To see the other types of publications on this topic, follow the link: Copper(II) Ternary Complexes.
Dissertations / Theses on the topic 'Copper(II) Ternary Complexes'
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(II) Ternary Complexes.'
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
Jönsson, Jörgen. "Phase transformation and surface chemistry of secondary iron minerals formed from acid mine drainage." Doctoral thesis, Umeå University, Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-156.
Full textAbstract:
<p>The mining of sulphidic ore to extract metals such as zinc and copper produces huge quantities of waste material. The weathering and oxidation of the waste produces what is commonly known as Acid Mine Drainage (AMD), a dilute sulphuric acid rich in Fe(II) and heavy metals. This thesis serves to summarise five papers reporting how the precipitation of Fe(III) phases can attenuate the contamination of heavy metals by adsorption processes. </p><p>Schwertmannite (Fe8O8(OH)6SO4) is a common Fe(III) mineral precipitating in AMD environments at pH 3-4. The stability and surface chemistry of this mineral was investigated. It was shown that the stability depended strongly on pH and temperature, an increase in either promoted transformation to goethite (α-FeOOH). Two pH dependent surface species of SO42- were detected with infrared (ATR-FTIR) spectroscopy.</p><p>The adsorption of Cu(II), Pb(II) and Zn(II) to schwertmannite occurred at lower pH than to goethite, whereas Cd(II) adsorption occurred in a similar pH range on both schwertmannite and goethite. Extended x-ray absorption fine structure (EXAFS) spectroscopy suggests two surface species for Cu(II) and Cd(II) at the schwertmannite surface. Cu(II) adsorbs monodentately and Cd(II) bridging bidentately to adsorbed SO42-. Both metal ions also adsorb in a bridging bidentate mode to the surface hydroxyl groups. At pH 7.5 up to 2.7 μmol Cd(II) m-2 could be adsorbed to schwertmannite, indicating a large adsorption capacity for this mineral.</p><p>The acid-base properties of two NOM samples were characterised and could be well described as diprotic acids below pH 6. The adsorption of NOM to schwertmannite and goethite was very similar and adsorption occured in a very wide pH range.</p><p>High concentrations of NOM increased the adsorption of Cu(II) to goethite at low pH whereas a slight decrease was noted at low concentrations of NOM. No effect was detected in the schwertmannite system. </p><p>The formation of Fe(III) phases from precipitation of AMD was shown to be very pH dependent. At pH 5.5 a mixture of minerals, including schwertmannite, formed whereas at pH 7 only lepidocrocite (γ-FeOOH) formed. The concentration of Zn(II) in AMD could by adsorption/coprecipitation be reduced to environmentally acceptable levels.</p>
2
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
3
Shemesh, Ely 1962. "TERNARY COMPLEXES OF COPPER(I), CYANIDE, AND 2,9-DIMETHYL-1,10-PHENANTHROLINE." Thesis, The University of Arizona, 1986. http://hdl.handle.net/10150/291268.
Full text
4
Essex, Sarah Jane. "Spectral intensities in planar copper(II) complexes." Thesis, University of Cambridge, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239622.
Full text
5
Zhang, Yousheng. "Polynuclear magnetic complexes of manganese(II), cobalt(II), nickel(II) and copper(II)." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape2/PQDD_0014/NQ52856.pdf.
Full text
6
Quinlan, D. J. "Hydrogen bonding in N-ligated copper(II) complexes." Thesis, University of Nottingham, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262983.
Full text
7
Crowder, Janell M. "Homo- and Heterometallic Bis(Pentafluorobenzoyl)Methanide Complexes of Copper(II) and Cobalt(II)." Thesis, State University of New York at Albany, 2017. http://pqdtopen.proquest.com/#viewpdf?dispub=10680674.
