To see the other types of publications on this topic, follow the link: Copper(III).
Dissertations / Theses on the topic 'Copper(III)'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the top 50 dissertations / theses for your research on the topic 'Copper(III).'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Browse dissertations / theses on a wide variety of disciplines and organise your bibliography correctly.
1
Gronow, Martin. "Separation of rhodium(III) from copper(II) in acidic chloride media." Thesis, University of Reading, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.303893.
Full text
2
Xie, Zheng. "New luminescent organometallic complexes of platinum (II), iridium (III), copper (I) and gold (III) and their optoelectronic applications." HKBU Institutional Repository, 2013. http://repository.hkbu.edu.hk/etd_ra/1520.
Full text
3
Spicer, M. D. "Higher oxidation state complexes of group Vb and VIb donor atom ligands : Compounds with cobalt(III) and copper(III)." Thesis, University of Southampton, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.382971.
Full text
4
Ireland, David Rey. "Copper(II) and Ruthenium(II) Complexes from Polydentate Ligands." University of Dayton / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1523008522727672.
Full text
5
Casitas, Montero Alícia. "Reactivity of well-defined organometallic copper(III) complexes in carbon-heteroatom bond forming reactions." Doctoral thesis, Universitat de Girona, 2012. http://hdl.handle.net/10803/81985.
Full textAbstract:
This thesis is focused on the unexplored field of organometallic copper(III) chemistry. Arylcopper(III) complexes have been proposed as key intermediates in Ullmann condensation reactions that consist in the coupling of aryl halides and heteroatom nucleophiles catalyzed by copper. The study of the reactivity of well-defined arylcopper(III) complexes may provide a better understanding of the mechanism of Ullmann condensation reactions, which is still under intense debate. In this doctoral dissertation we study the feasibility of well-defined arylcopper(III) complexes, which are stabilized within macrocyclic ligands, to participate in C-heteroatom bond forming reactions. We develop copper-catalyzed C-N and C-O bond forming reactions, as well halide exchange reactions, including fluorinations, based on Cu(I)/Cu(III) catalytic cycle within model aryl halide substrates. We uncover the fundamental understanding of the two-electron redox steps, oxidative addition and reductive elimination, at copper.Aquesta tesi es centra en el camp de la química organometàl•lica del coure(III) que roman sense explorar. Els complexos arilcoure(III) s'han proposat com a intermedis clau en les reaccions de condensació Ullmann que consisteixen en l'acoblament d'halurs d'arils i nucleòfils basats en heteroàtoms catalitzades amb coure. L'estudi de la reactivitat de complexos arilcoure(III) ben definits pot proporcionar una millor comprensió del mecanisme de les reaccions de condensació Ullmann, el qual es troba sota un intens debat. En aquesta tesi doctoral s'estudia la viabilitat del complexos arilcoure(III), estabilitzats en lligands macrocíclics, de participar en reaccions de formació d'enllaç carboni-heteroàtom. S'han desenvolupat reaccions de formació d'enllaç C-N i C-O així com reaccions d'intercanvi d'halurs, on s'inclouen fluoracions, catalitzades amb coure i basades en un cicle catalític Cu(I)/Cu(III) utilitzant substrats models d'halur d'aril. S'ha obtingut una comprensió fonamental de les etapes redox a dos electrons, addició oxidant i eliminació reductiva, en coure.
6
Altahan, Mohammed Abdulredha. "Cobalt(III), copper(II), and nickel(II) coordination compounds as cations in polyborate chemistry." Thesis, Bangor University, 2017. https://research.bangor.ac.uk/portal/en/theses/cobaltiii-copperii-and-nickelii-coordination-comppounds-as-cations-in-polyborate-chemistry(ba5f189b-2229-481f-9d8d-0bdce17903a8).html.
Full textAbstract:
This thesis describes the synthesis and characterization of a number of polyborate compounds containing transition metal complex cations; most of these compounds contain 6-membered B3O3 boroxole rings within their structures. A total of twenty-six transition metal complex polyborate salts are reported: one contains the triborate monoanion, [B3O3(OH)4]-, three contain the tetraborate dianion [B4O5(OH)4]2-, twelve contain the pentaborate anion, [B5O6(OH)4]-, three contain the hexaborate dianion, [B6O7(OH)6]2- and five contain heptaborate anions (three of which are [B7O9(OH)5]2-, and two are [B7O9(OH)6]3-). Additionally, two compounds contain two isolated polyborate anion species (octaborate dianion [B8O10(OH)6]2- with pentaborate anion [B5O6(OH)4]-, and triborate anion [B3O3(OH)4]- with [B5O6(OH)4]-). The crystal structures of fifteen salts containing these polyborate anions are reported: [Co(en)3][B5O6(OH)4][B8O10(OH)6]∙5H2O (6), [Co(NH3)6]2[B4O5(OH)4]3∙11H2O (9), s-fac-[Co(dien)2][B7O9(OH)6]∙9H2O (11), [Co(diNOsar)]2[B3O3(OH)4]Cl5∙4.75H2O (12), [Cu(en)2][B5O6(OH)4]2∙2H2O (20), [Cu(pn)2{B5O6(OH)4}][B5O6(OH)4]∙4H2O (22), [Cu(TMEDA){B6O7(OH)6}]∙6H2O (23), [Cu(dac)2(H2O)2][Cu(dac)2][B7O9(OH)5]2∙4H2O (24), [Cu(N,N-dmen)2(H2O)][B5O6(OH)4]2·3H2O (27), [Cu(N,N-dmen){B6O7(OH)6}]·4H2O (28), [Ni(en){B6O7(OH)6}(H2O)2]∙H2O (37), [Ni(AEN)][B5O6(OH)4]∙H2O (38), [Ni(dac)2(H2O-)2][Ni(dac)2][B7O9(OH)5]2∙4H2O (39), [Ni(hn)2][B5O6(OH)4]2 (40), and s-fac-[Ni(dien)2][B5O6(OH)4]2 (41). All the synthesized compounds reported were characterized using spectroscopic (IR, multi-element NMR) and analytical (melting point, elemental analysis, magnetic susceptibility, thermal analysis, powder X-ray diffraction) techniques. The solid-state structures of transition metal complex polyborate salts all display multiple cation-anion H-bond interactions and these undoubtedly play a major role in the energetics of engineering these structures. For example, in compound [Co(NH3)6]2[B4O5(OH)4]3∙11H2O (9), fourteen of the 18 amino hydrogen atoms of the [Co(NH3)6]3+ cation are involved in secondary coordination to anions via H-bonds. Two unique polyborate anions, [B8O10(OH)6)]2- and [B7O9(OH)6]3- have been prepared and characterized in [Co(en)3][B5O6(OH)4][B8O10(OH)6]∙5H2O (6) and s-fac-[Co(dien)2][B7O9(OH)6]∙9H2O (11), respectively. vii The reaction of transition metal complex cations with boric acid in different ratios produced polyborate compounds with different polyborate anions e.g. reaction of [Cu(en)2]2+ with boric acid in 1:10 and 1:5 ratios produce polyborate compounds with pentaborate(1-) and tetraborate(2-) anions, respectively. New polyborate anion structural architectures are identified in this thesis: (i) the pentaborate(1-) anion in [Cu(pn)2{B5O6(OH)4}][B5O6(OH)4]∙4H2O (22) acts as a monodentate ligand coordinated to the Cu(II) cation, (ii) the hexaborate(2-) anion in [Cu(TMEDA){B6O7(OH)6}]∙6H2O (23) and [Cu(N,N-dmen){B6O7(OH)6}]·4H2O (28) coordinates as a tridentate ligand with the Cu(II) cations, and (iii) the hexaborate(2-) anion in [Ni(en){B6O7(OH)6}(H2O)2]∙H2O (37) coordinates as a bidentate ligand with the Ni(II) cation. This is the first time that such coordination mode (i) and (iii) have been observed.
7
Blons, Charlie. "Complexes organométalliques d'or(III) et de cuivre(III) et leur réactivité vis-à-vis des substrats π." Thesis, Toulouse 3, 2018. http://www.theses.fr/2018TOU30248/document.
Full textAbstract:
Cette thèse porte sur la synthèse de composés d'Au(III) et de Cu(III) ainsi que sur l'étude de leur stabilité et de leur réactivité vis-à-vis de substrats p. Une approche conjointe expérimentale et théorique a été exploitée afin d'accéder à des complexes capables d'induire des processus d'insertion migratoire. Le premier chapitre aborde de manière globale la chimie organométallique de l'or et du cuivre sur le plan bibliographique. L'importance du degré d'oxydation +III est mis en évidence par la description des principaux exemples ayant contribué à la compréhension des processus associés à l'accès et la réactivité des complexes d'Au(III) et de Cu(III). Le second chapitre traite de la synthèse de deux complexes p-arènes d'Au(III) par insertion migratoire d'oléfines dans la liaison Au-C(sp)2 d'un composé (P,C) cyclométallé. Les interactions entre les systèmes aromatiques et l'or ont été mises en évidence par RMN, DFT et DRX pour un des complexes. Sur la base de cette réactivité, un processus d'arylation directe de l'éthylène a été mis en évidence. Le chapitre trois a pour objet la mise au point d'une réaction d'hydroarylation intermoléculaire d'alcynes catalysée par des complexes de type [(P,C)Au(III)(OAcF)2]. Ces derniers se sont avérés très actifs et robustes en présence d'acide trifluoroacétique. La réaction a pu être généralisée à un large panel de substrats et une étude comparative, notamment avec des complexes (N,C) cyclométallés, a mis en évidence la supériorité des complexes (P,C) pour l'hydroarylation des alcynes. Le quatrième chapitre expose la stratégie envisagée pour le développer d'un processus d'oligomérisation de l'éthylène catalysé par le cuivre. Une approche prédictive basée sur les calculs DFT a permis de mettre en évidence des insertions migratoires plus aisées dans les liaisons Cu(III)-C que dans les Cu(I)-C. Deux stratégies d'accès aux complexes de Cu(III) par addition oxydante de liaisons C-I sur des précurseurs de Cu(I) ont été évaluées théoriquement. Les calculs les plus favorables ont orienté le choix des modèles de ligands envisagés dans les chapitres cinq et six. Le cinquième chapitre aborde l'étude expérimentale associée à la première stratégie d'accès au Cu(III) : l'addition oxydante intramoléculaire dirigée par des ligands naphthylphosphine et naphthylamine peri-iodées. [...]The present work deals with the synthesis of Au(III) and Cu(III) compounds and the study of their stability and reactivity toward p substrates. An experimental and theoretical approach has been used in order to access complexes capable of undergoing migratory insertion processes. The first chapter delivers a bibliographic overview of the organometallic chemistry of gold and copper. The importance of the high oxidation state +III is highlighted by the description of important examples having contributed to the understanding of processes associated to the access and reactivity of Au(III) and Cu(III) complexes. The second chapter describes the synthesis of two p-arene Au(III) complexes by migratory insertion of olefins in the Au-C(sp)2 bond of a (P,C) cyclometallated complex. Interactions between the metallic center and the aromatic systems have been characterized by NMR, DFT and XRD for one of the complexes. Based on this insertion reactivity, a process of direct arylation of ethylene has been evidenced. The third chapter concerns the development of an intermolecular hydroarylation of alkynes process, catalyzed by [(P,C)Au(III)(OAcF)2] complexes. These have shown great activity and robustness in presence of trifluoroacetic acid. The reaction has been generalized to a broad substrate scope and a comparative study has been carried on, especially with (N,C) cyclometallated complexes, showing the superiority of (P,C) complexes for the hydroarylation of alkynes. The fourth chapter presents the envisioned strategy to develop a copper-catalyzed oligomerization of ethylene process. A predictive approach based on DFT calculations permitted to evidence easier migratory insertions in the Cu(III)-C bond than in the Cu(I)-C bond. Two strategies for the access to Cu(III) species have been theoretically evaluated. The most favourable calculations have oriented the choice of ligand models used in chapters five and six. The fifth chapter deals with the experimental study related to the first strategy of access to Cu(III) species: the directed intramolecular oxidative addition by peri-iodo napthylphosphine and naphthylamine ligands. [...]
