 / Chapter 4.4.6 --- Determination of Cr(VI) in a microbial degraded chromium azo dye solution --- p.95 / Chapter 4.5 --- Chromium distribution in a free cells treated solution --- p.95 / Chapter 4.6 --- Distribution of AY99 in free cells treated solution --- p.96 / Chapter 4.7 --- Optimization of decolorization process with RSM --- p.98 / Chapter 4.7.1 --- Correlation of cell mass and cell density of selected bacteria --- p.98 / Chapter 4.7.2 --- MR5 design --- p.100 / Chapter 4.7.3 --- Path of steepest ascent (PSA) --- p.102 / Chapter 4.7.4 --- Central composite design (CCD) and RSM --- p.103 / Chapter 4.8 --- Immobilization of bacterial cells --- p.106 / Chapter 4.8.1 --- Performance of immobilized cells and free cells --- p.106 / Chapter 4.8.2 --- Storage stabilities of immobilized cells and free cells --- p.108 / Chapter 4.9 --- Performance of the laboratory scale bioreactor --- p.108 / Chapter 4.9.1 --- Treatment efficiencies of the bioreactor --- p.108 / Chapter 4.9.2 --- Performance stability of the bioreactor in 5 consecutive runs --- p.111 / Chapter 4.9.3 --- Chromium distribution in the bioreactor --- p.114 / Chapter 4.9.4 --- Distribution of AY99 in the bioreactor --- p.115 / Chapter 4.9.5 --- FT-IR analysis of suspended particles in the treated solution --- p.115 / Chapter 5. --- Discussion --- p.117 / Chapter 5.1 --- Chromium speciation with interferences of chromium organic complexes --- p.117 / Chapter 5.2 --- Chromium distribution --- p.117 / Chapter 5.3 --- Distribution of AY99 --- p.122 / Chapter 5.4 --- Optimization of decolorization process with RSM --- p.124 / Chapter 5.4.1 --- MR5 design --- p.124 / Chapter 5.4.2 --- Path of steepest ascent (PSA) --- p.125 / Chapter 5.4.3 --- Central composite design (CCD) and RSM --- p.126 / Chapter 5.5 --- Immobilization of bacterial cells --- p.126 / Chapter 5.5.1 --- Performance of immobilized cells and free cells --- p.126 / Chapter 5.5.2 --- Storage stability of immobilized cells and free cells --- p.128 / Chapter 5.6 --- Performance of the laboratory scale bioreactor --- p.130 / Chapter 5.6.1 --- Treatment efficiencies of the bioreactor --- p.130 / Chapter 5.6.2 --- Performance stability of the bioreactor in 5 consecutive runs --- p.131 / Chapter 5.6.3 --- FT-IR analysis of suspended particles in the treated solution --- p.132 / Chapter 5.6.4 --- Post treatments of bioreactor treated effluents / Chapter 6. --- Conclusions --- p.136 / Chapter 7. --- References --- p.142

本項研究工作主要對五個結構類似的胍基配體， 即 [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹)， [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²)， [(2,6-Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³)， [(2,6-Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) 和 [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵) 與二價鉻以及二價鑭系金屬[Sm(II)、Eu(II) 及 Yb(II)] 的配位化學進行研究，同時，一系列由 L¹ 配體所衍生的三價鑭系金屬配合物亦成功被合成。 / 第一章概括介紹了由胍基配體所構築的金屬配合物的研究背景。 / 第二章敍述了含 L¹ 與 L⁴ 的二價鉻配合物的合成、結構及其化學反應。 通過胍基鉀化合物 [KL¹･0.5PhMe] (1) 與二氯化鉻反應可得到單核二價鉻雙胍基配合物 [Cr(L¹)₂] (3)。 通過胍基鋰化合物 [LiL⁴(Et₂O)] (2) 與二氯化鉻反應，成功製備了單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4)。 而把二價鉻配合物 4於甲苯溶液中重結晶可得到二聚體的二價鉻配合物 [{Cr(L⁴)(μ-Cl)}₂] (5)。 另外，我們對二價鉻配合物 3 及 4 的反應特性也進行了研究。 [Cr(L¹)₂] (3) 與單質碘、二苯基硫族化合物 PhEEPh (E = S, Se, Te) 以及叠氮金剛烷反應可得相對應的三價鉻混合配體化合物，分別爲 [Cr(L¹)₂I] (6)、[Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)]，及四價鉻配合物 [Cr(L¹)₂{N(1-Ad)}] (10)。 透過單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4) 與 NaOMe反應可得甲氧基-胍基配合物 [{Cr(L⁴)(μ-OMe)}₂] (11)。 / 第三章主要報導含 L¹， L²， L³ 和 L⁵ 配基的二價鑭系配合物的合成、結構和化學反應特性。 透過 [LnI₂(THF)₂] (Ln = Sm, Eu, Yb) 與胍基鉀鹽反應，我們成功合成一系列二價鑭系絡合物，包括 [{Eu(L¹)(μ-L¹)}₂] (15)， [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)，[Yb(L²)₂(THF)₂] (18)， [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]， [{Sm(L³)(μ-I)(THF)}₂] (21) 和 [Sm(L⁵)₂] (22)。 本章亦同時探討二價鑭系配合物15， 18， 20 和 22 作爲還原劑的化學反應特性。 配合物 15 與單質碘反應可得三價銪配合物 [{Eu(L¹)₂(μ-I)}₂] (23)。 配合物 18 與二苯基硫族化合物 PhEEPh (E = S, Se) 反應，可得相對應的三價鐿配合物 [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)]。 18 與氯化亞銅反應得到三價鐿配合物 [{Yb(L²)₂(μ-Cl)}₂] (26)。 除此之外，配合物 18 與偶氮苯反應得到雙核配合物 [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27)， 而 20 與偶氮苯的反應可得單核配合物 [Yb(L³)₂(η²-PhNNPh)･PhMe] (28)。 配合物 22 與二硫化碳的反應得出不對稱偶合配合物 [(L⁵)₂Sm(μ-η³:η²-S₂CSCS)Sm(L⁵)₂] (29)。 / 第四章敍述由胍基配體 L¹ 所衍生的一系列三價鑭系金屬配合物 [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] 的合成及其結構。 通過相對應的鑭系金屬三氯化物與 1 反應可得配合物 30-36。 另外， CeCl₃及 LuCl₃與 1 反應亦可合成 [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]。 / 第五章總結了本項研究工作，並對本工作的未來發展作出建議。 / This research work is focused on the coordination chemistry of five closely related guanidinate ligands, namely [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹), [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²), [(2,6Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³), [(2,6Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) and [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵), with divalent chromium and lanthanide metal ions. A series of trivalent lanthanide derivatives of the L¹ ligand were also prepared and structurally characterized in this work. / Chapter 1 gives a brief introduction to the chemistry of metal guanidinate complexes. / Chapter 2 reports on the synthesis, structure and reactivity of chromium(II) complexes derived from the bulky L¹ and L⁴ ligands. Treatment of CrCl₂ with [KL¹･0.5PhMe] (1) afforded the mononuclear Cr(II) bis(guanidinate) complex [Cr(L¹)₂] (3). Reaction of CrCl₂ with [LiL⁴(Et₂O)] (2) resulted in the isolation of ate-complex [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4). Recrystallization of 4 from toluene gave neutral, dimeric [{Cr(L⁴)(μ-Cl)}₂] (5). The reaction chemistry of the Cr(II) complex 3 and 4 was studied. Treatment of 3 with I₂, PhEEPh (E = S, Se, Te), 1-AdN₃ (1-Ad = 1-adamantyl) gave the corresponding mixed-ligand Cr(III) complexes, namely [Cr(L¹)₂I] (6) and [Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)] and Cr(IV) complex [Cr(L¹)₂{N(1-Ad)}] (10). Besides, the reaction of 4 with NaOMe resulted in the isolation of the Cr(II) methoxide-guanidinate complex [{Cr(L⁴)(μ-OMe)}₂] (11). / Chapter 3 deals with the synthesis, structure and reactivity of lanthanide(II) complexes supported by the L¹, L², L³ and L⁵ ligands. Lanthanide(II) guanidinate complexes were prepared by the reactions of an appropriate lanthanide diiodide with the corresponding potassium guanidinate complexes [KL¹･0.5PhMe] (1), [KL²(THF)₀.