Full textAbstract:
<p> β-Diketones are well known to form metal complexes with practically every known metal and metalloid. Metal complexes of fluorinated β-diketones generally exhibit increased volatility and thermal stability compared to the non-fluorinated analogues, and thus are used extensively in various chemical vapor deposition (CVD) processes for the deposition of metal, simple or mixed metal oxides, and fluorine-doped metal oxide thin films. Furthermore, the electron-withdrawing nature of the fluorinated ligand enhances the Lewis acidity of a coordinatively unsaturated metal center which facilitates additional coordination reactions. The physical and structural properties of fluorinated β-diketonate complexes are discussed in Chapter 1 and a few key application examples are given.</p><p> The focus of this work is the synthesis and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated metal complexes of bis(pentafluorobenzoyl)- methanide (L, C<sub>6</sub>F<sub>5</sub>COCHCOC<sub> 6</sub>F<sub>5</sub><sup>-</sup>). In Chapter 2, we present the preparation and isolation of the unsolvated complex [Cu(L)<sub>2</sub>] in pure crystalline form for the first time. We subsequently investigated the reaction of unsolvated [Cu(L)<sub>2</sub>] with sodium hexafluoroacetylacetonate [Na(hfac)] in a solvent-free environment. This reaction allowed the isolation of the first heterometallic Na–Cu diketonate [Na<sub>2</sub>Cu<sub>2</sub>(L)<sub> 4</sub>(hfac)<sub>2</sub>] structurally characterized by single crystal X-ray crystallography. Thermal decomposition of [Na<sub>2</sub>Cu<sub>2</sub>(L)<sub> 4</sub>(hfac)<sub>2</sub>] was investigated for its potential application in MOCVD processes. In the final chapter, we present the first exploration of the anhydrous synthesis of Co(II) complexed with bis(pentafluorobenzoyl)methanide in order to produce a complex without ligated water. Single crystal X-ray crystallographic investigations revealed the isolation of the ethanol adduct, [Co<sub>2</sub>(L)<sub>4</sub>(C<sub>2</sub>H<sub>5</sub>OH)<sub>2</sub>], and following the removal of ethanol, a 1,4-dioxane adduct, [{Co<sub> 2</sub>(L)<sub>4</sub>}<sub>2</sub>(C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>)]. </p><p> In this work, we have provided the first investigation of the synthesis, isolation and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated Cu(II) and Co(II) complexes of bis(pentafluorobenzoyl)methanide ligand. These studies demonstrate how the electrophilicity of a coordinatively unsaturated metal complexed to highly-fluorinated â-diketone ligands can be utilized for the formation of new adducts or new and interesting heterometallic complexes. This body of work provides a basis upon which future research into unsolvated and unligated bis(pentafluorobenzoyl)methanide metal complexes can expand.</p><p>
8
Jamadar, Abeda. "Copper(II) and Zinc(II) complexes of aroyl hydrazones as potential antitubercular agents." Thesis, University of York, 2012. http://etheses.whiterose.ac.uk/3099/.
Full textAbstract:
There is a continuing need to make new antitubercular drugs due to development of resistance towards present drugs. To do this, series of pyruvate hydrazones (PVAHs) and their respective Cu(II) complexes and Zn(II) complexes were synthesized and fully characterised. Variable temperature NMR studies of PVAHs indicate the presence of E and Z isomers in the solution. Determination of the obtained single crystal X-ray structures reveals that Cu(II) ion binds to PVAH ligand in 1:1 ratio resulting in square pyramidal geometry in most of the Cu(II) complexes, whereas Zn(II) ion binds to two PVAH ligands in 1:2 ratio giving rise to octahedral geometry. The electrochemical studies of Cu(II) complexes of PVAH performed using cyclic voltammogram indicate the presence of quasi-reversible behaviour assigned to a Cu2+/Cu1+ peak potential. This indicates structural reorganisation of Cu(II) square pyramidal geometry towards Cu(I) tetrahedral geometry. The tetrahedral geometry of a synthesized Cu(I) complex of PVAHs was confirmed by X-ray crystal structure. The stability studies of selected PVAH ligands and their metal complex indicate that the investigated compounds were stable in extreme basic conditions, but they were unstable in extreme acidic conditions due hydrolysis of azomethine bond. However, stability of these compounds in physiological conditions, i.e. in PBS buffer, reveals that ligand hydrolyses slowly over a period of time, whereas the Cu(II) complex remains quite stable over a monitored period of 120 hours. Interestingly, dihydrazide analogue of PVAH was fairly stable in PBS buffer. EPR studies of investigated Cu(II) complexes in DMSO indicate that PVAHs remains strongly coordinated to Cu(II) centre. The evaluation of the antimycobacterial activity showed that the anionic PVAHs and Zn(II) complexes are essentially inactive. Some of the corresponding neutral Cu(II) complexes, however, exhibit promising antimycobacterial activities if tested under high iron (8 μg Fe per mL) conditions. As observed for the related antimycobacterial agent isoniazid, the activity of the complexes decreases if the M. tuberculosis cells are grown under low iron (0.02 μg Fe per mL) conditions. The Cu(II) complexes may thus have a similar mode of action and may require an iron-containing heme-dependent peroxidase for activation. A series hydrophobic cinnamaldehyde hydrazones (CAHs) and their Cu(II) complexes were also synthesized and tested for their antitubercular activity under similar conditions to that of PVAH series. But they failed to show any inhibitory activity due to their poor cellular uptake owing to their limited solubility in aqueous buffer.
9
Doddridge, Bruce Germein. "Ligand exchange and substitution on five-coordinate complexes of copper (II), nickel (II) and cobalt (II) /." Title page, contents and summary only, 1986. http://web4.library.adelaide.edu.au/theses/09PH/09phd641.pdf.
Full text
10
Chen, Wei. "Studies on immobilized polymer-bound imidazole copper(II) complexes as catalysts." [S.l. : [Groningen : s.n.] ; University Library Groningen] [Host], 1991. http://irs.ub.rug.nl/ppn/293908745.
Full text
11
Oakley, Michael Andrew. "Synthesis, structure and properties of copper(II) complexes and their ligands." Thesis, University of Hull, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.296239.