8
Docherty, Paul Henry. "Diastereocontrolled synthesis of hetero- and carbocycles via manganese(III) and copper(II) : towards a novel prostaglandin total synthesis." Thesis, University of Oxford, 2008. http://ora.ox.ac.uk/objects/uuid:6ca5556a-3d2d-454a-abbd-0a3a269c5724.
Full textAbstract:
The prostaglandins are a unique family of natural products found in all mammalian life, including humans. Their biological significance is profound, and they are responsible for a vast array of bodily functions. This importance, coupled with their low concentration in vivo, has made them attractive targets for total chemical synthesis. The work herein describes synthetic efforts towards their synthesis using an oxidative radical cyclisation to construct the key [3.3.0]-bridged bicyclic lactone, from which the prostaglandin skeleton may be derived. Key to this was the development of manganese(III) acetate and copper(II) triflate as optimal reagents for this cyclisation of unsaturated malonate/malonic acid derivatives. To study this, several model substrates for this crucial cyclisation were synthesised, and their cyclisation analysed. Chapter 5 describes the design and synthesis of several model substrates containing malonate groups for the oxidative radical cyclisation. The results of the cyclisation with manganese(III) and various copper(II) salts influenced the design of the substrates, and led to the use of malonic acids as more effective substrates for the formation of [3.3.0]-bicyclic lactones. A catalytic process, in which atmospheric oxygen is the terminal oxidant was also developed. Chapter 6 describes the studies towards a total synthesis of the prostaglandin family. Two potential routes are followed, the first of which used a key asymmetric epoxidation to install asymmetry. A Suzuki coupling was used to deliver the desired diene required for the cyclisation substrate, which was successfully cyclised using manganese(III) acetate and copper(II) triflate, creating the desired [3.3.0]-bicyclic lactone in good yield and with excellent diastereomeric control. A second, shorter route to the same lactone was also developed, using a novel asymmetric deconjugative aldol condensation to establish asymmetry. Cyclisation of this analogous substrate was also successful, delivering the same lactone after olefin metathesis.
9
Goswami, Vandana Esther. "Small Molecule Activation of Copper and Iron Complexes with Bis(oxazoline) Ligands." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2016. http://hdl.handle.net/11858/00-1735-0000-0023-3F0E-B.
Full text
10
McGeorge, Barry. "Exploration of the mechanism of rhodium(III) co-precipitation with copper sulfide (at low rhodium concentrations) incorporating the cationic substitution reaction path." Master's thesis, University of Cape Town, 2007. http://hdl.handle.net/11427/5442.
Full textAbstract:
Includes abstract.Includes bibliographical references.
This study is a preliminary investigation into the mechanism and kinetics of Rh3+ coprecipitation with CuS upon aqueous thiosulphate addition to acidic base metal sulphate solutions, where Rh3+ concentration is two orders of magnitude lower than Cu2+, over 50 - 150 °C. The heterogeneous cationic substitution has been identified as a new precipitation path in metal sulfide co-precipitation, namely, the reaction between more soluble, co-precipitated metal sulphide (CuS) and the less soluble cation in solution (Rh3+), with the large KSP difference providing the chemical driving force.
11
Maraldi, Vitor Alexandre. "Preparo, caracterização e aplicação eletroanalítica de nanopartículas de pentacianonitrosilferrato(III) de cobre sobre a superfície de óxido de grafeno." Ilha Solteira, 2018. http://hdl.handle.net/11449/157120.
Full textAbstract:
Orientador: Devaney Ribeiro do CarmoResumo: Este trabalho apresenta a preparação do óxido de grafeno (OG) através do Método de Hummers Modificado e subsequente modificação química de sua superfície com nanopartículas de pentacianonitrosilferrato(III) de cobre (OGCuNP). Os materiais obtidos foram caracterizados por diferentes técnicas, tais como: Espectroscopia na Região do Infravermelho com Transformada de Fourier, Espectroscopia Raman, Espectroscopia de Fotoelétrons Excitados por Raios-X, Microscopia Eletrônica de Varredura, Microscopia Eletrônica de Transmissão e Difração de Raios-X. O OGCuNP foi caracterizado por Voltametria Cíclica, empregando um eletrodo de pasta de grafite. O voltamograma cíclico do OGCuNP exibiu dois pares redox bem definidos com potencial médio (Eθ’) de 0,27 V e 0,77 V, para o primeiro e segundo par redox, que foram atribuídos aos processos redox Cu(I)/Cu(II) e Cu(II)Fe(II)(CN)5NO/Cu(II)Fe(III)(CN)5NO, respectivamente. O eletrodo de pasta de grafite modificado com OGCuNP apresentou resposta eletrocatalítica à três substâncias, a saber: hidrazina, isoniazida e N-acetilcisteína. Para a eletro-oxidação catalítica da hidrazina, o eletrodo de pasta de grafite modificado com OGCuNP apresentou resposta linear com concentração em um intervalo de 1,0×10-5 a 5,0×10-3 mol L-1 de hidrazina, com limite de detecção de 1,58×10-6 mol L-1. O eletrodo modificado também exibiu atividade eletrocatalítica para isoniazida, nos picos anódicos I e II, apresentando limite de detecção de 6,93×10-5 mol L-1 e de 2,16×10-5... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: This work presents the prepare of graphene oxide (OG) by the Modified Hummers Method, besides the chemical modification of its surface with nanoparticles of copper pentacyanonitrosylferrate(III) (OGCuNP). The materials obtained were characterized by different techniques, such as: Fourier Transform Infrared Spectroscopy, Raman Spectroscopy, X-Ray Photoelectron Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microcopy and X-Ray Diffraction. The OGCuNP was characterize by the Cyclic Voltammetry technique, where the graphite paste electrode was used. The cyclic voltammogram of the OGCuNP exhibited two well-defined redox pairs with medium potential (Eθ’) 0,27 V and 0,77 V, for the first em second redox process, attributed to the redox processes of Cu(I)/Cu(II) and Cu(II)Fe(II)(CN)5NO/Cu(II)Fe(III)(CN)5NO, respectively. The graphite paste electrode modified with OGCuNP presented electrocatalytic response for three substances: hidrazine, isoniazide and N-acetylcysteine. For catalytic electro-oxidation of hidrazine, the grafite paste electrode modified with OGCuNP presented linear response in the concentration between 1,0×10-5 and 5,0×10-3 mol L-1 of hidrazine, with detection limit of 1,58×10-6 mol L-1. The modified electrode too exhibited electrocatalytic activity for isoniazide for the both anodic peaks I and II, and it presented detection limit of 6,93×10-5 mol L-1 and 2,16×10-5 mol L-1 in a concentration range of 6,0×10-5 to 6,0×10-3 mol L-1 and 6,0×10-4 to 7,0×... (Complete abstract click electronic access below)
Mestre
12
Ashie, Jennifer Bernice. "Study on Methods of Simultaneous Multi-Component Analysis." Digital Commons @ East Tennessee State University, 2008. https://dc.etsu.edu/etd/1989.
Full textAbstract:
Many new instrumentation and different instrumental techniques have been developed to deal with increasing complexity of samples encountered. Many researchers also have coupled these instrumental techniques with chemometric algorithms to assist in the quantitative analysis of multi-component samples in the hope of alleviating the need of tedious separation and cleanup procedures. These newer chemometric procedures tend to be complex and difficult to understand and implement and are successful under different circumstances and conditions. In this study, we start from the very simple beginning and examine the factors that can present difficulties with obtaining the correct results and observe how the system behaves so as to find a better and simpler chemometric procedure to perform mixture quantitative analysis. We have used simulated and actual experimental data obtained from a UV-VIS spectrophotometric measurement of metal complexes to conduct the study. Well understood and defined systems tend to give good results. The main obstacle has been, and still is, interferences in spectral information one gets from the measurement.
13
Oliveira, M?nica Rodrigues de. "Efici?ncia de extra??o de cobre e n?quel utilizando sistemas microemulsionados bif?sicos e trif?sicos." Universidade Federal do Rio Grande do Norte, 2014. http://repositorio.ufrn.br:8080/jspui/handle/123456789/17785.