₅]n (12), KL³ (13) and [KL⁵(THF)₂] (14). Reaction of EuI₂(THF)₂ with 1 gave the homoleptic complex [{Eu(L¹)(μ-L¹)}₂] (15). Metathesis reactions of LnI₂(THF)₂ (Ln = Yb, Eu) with 12 and 13 led to the isolation of [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)], [Yb(L²)₂(THF)₂] (18) and [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]. Direct reaction of SmI₂(THF)₂ with 13 yielded the iodide bridged Sm(II) complex [{Sm(L³)(μ-I)(THF)}₂] (21), whilst reaction of SmI₂(THF)₂ with 14 gave homoleptic [Sm(L⁵)₂] (22). The reaction chemistry of 15, 18, 20 and 22 as reducing agents was examined. Oxidation of 15 with I₂ afforded the Eu(III) complex [{Eu(L¹)₂(μ-I)}₂] (23). Reactions of 18 with PhEEPh (E = S, Se) gave the corresponding Yb(III) chalcogenide complexes [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)], whilst treatment of 18 with CuCl led to the isolation of [{Yb(L²)₂(μ-Cl)}₂] (26). Besides, addition of complex 18 to PhNNPh yielded binuclear [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27), whereas treatment of 20 with PhNNPh resulted in the isolation of mononuclear [Yb(L³)₂(η²-PhNNPh)･PhMe] (28). Addition of CS₂ to 22 gave the unsymmetrical coupling product [(L⁵)₂Sm(μ-η³:η²S₂CSCS)Sm(L⁵)₂] (29). / Chapter 4 describes the preparation and structural characterization of lanthanide(III) complexes derived from L¹. A series of homoleptic lanthanide(III) tris(guanidinate) complexes [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] were prepared by the reactions of an appropriate LnCl₃ with three molar equivalents of 1. Treatment of CeCl₃ and LuCl₃ with two equivalents of 1 gave the corresponding chloride bridged guanidinate complexes [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]. / Chapter 5 summarizes the findings of this study. A short description on the future prospect of this work will also be given. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Au, Chi Wai. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references. / Abstracts also in Chinese.

Hexavalent Chromium (Cr(VI) induces malignant cell transformation in normal bronchial epithelial (BEAS-2B) cells. Cr(VI)-transformed cells exhibit increased level of antioxidants, are resistant to apoptosis, and are tumorigenic. RNAseq analysis in Cr(VI)-transformed cells showed that expression of transcripts associated with mitochondrial oxidative phosphorylation is reduced, and the expression of transcripts associated with pentose phosphate pathway, glycolysis, and glutaminolysis are increased. Sirtuin-3 (SIRT3) regulates mitochondrial adaptive response to stress, such as metabolic reprogramming and antioxidant defense mechanisms. SIRT3 was upregulated and it positively regulated mitochondrial oxidative phosphorylation in Cr(VI)-transformed cells. Our results suggests that SIRT3 plays an important role in mitophagy deficiency of Cr(VI)-transformed cells. Furthermore, SIRT3 knockdown suppressed cell proliferation and tumorigenesis of Cr(VI)-transformed cells. Nrf2 is a transcription factor that regulates oxidative stress response. This study investigated the role of Nrf2 in regulating metabolic reprogramming in Cr(VI)-transformed cells. We observed that in Cr(VI)-transformed cells p-AMPKthr172 was increased, when compared to normal BEAS-2B cells. Additionally, Nrf2 knockdown reduced p-AMPKthr172. Our results suggest that Nrf2 regulated glycolytic shift via AMPK regulation of PFK1/PFK2 pathway. Furthermore, our results showed that Nrf2 constitutive activation in Cr(VI-transformed cells increased cell proliferation and tumorigenesis. Overall this dissertation demonstrated that Cr(VI)-transformed cells undergo metabolic reprogramming. We demonstrated that Nrf2 constitutive activation plays decisive role on metabolic reprogramming induction, and SIRT3 activation contributing to increased cancer cell proliferation and tumorigenesis.