Full text
12
REIS, ALINE CRUZ DE MORAES. "SYTHESIS AND CHARACTERIZATION OF COPPER (II) AND ZINC (II) COMPLEXES WITH DIPEPTIDES OF BIOLOGICAL INTEREST." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2010. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=16186@1.
Full textAbstract:
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>FUNDAÇÃO DE APOIO À PESQUISA DO ESTADO DO RIO DE JANEIRO<br>Este trabalho descreve a síntese e caracterização de quatro complexos de cobre (II) e quatro complexos de zinco (II), com dipeptídeos, no estado sólido. Os dipeptídeos envolvidos foram: glicil-glicina, glicil-valina, metionil-metionina, metionil-glicina e cisteinil-glicina, cujos aminoácidos fazem parte de algumas proteínas envolvidas em processos de neurodegeneração, mais especificamente na doença de Alzheimer. Embora os mecanismos que desencadeiam esta patologia não estejam ainda totalmente esclarecidos, sabe-se que os íons metálicos, como o cobre (II) e o zinco (II), interagem com o peptídeo beta-amilóide. Acredita-se que tais interações favoreçam a formação de agregados protéicos sólidos deste peptídeo, observados nos cérebros de pacientes com essa doença. Dessa forma, a obtenção e o estudo de modelos simples no estado sólido, sintetizados em condições próximas ao meio biológico, podem permitir uma melhor compreensão de possíveis interações de tais metais neste sítio protéico. Os compostos obtidos foram caracterizados utilizando as seguintes técnicas: análise elementar, absorção atômica, espectroscopia de infravermelho, espectroscopia Raman, espectroscopia de ultravioleta-visível, termogravimetria, RPE (para os complexos de cobre) e condutivimetria. Para os complexos de zinco, foram realizados cálculos teóricos mecânico-quânticos para obtenção de parâmetros geométricos e espectros de infravermelho. A análise dos compostos obtidos mostrou que os complexos de cobre e zinco com os dipeptídeos estão coordenados por átomos de oxigênio e nitrogênio. Nos complexos de peptídeos contendo enxofre, a coordenação também ocorre pelo átomo de enxofre (cobre com metionil-metionina e metionil-glicina e zinco com cisteinil-glicina). Os compostos obtidos para ambos os metais na proporção metal-ligante (1:1) mostram comportamento diferente dos estudos em solução e aqueles obtidos na proporção metal-ligante (1:2) mostram comportamento similar a complexos de metais com aminoácidos.<br>This work describes the synthesis and characterization of copper (II) and zinc (II) complexes, with dipeptides in solid state. The dipeptides involved were:
glycyl-glycine, glycyl-valine, methionyl-methionine, methionyl-glycine and cysteinyl-glycine, whose aminoacids take part in some proteins involved in neurodegeneration processes, more specifically in Alzheimer’s disease. Although the mechanisms that trigger this pathology are still not totally clear, it is known that metallic ions, such as copper (II) and zinc (II) interact with the beta-amyloid peptide. It seems that such interactions favor the formation of solid proteic aggregates of this peptide, observed in the brains of patients with Alzheimer’s disease. Thus, the obtaining and study of simple models in the solid state, synthesized in similar conditions to the biological medium, may allow a better understanding of the possible interactions of such metals in this proteic site. The compounds obtained were characterized using the following techniques: elemental analysis, atomic absorption, infrared spectroscopy, Raman spectroscopy, ultraviolet-visible spectroscopy, thermogravimetry, EPR (for the copper complexes) and conductivimetry. For the zinc complexes, quantum-mechanical theoretical calculations were performed to obtain geometrical parameters and infrared spectra. The analysis of the compounds showed that the copper and zinc complexes with dipeptides are coordinated through oxygen and nitrogen atoms. In complexes of dipeptides containing sulfur, coordination trough the sulfur atom occurs too (copper with methionyl-methionine and methionyl-glycine and zinc with cysteinyl-glycine). The compounds obtained for both metals at the metal-ligand ratio (1:1) behave differently from those studied in solution e those obtained in the metal-ligand ratio (1:2) show similar behavior of metal complexes with aminoacids.
13
SZYFMAN, NATALIE WAISSMANN. "STUDY OF COPPER(II) AND ZINC(II) COMPLEXES WITH SOME POLYAMINES AND PHOSPHOCREATINE OR ATP." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2011. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=18244@1.
