The original purpose of this investigation was to attempt to apply the coulostatic method directly to a molten salt system. The inability to duplicate the reported capacity data for this system resulted in an investigation of the probable cause of this discrepancy between the data obtained by these different methods (14, 15).

A presente pesquisa teve como objetivo a otimização de processos de precipitação química na remoção de fósforo de esgotos sanitários mediante a utilização de sais de ferro como coagulante. Analisou-se a remoção de matéria orgânica e produção de lodo obtidas. O trabalho foi desenvolvido com efluentes provenientes de duas estações de tratamento da SABESP, sendo elas a ETE Barueri lodos ativados convencional e ETE Ribeirão Pires tratamento anaeróbio com reatores UASB. Os ensaios de Jar-Test foram conduzidos em laboratório e o coagulante utilizado foi o cloreto férrico. Os resultados obtidos demonstram que a dosagem do coagulante, em ambos os efluentes estudados, resulta na remoção de fósforo total a valores inferiores a 1 mg/L. As dosagens de coagulante necessárias foram de 80 mg/L para a ETE Barueri e 60 mg/L para a ETE Ribeirão Pires. A remoção de carga orgânica também foi alcançada e valores de DBO5,20 inferiores a 10 mg/L são obtidos com dosagens inferiores às necessárias para a remoção de fósforo. A dosagem de coagulante necessária para a remoção de DBO5,20 a valores inferiores a 10 mg/L foi de 40 mg/L. A produção de lodo é o principal problema encontrado quando se utiliza precipitação química, a quantidade de lodo produzida é significativa e deve ser levada em consideração no dimensionamento do sistema de tratamento e disposição final. Incrementos na produção de lodo da ordem de 113% foram obtidos para a ETE Barueri e 51% para a ETE Ribeirão Pires quando foram consideradas as dosagens de coagulante necessárias a remoção de fósforo totais a valores inferiores a 1 mg/L. / The aim of the present study was the chemical precipitation optimization of phosphorus from domestic wastewater with a ferric salt as coagulant. The organic matter removal and the sludge production obtained were analyzed. The study was developed with effluents from two wastewater plants from SABESP, such as ETE Barueri conventional activated sludge and ETE Ribeirão Pires anaerobic treatment with UASB reactors. Jar-Test tests were done in laboratory and the coagulant used was the ferric chloride. The results show that the coagulant dosage, in both effluents studied, results in a total phosphorus removal to values lower than 1 mg/L. The necessary coagulant dosages were 80 mg/L to ETE Barueri and 60 mg/L to ETE Ribeirão Pires. The organic matter removal also was obtained and values of BOD lower than 10 mg/L are obtained to lower dosages than the necessary dosage to phosphorus removal. The necessary coagulant dosage to BOD removal to values lower than 10 mg/L was 40 mg/L. The sludge production is the main problem when chemical precipitation is used, the amount of sludge produced is significant and must be taken into consideration in the system project of treatment and final disposal. Increases in the sludge production were around 113% to ETE Barueri and 51% to ETE Ribeirão Pires when the necessary coagulants dosages were considered to total phosphorus removal to values lower than 1 mg/L.

BODIPYs são compostos fluorescentes que possuem uma ampla gama de aplicações tecnológicas em diversas áreas do conhecimento, recebendo considerável destaque na literatura, tanto do ponto de vista fotoquímico, quanto sintético. Entretanto, a reatividade química desses fluorórofos ainda não é totalmente compreendida. Neste sentido, neste trabalho utilizou-se a química de sais de diazônio aplicada aos BODIPYs, explorando uma série de perspectivas para diversificação estrutural desses fluoróforos. Como estratégias para a obtenção do BODIPY funcionalizado com o grupo diazo foram testados três diferentes métodos, que envolvem a utilização de NOBF4, NaNO2/HCl e NaNO2/HBF4. O método que envolve a utilização de NOBF4 não levou a obtenção do composto diazotado, no entanto, resultou na obtenção de compostos nitrosilados. Quando utilizado NaNO2/HCl, o composto diazotado foi obtido in situ, seguido pela reação de acoplamento diazóico. Com o método que envolve o uso de NaNO2/HBF4 foi possível obter melhores rendimentos para as reações de acoplamento diazóico, e abriu a possibilidade de novas explorações química dos sais de diazônio-BODIPY / BODIPYs are fluorescent compounds which have a wide range of technological applications in different areas of knowledge. They have remarkable presence in the literature because of their synthetic and photochemical properties. However, the chemical reactivity of these fluorophores are not fully known. Considering this, our study applied the diazonium salts chemistry to BODIPYs aiming to explore the structure diversification of these fluorophores. Three different methods were used to obtain the diazo derivatives of BODIPYs: NOBF4, NaNO2/HCl and NaNO2/HBF4. The method using the NOBF4 instead of afford the diazotized compound as expected, a nitrosylated compound was obtained. When NaNO2/HCl was used, the diazotized compound was obtained in situ, followed by diazo coupling reaction. The best yields diazo coupling reactions were obtained when NaNO2/HBF4 was used. The reactions described in our work showed new possibilities of chemical tractability of BODIPY compounds.