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The bulk of the world's known nickel reserves are contained in laterite ores but sulphidic ores remain the main source of the Western world's nickel production. With the continuing increase in nickel consumption and the depletion of sulphidic ores, the traditional source of nickel, the extraction of nickel from lateritic ores has been the subject of research interest worldwide. Advances in pressure acid leaching (PAL) technology have resulted in significant commercial attempts to extract nickel from these ores. Leaching the ore with sulphuric acid at elevated temperatures and pressures allows almost complete dissolution of the nickel and cobalt, a valuable byproduct of these ores, but yields highly contaminated pregnant leach solutions. Separating and purifying the nickel and cobalt from these solutions remains a hindrance to full commercial production. Several purifying techniques have been commercialised but all suffer from continuing technical problems. Among them, however, the direct solvent extraction (DSX) technique offers several advantages. Direct solvent extraction involves the separation of the nickel and cobalt directly from the partially neutralised pregnant liquor stream (PLS) by solvent extraction with Cyanex(R) 272 as the extractant. However certain contaminants adversely affect the solvent extraction process. Among them is chromium and little is known about the solvent extraction behaviour of this metal. The present work investigated the solvent extraction of chromium with Cyanex(R) 272. It was found that the solvent extraction behaviour of chromium(III) and chromium(VI), both of which could be found in PAL-generated PLS, are distinctly different. / For chromium(III), solvent extraction tests showed that (a) it is extracted in the pH range 4-7; (b) the extraction is partly influenced by diffusion; (c) the apparent equilibration time is significantly longer than most transition metals; (d) increases in temperature from 22 to 40 C resulted in increases in the extraction; (e) the pH0.5 increases in the order nitrate < chloride < sulphate in the presence of these anions; (f) the presence of acetate depresses extraction of chromium(III) when the solution is allowed to stand before extraction; (g) in the PLS, chromium(III) precipitated at lower pH than that predicted by the solubility product principle; and (h) the pH0.5 decreases as the Cyanex(R) 272 concentration increases. Chromium(III) is initially extracted by solvation of its inner sphere complex, which then undergoes further reaction in the organic phase leading to the formation of a much more stable species that is difficult to strip. A reaction scheme together with a description of both the initially extracted and resulting stable species is proposed. Extraction of chromium(VI), on the other hand, (a) occurs at pH less than 2 by solvation of chromic acid; (b) is independent of the aqueous phase composition; (c) does not occur in the pH range (3-6) used in the separation of nickel and cobalt. The latter is irrespective of temperature up to 40 C, the use of industrial PLS as the aqueous phase or the presence of an anti-oxidant in the organic phase. The stripping of chromium(III) from a loaded organic phase can be achieved using 1-4 mol L-1 mineral acids provided the stable organic species have not formed making industrial scale stripping of chromium(III) from Cyanex(R) 272 difficult. The exact composition of the aqueous phase during extraction affects the stripping efficiency.

Iron-based alloys containing 15% chromium, 2-3% molybdenum and 0.02-1.7% carbon, consisting of M23C6 and M6C carbides in an austenitic matrix were oxidised at 8500C to study their oxidation resistance and a precipitate-free zone formation. Alloy design was carried out using a thermodynamic software Thermo-Calc. Carbides in these alloys were expected to dissolve during oxidation, releasing chromium required for the protective oxide formation. Decarburisation of the matrix was expected to trigger the carbide dissolution, and form a precipitate-free zone. Transformation of the austenitic into ferritic matrix in the precipitate-free zone was expected be essential for providing a fast chromium supply to the oxide/alloy interface. Upon exposure to pure oxygen, most of the alloys oxidised non-protectively due to the fast oxidation attack and low chromium content in the matrix, while carbide dissolution was too slow. The alloys were then pre-oxidised in H2+10%H2O to grow a purely chromia scale. In this low oxygen partial pressure environment, carbides in the alloy's sub-surface dissolved and formed a ferritic precipitate-free zone. The precipitate dissolution model developed by previous investigators was then tested and proven to be valid in this iron-based alloy system. The endurance of the pre-formed chromia scale with its underlying precipitate-free zone was then tested in pure oxygen environment. All of the alloys that had successfully developed a ferritic precipitate-free zone in the pre-oxidation stage, survived the subsequent oxidation in pure oxygen up until 3 weeks observation. Although x-ray diffraction found some minor iron oxides, the oxide consisted of mainly Cr2O3. Since iron activity had increased and iron oxides had become stable after the pure oxygen gas was introduced, the growth of the precipitate-free zone had to compete with the rate at which it was consumed by oxidation. It was concluded that the transformation from austenite to ferrite at the subsurface region of the alloy could be achieved provided that the volume fraction of the carbides did not exceed 0.2. Evidence indicated that the chromia scale grew by chromium provided by the dissolving carbides. Pre-oxidation led to a promising use of the alloys at atmospheric oxygen pressure.