Full textAbstract:
Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1
MonicaRO_TESE.pdf: 4155777 bytes, checksum: 6bff63b5cb0f37e64dfe6fcb144dae79 (MD5)
Previous issue date: 2014-01-23The environmental impact due to the improper disposal of metal-bearing industrial effluents imposes the need of wastewater treatment, since heavy metals are nonbiodegradable and hazardous substances that may cause undesirable effects to humans and the environment. The use of microemulsion systems for the extraction of metal ions from wastewaters is effective when it occurs in a Winsor II (WII) domain, where a microemulsion phase is in equilibrium with an aqueous phase in excess. However, the microemulsion phase formed in this system has a higher amount of active matter when compared to a WIII system (microemulsion in equilibrium with aqueous and oil phases both in excess). This was the reason to develop a comparative study to evaluate the efficiency of two-phases and three-phases microemulsion systems (WII and WIII) in the extraction of Cu+2 and Ni+2 from aqueous solutions. The systems were composed by: saponified coconut oil (SCO) as surfactant, n-Butanol as cosurfactant, kerosene as oil phase, and synthetic solutions of CuSO4.5H2O and NiSO4.6H2O, with 2 wt.% NaCl, as aqueous phase. Pseudoternary phase diagrams were obtained and the systems were characterized by using surface tension measurements, particle size determination and scanning electron microscopy (SEM). The concentrations of metal ions before and after extraction were determined by atomic absorption spectrometry. The extraction study of Cu+2 and Ni+2 in the WIII domain contributed to a better understanding of microemulsion extraction, elucidating the various behaviors presented in the literature for these systems. Furthermore, since WIII systems presented high extraction efficiencies, similar to the ones presented by Winsor II systems, they represented an economic and technological advantage in heavy metal extraction due to a small amount of surfactant and cosurfactant used in the process and also due to the formation of a reduced volume of aqueous phase, with high concentration of metal. Considering the reextraction process, it was observed that WIII system is more effective because it is performed in the oil phase, unlike reextraction in WII, which is performed in the aqueous phase. The presence of the metalsurfactant complex in the oil phase makes possible to regenerate only the surfactant present in the organic phase, and not all the surfactant in the process, as in WII system. This fact allows the reuse of the microemulsion phase in a new extraction process, reducing the costs with surfactant regeneration
O impacto ambiental gerado pelo descarte de efluentes industriais carregados de metais pesados imp?e a necessidade do tratamento desses rejeitos, uma vez que s?o t?xicos e n?o biodegrad?veis, podendo causar s?rios danos ? popula??o e ao meio ambiente. O processo de extra??o de c?tions met?licos utilizando microemuls?es ? eficaz quando acontece em WII, onde a fase microemulsionada encontra-se em equil?brio com uma fase aquosa em excesso. No entanto, a microemuls?o formada nesse sistema possui uma maior quantidade de mat?ria ativa quando comparada ao equil?brio de WIII (microemuls?o em equil?brio com fases aquosa e oleosa, ambas em excesso), ainda pouco estudado, motivando, assim, o desenvolvimento de um estudo comparativo da efici?ncia de extra??o dos ?ons Cu2+ e Ni2+ por sistemas microemulsionados bif?sicos e trif?sicos (WII e WIII). Os constituintes utilizados nos sistemas de extra??o foram: ?leo de coco saponificado - OCS (Tensoativo), n- Butanol (Cotensoativo), querosene (Fase Oleosa) e solu??es sint?ticas de CuSO4.5H2O e NiSO4.6H2O com NaCl 2% (fases aquosas). Foram obtidos os diagramas de fases pseudotern?rios e os sistemas microemulsionados foram caracterizados atrav?s das t?cnicas de tens?o superficial, tamanho de part?culas e microscopia eletr?nica de varredura (MEV). A concentra??o dos ?ons foi determinada por espectrometria de absor??o at?mica. O estudo da extra??o dos c?tions met?licos Cu2+ e Ni2+ na regi?o de WIII contribuiu para um melhor entendimento dos processos de extra??o por microemuls?o, elucidando os v?rios comportamentos apresentados na literatura para esses sistemas. Al?m disso, uma vez que houve uma alta efici?ncia de extra??o, similar aos sistemas de Winsor II, o sistema trif?sico (WIII), por apresentar uma menor quantidade de tensoativo e cotensoativo, e um menor volume de fase aquosa ap?s a extra??o, levou a uma maior concentra??o do metal, representando uma vantagem econ?mica e tecnol?gica do processo. Assim, a extra??o em sistema trif?sico ? vi?vel e, apesar dos percentuais de extra??o em WII e WIII serem semelhantes, o sistema de WIII leva a uma maior concentra??o do metal na fase extrato. O presente trabalho mostrou, ainda, que a etapa de reextra??o para os sistemas em WIII ? mais eficaz pois, diferentemente da extra??o em Winsor II, ela ? realizada na fase oleosa, onde est? depositado o complexo metal/tensoativo, regenerando somente o tensoativo que complexa com o metal na fase org?nica, e n?o todo o tensoativo utilizado, como ? o caso do equil?brio em Winsor II. Este fato viabiliza a reutiliza??o da fase microemuls?o no processo de extra??o, diminuindo os custos de regenera??o do tensoativo
14
Firmino, Gisele dos Santos Silva. "Síntese, caracterização e estudo da ação antituberculose e citotóxica de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III)." Universidade do Estado do Rio de Janeiro, 2015. http://www.bdtd.uerj.br/tde_busca/arquivo.php?codArquivo=8528.
Full textAbstract:
Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorNo presente trabalho é descrita a obtenção de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III) candidatos a protótipos de fármacos antituberculose e antitumoral. Para investigar o efeito da modificação química sobre as bioatividades do fármaco isoniazida, foram preparados cinco derivados hidrazônicos: 2-piridinocarboxaldeído isonicotinoil hidrazona (HPCIH, 1), 2-acetilpiridina isonicotinoil hidrazona (HAPIH, 2), 2-benzoilpiridina isonicotinoil hidrazona (HBPIH, 3), 2-piridinoformamida isonicotinoil hidrazona (HPAmIH, 4) e 2-pirazinoformamida isonicotinoil hidrazona (HPzAmIH, 5), sendo o composto HPAmIH (4) inédito. Análises de ponto de fusão, espectroscopia de infravermelho (IV), espectrometria de massas, ressonância magnética nuclear (RMN), análise elementar e termogravimetria confirmaram a obtenção e pureza das hidrazonas. Foi determinada ainda a estrutura de HPCIH (1) por difração de raios X de monocristal. Essas moléculas foram efetivas em inibir o crescimento de cepas de micobactérias Mycobacterium tuberculosis H37Rv (ATCC 27294) nas concentrações testadas, com exceção de HPzAmIH (5). As hidrazonas HAPIH (2) e HBPIH (3) foram os compostos orgânicos mais ativos (concentração inibitória mínima, CIM = 0,625 g/mL), apresentando atividade antimicobacteriana apenas duas vezes inferior à do fármaco isoniazida.Quanto à ação contra células tumorais, as hidrazonas HAPIH (2) e HBPIH (3) foram as mais potentes contra as linhagens OVCAR-8 (tumor de ovário - humano), HCT-116 (tumor de cólon - humano) e SF-295 (glioblastoma humano), com inibições de 34,98 a 98,63% do crescimento celular, na concentração de 5 g/mL, enquanto que a isoniazida não foi efetiva contra as linhagens estudadas. Para avaliar o efeito da coordenação a metais sobre a atividade farmacológica das hidrazonas, foram sintetizados os complexos de cobre(II) e gálio(III), sendo todos inéditos: [Cu(HPCIH)Cl2]∙H2O (6), [Cu(HAPIH)Cl2]∙H2O (7), [Cu2(HBPIH)2Cl2]Cl2∙4H2O(8), [Cu(HPAmIH)Cl2]∙H2O (9), [Cu(HPzAmIH)Cl2]∙H2O (10), [Ga(HPCIH)2](NO3)32H2O (11), [Ga(HAPIH)(APIH)](NO3)22H2O (12), [Ga(HPAmIH)(PAmIH)](NO3)22H2O(13) e [Ga(HPzAmIH)(PzAmIH)](NO3)2H2O (14). Os complexos foram caracterizados por espectroscopia de IV, análise elementar, condutivimetria, RMN e espectroscopia eletrônica. Em geral, os complexos também demonstraram ação contra M. tuberculosis, sendo que apenas para 6, 9, 10 e 14 foi verificada melhor atividade em relação às hidrazonas livres. Os complexos metálicos foram tanto quanto ou mais ativos contra as células tumorais OVCAR-8, HCT-116 e SF-295 do que as hidrazonas livres. Merecem destaque os complexos 79 e 12, que apresentaram inibição de crescimento celular de 72,2100%, na concentração de 5 g/mL. Os resultados demonstram portanto que em geral os compostos 114 são menos ativos do que a isoniazida contra M. tuberculosis, enquanto que a modificação química do fármaco, formando-se hidrazonas com posterior complexação cobre(II) e gálio(III) constituíram uma estratégia interessante na obtenção de compostos mais potentes contra células tumorais
In this work we describe the synthesis of isoniazide-derived hydrazones and their copper(II) and gallium(III) complexes candidates for drug prototypes to treat antituberculosis and cancer. Five hidrazone derivatives have been prepared in order to investigate the effect of chemical modification on the bioactivities of the drug isoniazid: 2-pyridinecarboxaldehyde isonicotinoyl hydrazone (HPCIH, 1), 2-acetylpyridine isonicotinoyl hydrazone (HAPIH, 2), 2-benzoylpyridine isonicotinoyl hydrazone (HBPIH, 3), 2-pyridineformamide isonicotinoyl hydrazone (HPAmIH, 4) and pyrazineformamide 2-isonicotinoyl hydrazone (HPzAmIH, 5), being HPAmIH (4) unpublished. Melting point, infrared spectroscopy (IR), mass spectrometry, nuclear magnetic resonance (NMR), elemental analysis and thermogravimetric analysis has confirmed the formation of hydrazones as well as its purity. All compounds have been effective in inhibiting the growth of Mycobacterium tuberculosis H37Rv (ATCC 27294) mycobacteria strains in the tested concentrations, except HPzAmIH (5). The hydrazones HAPIH (2) and HBPIH (3) have been the most active compounds (minimum inhibitory concentration, MIC = 0.625 g/mL), which have presented the antimycobacterial activity only two times lower than isoniazid drug. In relation to the action against tumor cells, the hydrazones HAPIH (2) and HBPIH (3) have been the most potent compounds against the cell lines OVCAR-8 (ovarian tumor - human), HCT-116 (colon tumor - human) and SF-295 (glioblastoma - human), with inhibitions from 34.98 to 98.63% of cellular growth at a concentration of 5 g/mL. Isoniazid, in turn, hasnt been effective against all cell lines studied. To evaluate the effect of coordinating the metal on the pharmacological activity of hydrazones, complexes of copper (II) and gallium (III) have been synthesized, being all novel compounds: [Cu(HPCIH)Cl2]∙H2O (6), [Cu(HAPIH)Cl2]∙H2O (7), [Cu2(HBPIH)2Cl2]Cl2∙4H2O(8), [Cu(HPAmIH)Cl2]∙H2O (9), [Cu(HPzAmIH)Cl2]∙H2O (10), [Ga(HPCIH)2](NO3)32H2O (11), [Ga(HAPIH)(APIH)](NO3)22H2O (12), [Ga(HPAmIH)(PAmIH)](NO3)22H2O (13) and [Ga(HPzAmIH)(PzAmIH)](NO3)2H2O (14).The complexes have been characterized by IR spectroscopy, NMR, elemental analysis, conductivimetry and electron spectroscopy. In general, these complexes have also shown action against M. tuberculosis, whereas only 6, 9, 10 and 14 have demonstrated better activity than the free hydrazones. The metal complexes have been equally or more active against human the cancer cell lines OVCAR-8, HCT-116 and SF-295 than the free hydrazones. The complexes 79 and 12 deserve to be highlighted, which have shown 72.2100% inhibition of cell growth in the 5 g/mL concentration. The results therefore demonstrate that in general compounds 114 are less active than isoniazid against M. tuberculosis, while chemical modification of the drug, forming hydrazones and subsequent complexation with the copper (II) and gallium(III) metal ions have been an interesting strategy to obtain compounds more potent against tumor cells
15
Chen, Jianxian. "I. Chemoselective catalytic hydrogenation of Ã, ß-unsaturated aldehydes and ketones using soluble copper(I) hydrides, II. Free radical alkylation of titanium(III) allyl and propargyl complexes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0005/NQ39514.pdf.