Thesis submitted in fulfilment of the requirements for the degree Magister Technologiae: Chemistry in the Faculty of Applied Sciences at the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY 2014 / The solid state modification of a given active pharmaceutical ingredient is a desired way to alter its physicochemical properties, such as solubility or bioavailability. The solubilitymelting point relationship of the ensuing co-crystal or salt is not fully understood. In this thesis, a series of model co-crystals and pharmaceutical co-crystals and salts of baclofen were investigated. The model co-crystals were prepared from 4,4’-bipyridine (BIPY) and 1,2-bis(4-pyridyl)ethane (ETBIPY) used as host compounds which were combined with a series of carboxylic acids as co-formers, such as p-toluic acid (PTA), rac-phenylbutyric acid (racPBA), racemic and S-phenylsuccinic acid (racPSA and S-PSA, respectively). In the second part, six new multicomponent crystals of baclofen (BAC, (RS) 4-amino-3-(4- chlorophenyl)-butanoic acid), were prepared with mono- and dicarboxylic acids: two pharmaceutical co-crystals obtained with benzoic acid (BAC•BA) and p-toluic acid (BAC•PTA) and four pharmaceutical salts with 1-hydroxy-2-naphthoic acid, (BAC+)(HNA-), oxalic acid, 2(BAC+)(OA2-), maleic acid, (BAC+)(MA-) and p-toluene sulfonic acid, (BAC+)(PTSA-)•IPA. The compounds prepared were analysed by single crystal and powder X-ray diffractometry, differential scanning calorimetry and their solubility was measured in water and ethanol. From the analysis of the model co-crystals it was concluded that their aqueous solubility is inversely related to the melting point values and this can be explained by packing features. Also, the introduction of a chiral building block, compared to its racemic counterpart, is a valuable way to limit the formation of the intermolecular interactions in the new multicomponent crystal and thus decrease the efficiency of the packing which eventually leads to lower melting points and better solubility. The analysis of the baclofen crystals suggests that a strong, robust and predictable hydrogen bonding network with a combination of molecular building blocks which show acceptable molecular flexibility is a good recipe for successful co-crystal design.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2015. / Solvatomorphism of an active pharmaceutical ingredient (API) is one of the most studied areas in pharmaceutical science. Since APIs are exposed to solvents during many stages of their production, knowledge of the consequences from such exposure is essential. Salt formation has been known to improve some physicochemical properties of an API. Amongst these properties, API solubility is one of the most important characteristics as their use in the market is determined by this feature. Research presented here investigated the solvates and salts of mefenamic acid (MA) and tolfenamic acid (TFA); both representing fenamic acids belonging to a class of non-steroidal anti-inflammatory drugs (NSAIDs). Solvates were obtained by reactions of TFA and MA with the solvents 2-picoline, 3-picoline, 4-picoline, 3-bromopyridine and 3-chloropyridine. A solvate polymorph of MA and 2-picoline was isolated. The salts were obtained by using diethanolamine, ethylenediamine, 1-methylpiperazine, and triethylamine in combination with the fenamic acids. Morpholine formed a salt with TFA, but not with MA. Instead a zwitterionic form of MA was synthesised when the latter was mixed with morpholine. The resulting compounds were characterised and their crystal structures analysed. It was found that the conformation of the acids in the solvate and the salt compounds differed. Moreover, within the solvates, the conformation of the fenamate backbone varied depending on the acid and the solvent used for crystallisation. Although similar solvents were utilized, the structural packing arrangements of TFA solvates were very different from the arrangements associated with MA. The thermal analyses of the salts/solvates were determined by using both thermogravimetry and differential scanning calorimetry. The compounds were further investigated after manual grinding and the preparation of slurries. These preparation methods were successful for most compounds but not for MA•2PIC and (MA-)(EDM+). Instead, the recrystallization, grinding and slurry investigations of MA•2PIC yielded a polymorph of this particular solvate. In the case of (MA-)(EDM+), the PXRD results obtained from both the pulverised and slurry samples were completely different from one another and also from those determined for the starting materials. Generally, the desolvation studies of the MA salts and solvates produced the same crystal form as occurred in the starting material. The exception was (MA-)(TA+) wherein desolvation produced a mixture of two polymorphs of MA.