Full textAbstract:
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>Foram estudados alguns sistemas binários de Cu(II) e Zn(II) formados com as poliaminas (PA= En, Tn, Put, Spd e Spm) e os complexos ternários (MLPA), onde L foi a PCr ou o ATP e PA uma das cinco poliaminas. O estudo foi realizado em solução aquosa por potenciometria, espectroscopia de ultravioleta-visível, Raman, RMN e RPE e cálculos de menor energia de estabilização e modelagem molecular. As constantes de estabilidade foram determinadas pela potenciometria. Os valores das constantes dos complexos com as poliaminas apresentam um comportamento bastante diferenciado entre os sistemas formados com o Cu(II) e Zn(II). A ordem dos valores das constantes de estabilidade dos sistemas com o Cu(II) é:CuPut<CuTn<CuEn<CuSpd<CuSpm, e dos sistemas com Zn(II) é: ZnPut<ZnEn<ZnTn<ZnSpm<ZnSpd. Esse comportamento diferenciado se deve a estrutura formada nos complexos. Enquanto o anel de 5 membros formado pelo complexo CuEn é mais estável do que o anel de 6 e 7 membros formados pelos complexos CuTn e CuPut, respectivamente, nos sistemas com o Zn(II) o complexo que forma anel de 6 membros (ZnTn) é mais estável do que o complexo que forma anel de 5 membros (ZnEn). Já o complexo ZnPut é o menos estável pela coordenação monodentada da poliamina ao Zn(II). Os complexos formados com Cu(II) e Zn(II) com a Spd e Spm também apresentam comportamento diferenciado. Com o Cu(II) as poliaminas Spd e Spm formam complexos se coordenando com três e quatro grupamentos amino, respectivamente. Com o Zn(II) a coordenação deve ser por três grupamentos amino nos dois complexos formados. Interações entre as poliaminas protonadas e os dois ligantes são observadas de um modo geral exceto no sistema Zn:ATP:Spd, e isso se deve a conformação que a molécula formada sofre que desfavorece a interação entre os ligantes. Interações entre as triamina (Spd) e tetramina (Spm) e a PCr, são observadas nos complexos ternários, para ambos os íons, mesmo quando estas não estão protonadas. Esta interação deve ser pelo átomo de nitrogênio não coordenado da poliamina e o átomo de oxigênio não coordenado da PCr. Neste trabalho foi possível esclarecer o modo de coordenação do Cu(II) com a PCr em solução, que é pelos grupamentos guanidino e fosfato do ligante, tanto no complexo binário como nos complexos ternários. Também para o Zn(II) a PCr se complexa do mesmo modo. O modo de coordenação do ATP ao Zn(II) tanto nos complexos binários como ternários, deve ser através dos grupamentos fosfatos PB e Py .<br>Some binary systems of Cu(II) and Zn(II) with polyamines (PA=En, Tn, Put, Spd and Spm), and ternary complexes (MLPA) of Cu(II) and Zn(II), where L is PCr or ATP, and PA is one of the five polyamines, were studied. The study was performed in aqueous solution using potentiometry, ultraviolet-visible, Raman, NMR and EPR spectroscopies, and, calculations of the lowest stabilization energy for formed complexes and molecular modeling. The stability constants were determined by potentiometry. The order of the values of stability constants of the systems with Cu(II) is: CuPut<CuTn<CuEn<CuSpd<CuSpm. For systems with Zn(II) it is: ZnPut<ZnEn< ZnTn<ZnSpm<ZnSpd. This different behavior is due to the structures formed by the complexes. While the 5-membered ring formed by CuEn complex is more stable than the 6- and 7-membered ring complexes formed by CuTn and CuPut, respectively, in systems with Zn(II) the complex that forms the 6-membered ring (ZnTn) is more stable than 5-membered ring (ZnEn). The complex ZnPut is less stable than systems formed with other diamines, suggesting a monodentate coordination of this polyamine with Zn(II). The complexes formed by Cu(II) and Zn(II) with Spd and Spm also have a peculiar behavior. With Cu(II) the polyamines Spd and Spm form complexes by coordinating with three and four amino groups, respectively. With Zn(II) coordination should be through three amino groups in both complexes. Interactions between protonated polyamines and the two ligands are generally observed, except in the system Zn:ATP:Spd. This can be because of the conformation suffered by the molecule, hindering the interaction between the ligands. Interactions between the tridentate (Spd) and tetradentate (Spm) polyamines and PCr are observed in the ternary complexes for both ions, even when the PA´s are not protonated. This interaction should be between the non-coordinated nitrogen atom from the PA and the non-coordinated oxygen atom from PCr. It was possible to clarify the coordination mode of Cu(II) with PCr in solution, which occurs through the guanidine and phosphate groups of PCr, both in the binary and ternary complexes. The ion Zn(II) also coordinates in the same way. The coordination mode of ATP with Zn(II) in the binary and ternary complexes probably takes place through the PB and PY phosphates groups.
14
Gichinga, Moses G. Striegler Susanne. "Synthesis, spectroscopic investigation and immobilization of copper(II) complexes as oxidation catalysts." Auburn, Ala, 2009. http://hdl.handle.net/10415/1857.
Full text
15
TRUDU, FEDERICA. "Studio di complessi di rame (II) e platino (II) con proprietà antitumorali." Doctoral thesis, Università degli Studi di Cagliari, 2015. http://hdl.handle.net/11584/266557.