Full text
16
Mirjana, Radanović. "Kompleksi nekih prelaznih metala sa Šifovim bazama aminogvanidina." Phd thesis, Univerzitet u Novom Sadu, Prirodno-matematički fakultet u Novom Sadu, 2015. https://www.cris.uns.ac.rs/record.jsf?recordId=95548&source=NDLTD&language=en.
Full textAbstract:
U ovoj doktorskoj disertaciji opisane su sinteze novih kompleksa prelaznih metala sa piridoksiliden- (PLAG), odnosno saliciliden-aminogvanidinom (SALAG). Dobijenikompleksi su okarakterisani elementalnom analizom, IR spektrima, konduktometrijskim i magnetnim merenjima, a većina i rendgenskomstrukturnom analizom. Osim toga, dobijene su i nove forme ovih Šifovih baza, i to u vidu monokristala, čime su omogućena ispitivanja njihovih molekulskih i kristalnih struktura, kao i uporedna analiza sa koordinovanim ligandima. Sa PLAG je sintetisano 7 novi kompleksa Cu(II), a pored toga po prvi put suizolovani mono i bis(ligand) kompleksi Fe(III) i Co(III), mono(ligand) kompleksi V(V), kao i jedan kompleks Zn(II) u kojem ovaj potencijalno tridentatni ONN ligand, umonoprotonovanoj formi, ima ulogu kontra-jona. Sa stanovišta geometrije zajedničko za izolovane komplekse Cu(II) i V(V) je da imaju kvadratno-piramidalnu strukturu, sa izuzetkom jednog kvadratno-planarnog kompleksa Cu(II), dok je u kompleksima Fe(III) i Co(III) nađeno očekivano oktaedarsko okruženje centralnogjona. Pored ovih, sintetisano je i pet novih kompleksa sa SALAG, od kojih su dvakompleksa Cu(II) i kompleks V(V) okarakterisani rendgenskom strukturnomanalizom, dok je mikrokristalnim bis(ligand) kompleksima Co(III) i Ni(III) na osnovufizičko-hemijskih karakteristika predložena odgovarajuća struktura. Zajedničko za obe opisane Šifove baze je da se koordinuju na ONN tridentatni način, i to preko atoma kiseonika deprotonovane fenolne grupe i atoma azota azometinske i imino grupe AG fragmeta. Posebno je naglašeno da su saPLAG izolovana dva dimerna kompleksa Cu(II) u kojima je po prvi put nađena tetradentatna koordinacija ovog liganda, u koju je dodatno uključen atom kiseonika hidroksimetil-grupe PL-ostatka. Za razliku od SALAG, koji je u izolovanim kompleksima koordinovan isključivo kao monoanjon, nastao deprotonacijom fenolneOH-grupe, za PLAG je osim ove, potvđena koordinacija u neutralnoj, zwitter-jonskoj, ali i dvostruko deprotonovanoj formi. Zwitter-jonska forma liganda nastaje migracijom atoma vodonika sa fenolnog hidroksila na piridinski atom azota PL-ostatka, dok deprotonacijom piridinskog ili hidrazinskog atoma azota, odnosno oba pomenuta atoma nastaju monoanjon i dianjon helatnog liganda, respektivno. Na kraju, urađena su i ispitivanja antimikrobne aktivnosti odabranih jedinjenjaprema predstavnicima grampozitivnih i gramnegativnih bakterija, kao i dve kulturekvasca. Tom prilikom nije utvrđena nikakva inhibitorna aktivnost prema primenjenimbakterijskim sojevima, dok su u slučaju kvasaca izvesno mikrobicidno dejstvo pokazali samo kompleksi Cu(II).This PhD thesis describes the syntheses of some new transition metal complexes with pyridoxilidene- (PLAG) and salicylideneaminoguanidine (SALAG). Obtained complexes are characterized by elemental analysis, IR spectroscopy, conductometric and magnetic measurements. Besides, the structural analysis of majority of the obtained complexes was performed. Some new forms of these Schiff bases are synthesized in form of single crystals, which made their X-ray analysis as well as comparison with coordinated forms possible.With PLAG, 7 new Cu(II) complexes were obtained and for the first time mono and bis(ligand) complexes of Fe(III) and Co(III) as well mono(ligand) complexes of V(V) were isolated. Furthermore, the structure of Zn(II) complex in which PLAG in its monocationic form has a role of counter ion is presented. With the exception of one Cu(II) complex, all reported Cu(II) and V(V) complexes have a square-pyramidal geometry, whilst Fe(III) and Co(III) are situated in octahedral surroundings. Also, five new complexes of Cu(II), Co(III), Ni(II) and V(V) with SALAG were synthesized. In both Cu(II) complexes and V(V) complex the expected coordination mode and geometry were confirmed by X-ray analysis, while octahedral structure of bis(ligand) complexes with Co(III) and Ni(II) was proposed based on results of physico-chemical characterization.Both PLAG and SALAG coordinate the metal ion in tridentate ONN manner, through the oxygen atom of deprotonated phenolic group and nitrogen atoms of azomethine and imino groups of AG moiety. It is also emphasized that in two dimeric Cu(II) complexes with PLAG tetradentate coordination mode was found, in which the oxygen atom of hydroxymethyl group of PL residue was additionally involved. Unlike SALAG, which is coordinated as monoanion in all of the examined complexes, PLAG can have one of three degrees of deprotonation. Zwitter-ion of PLAG is formed by migration of H-atom from phenolic oxygen to pyridine nitrogen, while the deprotonation of pyridine or/and hydrazine nitrogen, makes it mono-and dianion, respectively.Also, microbiological tests on the selected compounds were preformed. Namely, antimicrobial activity of these compounds against some gram-positive and gram-negative bacteria, as well as some yeast cultures was examined and none of the samples showed antimicrobial activity against bacteria, whilst only Cu(II) complexes showed certain inhibitory effect against yeasts.
17
Provent, Christophe. "Vers des modèles biomimétiques de métalloenzymes antioxydantes." Université Joseph Fourier (Grenoble), 1996. http://www.theses.fr/1996GRE10048.
Full textAbstract:
La preparation de complexes metalliques, modeles des sites actifs de la superoxyde dismutase ou de la catalase, est un enjeu important dans le domaine des therapeutiques antioxydantes. Dans cette optique, differentes series de ligands, de structures ouvertes, macrocycliques ou macrobicycliques, ont ete synthetisees et leurs complexes du cuivre (ii) ou du fer (iii) ont ete etudies. Dans une premiere partie, la complexation du cu(ii) par onze ligands macrocycliques ou a chaine ouverte, a quatre sites de coordination azotes ou soufres (n#2s#2, n#3s), a ete etudiee par differentes methodes spectroscopiques (uv-visible, rpe) et des mesures electrochimiques ont ete effectuees. L'influence de la taille des cycles chelatants et de la nature des atomes donneurs sur le potentiel redox et sur la geometrie des complexes a ainsi ete mise en evidence. Certains complexes soufres possedent une bonne activite sod in vitro, mais la perdent en presence de serumalbumine. Dans une seconde partie, les strategies de preparation de modeles synthetiques non porphyriniques de catalase, pouvant complexer le fer soit sous forme d'acetylacetonates, soit sous forme de macrobicycles tetrazazote, sont decrites. De nombreuses syntheses originales ont ete realisees: protection-deprotection de 1,3-dicetones, double condensation de reactifs de wittig fonctionnalises, essais de macrobicyclisation avec ni#2#+ comme gabarit. Une serie de cinq complexes fe(iii)-bisacac a ete identifiee par spectrometrie de masse (fab) et leur stoechiometrie verifiee par spectrophotometrie uv-visible. Leur formation en absence de base semble la plus favorable pour l'obtention de complexes mononucleaires. L'activite catalase de ces complexes s'est averee assez faible
18
Mao, Baodong. "Synthesis and Property Characterization of Novel Ternary Semiconductor Nanomaterials." Case Western Reserve University School of Graduate Studies / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=case1334065821.
Full text
19
Chauvin, Camille. "Caracterisation d'oxydes de zinc et de catalyseurs de synthese du methanol cu-znal::(2)o::(4) : etude par spectroscopie infrarouge des sites d'adsorption et des mecanismes reactionnels." Caen, 1987. http://www.theses.fr/1987CAEN2017.
Full text
20
Weske, Sebastian. "From Copper to Gold: Identification and Characterization of Coinage-Metal Ate Complexes by ESI Mass Spectrometry and Gas-Phase Fragmentation Experiments." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0005-12EA-F.
Full text
21
Campbell, Matthew James Johnson Jeffrey Scott. "I. Mechanistic studies of a copper-catalyzed electrophilic amination of diorganozinc reagents reagents by O-benzoyl N,N-dialkylhydroxylamines II. Development of a 3-Exo-Dig cyclization for the preparation of vinylidene cyclopropanes III. Total synthesis of +-polyanthellin A." Chapel Hill, N.C. : University of North Carolina at Chapel Hill, 2009. http://dc.lib.unc.edu/u?/etd,2881.
Full textAbstract:
Thesis (Ph. D.)--University of North Carolina at Chapel Hill, 2010.Title from electronic title page (viewed Jun. 23, 2010). "... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry." Discipline: Chemistry; Department/School: Chemistry.
22
Mereshchenko, Andrey S. "ULTRAFAST PHOTOCHEMISTRY OF POLYATOMIC MOLECULES CONTAINING LABILE HALOGEN ATOMS IN SOLUTION." Bowling Green State University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1369774991.