Incorporation of heteroaromatic rings (pyridyl, pyrazinyl, pyrimidyl and thienyl) in the silver-ethynide supramolecular synthon led to a series of silver(I) double salts of various heterocyclic ethynide ligands. Through variation of the relative orientations between the ethynide moiety and heteroatom as well as between heteroatoms, different coordination networks were generated. / Synthetic and structural studies were carried out on a series of silver(I) complexes of phenylethynide and phenylethynide derivatives with alkyl substituents (methyl, tert- butyl, trifluoromethyl) at variable positions (p-, m-, o-) on the aromatic ring. The invariable appearance of the mu4- and mu5-ligation modes of the ethynide moiety in ten silver(I) complexes reaffirms the general utility of the silver-arylethynide supramolecular synthon Ar-C≡C⊃Agn( n = 4, 5) in coordination network assembly. / Systematic investigation on silver(I) tert-butylethynide complexes resulted in the establishment of the general utility of the silver-ethynide supramolecular synthon with an alkyl tail. Upon the addition of nitrile ligands from CH3CN, CH3CH2CN to (CH3) 3CCN, adjacent silver ethynide moieties tBu-C≡C⊃Ag 5 approach closer to each other, and the resulting crystal structure transforms from a 2-D hydrogen bonding network, through a 2-D network held by hydrogen bonding and coordination, to a 2-D coordination network. Employment of the multidentate dicarboxylate ligand O2CCF2CF 2CO2 and the dinitrile ligand NC(CH2)4CN led to the formation of higher-dimensional networks. / The above-mentioned structural studies of silver-ethynide complexes of aromatic or heteroaromatic ligands indicate that pi-pi stacking plays a pivotal role in the self-assembly of corresponding silver-ethynide synthons. Investigation of the silver(I) complexes of phenylethynide and its derivatives with different substituents (methyl, tert- butyl) in variable positions (o-, m-, p-) on the aromatic ring shows the relative position and the bulk of substituents both affect the pi-pi stacking between adjacent phenyl rings. Furthermore, a comparative study of pi-pi stacking in the nitrate complexes Ag2(m-C≡CC 6H4C≡C)] · 5AgNO3 · 3H 2O (38), [(3-AgC≡C)-py] · 3AgNO3 (45), 2[(2-AgC≡C)-pyraz] · 6AgNO3 3H 2O (50) and 2[2,3-(AgC≡C)2-thienyl] · 10AgNO3 (56) suggests that the pi-electron deficiency of the aromatic ring also weakens this non-covalent interaction. (Abstract shortened by UMI.) / The ensuing study of silver(I) phenylenediethynide complexes led to the recognition of another kind of supramolecular synthon, Agn⊂ C2---R---C2⊃Agn (R= p-, m-, o-C6H4; n = 4, 5). / The reaction of Li-C≡C-Ca≡C-Li (generated in situ from hexachloro-1,3-butadiene and nBuLi) with AgNO3 led to the generation of a new silver carbide, silver 1,3-butadiynediide (Ag2C4). A series of fifteen double and multiple salts of Ag2C4 were synthesized by dissolving this polymeric starting material Ag2C4 in a concentrated aqueous solution of soluble silver salts (e.g. AgNO3, AgCF 3CO2, AgC2F5CO2). The silver-ethynide interaction may be conceived as a new kind of supramolecular synthon for the construction of 1-D, 2-D and 3-D coordination polymers. The terminal silver-ethynide interactions that are assigned in diverse configurations can be conveniently classified into three types: sigma, pi and mixed (sigma,pi), and tuned by variation of ancillary anionic ligands. In addition, the controlled hydrolysis of hexafluorophosphate led to the generation of the second silver quadruple salt Ag2C4 · 4AgNO3 · AgPF 2O2 · Ag3PO4 (4). The (F)2(H2O)18 fluoride-water tape in Ag 2C4 · 2AgF · 10AgC2F5CO 2 · CH3CN · 12H2O (10) and the (C4)3 Ag18 aggregate in 3Ag 2C4 · 12AgC2F5CO2 · 5[BzMe3N)C2F5CO2] · 4H 2O (15) are both unprecedented among silver(I)complexes. / This thesis describes our effort to explore, develop and utilize the silver-ethynide interaction in new kinds of metal-ligand supramolecular synthons for the construction of silver(I) coordination networks. / Zhao, Liang. / Adviser: Thomas C. W. Mak. / Includes supplementary digital materials. / Source: Dissertation Abstracts International, Volume: 69-02, Section: B, page: 1011. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 208-228). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Phang Tsui-Hung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 146-162). / Abstracts in English and Chinese. / Thesis committee --- p.i / Statement --- p.ii / Abstract --- p.iii / Acknowledgement --- p.vi / Abbreviations --- p.viii / Table of contents --- p.xii / List of figures --- p.xviii / List of tables --- p.xx / Chapter 1. --- Literature Review --- p.1 / Chapter 1.1 --- Salinity as a global problem --- p.1 / Chapter 1.2 --- Formation of saline soil --- p.1 / Chapter 1.3 --- Urgent need to reclaim saline lands --- p.2 / Chapter 1.4 --- Cellular routes for Na+ uptake --- p.2 / Chapter 1.4.1 --- Carriers involved in K+ and Na+ uptake --- p.2 / Chapter 1.4.2 --- Channels involved in K+ and Na+ uptake --- p.4 / Chapter 1.5 --- Adverse effects of high salinity --- p.5 / Chapter 1.5.1 --- Hyperosmotic stress --- p.5 / Chapter 1.5.2 --- Ionic stress --- p.6 / Chapter 1.5.2.1 --- Deficiency of K+ --- p.6 / Chapter 1.5.2.2 --- Perturbation of calcium balance --- p.7 / Chapter 1.5.3 --- Toxicity of specific ions --- p.7 / Chapter 1.5.4 --- Oxidative stress --- p.10 / Chapter 1.6 --- Mechanisms of salt stress adaptation in plants --- p.11 / Chapter 1.6.1. --- Maintenance of ion homeostasis --- p.12 / Chapter 1.6.1.1 --- Regulation of cytosolic Na+ concentration --- p.12 / Chapter 1.6.1.2 --- SOS signal transduction pathway --- p.15 / Chapter 1.6.2 --- Dehydration stress adaptation --- p.17 / Chapter 1.6.2.1 --- Aquaporins ´ؤ water channel proteins --- p.17 / Chapter 1.6.2.2 --- Osmotic adjustment --- p.20 / Chapter 1.6.2.2.1 --- Genetic engineering of glycinebetaine biosynthesis --- p.23 / Chapter 1.6.2.2.2 --- Genetic engineering of mannitol biosynthesis --- p.27 / Chapter 1.6.3 --- Morphological and structural adaptation --- p.28 / Chapter 1.6.4 --- Restoration of oxidative balance --- p.29 / Chapter 1.6.5 --- Other metabolic adaptation --- p.31 / Chapter 1.6.5.1 --- Induction of Crassulacean acid (CAM) metabolism --- p.34 / Chapter 1.6.5.2 --- Coenzyme A biosynthesis --- p.34 / Chapter 1.7 --- Soybean as a target for studying salt tolerance --- p.36 / Chapter 1.7.1 --- Economical importance of soybean --- p.36 / Chapter 1.7.2 --- Reasons for studying salt stress physiology in soybeans --- p.38 / Chapter 1.7.3 --- Salt tolerant soybean in China --- p.39 / Chapter 1.7.4 --- Exploring salt tolerant crops by genetic engineering --- p.41 / Chapter 1.8 --- Significance of this project --- p.47 / Chapter 2. --- Materials and methods --- p.48 / Chapter 2.1 --- Materials --- p.48 / Chapter 2.1.1 --- Plant materials used --- p.48 / Chapter 2.1.2 --- Bacteria strains and plasmid vectors --- p.48 / Chapter 2.1.3 --- Growth media for soybean --- p.48 / Chapter 2.1.4 --- Equipment and facilities used --- p.48 / Chapter 2.1.5 --- Primers used --- p.48 / Chapter 2.1.6 --- Chemicals and reagents used --- p.49 / Chapter 2.1.7 --- Solutions used --- p.49 / Chapter 2.1.8 --- Commercial kits used --- p.49 / Chapter 2.1.9 --- Growth and treatment condition --- p.49 / Chapter 2.1.9.1 --- Characterization of salt tolerance of Wenfeng7 --- p.49 / Chapter 2.1.9.2 --- Samples for subtractive library preparations --- p.50 / Chapter 2.1.9.3 --- Samples for slot blot and northern blot analyses --- p.50 / Chapter 2.1.9.4 --- Samples for gene expression pattern analysis --- p.50 / Chapter 2.2. --- Methods --- p.52 / Chapter 2.2.1 --- Total RNA extraction --- p.52 / Chapter 2.2.2 --- Construction of subtractive libraries --- p.53 / Chapter 2.2.3 --- Cloning of salt-stress inducible genes --- p.53 / Chapter 2.2.3.1 --- Preparation of pBluescript II KS(+) T-vector for cloning --- p.53 / Chapter 2.2.3.2 --- Ligation of candidate DNA fragments with T-vector --- p.53 / Chapter 2.2.3.3 --- Transformation --- p.54 / Chapter 2.2.3.4 --- PCR screening --- p.54 / Chapter 2.2.4 --- Preparation of recombinant plasmid for sequencing --- p.55 / Chapter 2.2.5 --- Sequencing of differentially expressed genes --- p.55 / Chapter 2.2.6 --- Homology search of differentially expressed genes --- p.56 / Chapter 2.2.7 --- Expression pattern analysis --- p.56 / Chapter 2.2.7.1 --- Preparation of single-stranded DIG-labeled PCR probes --- p.56 / Chapter 2.2.7.2 --- Preparation of cRNA DIG-labeled probes --- p.57 / Chapter 2.2.7.3 --- Testing the concentration of DIG-labeled probes --- p.58 / Chapter 2.2.7.4 --- Slot blot --- p.58 / Chapter 2.2.7.5 --- Northern blot --- p.59 / Chapter 2.2.7.6 --- Hybridization --- p.60 / Chapter 2.2.7.7 --- Stringency washed --- p.60 / Chapter 2.2.7.8 --- Chemiluminescent detection --- p.60 / Chapter 3. --- Results --- p.61 / Chapter 3.1 --- Characterization of salt tolerance of Wenfeng7 --- p.61 / Chapter 3.2 --- Identification of salt-stress induced genes from Wenfeng7 --- p.70 / Chapter 3.2.1 --- Screening subtractive libraries of Wenfeng 7 for salt inducible genes --- p.70 / Chapter 3.2.1.1 --- Results of homology search for salt inducible genes --- p.71 / Chapter 3.2.1.2 --- Northern blot showing the salt inducibility of selected clones --- p.72 / Chapter 3.3 --- Genes expression pattern of selected salt inducible genes --- p.104 / Chapter 3.3.1 --- Expression of genes related to dehydration adjustment --- p.104 / Chapter 3.3.1.1 --- Dehydration responsive protein RD22 (Clone no.: HML806) --- p.104 / Chapter 3.3.1.2 --- Beta-amylase (Clone no.: HML767) --- p.104 / Chapter 3.3.2 --- Expression of genes related to structural modification --- p.105 / Chapter 3.3.3 --- Expression of genes related to metabolic adaptation --- p.105 / Chapter 3.3.3.1 --- Subgroup 1: Gene related to protein synthesis --- p.105 / Chapter 3.3.3.1.1 --- Translational initiation factor nsp45 (Clone no.: HML1042) --- p.105 / Chapter 3.3.3.1.2 --- Seed maturation protein PM37 (Clone no.: HML931) --- p.106 / Chapter 3.3.3.2 --- Subgroup 2: Genes related to phosphate metabolism (Clone no.: HML1000) --- p.107 / Chapter 3.3.3.3 --- Subgroup 3: Genes related to storage and mobilization of nutrient resources --- p.107 / Chapter 3.3.3.3.1 --- Vegetative storage protein A (Clone no.: HML762) --- p.107 / Chapter 3.3.3.3.2 --- Cysteine proteinase (Clone no.: HML928) --- p.107 / Chapter 3.3.3.4 --- Subgroup 4: Genes related to senescence --- p.109 / Chapter 3.3.4 --- Expression of genes encoding novel protein (Clone no.: HML782) --- p.109 / Chapter 4. --- Discussion --- p.125 / Chapter 4.1 --- Evaluation of salt tolerance of Wenfeng7 --- p.125 / Chapter 4.2 --- Isolation of salt inducible genes in Wenfeng7 --- p.127 / Chapter 4.2.1 --- Genes associated with dehydration adaptation --- p.129 / Chapter 4.2.1.1 --- Dehydration responsive protein RD22 --- p.129 / Chapter 4.2.1.2 --- Beta-amylase --- p.130 / Chapter 4.2.2 --- Genes associated with structural adaptation --- p.132 / Chapter 4.2.3 --- Genes associated with metabolic adaptation --- p.133 / Chapter 4.2.3.1 --- Subgroup 1: Genes related to protein