The reactivities of several electron rich, low-valent group 6 complexes with a series of N-donor ligands were explored in order to gain information about the nature of M-N binding. Reactions of trimethylsilyl diazomethane (N=N=CHSiMe3) and 1-adamntyl azide (N=N=N-Ad) with the organometallic complexes [Cr(CO)3(C5R5)]2 (R = H, Me) and HMo(CO)3(C5R5) (R = H, CH3) were studied from both a kinetic and thermodynamic aspect. Ultimately, this information was used to propose plausible mechanisms by which the reactions take place. Furthermore, reactions of M(PiPr3)2(CO)3 (M = Mo, W; iPr = isopropyl) with N2, trimethylsilyl diazomethane, 1-adamantyl azide, a series of nitriles, and a choice group of N-heterocyclic compounds were studied. The use of the coordinatively unsaturated but sterically hindered M(PiPr3)2(CO)3 complex was used to evaluate the importance of sigma and pi bonding in these complexes.

Chitosan films are an excellent media for binding metal ions due to the electrostatic nature of the chitosan molecules. Addition of cross-linking or plasticizing agents alters texture of the films, but their effect on metal-binding capacity has not been fully characterized. The objective of this research was to determine effects of plasticizers and cross-linkers on physical and metal-binding properties of chitosan films and coatings prepared by casting and by spincoating. Chitosan films were prepared using 1% w/w chitosan in 1% acetic acid with or without (control) additives. Plasticizing agents were tetraethylene glycol (TEG) and glycerol while citric acid, ethylenediamine tetraacetic acid (EDTA), and tetraethylene glycol diacrylate (TEGDA) were used as cross-linkers. The additives were applied in concentrations of 0.10%, 0.25%, and 0.50% w/w of film-forming solution. The films were prepared by casting and by spincoating. Films were cast at ambient conditions for tests within one week (fresh films) and eight weeks (aged) after casting. The cast films were evaluated for thickness, residual moisture (by the Karl Fischer method), Cr(VI) binding capacity, puncture strength, and puncture deformation while the chitosan coatings were tested for thickness, Cr(VI) binding capacity, solubility in aqueous solution, and surface morphology (using atomic force microscopy). Cast films with cross-linkers showed an increase in resistance to puncture while plasticized films become more elastomeric. Control films bound 97.2% Cr(VI) ions from solution (0.56 mg Cr(VI)/g film), and addition of plasticizers did not affect chromium binding, tying up to 96.7% Cr(VI) ions from solution (0.56 mg Cr(VI)/g film). Films containing cross-linkers yielded binding capabilities ranging from 42.3% to 94.3% bound Cr(VI) ions (0.26-0.52 mg Cr(VI)/g film). Ultrathin coatings also possess the ability to bind Cr(VI) from solution, though only a maximum of 7.4% of Cr(VI) ions could be bound from solution, the thin films had the ability to bind up to 224 mg Cr(VI)/g ultrathin film. These coatings use less chitosan, but they display greater binding per mass. Overall, plasticizers do not alter, while cross-linkers may reduce, the binding capacity of chitosan films, but physical properties of the films can be controlled by inclusion of additives.