Full text
23
Prada, Silvio Miranda. "Caracterização estrutural do complexo Cu(II) / DPKBH e desenvolvimento/aplicação de método espectrofotométrico em fluxo, empregando multicomutação e amostragem binária, para determinação de Cu(II), Fe(II) e Fe(III)." Universidade de São Paulo, 2001. http://www.teses.usp.br/teses/disponiveis/46/46133/tde-11032019-103333/.
Full textAbstract:
Desenvolveu-se um método espectrofotométrico para determinação de íons Cu(II), Fe(II) e Fe(III) com o reagente cromogênico di-2-piridil cetona benzoilhidrazona (DPKBH), em condições estacionárias e em fluxo. Fez-se a caracterização estrutural e estequiométrica do complexo de Cu(II) com DPKBH usando-se técnicas espectroscópicas de infravermelho e massas, além de análise térmica e elementar. Estudou-se, ainda, a estequiometria dos complexos de Fe(II) e Fe(III) com DPKBH utilizando espectrometria de massas com ionização por electrospray. Desenvolveu-se, preliminarmente, um método espectrofotométrico para a determinação de íons Cu(II) com DPKBH e aplicou-se em amostras de aguardente. Posteriormente, adaptou-se para análise por injeção em fluxo, utilizando-se injetor comutador manual. Em seguida, desenvolveu-se em condições estacionárias um método espectrofotométrico para determinação de Fe(II) e Fe(III) e Cu(II) em uma mesma amostra, com o uso de agentes mascarantes. Fez-se também a adaptação do método para análise em fluxo empregando multicomutação e amostragem binária. Finalmente, determinou-se a concentração de íons Cu(II), Fe(II) e Fe(III) em amostras sintéticas e Cu(II) e ferro total em amostras de sedimento coletadas no reservatório de Guarapiranga. Os resultados obtidos foram comparados com o método de referência de ICP-OES, apresentando concordância para um nível de confiança de 95% da média.A spectrophotometric method was developed to the determination of Cu(II), Fe(II) and Fe(III) with the chromogenic reagent di-2pyridyl ketone benzoylhydrazone (DPKBH) in stationary conditions as a flow injection process. The structural characterization and the stoichiometry of Cu(II)/DPKBH complex were achieved using infrared spectrometry, mass spectrometry, thermal and elementar analysis. Toe stoichiometry of the Fe(II) and Fe(III) complexes with DPKBH was studied by electrospray ionization mass spectrometry. The spectrophotometric method for the determination of Cu(II) with DPKBH was developed in stationary conditions and, after this, it was adapted to flow injection analysis, using a manual commutator. Subsequently, a spectrophotometric method was developed to determine Fe(II), Fe(III) and Cu(II) in the same sample, in stationary conditions, using masking reagents. This method was also adapted to flow injection analysis, using multicommutation and binary sampling. Finally, Cu(II), Fe(II) and Fe(III) were determined in sediments from Guarapiranga reservoir. The obtained results were compared with the ICP-OES standard methods, showing a good agreement into a 95% confidence level (t-test).
24
Fiallo, Maria Lorenzo. "Une Nouvelle classe d'antitumoraux : les complexes metal-anthracyclines, synthèse, caractéristiques physicochimiques et propriétés tumorales." Paris 13, 1986. http://www.theses.fr/1986PA132003.
Full text
25
Gennarini, Federica. "Dioxygen reactivity of new models of copper oxygenases : electrochemical and spectroscopic studies." Thesis, Brest, 2017. http://www.theses.fr/2017BRES0108/document.
Full textAbstract:
La molécule de méthane possède la liaison C-H la plus forte parmi les hydrocarbures (BDE = 104 kcal mol-1) : son oxydation en conditions douces représente un challenge d'importance. La Méthane Monoxygénase particulaire (pMMO) est une enzyme à cuivre qui catalyse l'oxydation du méthane (CH4) en méthanol (CH3OH). Le site actif de l'enzyme est composé d'atomes de cuivre séparés par 2.6 Å. Des recherches récentes suggèrent qu'un cluster Cu2 III,II/O2 à valence mixte soit un intermédiaire-clé du cycle catalytique. L'objectif de ce travail vise à la synthèse et caractérisation de nouveaux complexes dinucléaires à valence mixte de type bis(µ-oxo)Cu2 III,II ou (µ-OH, µ-O)Cu2 III,II. Deux familles de motifs coordinants ont été mises en oeuvre, polypyridyle ou polyamide ; les deux sites sont assemblés par des ponts courts et rigides, phenoxo, naphthyridine ou alkoxo. De nouveaux complexes ont été caractérisés par électrochimie, spectroscopies UV-visible et RPE, et par des calculs théoriques. Un dispositif original de cryo-spectroélectrochimie UV-vis-NIR a été développé en parallèle de cette étude : il permet l'identification spectroscopique d'intermédiaires transitoires, réputés très instables à température ambiante. De nouveaux composés à valence mixte, Cu2 III,II(μ-OH, μ-O) et Cu2 III,IIbis(μ-OH) ont été identifiés. Ces résultats élargissent le champ des données de cette famille d'intermédiaires instables limitée jusqu'ici à un seul exempleMethane has the strongest C-H bond of any hydrocarbon (BDE = 104 kcal mol-1); its oxidation under mild conditions remains a great challenge. The particulate Methane Monooxygenase (pMMO) is a copper enzyme that oxides methane (CH4) to methanol (CH3OH). In the active site of the enzyme, two copper ions are located at a short distance (2.6 Å). Recent researches have suggested a mixed-valent Cu2III,II/O2 cluster as a key intermediate in the catalytic cycle. The main objective of this work was the synthesis and characterization of new mixed-valent CuIIICuII bis(μ-oxo) and (μ-OH, μ-O) dinuclear complexes. For this purpose we designed promising symmetrical and unsymmetrical complexes based on specific and distinct scaffolds for each side of the structure. Two families of coordination pattern have been used, polypyridyle or polyamide; the two sites are shortly and rigidly bridged by phenoxo, alkoxo or naphthyridine linkers. New complexes have been characterized by electrochemistry, UV-vis and EPR spectroscopies, and by theoretical calculations. A new cryo-UV-Vis-NIR spectroelectrochemical set up, developed in parallel during this work, has allowed the spectroscopic identification of these transient intermediate species, known to be unstable at room temperature. New mixed-valence Cu2 III,II(μ-OH, μ-O) and Cu2 III,IIbis(μ-OH) complexes have been characterized. These results expand the recent knowledge on the only mixed valent CuIII(μ-OH)CuII species described so far
26
Er-Rakho, Lahcen. "Oxydes de cuivre a valence mixte : perovskites deficitaires en oxygene." Caen, 1987. http://www.theses.fr/1987CAEN2036.
Full textAbstract:
Mise en evidence et etude de deux grandes familles de composes dans le systeme la::(2)o::(3)-ao-cuo(a=ca,ba,sr) : la::(2-x)ba::(1-x)cu::(1-x/2)o::(5-x)(ln=la,nd) ou cu est essentiellement au degre d'oxydation 2 et une seconde famille caracterisee par la valence mixte du cuivre, les quantites de cuivre 3 pouvant atteindre dans certains cas 40%. Tous ces oxydes ont en commum leur appartenance a la structure perovskite. Proprietes electriques et magnetiques
27
Cox, Jennifer Jane. "Structure of organic molecular thin films vapour deposited on III-V semiconductor surfaces." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.327025.
Full text
28
Moreno, Ruben Gregorio Moreno. "Estudos de lesão ao DNA promovida pela autoxidação de S(IV) na presença de complexos de Cu(III)/tetraglicina. Efeito sinérgico de Ni(II), Co(II) e Mn(II)." Universidade de São Paulo, 2005. http://www.teses.usp.br/teses/disponiveis/46/46133/tde-04062007-032229/.
Full textAbstract:
O presente trabalho apresenta estudos de lesão em biomoléculas (DNA e 2\'-deoxiguanosina) induzida por Cu(III)/tetraglicina (Cu(III)/G4), radicais de óxidos de enxofre (SO3·-, SO4·-, SO5·-), HO· e HSO5-, espécies estas geradas durante a autoxidação de S(IV) na presença de Cu(II)/G4 ou Cu(II) (ausência de tetraglicina) e traços de um segundo íon metálico (Ni(II), Co(II) ou Mn(II)). A formação dos radicais SO3·- e HO· foi detectada pela técnica de ressonância paramagnética eletrônica (EPR). As técnicas de espectrofotometria e dicroísmo circular foram empregadas para avaliar a formação de Cu(III)/G4 em diferentes condições experimentais, na presença e ausência de S(IV), e a interação entre os complexos de cobre (II)/(III) e a molécula de DNA. A eficiência da formação de Cu(III) depende da acidez, concentração de S(IV) e dos tampões utilizados. A lesão no DNA plasmidial pUC19 foi verificada empregando-se a técnica de eletroforese em gel de agarose. A extensão da lesão no DNA depende da acidez, concentração de S(IV), tempo de incubação e da presença de um segundo íon metálico. Usando a técnica de cromatografia líquida de alta eficiência (HPLC) foi possível estudar a oxidação de 2\'-deoxiguanosina a 8-oxo-7,8-dihidro-2\'-deoxiguanosina na presença dos oxidantes fortes gerados durante a autoxidação de S(IV) catalisada por Cu(II)/G4. Um estudo comparativo do efeito de vários íons metálicos evidenciou o sinergismo de Cu(II) e traços de um segundo íon metálico (Ni(II), Co(II) ou Mn(II), complexados ou não com tetraglicina).The present work presents studies related to biomolecules damage (DNA and 2\'-deoxyguanosine) induced by Cu(III)/tetraglycine (Cu(III)/G4), oxysulfur radicals (SO3·-, SO4·-, SO5·-) and HSO5-, species generated during S(IV) autoxidation in the presence of Cu(II)/G4 or Cu(II) (absence of tetraglycine) and trace level of a second metal ion (Ni(II), Co(II) or Mn(II)). The formation of SO3·- and HO· radicals was detected by electronic paramagnetic resonance technique (EPR). Spectrophotometric and circular dichroism techniques were used to evaluate the Cu(III)/G4 formation in different experimental conditions, in the presence and the absence of S(IV), and the interaction of copper (II)/(III) complexes and DNA molecule. The effectiveness of Cu(III) formation depends on the acidity, S(IV) concentration, and buffers used. The damage on pUC 19 plasmid DNA was verified by agarose gel electrophoresis. The extent on the DNA damage was related to acidity, S(IV) concentration, incubation time and to the presence of a second metal ion. Using the high performance liquid chromatography technique (HPLC) it was possible to study the oxidation of 2\'-deoxyguanosine to 8-oxo-7,8-dihydro-2\'-deoxyguanosine in the presence of strong oxidants generated during the S(IV) autoxidation catalyzed by Cu(II)/G4. A comparative study of the effect of several metal ions showed the synergism of Cu(II) and traces of a second metal ion (Ni(II), Co(II) or Mn(II), as tetraglycine complexes or not).