Full textAbstract:
Cisplatin is one of the most active drugs in anticancer therapy, and it is currently used
for the treatment of a wide range of cancers, in particular advanced ones. After its
introduction in clinical therapy, the research in this field has focused on the preparation
of new metal complexes with increased activity and lower side-effects. Besides, the use
of drug combinations with synergistic effect, i.e. an effect greater than the sum of the
effects of the single drugs, has been introduced. This thesis is focused on the preparation
of Cu(II) and Pt(II) complexes and on the study of their cytotoxic properties, alone or in
combination with cisplatin.
Cu(II) complexes with 1,10-phenantroline (phen), 1,10-phenantrolin-5,6-dione and 1,10-
phenantrolin-5,6-diol, with 1:1 or 1:2 metal:ligand stoichiometry, have been synthesized.
In addition, mixed Cu(II) complexes with phen and thiophene derivatives of general
formula [Cu(phen)2(T)](ClO4)2 (T=1-methylthio-thiophene-2-carboxylic acid, 2-
methylthio-thiophene-1-carboxylic acid, 2-thiophenecarboxamide, 2-
thiophenecarboxylate) have been prepared. A family of Pt(II) complexes of general
formula [Pt(P)(D)2](ClO4)2, being P a derivative of phen and D a derivative of
imidazolidin-2-thione, has been synthesized.
In order to find the species present in solution in conditions similar to the physiological
ones (37 °C and NaCl 0.1 M), the formation constants of the complexes have been
determined through potentiometric titrations. The dipole moments of the platinum
complexes have been determined through quantum mechanical calculations.
The in vitro cytotoxic activity of ligands and metal complexes has been evaluated against
a panel of human tumour cell lines, and it has been correlated to their structures.
Finally, a new method, based on experimental design and artificial neural networks, has
been proposed for the evaluation of the synergy in mixtures of two or more drugs.
Exploiting this method, the cytotoxic activity of mixture of cisplatin and three Cu(II)
complexes ([Cu(phen)(H2O)2(ClO4)2], [Cu(phen)2(H2O)](ClO4)2 e
[Cu(phen)2(imidazolidin-2-thione)](ClO4)2) has been studied, and the combination with
higher synergistic effect have been identified.
16
Suksangpanya, Unchulee. "Hydrogen bonded supramolecular architectures of copper (II) complexes of amidino #OMICRON# alkylurea derivatives." Thesis, University of Nottingham, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.273124.
Full text
17
PINTO, LUCIANA DORNELAS. "STUDY OF COPPER(II) COMPLEXES CONTAINING AMINO ACIDS OF INTEREST FOR BRAIN CHEMISTRY." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2010. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=16189@1.
Full textAbstract:
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>Foram sintetizados 16 complexos de cobre(II) coordenados com seis aminoácidos presentes na placa b-amilóide, que está associada à Doença de Alzheimer - ácido aspártico, ácido glutâmico, metionina, glicina, serina e arginina, outros dois aminoácidos também encontrados no cérebro - cisteína e homocisteína, além da L-carnitina e acetil-L-carnitina que vêm sendo utilizados como suplemento alimentar em pacientes com doenças neurodegenerativas. Nosso objetivo foi verificar a afinidade do cobre(II) com estes aminoácidos, uma vez que o envelhecimento provoca aumento no cérebro tanto das concentrações de íons cobre como dos níveis de todos estes aminoácidos (que são consequência de fragmentações peptídicas). Por esta razão, procurou-se trabalhar in vitro com condições próximas ao meio biológico utilizando apenas água deionizada como solvente. Os complexos obtidos foram caracterizados pelas seguintes técnicas: análise elementar (espectrometria de absorção atômica e CHN), condutimetria, análise termogravimétrica, ressonância paramagnética eletrônica, voltametria cíclica e espectroscopia no infravermelho. Foi possível verificar que, exceto a acetil-L-carnitina, todos se comportam como ligantes bidentados e complexam facilmente ao cobre(II). Ácido aspártico, ácido glutâmico, serina, metionina, glicina e arginina se coordenaram através do átomo de oxigênio do grupo carboxilato e do átomo de nitrogênio do grupo amino, cisteína e homocistéina através do átomo de enxofre e do átomo de nitrogênio do grupo amino, L-caritina através do átomo de oxigênio do grupo carboxilato e do átomo de oxigênio alcoólico e acetil-L-carnitina se coordena monodentadamente através do átomo de oxigênio do grupo carboxilato.<br>Sixteen complexes of copper(II) with six amino acids that are present in the b-amyloid peptide, which is associated with Alzheimer’s disease - aspartic acid, glutamic acid, methionine, glycine, serine and arginine -, two amino acids also found in the brain - cysteine and homocysteine -, as well as L-carnitine and acetyl-L-carnitine, which have been used as food supplement in patients with neurodegenerative diseases, were studied. Our aim was to determine the affinity of copper(II) with these amino acids, since aging causes an increase in brain concentrations of copper ions as well as in the level of all of these amino acids, as a consequence of peptide fragmentation. For this reason, we decided to do an in vitro study in similar conditions as the biological environment, using only deionized water as solvent. These compounds were characterized through the following techniques: elementary analysis (atomic absorption spectrometry and CHN), conductimetry, thermogravimetric analysis, electron paramagnetic resonance, electrochemical analysis, and infrared spectroscopy. It was possible to verify that, except for acetyl-L-carnitine, all amino acids behaved as bidentate ligands. They all form complexes with copper(II) easily. Aspartic acid, glutamic acid, serine, methionine, glycine and arginine coordinate through the oxygen atom of the a-carboxylate group and the nitrogen atom of the amine group. Cysteine and homocysteine coordinate through the sulfur atom and the nitrogen atom of the amine group, L-Carnitine coordinates through one oxygen atom of the carboxylate group and one oxygen atom of the alcohol group, and acetyl-L -carnitine coordinates through the oxygen atom of the carboxylate group.