synthesis --- p.133 / Chapter 4.2.3.2 --- Subgroup 2: Genes related to phosphate metabolism --- p.137 / Chapter 4.2.3.3 --- Subgroup 3: Genes related to storage and mobilization of nutrient resources --- p.138 / Chapter 4.2.3.4 --- Subgroup 4: Genes related to senescence --- p.140 / Chapter 4.2.4 --- Novel genes --- p.142 / Chapter 4.3 --- Brief summary --- p.142 / Chapter 5. --- Conclusion and perspectives --- p.144 / References --- p.146 / Appendix I: Screening for salt tolerant soybeans --- p.163 / Appendix II: Major equipment and facilities used --- p.165 / Appendix III: Major chemicals and reagents used in this research --- p.166 / Appendix IV: Major common solutions used in this research --- p.168 / Appendix V: Commercial kits used in this research --- p.170

Hu, Ting. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 185-198). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

本論文對炔銀化合物提出系統性的合成和結構硏究，使用一種新型的多核屬的超分子合成子，從而建構出一系配位元網絡。 / 我們開發出同的結晶技術，在PhC≡C⊃Agn (n = 3, 4, 5)超分子合成子，通過加入同銀鹽，從而相對地獲得獲得銀鏈4AgC≡CPh・10AgCF₃CO₂・8DMSO (4)，層銀銀平面AgC≡CPh・AgNO₃ (1) 和2AgC≡CPh・AgNO₃ (2)，粗銀柱5AgC≡CPh・AgNO₃AgCF₃SO₃・2DMSO (5)，陽子銀柱[Ag₅(PhC≡C)₄(DMSO)₂]X (X = ClO₄, BF₄, PF₆, AsF₆ and SbF₆) (3)。 / 上述結果鼓我們展開進一步的硏究，通過改變芳香環上取代基的性質或位置 (F, Cl, Br, I, Me, C(=O)CH₃, NO₂ 和 C≡N) 產出同的銀結構，如鏈，柱，帶，層，三維多孔配位聚合物，以及多面體銀柱。如，化合物[(NO₃)@Ag₁₅(C≡CC₆H₄F-2)₁₀](NO₃)₄ (15)內有一個硝酸子作為模板所組成的十五核橄欖形銀簇多面體。此 Ag₁₅簇可接在一起，形成一條銀鏈。個硝酸子被包裏在一個 Ag₂₆花生雙中，花生銀雙繫在一起並形成一條多面體銀柱[(NO₃)₂@Ag₂₆(C≡CC₅H₄Me-2)₁₆](NO₃)₈ (23)。 / 在炔銀超分子合成子中，銀烯基和銀氰基相互作用發揮重要作用生成二維有機銀網絡AgC≡CCH₂OC₆H₄(CH=CH₂-2) · 6AgCF₃CO₂ · 3H₂O (31) 和2AgC≡CC₆H₄(C≡N-4) · 4AgO₂CCF3 · 2DMSO · H₂O (36)。 / 多環芳烴(PAHs)中的 π 電子體系具有鍵合屬子的能。此陽子與 π 電子間的相互作用提供一個潛在有效的做法去建新型固態結構。我們的構思是硏究 π-π 堆積和銀雜環作用，在RC≡C⊃Agn (n = 4, 5; R = 萘基或喹啉基) 超分子合成子建設配位聚合物。在(C₁₀H₇C≡C-1)Ag · 3AgO₂CCF₃ · 3H₂O (38) 和 (C₁₀H₇C≡C-2)Ag · 3AgO₂CCF₃ · 2H₂O · MeCN (39) 中，Ag-π 作用成功引進在炔銀超分子合成子系統。分子間的 π-π 堆積作用有助於炔銀化合物的超分子合成子組裝 Ag(1-NC₉H₆C≡C-2) · 3AgO₂CCF₃ · 3H₂O (44) 和 Ag(1-NC₉H₆C≡C-4) · 3AgO₂CCF₃ · 2H₂O (47)。 / 傳統上，陰子模板是合成高核密堆積銀簇合物的簡方法。銀簇合物的核密堆積可以通過調整陰子模板的大小和使用同炔基配體。在使用巨型多酸(POMs)陰子，Mo₆O₂₂⁸⁻，形成一個龐大的十核炔銀簇合物後，我們硏究出另一種方法合成高核密堆積銀簇合物。一個形十二面體十四核炔銀簇合物通過在溶液中的重新組裝過程產生出三十八核炔銀簇合物，把在小銀簇合物中的氯模板轉化為偽八面體Cl₆Ag₈核心的巨型簇合物 Ag₃₈C₁[₆(tBuC≡C)₂₀(ClO₄)₁₂ · Et₂O (48) 和Ag₃₈C₁₆(chxC≡C)₂₀(ClO₄)₁₂ · 1.5Et₂O (49). / This thesis presents a systematic synthetic and structural study of silver(I) ethynide complexes employing a new kind of polynuclear metal-ligand supramolecular synthon for the construction of silver(I) coordination networks. / We have developed different crystallization techniques in the supramolecular assembly of the Ph-C≡C⊃Ag[subscript n] (n = 3, 4, 5) metal-ligand synthon and various anions to obtain an infinite silver(I) chain in 4AgC≡CPh10AgCF₃CO₂・8DMSO (4), silver(I) layers in 2AgC≡CPh・AgNO₃(2) and AgC≡CPh・AgNO₃ (1), a thick silver(I) column in 5AgC≡CPh・AgNO₃・AgCF₃SO₃・2DMSO (5), and cationic silver(I) columns in [Ag₅(PhC≡C)₄(DMSO)₂]X (X = ClO₄, BF₄, PF₆, AsF₆ and SbF₆) (3). / The above results encouraged us to carry out further investigation through variation of the nature or position of substituents (F, Cl, Br, I, Me, C(=O)CH₃, NO₂ and C≡N) on the aromatic ring to yield silver(I) chain, column, ribbon, layer, and 3D porous coordination polymers, as well as a polyhedral silver(I) column. For example, an oliveshaped Ag₁₅ core exists in [(NO₃)@Ag₁₅(C≡CC₆H₄F-2)₁₀](NO₃)₄ (15), in which the encapsulated nitrate ion acts as a template for the formation of the Ag₁₅ cluster. Such Ag₁₅ clusters are then joined together to form a polymeric silver(I) chain. Peanut-shaped silver(I) double cages, each formed from two nitrate ions encapsulated within a Ag₂₆ cage, are linked together to form a polyhedral silver(I) chain in [(NO₃)₂@Ag₂₆(C≡CC₅H₄Me-2)₁₆](NO₃)₈ (23). / The silver(I)-ethynide supramolecular synthon participating in silver(I)vinyl and silver(I)cyano interactions plays an important role to generate 2-D silver-organic networks in AgC≡CCH₂OC₆H₄(CH=CH₂-2) · 6AgCF₃CO₂ · 3H₂O (31) and 2AgC≡CC₆H₄(C≡N-4) · 4AgO₂CCF3 · 2DMSO · H₂O (36). / The π-electron system of polycyclic aromatic hydrocarbons (PAHs) is known to be capable of bonding to metal ions. The exploitation of such cation-π interactions provides a potentially fruitful approach to building novel solid-state architectures. Our conceived idea is to investigate the π-π stacking and silver(I)-heteroaromatic interactions for the construction of coordination polymers using the R-C≡C⊃Ag[subscript n] (n = 4, 5; R = naphthalenylethynide or quinolinylethynide) supramolecular synthon. In the compounds (C₁₀H₇C≡C-1)Ag · 3AgO₂CCF₃ · 3H₂O (38) and (C₁₀H₇C≡C-2)Ag · 3AgO₂CCF₃ · 2H₂O · MeCN (39), silver-π interaction has been successfully introduced into silver(I)ethynide systems. Intermolecular π-π interaction contributes to the assembly of supramolecular synthons in compounds Ag(1-NC₉H₆C≡C-2) · 3AgO₂CCF₃ · 3H₂O (44) and Ag(1-NC₉H₆C≡C-4) · 3AgO₂CCF₃ · 2H₂O (47). / Traditionally, anion templates are used in a facile approach for the synthesis of high-nuclearity silver(I) clusters. The cluster nuclearity can be controlled by adjusting the size of the templating anions and by using different alkynyl ligands. After using the giant polyoxometalates (POMs) anion, Mo₆O₂₂⁸⁻, to form a large Ag₆₀ alkynyl cluster, we have developed another approach to synthesize high-nuclearity silver(I) clusters. Generation of a Ag₃₈ ethynide cluster from a rhombic dodecahedral Ag₁₄ ethynide cluster as precursor occurs in solution via a re-assembly process that involves transformation of the encapsulated chloride template in the small cluster into a pseudo-Oh Cl6Ag8 core in the giant cluster complexes Ag₃₈C₁₆([superscript t]BuC≡C)₂₀(ClO₄)₁₂ · Et₂O (48) and Ag₃₈C₁₆(chxC≡C)₂₀(ClO₄)₁₂ · 1.5Et₂O (49). / 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. / Cheng, Ping Shing. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 216-225). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Chapter Acknowledgment --- p.i / Chapter Abstract --- p.ii / Chapter Table of Contents --- p.vi / Chapter Index of Compounds --- p.viii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Coordination Polymers and Supramolecular Architectures --- p.1 / Chapter 1.1.1 --- Influence of Metal Cations --- p.2 / Chapter 1.1.2 --- Influence of Spacer Ligands --- p.3 / Chapter 1.1.3 --- Influence of Counter Anions --- p.4 / Chapter 1.1.4 --- Influence of Crystallization Techniques --- p.6 / Chapter 1.2 --- Argentophilic Interaction --- p.7 / Chapter 1.2.1 --- Multinuclear Silver-Ethynide Aggregates and Discrete Molecules --- p.9 / Chapter 1.2.1.1 --- Silver(I)-Ethynide Aggregates to Multi-dimensional Structures --- p.10 / Chapter 1.2.1.2 --- High-Nuclearity Homo- and Hetero-d¹° Metal Alkynyl Clusters --- p.13 / Chapter 1.2.2 --- Argentophilic chain and column --- p.15 / Chapter 1.2.3 --- Argentophilic layer --- p.18 / Chapter 1.3 --- Supramolecular Synthons in Crystal Engineering --- p.20 / Chapter 1.3.1 --- Coordination Chemistry of silveralkynyl complexes --- p.22 / Chapter 1.3.2 --- Coordination Chemistry of silveralkene complexes --- p.25 / Chapter 1.3.3 --- Coordination Chemistry of silveraromatic complexes --- p.26 / Chapter 1.4 --- Research strategy and Plan --- p.29 / Chapter Chapter 2 --- Argentophilic Infinite Chain, Column and Layer Structures Assembled with the Multinuclear Silver(I)Phenylethynide Supramolecular Synthon Syntheses of Silver(I)- Ethynide Complexes --- p.32 / Discussion --- p.52 / Conclusion --- p.55 / Chapter Chapter 3 --- Assembly of Multinuclear Supramolecular Synthon X-C₆H₄-C≡C⊃Ag[subscript n] (n = 3, 4; X = F, Cl, Br, I) Incorporating Isomeric Halophenylethynides and Silver Nitrate --- p.57 / Discussion --- p.84 / Summary --- p.86 / Chapter Chapter 4 --- Supramolecular Assembly of Silver(I) Alkyl and Aryl Ethynide with Silver(I) Nitrate in the Formation of Argentophilic Layers --- p.87 / Discussion --- p.121 / Summary --- p.122 / Chapter Chapter 5 --- Assembly of Organometallic Networks with Bifunctional Multinuclear Silver(I)-Ethynide Supramolecular Synthons and Silver Trifluoroacetate --- p.123 / Discussion --- p.149 / Summary --- p.151 / Chapter Chapter 6 --- Network Assembly with Multinuclear Silver(I) Naphthalenyl and Quinolinyl Ethynide Supramolecular Synthons R-C≡C⊃Ag[subscript n] (n = 4, 5) --- p.152 / Discussion --- p.179 / Summary --- p.180 / Chapter Chapter 7 --- Enlargement of Globular Silver Ethynide Cluster via Core Transformation and Re-Assembly --- p.181 / Discussion --- p.187 / Conclusion --- p.189 / Chapter Chapter 8 --- Experimental Section --- p.190 / Chapter 8.1 --- General --- p.190 / Chapter 8.2 --- Preparation of polymeric silver(I) ethynide complexes --- p.190 / Chapter 8.3 --- Preparation of complexes 1-49 --- p.196 / Chapter 8.4 --- X-Ray Crystallographic Analysis --- p.215 / References --- p.216 / Chapter Appendix I --- Publication Based on Research Findings --- p.226 / Chapter Appendix II --- Crystal Data --- p.228 / Chapter Appendix III --- Atomic Coordinates, Thermal Parameters, Bonds Lengths and Bond Angle (Available as an Electronic File) --- p.239

In recognition of the shortcomings inherent to the operating temperature ranges of current fuel cell systems, namely the“temperature gap" between 200C and 600C, an effort to develop an intermediate-temperature molten-salt electrolyte fuel cell (IT-MSFC) was undertaken. In this type of fuel cell, the molten salt electrolyte is supported on a porous support, in a planar or other geometry similar to that used in existing fuel cell technologies, such as phosphoric acid fuel cell (PAFC) and molten carbonate fuel cells (MCFC). Such a fuel cell using a molten hydroxide electrolyte and Pt/C catalyst was constructed and tested using hydrogen and oxygen as fuel. The performance was comparable to that which has been obtained from PEM fuel cells at the low end of the voltage range, reaching 950ma/cm2 at 0.4 V in the highest performing test. Performance was superior to PEM fuel cells at the high end of the voltage range, due to the more favorable kinetics at the higher temperatures, with an open circuit voltage (OCV) of 1.0 V with a linear performance curve between 1.0 V and 0.6 V, which is characteristic of fuel cells with low kinetic overpotentials. Longevity of the fuel cell was very poor, however a number of experiments were undertaken to improve it, enabling extension of operating life from 5 minutes to 30 minutes, which is still far too low for practical use. The key problem was identified as electrolyte retention by the support matrix and possible degradation of the gas diffusion layer and catalyst. Experiments were also conducted using methanol vapor as fuel, and it was found to provide performance close to that recorded with pure hydrogen. Experiments were also conducted using several alternative molten salts, including nitrate and chloride eutectics. Combinations of nitrates with hydroxides added to act as a charge carrier produced a working fuel cell, however performance was greatly reduced. Though preliminary, the work described herein demonstrates the great potential of IT-MSFC, and outlines the work needed to make this type of fuel cell practical.