29
Liu, Wen-Chi, and 劉玟季. "Formation of Trigonal Bipyramidal Copper(III) Complexes with PS3′ Ligand." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/01290583538778035573.
Full textAbstract:
碩士國立臺灣師範大學
化學系
103
Formation of copper(III) complexes is of great importance for the understanding of dioxygen cleavage in enzymatic systems. However, there are only few examples of structurally characterized mononuclear CuIII complexes, most of them possessing square-planar geometry. The tripodal tetradentate ligand P(C6H3-3-SiMe3-2-SH)3 (H3PS3′) was deprotonated by NaH, and further reacted with CuCl2 in MeCN/THF mixed solvent. The disproportionation of copper(II) species occurred to form [PPN][PS3′CuCl] (1) and [PPN][CuCl2]. The X-ray structure, X-ray absorption spectrum and NMR spectra of 1 unambiguously indicate that complex 1 is a diamagnetic copper(III) species with a trigonal bipyramidal geometry. Cyclic voltammogram analysis of 1 shows irreversible redox waves in either MeCN or CH2Cl2 revealing that complex 1 is an electrochemically unstable species. Based on yield analysis for the formation of 1 under different conditions, we propose that disproportionation of copper(II) species occurs through an inner-sphere electron transfer as dimeric copper(II) species encounters deprotonated PS3′3− ligand. The dimeric copper(II) species will be regenerated from resulting copper(I), [PPN][CuCl2], by O2 oxidation. This study provides useful insight for further understanding the characteristic of the five-coordination trigonal bipyramidal copper(III) complexes.
30
Lin, Hsin-Ping, and 林欣平. "A new gadolinium(III) complex with dansyl based copper MRI sensor." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/94728462100636621483.
Full textAbstract:
碩士國立交通大學
分子醫學與生物工程研究所
101
In the present study, we designed and synthesized MR-optical imaging agent, [Gd(DNS-DOTA)], for the detection of the divalent copper ion(Cu2+). Luminescence lifetime measurement shows the number of inner-sphere water molecules (q) in [Gd(DNS-DOTA)] is zero. However, upon addition of Cu2+ to [Gd(DNS-DOTA)], the q value changes from 0 to 1. Consequently increase in the relaxivity of [Gd(DNS-DOTA)] was observed in the presence of Cu2+. Consistent to relaxometric study, magnetic resonance imaging (MRI) experiments display the increase in signal strength with the increase in the Cu2+ ion concentration. In addition, attenuation in the fluorescence intensity of [Gd(DNS-DOTA)] was observed on adding Cu2+ ion which substantiate that the coordination profile of [Gd(DNS-DOTA)] is alter in the presence of Cu2+ ion. High coordination preference of [Gd(DNS-DOTA)] for Cu2+ ion over other metal ion was observed under the same condition. Last but not least, confocal imaging experiment shows that the fluorescence intensity [Gd(DNS-DOTA)] suppressed on incubating with 3T3 cell pretreated with Cu2+. Therefore, [Gd(DNS-DOTA)] is a potential MR-optical imaging agent for the detection of intracellular Cu2+ ion with high specificity.
31
Chang, Ya-Fan, and 張雅帆. "Synthesis Mechanism and Replacement Study of Trigonal Bipyramidal Copper(III) Phosphineimine Complex." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/05166382720310669647.
Full textAbstract:
碩士國立臺灣師範大學
化學系
104
A trigonal bipyramidal copper(III) complex, [PPN][(TMSPS3)CuIII(NCBH3)] (2), an analogue of [PPN][(TMSPS3)CuIII(NCCH3)], was synthesized from the reaction of [PPN][(TMSPS3)CuIII(Cl)] (1) with sodium cyanoborohydride (NaBH3CN) in THF. Interestingly, complex 1 was converted to (TMSPS3)CuIII(NH=PPh3) (3) in THF as NaOMe was added. The added NaOMe is proposed to react with trace of water in THF solution to produce OH- anion. Then, the in-situ produced OH- anion attacks [PPN]+, and generates O=PPh3 and NH=PPh3. Further, NH=PPh3 coordinates to the copper(III) center to form the five-coordinate copper(III) complex. UV-vis titration of 3 by adding N3- (Keq = 0.25) or DABCO (Keq = 0.15) complies 1:1 ligand exchange in solution. This result demonstrates that the binding ability of NH=PPh3 ligand is strong than that of DABCO and N3-. This finding is related to basicity and donor capacity of the axial ligand.
32
藍國峻. "Structural and Functional Models for the Trinuclear Copper Clusters of the Particulate Methane Monooxygenase (III)." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/19580172683487084440.
Full textAbstract:
碩士國立臺灣師範大學
化學系
99
In this study, a new ligand 7-N3Et has been synthesized, and it can coordinate with 3 equivalents of CuI ions to form a trinuclear copper complex [CuICuICuI(7-N3Et)](X) (X = ClO4 or BF4) (2). This 7-N3Et ligand is similar to our previous developed 7-Dipy ligand in the scaffold to trap three CuI ions. They all have a pair of symmetric N3 coordination which consists of N1-(2-(diethylamino)ethyl) -N2,N2-diethylethane-1,2-diamine in 7-N3Et instead of 2,2-bis(pyridylmethyl)amine group for 7-Dipy. According to the efficient oxidation of cyclohexane catalyzed by [CuICuICuI(7-Dipy)]+, the [CuICuICuI(7-N3Et)]+ was adopted for comparing the catalytic effects arisen from substitution groups. The ESI-MS spectra of oxygenated [CuICuICuI(7-N3Et)]+ by dioxygen molecules, two equivalents of H2O2, and two equivalents of TBHP present a exactly same cluster signal associated with a [CuIICuII(-O)CuII(7-N3Et)]2+ trinuclear copper complex. However, with more than two equivalents of TBHP, it will encounter N-deethylation to loss a molecular weight in m/z of 28 amu and 56 amu. When one equiv. of [CuICuICuI(7-Dipy)]+ is added in the presence of 10, 25, 50 and 75 equiv. of TBHP , respectively, as oxidant with external substrates such as cyclohexane (C-H BDE : 99.3 kcal/mol) and toluene (C-H BDE : 90 kcal/mol) in the solvent of CH3CN for two hours, substrates can be oxygenated with lower TON because of competing reactions between intra-N-deethylation and inter-oxygenation. In contrast, no external substrate was added in the above condition, and the acetalaldehyde was detected by GC-MS when 50 equiv. of TBHP was used. The production of acetalaldehyde is postulated from first hydroxylation on the -CH2- of the amine group, and then disassociation by proton migration of hydroxyl group to the nitrogen atom of amine.
33
Chen, Yi-Pei, and 陳沂珮. "Reductive Defluorination of Perfluorooctanoic Acid by Titanium(III) Citrate with Vitamin B12 and Copper Nanoparticles." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/16796699024464961837.
Full textAbstract:
碩士國立臺灣大學
環境工程學研究所
104
Perfluorooctanoic acid (PFOA) has been considered as emerging persistent organic pollutants. It is a fluorosurfactant, widely used as emulsifying agents, surface treatment ingredients and water repellents due to its unique high stability, compatibility, high surface-active effect, low surface tension as well as both hydrophobic and oleophobic properties. In recent years, as the use of PFOA has increased, it is globally present in the environment. The stability, persistence and bioaccumulative properties of PFOA make it have an adverse effect on human health and ecosystem, and has drawn considerable interest from the public and regulatory agencies. It is thus crucial to evolve effective methods for the degradation of PFOA. This compound shows high chemical stabilization and it is not degraded in the natural environment or by conventional treatment methods, such as biology, ozonation, Fenton processes, photolysis, or photocatalysis. Using persulfate and Ti(III) citrate as reaction medium for oxidation and reduction degradation of PFOA, reductive defluorination of PFOA is more efficient than oxidative defluorination. Due to its strong electronegativity, the fluorine atom has high electron withdrawing capability, and acts as the reaction center. Thus, reductive defluorination of PFOA is more practical than oxidative defluorination. Catalyzed by vitamin B12 and copper nanoparticles was examined in batch systems using sodium borohydride, nano zero valent iron and titanium (III) citrate as the bulk reductant, a very efficient reduction for the conversion of PFOA to less-noxious compounds was achieved with Ti(III) citrate. A maximum removal was observed with an copper dose of 2 g L-1, Ti(III) citrate (45 mM), vitamin B12 (0.2 mM) at an initial pH of 9.0 and 70°C. In anoxic aqueous solution, the biomimetic reduction system was effectively removed 65% of PFOA. The products characterized by X-Ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The mass balance of fluoride matched the observed degradation of PFOA, while no short-chain perfluorocarboxylic acids byproducts were detected using HPLC. Consequently, highly efficient enhanced reduction systems were constructed for remediation of PFOA contaminated water. The removal of PFOA by TC/VB12/Cu can be attributed to the following main mechanisms: (i) adsorption onto copper surface and (ii) reduction via defluorination.
34
Chang, Hao-Ching, and 張皓晴. "Electronic Structure and Reactivity of Trigonal Bipyramidal Copper(III) Complexes with an Exchangeable Axial Ligand." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/83660685394242053568.
Full textAbstract:
博士國立臺灣師範大學
化學系
104
A trigonal bipyramidal copper(III) complex, [PPN][Cu(TMSPS3)(Cl)] (complex 1), was synthesized following our previous studies. Basing on the correlation between yields and preparation conditions as well as DFT calculations, we propose a thermodynamically favored copper(II) disproportionation occurs within a TMSPS3–Cu2Cl4 intermediate, producing complex 1 and a copper(I) side-product. UV–vis titrations of complex 1 with various additive ligands, such as N3− (Keq = 18), DABCO (8), pyridine (0.13) and 2,6-lutidine (0.0010), comply 1:1 ligand–chloride exchange in solution, hence clarifying the semi-stability of complex 1 in solution phase. Derivatized [PPN][Cu(TMSPS3)(N3)] (complex 2), [Cu(TMSPS3)(DABCO)] (complex 3) and [PPN][Cu(TMSPS3)(NCS/Cl)] (complex 4/1) were then accordingly synthesized. Cu and S K-edge X-ray absorption spectra of complexes 1–3 reveal the elevated LUMO (3dz2 feathered) in TBP ligand field with their +3 oxidation state of copper and the Cu–thiolate covalency. These indicate the electron density compensation (S→Cu) within Cu(TMSPS3) moiety, which not only stabilizes copper(III) center but also supresses the electrostatic demand for the axial ligand binding. A cyano derivative, [PPN][Cu(TMSPS3)(CN)] (complex 5), was isolated from the reaction of complex 1 with NaOH in CH3CN; and a cyanomethide-bound copper(III) intermediate is evidenced by NMR, UV–vis, and IR spectra, responsible for the C–CN bond cleavage of CH3CN solvent. Additionally, chloride of complex 1 is abstracted by Sc(OTf)3, which exposes the copper(III) moiety and leads the formation of dimeric [Cu(TMSPS3)]2 (complex 6). These results facilitate further development of high-valent copper catalysts.