18
LeCloux, Daniel D. (Daniel David) 1970. "Synthesis and reactivity of copper(I) and iron(II) carboxylate-bridged dimetallic complexes." Thesis, Massachusetts Institute of Technology, 1998. http://hdl.handle.net/1721.1/50411.
Full text
19
Reed-Mundell, Joseph Jerome. "Binuclear and tetranuclear copper(II) complexes containing ligands derived from phenol or hydroquinone." Case Western Reserve University School of Graduate Studies / OhioLINK, 1990. http://rave.ohiolink.edu/etdc/view?acc_num=case1058302716.
Full text
20
Walli, Adam. "Biomimetic Copper(I)-Mediated Activation of Dioxygen and Redox Non-Innocence in Copper(II) Complexes of Bis(oxazoline)s." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2014. http://hdl.handle.net/11858/00-1735-0000-0023-9636-9.
Full text
21
Sobola, Abdullahi Owolabi. "Synthesis, characterization and antimicrobial activity of copper (II) complexes of some hydroxybenzaldimines and their derivatives." Thesis, Rhodes University, 2012. http://hdl.handle.net/10962/d1016258.
Full textAbstract:
This study focuses on the antimicrobial activity of Cu(II) complexes of some orthohydroxybenzaldimines and its derivatives. Four different categories of Schiff base ligands were prepared by condensing salicylaldehyde, o-vanillin, p-vanillin and vanillin with p- and osubstituted anilines; 1-aminonaphthalene; 2- and 3-aminopyridine; 2- and 3- aminomethylpyridine as well as 2-aminobenzimidazole. The last category was prepared from ophenylenediamine and o-vanillin. The Schiff base ligands have been characterized by a combination of elemental analysis and spectral (¹H- and ¹³C-NMR, UV/Visible, infrared and Raman) data. The existence of strong intramolecular hydrogen bonding in the orthohydoxybenzaldimines was evident from the chemical shift values of the hydroxyl proton in the ¹H-NMR spectra of the Schiff base ligands. The hydroxyl proton resonates at high frequency and thus absorbed far downfield at 13.46-11.83 ppm, reflecting the presence of hydrogen bonding between the hydroxyl proton and the imine nitrogen. In the p-substituted aniline analogues of the Schiff base, a plot of the chemical shift values of the hydroxyl proton against the Hammett's substituent parameters gave a linear correlation between the electronegativities of the substituents and the chemical shift values. The nitro group with the highest electronegativity caused the least deshielding of the hydroxyl proton and thus absorbed upfield compared to the less electronegative substituents such as the CH3 and OCH3 analogues. Likewise, in the solid state infrared spectra of the ligands, the hydroxyl stretching band of the ortho-hydroxyl Schiff base ligands was observed as a very broad band and at much lower frequency, 3100-2100 cm⁻¹, indicating the existence of strong intramolecular hydrogen bonding. In the same vein, ¹H- and ¹³C-NMR spectral data for the Schiff base ligands indicated that the prepared compounds exist in the enol form in aprotic solvent, chloroform. The methine proton appeared as singlet and there was no carbonyl signal in the ¹³C-NMR spectra of the Schiff base ligands. This was supported by the infrared data having no vibrational band attributable to the carbonyl stretching of the keto-form of the Schiff base ligands in solid state. However, the UV/Visible study of the Schiff base ligands in protic solvent, methanol, suggested the existence of some of the Schiff base ligands in keto-enol form. A band at greater than 400 nm was observed in the UV/Visible spectra of the ligands and this has been attributed to the presence of the keto form of orthohydroxyl Schiff base ligands in solution. A plot of the molar absorptivity (ε) of the band at greater than 400 nm against Hammett substituent parameters revealed that the intensity of the bands increased with the electronegativity of the substituents. The Cu(II) complexes of salicylaldehyde, o-vanillin and a few p-vanillin based Schiff base ligands are reported in this work. It was observed that introduction of Cu(II) ions into the ligand system resulted in the hydrolysis of the imine band in few cases. All the isolated complexes have been characterized by elemental analysis, conductivity measurement, infrared and UV/Visible spectral data. The structures of three of the Cu(II) complexes were further confirmed by X-ray single crystal diffraction. The Schiff base ligands either coordinated as neutral base through the imine nitrogen or via the imine nitrogen and the phenolic oxygen atoms. In addition, the benzimidazole-based and ovan-2-pico analogues equally coordinated through the imidazole N-3 nitrogen and the azine nitrogen