35
Chiang, Tsung-Hsien, and 江宗憲. "A new gadolinium(III) complex with 8-hydroxyquinoline based ligand as a copper sensor for MRI." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/55142121332765553096.
Full textAbstract:
碩士國立交通大學
生物科技學系
99
Over the past few years, more and more evidence indicated that the metal ion imbalance in the brain will give rise to many diseases. Magnetic resonance imaging (MRI) is a non-invasive and high resolution technique that has become a powerful diagnostic tool in medicine. In this study, we have developed a new contrast agent [Gd(HQ-DO3A)] that can recognize Cu2+ ion in the cells. The significant increases in the relaxivity (r1) and hydration number (q) in the present of Cu2+ were observed. Moreover, the Gd3+ complex attributes excellent selectivity for Cu2+ over a choice of other metal ions. A gradual increase was shown in the signal enhancement of MR imaging upon copper ion detection. On the other hand, we observed fluorescence intensity decreased via transferring the inner system energy from qunoline ring to Eu3+ when copper was absent. These results implicate that a new MR based contrast agent can serve as a Cu2+ sensor using MR imaging.
36
Chen, Wei-Chen, and 陳韋禎. "Rhodium(III) and Copper(II)-Catalyzed Cyclization Reaction for the Synthesis of Benzofurans and Quinolinium Salts." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/4s227k.
Full textAbstract:
博士國立清華大學
化學系所
105
Chapter 1 Benzofuran derivatives are important molecules of heterocycles found in many natural and biologically active molecules and are often used as building blocks in organic materials.In chapter 1，a new strategy for the synthesis of highly substituted benzofurans from meta-substituted hydroxybenzenes and alkynes via a rhodium(III)-catalyzed activation of a sterically hindered C–H bond is demonstrated. A possible mechanism involving dual directing group assisted ortho C–H bond activation is proposed. Interestingly, the products we synthezied could support second C-H bond activation for further modification owing to the retention of O-methyloxime group attatched on them. Chapter 2 A novel copper-promoted multiple aza-[4 + 2] cycloaddition reaction of N-methyleneanilines generated in situ from benzylic azide and alkenes afforded quinolinium salts, biquinolinium salts, biquinolines or substituted quinolines depending on the substitution on the phenyl ring of benzylic azide.The reaction likely started by Lewis acidic CuII-assisted rearrangement of benzylic azide to N-methyleneaniline, followed by a [4 + 2] cycloaddition with alkene. Detailed mechanistic studies suggest that the biquinoline and biquinolinium salts are probably formed via radical processes. Besides the reaction of benzylic azides with alkenes, a one-pot multicomponent reaction of anilines, alkenes and formaldehyde was also investigated. Chapter 3 To continue our research result, we have successfully established an efficient copper-catalyzed aerobic oxidation of anilines, ketones and aldehydes to afford diverse functionalized N-aryl and -alkyl quinolinium salt in good to excellent yields.The reaction possibly proceeds via Lewis acid induced N-aryliminium ion and nucleophilic addition of enol formed of ketone. The cascade reaction is highly compatible with different π-components such as styrene, alkyne and activated alkenes as alternatives to ketones. Base on this study, we also improved the reaction in chapter 2 to an efficient copper-catalyzed aerobic oxidation reaction.
37
黃崇維. "Synthesis and molecular structure of (5,10,15,20-tetrakis(4-bromphenyl)porphyinato)-indium(III), (5,10,15,20-tetrakis(4-bromphenyl)porphyinato)-thallium(III), (5,10,15,20-tetrakis(4-bromphenyl)porphyinato)-copper(II), (5,10,15,20-tetrakis(4-bromphenyl)por." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/67204241030330220896.
Full text
38
林宗翰. "Synthesis and Structure of Novel Copper(III) Complexes with a Supporting Polydentate Ligand of Tris(3-(trimethylsilyl)2-mercaptophenyl)phosphine and their Property Study." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/88959994093476890760.
Full textAbstract:
碩士國立臺灣師範大學
化學系
99
The tripodal tetradentate ligand P(C6H3-3-SiMe3-2-SH)3 (PS3TMSH3) was deprotonated by NaH, and further reacted with CuCl2 in CH3CN and THF. The disproportionation of CuCl2 was occurred to form [PPN][CuClPS3TMS] (1) and PPNCuCl2. The yield of complex 1 in previous reaction could be improved by using dry O2 to oxidize Cu(II) ion. A similar ligand, P(C6H4- 2-SH)3 (PS3H3) was also employed to reacted with CuCl2. However, no CuIII complex was observed. Reaction of 1 with NaOMe afforded complex, [Cu(NHPPh3)PS3TMS] (3). This results suggested that an intermediates, [PPN][CuHPS3TMS], was generated through β-hydride elimination. The hydride attacted the cation, [PPN]+, to form NHPPh3, which coordinated to the CuIII center. To prove the formation of the [PPN][CuHPS3TMS] intermediates, complex 1 was reacted with KBEt3H to afford complex 3. If the counter ion of 1 changed to [PPh4]+ to form [PPh4][CuClPS3TMS] (2). Reaction of 2 with KBEt3H gave a new dinuclear complex, K2[(CuPS3TMS)2] (4) and H2 suggesting the possibility of [PPh4][CuHPS3TMS] formation.
39
Lin, Che-Hung, and 林哲弘. "1. Applications of Iron(III) Chloride in C-S Bond Cross-Coupling Reactions 2. Efficient Copper-Catalyzed Cross-Coupling Reaction of Alkynes with Aryl Iodides." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/uz8a7u.
Full textAbstract:
碩士國立中興大學
化學系所
98
The transition-metal-catalyzed cross-coupling reaction is one of the most powerful strategies for constructing carbon-carbon and carbon-heteroatom bonds. During the last decades, manifold transition metal catalysts especially based on precious metals such as palladium, nickel, and cobalt. Herein we report that iron can be used as a cheap, nontoxic and environmentally friendly metal. The combination of iron trichloride with Xantphos is a very active system for coupling reaction of alkyl thiols with a variety of aryl thiols for the first time. Sonogashira reaction is probably the most popular strategies for the syntheses of functionalized alkynes from aryl halides and terminal alkynes. The vast majority of the existing protocols involve the use of palladium catalyst. Recent years, copper-catalyzed Sonogashira reaction has gained much attention due to the lower cost of copper salts. However, among the known procedures, 5-10 mol% or higher copper salts are generally required along with high loading of ligands. The second part of this thesis, we describe the combination of Cu2O (1.0 mol%) with Xantphos (1.0 mol%) is a powerful system for this transformation. A broad spectrum of functional groups can be tolerated during the catalysis.
40
Lahiri, Debojyoti. "Studies On The Cobalt And Complexes Showing Anaerobic DNA Photocleavage Activity." Thesis, 2010. http://etd.iisc.ernet.in/handle/2005/1916.
Full textAbstract:
Photodynamic therapy (PDT) is a non-invasive treatment of cancer with an advantage of
having localized photo-activation of the drug at the targeted tumor cells leaving the healthy cells unaffected by the photo-toxicity of the PDT agent. Organic molecules and 4d/5d metal complexes have been extensively studied for their DNA cleavage activity and photo-cytotoxicity in UV and/or visible light. The photoactivity of the current PDT drugs is due to reactive singlet oxygen species. To address the hypoxic nature within neoplasia and to get a realistic scenario to build model and potent PDT agents, attempts have been made in this thesis work to design and synthesize new cobalt and copper complexes having a variety of ancillary ligands and planar phenanthroline bases showing efficient visible light-induced anaerobic plasmid DNA cleavage activity. The disulfide and thiol compounds are known to generate thyil radical in anaerobic medium in presence of some electron donating solvent. To exploit this chemistry of the sulfur anion radical as a reactive species damaging DNA under light irradiation, we have prepared copper(II) complexes of bis(2-hydroxybenzylamino-ethyl)disulfide and D-penicillaminedisulfide and characterized. The complexes are moderate binders to calf thymus DNA and exhibit plasmid DNA cleavage activity in red light. Near-IR light-induced double-strand DNA cleavage activity is observed for the complexes having 3,3' -dithiodipropionic acid and phenanthroline bases. These complexes show lethal double strand breaks in SC DNA responsible for the inhibition in DNA repair mechanism in the cells thus becoming potent candidates as transcription inhibitors. The work has been extended to achieve better visible light-induced plasmid DNA cleavage activity and UV light-induced photocytotoxicity using a more bio-compatible metal ion, viz. cobalt(II) with the same ligand system and enhancement in the photocytotoxicity is observed. To
investigate the role of the disulfide ancillary ligands, complexes of salicylideneaminothiophenol bound to the copper(II) are prepared and the complexes show significant plasmid DNA cleavage
activity in red light. Finally, ternary cobalt(III) phenanthroline base complexes are prepared to study their DNA cleavage activity in red light and photo-cytotoxicity in UV light. The complexes show efficient plasmid DNA cleavage activity in red light, significant cytotoxicity in UV light, low dark cytotoxicity, and protein (BSA, lysozyme) cleavage activity in UV light. The
mechanistic aspects of the photo-induced DNA and protein cleavage activity of the complexes have been studied. A dual involvement of the charge transfer and d-d band is observed in the photosensitization process leading to generation of reactive oxygen species.
In summary, the thesis work presents cobalt and copper complexes having thiolate and
disulfide moieties that are designed and synthesized as new photodynamic therapeutic agents showing anaerobic DNA cleavage activity in red light and photocytotoxicity. The present study opens up new strategies for designing and developing cobalt and copper based photosensitizers for their potential photochemotherapeutic applications under hypoxic reaction conditions.
References: Lahiri, D. et al., J Chern. Sci, 2010, 122, 321-333; Inorg. Chern., 2009, 48, 339-349; Dalton Trans. 2010,39,1807-1816; Polyhedron, 2010, 29, 2417-2425.
41
MARSH, BETTYE KAYE. "TOWARD MODEL COMPOUNDS FOR THE ACTIVE SITE STRUCTURE OF CYTOCHROME C OXIDASE: SULFUR-BRIDGED HETEROBIMETALLIC COMPOUNDS OF COPPER(II) WITH IRON(III), COBALT(II) AND MANGANESE(II) TETRAPHENYLPORPHYRIN CENTERS." Thesis, 1986. http://hdl.handle.net/1911/15995.
Full textAbstract:
In order to further examine the geometric and electronic properties associated with active sites in copper proteins, four new pentacoordinate model compounds, Zn('II)(imidH)(S)DAP (SO(,3)CF(,3)), Cu('II)(imidR)(S)DAP (SO(,3)CF(,3)), Zn('II)(imidR)(S)DAP (SO(,3)CF(,3)), and Cu('II)(imidR)(S)DAP (SO(,3)CF(,3)) containing M-N(imidazole) and M-S (thiolate) bonds have been synthesized and characterized. Through
comparative spectroscopic and electrochemical studies with "Blue" cuproprotein centers, the new mononuclear copper(II) compounds have been found to not well mimic the electronic properties of the copper(II) active sites in the proteins. The mononuclear copper(II) compounds (and their zinc(II) counterparts) have also been reacted with "axially-starved" iron(III), cobalt(II), and manganese(II) Tetra- phenylporphyrin compounds to yield a new class of twelve (mu)-thiolato
bimetallic complexes as model compounds for the proposed thiolate-bridged cyt. a(,3)('3+)-S-Cu(,U)('2+) active site structure of resting cyto- chrome c oxidase. The model compounds have been derived from LFe('III)(TPP) (TPP('2-) = tetraphenylporphyrinato and L = SO(,3)CF(,3)('-))
and M'('II)(imidH)(S)DAP (SO(,3)CF(,3)) or M'('II)(imidR)(S)DAP (SO(,3)CF(,3)) (M'('II) = Zn or Cu) to yield species containing LFe('III)-S-Zn('II)(imidH)- DAP ('+), LFe('III)-SCu('II)(imidH)DAP ('+), LFe('III)-S-Zn('II)(imidR)DAP ('+), and LFe('III)-S-Cu('II)(imidR)DAP ('+) cores. Furthermore, reaction of M('II)(TPP) (M('II) = Co or Mn) with M'('II)(imidH)(S)DAP (SO(,3)CF(,3)) or M'('II)(imidR)(S)DAP (SO(,3)CF(,3)) (M'('II) = Zn or Cu) has produced new model compounds containing Co('II)-S-Zn('II)(imidH)DAP ('+), Co('II)-S-Cu('II)(imidH)DAP ('+), Co('II)-S-Zn('II)(imidR)DAP ('+), Co('II)-S-Cu('II)(imidR)- DAP ('+), Mn('II)-S-Zn('II)(imidH)DAP ('+), Mn('II)-S-Cu('II)(imidH)DAP ('+), Mn('II)-S-Zn('II)(imidR)DAP ('+), and Mn('II)-S-Cu('II)(imidR)DAP ('+) centers as (SO(,3)CF(,3)('-)) salts. Through comparative magnetochemical and spectroscopic investigations of these novel heterobinuclear com- pounds with parallel studies on the enzyme active site, a cyt. a(,3)('3+)- S-Cu(,U)('2+) active site structure for the resting enzyme has been sys- tematically tested, for the first time, by a model compound approach.
42
"I-III-VI₂ and II-VI/I-III-VI₂ Alloyed nanocrystals and their heterostructures: synthesis, characterization and potential applications." Thesis, 2011. http://library.cuhk.edu.hk/record=b6075382.
Full textAbstract:
Xu, Yeming = I-III-VI₂χχχII-VI和I-III-VI₂χχχχχχχχχχχχχχχ : 合成, 表征以及潛在应用 / 徐業明.Thesis (Ph.D.)--Chinese University of Hong Kong, 2011.
Includes bibliographical references (leaves 130-134).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstract also in Chinese.
Xu, Yeming = I-III-VI₂ zu yi ji II-VI he I-III-VI₂ zu fu he na mi cai liao he tuo men de yi zhi jie gou : he cheng, biao zheng yi ji qian zai ying yong / Xu Yeming.
43
Flórido, Ana. "Role of redox : active sod mimics on the migration and invasion capabilities of human breast cancer cells." Doctoral thesis, 2019. http://hdl.handle.net/10451/42842.
Full text
44
Pousaneh, Elaheh. "Synthesis and Characterization of Metal Complexes for Thin Film Formation via Spin-Coating or Chemical Vapor Deposition." 2019. https://monarch.qucosa.de/id/qucosa%3A72463.
Full textAbstract:
The present thesis describes the synthesis and characterization of magnesium, copper, and iron complexes and their application in the MOCVD (Metal-Organic Chemical Vapor Deposition) process, as well as the synthesis and characterization of yttrium and gadolinium complexes and their use as spin-coating precursors for metal oxide thin layer formation. The objective of this scientific work is the development of the family of bis(β-ketoiminato) magnesium(II) complexes and a series of heteroleptic β-ketoiminato copper(II) precursors for the formation of magnesium oxide and copper/copper oxide layers by using the MOCVD process. Modifications of the ketoiminato ligands affect the physical and chemical properties of the respective complexes. Another central theme of this work is the development of β-diketonato iron(III) complexes for the deposition of carbon-free gamma- and alpha-Fe2O3 layers via MOCVD. The thermal behavior and vapor pressure of the precursors could be influenced by the variation of the β-diketonate ligands. In addition, the synthesis and characterization of yttrium and gadolinium β-diketonates and their use as spin-coating precursors are described. Field-effect transistors were successfully fabricated by the deposition of carbon nanotubes on top of the Y2O3 films.
45
LIN, CHUN-YEN, and 林君彥. "Part.I Hydrophobic Copper-based complexes: luminescence, oxygen and glucose-sensing in urinePart.II Four new lead(II)–iridium(III) heterobimetallic coordination frameworks: synthesis, structures, luminescence and oxygen-sensing propertiesPart.III Studies on the sample preparation and characterization of nanoparticles in cosmetic products." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/m8acq8.
Full text
46
Cymbál, Martin. "Interakce alkaloidů s přechodnými kovy III." Master's thesis, 2020. http://www.nusl.cz/ntk/nusl-412276.
Full textAbstract:
Charles University Pharmaceutical Faculty in Hradec Králové Department of Pharmaceutical Botany Candidate: Bc. Martin Cymbál, DiS. Supervisor: doc. Ing. Kateřina Macáková, Ph.D. Diploma thesis 2019/2020: Interactions of alkaloids with transition metals III., pp. 86. Copper is one of the important trace elements in the body. It regulates various enzymatic pathways. This work monitors the chelating and reducing activity of isochinoline alkaloids of the family Amaryllidaceae. The alkaloids of Amaryllidaceae have a large number of effects such as analgesic, narcotic, antiarrhythmic, antihypertensive, bronchodilatory, chemotherapeutic, antiparasitic, uteretonic, locally anesthetic, mydriatic and many other significant effects. An important representative is galanthamine hydrobromide, which is therapeutically used and is an inhibitor of acetylcholinesterase. Galanthamine type alkaloids (galanthamine, galanthamine hydrobromide, chlidanthine), lycorine type (lycorine, galanthine), haemanthamine type (haemanthnamine, vittatine) and montanine type (montanine) were studied. The methodology of the work was to determine the chelating and reducing activity with the use of the hematoxylin indicator and bathocuproindisulfonic acid, at different pH or in dimethylsulfoxide. Of the alkaloids studied, galanthamine and...
47
Sule, Rasidi. "Synthesis of copper-tantalum-ruthenium composites for electronics interconnection applications." 2011. http://encore.tut.ac.za/iii/cpro/DigitalItemViewPage.external?sp=1000299.
Full textAbstract:
M. Tech. Metallurgical Engineering.Aims at improving Cu interconnection problem by homogeneous distribution of ruthenium and tantalum in Cu matrix for excellent interconnection in electronics packaging. The aim will be achieved through the following objectives.Development of appropriate technology for homogenizing submicron metal powders with suitable methods for controlling grain growth during sintering. Study the mechanisms of synergistic incorporation of Ru, and Ta on improving copper interconnection properties. To investigate metallurgical interactions and phenomena occurring during sintering. To investigate specific property and behaviour advantages intrinsic due to the composites and material mix.
48
Van, der Merwe Ryno. "Leaching characteristics of copper refractory ore : effect of pre-oxidation stage." Thesis, 2010. http://encore.tut.ac.za/iii/cpro/DigitalItemViewPage.external?sp=1000303.
Full textAbstract:
M. Tech. Metallurgical Engineering.A novel process of leaching copper refractory ore from Nchanga mine, Zambia, in two stages consisting of a pre-oxidation step and an acid dissolution stage was investigated by means of a leach test rig.
49
Maphoru, Mabuatsela Virginia. "Oxidative coupling of naphthols on supported nanocrystalline platinum- and copper-group metals." Thesis, 2013. http://encore.tut.ac.za/iii/cpro/DigitalItemViewPage.external?sp=1000593.
Full textAbstract:
Thesis (M. Tech. degree in Chemistry) Tshwane University of Technology 2013.Discusses the nanostructured platinum group catalysts provide an efficient route for the oxidative coupling of naphthols. The potential of a new catalytic reaction described in the patent literature has not yet been fully explored, although the reaction could provide an efficient new route to chromophoric systems containing conjugated aromatic rings.
50
Molele, Tebogo Amelia. "Tribocorrosion behaviour of copper and zirconia reinforced nickel-titanium shape memory composites." 2013. http://encore.tut.ac.za/iii/cpro/DigitalItemViewPage.external?sp=1000990.
Full textAbstract:
M. Tech. Metallurgical Engineering.StudIes the tribocorrosion behaviour of copper-nickel-titanium shape memory composite reinforced by zirconia,synthesized through powder metallurgy process. The research aims to achieve the following objectives: 1. Study the tribocorrosion mechanisms of the composites in NaCl solution (typical human body fluid). 2. Investigate the tribocorrosion mechanisms of the composites in other environments typical of some engineering applications.The proposed study on incorporating zirconia into the matrix NiTiCu through powder metallurgical process and investigations of the phenomenon of joint wear-corrosion synergism occurring in sodium chloride considered typical of human body system and sulphuric acid environment typical of wide range engineering applications is therefore very novel. It is therefore aimed that information on the tribocorrosion behaviour of NiTiCu as well as with zirconia incorporation will form basis for typical compositional formulation approaches for improved bio-tribocorrosion improvement in biomedical applications and actuators used in other engineering applications.