respectively; thus acted as tridentate. In general, the synthesized Cu(II) complexes fell into seven categories viz: [Cu(LH)Cl(H₂O)]Cl; [Cu(LH)₂Cl₂].xH₂O; [CuL₂]; [Cu₂L₂]; [Cu(LH)Cl(H₂O)]Cl; and [MLCl]. The Cu(II) complexes of the form, M(LH)₂Cl₂.xH₂O were either 1:1 or non-electrolyte in methanol and DMF. The third category, CuL₂, was however, non-electrolyte existing as neutral four coordinate Cu(II) complexes. X-ray single crystal structure of Cu(II) complexes derived from the ammonia-based Schiff bases revealed a square planar geometry for the complexes and this agreed with the planar geometry that has been reported for Cu(II) complexes of N-arylsalicylaldimines of the type studied in this work. The complexes, [Cu₂L₂], resulted from the ortho-hydroxyaniline analogues and were polymeric with the Schiff base ligands coordinating to the Cu(II) ions as tridentate dibasic via the imine nitrogen, phenolic oxygen and the aminophenolic oxygen atoms. Cu(II) complexes prepared from ovan-2-ampy and ovan-2-pico Schiff bases were of the forms [Cu(LH)Cl(H₂O)]Cl and [CuLCl] respectively. The X-ray crystal structure of [Cu(ovan-2- pico)Cl] revealed a four-coordinate square planar geometry for the complex. In the same vein, the o-phenylenediamine complexes were of the form [Cu(L)(H₂O)], with the X-ray crystal structure of [Cu(bis-ovanphen)(H₂O)] revealing a square pyramidal geometry. The Schiff base ligands and the isolated Cu(II) complexes have been evaluated for their antimicrobial activity against three bacterial strains (Escherichia coli ATCC® 8739™*, Staphylococcus aureus subsp. aureus ATCC® 6538™* and Bacillus subtilis subsp. spizizeni ATCC® 6633™*) and one fungal strain, Candida albicans ATCC® 2091™*, using agar disc diffusion and broth dilution techniques. It was observed that the presence of the methoxyl group at the ortho-position of the aldehyde moiety of the Schiff base ligands enhanced the activity of the ligand tremendously and thus the o-vanillin analogues showed the highest potency against the tested organisms. In addition, the hydroxyaniline analogues were equally the most promising of all the substituted aniline based Schiff bases. The o-vanillin analogues of the aminopyridines and aminomethylpyridines also exhibited significant activity against the tested organisms. All the 2-aminobenzimidazole series were active against the tested organisms. It should be noted that E. coli was the least susceptible of all the microorganisms while the highest potency was exhibited against the fungus of choice, Candida albicans. Lastly, chelation of the Schiff base ligands with Cu(II) ions did not have significant influence on the activity of the free ligands.
22
Alcacio, Tim. "THE MOLECULAR SCALE NATURE OF COPPER(II) AND ARSENATE BONDING WITH GOETHITE-HUMATE COMPLEXES." NCSU, 2001. http://www.lib.ncsu.edu/theses/available/etd-20010113-190843.
Full textAbstract:
<p>Alcacio, Tim. The Molecular Scale Nature of Copper(II) and Arsenate Bonding With Goethite-Humate Complexes. In soils, interactions between clay minerals and natural organic matter are known to affect the cycling of heavy metals and anions. Contaminant structures at mineral surfaces that contain adsorbed organic matter will have a significant influence on the bioavailability of the contaminant. The structure of copper(II) and arsenate complexes on goethite in the presence and absence of adsorbed humic acid were studied with extended x-ray absorption fine structure (EXAFS) spectroscopy and with x-ray absorption near edge structure (XANES) spectroscopy. The copper(II) and arsenate formed edge shared inner-sphere surface complexes with goethite. The copper(II) itself was present in a distorted octahedral configuration, and ternary complexes involving bonding with both the humic acid and the goethite (Type A complexes) or adsorbed humic acid (Type B complexes), occurred at pH 5.6. At pH 8, the copper(II) was found to display a stronger affinity for the goethite surface and the formation of ternary complexes did not occur. The EXAFS analyses demonstrated that arsenate was present in a tetrahedral configuration and was predominantly bonded to goethite surface sites. Regardless of the level of adsorbed humic acid, the arsenic coordination environment was similar and indicated that ternary complexes could not be distinguished. <P>
23
PUPPIN, PEDRO ANTONIO LUZ. "STUDY OF TERNARY COMPLEXES OF CO(II) AND NI(II) WITH THE AMINO ACIDS GLYCINE, SERINE, ASPARTIC ACID AND GUANIDINOACETIC ACID, IN SOLUTION." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2006. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=9456@1.
Full textAbstract:
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>Foram estudados os sistemas binários e ternários de cobalto
(II) e de
níquel(II) com os aminoácidos glicina, serina, ácido
aspártico e ácido
guanidoacético. Os aminoácidos glicina - Gly, serina -
Ser, ácido aspártico - Asp
e ácido guanidoacético - Gaa estão envolvidos em muitos
processos bioquímicos.
Esses aminoácidos fazem parte de muitas proteínas que, por
sua vez, são bons
agentes complexantes. O estudo das interações metal-
aminoácido tem grande
interesse, visto que estas representam modelos
simplificados para a análise das
mudanças provocadas nas propriedades das proteínas, quando
estas se ligam aos
íons metálicos. Neste estudo foram determinadas as
constantes de formação e de
interação das espécies pertencentes aos sistemas binários
e ternários de cobalto(II)
e de níquel(II), e também foram realizados estudos
espectrofotométricos de UVVis
de todos os sistemas estudados. A comparação dos espectros
de UV-Vis em
diferentes valores de pH com os gráficos de distribuição
de espécies permitiu
relacionar as bandas d-d com as respectivas espécies
propostas. Analisando as
constantes de formação dos complexos ternários ML1L2,
constatou-se que os
complexos de Ni(II) apresentam valores mais altos que os
respectivos de Co(II), o
que está de acordo com a série de Irving-Williams.
Comparando-se os espectros
de UV-Vis com os da literatura, pode-se concluir que as
bandas encontradas,
assim como os seus respectivos posicionamentos e
absortividades molares
referem-se a complexos octaédricos não regulares.
Verificou-se que as maiores
interações intramoleculares dos ligantes nos complexos
estudados, ocorreram com as espécies contendo Gaa. A
partir dos gráficos de distribuição de espécies em
função do pH, pode-se verificar que, em pH biológico, para
os três sistemas de
Co(II), predominam as espécies ternárias protonadas. Para
os sistemas de Ni(II),
não é possível generalizar. No sistema Ni-Gly-Ser a
espécie NiGlySer está em
maior quantidade em pH em torno de 7; no sistema Ni-Asp-
Gly, as espécies
ternárias formam-se em menor quantidade em valores de pH
mais baixos e em pH
biológio, as espécies binárias de NiAsp hidrolizadas é que
predominam; no
sistema Ni-Ser-Gaa, as espécies ternárias protonadas é que
estão em maior
concentração. Em pH ~ 9, já encontramos espécies
hidrolisadas (binárias e/ou
ternárias) em todos os sistemas ternários. Em meio mais
básico, as espécies
ternárias fragmentam-se, gerando espécies binárias
hidrolisadas dos tipos
ML(OH)3 e ML(OH)4 que passam a ter maiores estabilidades.<br>The binary and ternary systems of cobalt(II) and nickel
(II) with the amino
acids glycine, serine, aspartic acid and guanidinoacetic
acid were studied. The
amino acids glycine - Gly, serine - Ser, aspartic acid -
Asp and guanidinoacetic
acid - Gaa are all involved in several biochemical
processes. These amino acids
are constituents of many proteins, which are in turn, good
complexing agents. The
study of metal-amino acid interactions are of great
interest, as they represent
simplified models for the analysis of the changes caused
in the proteins`
properties, when these bond to metal ions. It was
determined, in this work, the
formation and interaction constants of species belonging
to the binary and ternary
systems of cobalt(II) and nickel(II). UV-Vis
spectrophotometric analysis were
also made for each of the systems studied. The comparison
of the UV-Vis spectra
in different pHs with the species` distribution graphs
indicated a relationship
between the d-d bands and the respective proposed specie.
When analyzing the
formation constants of the ternary complexes ML1L2, the Ni
(II) complexes
showed higher values than those of respective Co(II)
complexes, a pattern which
is in accordance with the Irving-Williams series. In
conclusion to the comparison
of the UV-Vis spectra with those in literature, we have
that the bands found, as
well as their respective position and molar absortivities,
refer themselves to nonregular
octahedral complexes. It was verified that the greatest
intramolecular
interactions beetween the ligands in the complexes studied
were those of the
species cointaining Gaa. From the graphs of species
distribution in terms of pH, we were able to verify that
in biological pH, for all three systems of Co(II),
protonated ternary species were predominant. No
generalizations were visible for
the Ni(II) systems. In the Ni-Gly-Ser system, the specie
NiGlySer is present in
greater amounts in pH close to 7; in the Ni-Asp-Gly
system, the ternary species
are formed in lower quantities in lower pH values and in
higher and biological pH
values, binary species of hydrolyzed NiAsp are
predominant; in Ni-Ser-Gaa
systems, protonated ternary species are in higher
concentration. In pH ~ 9,
hydrolyzed (binary and/or ternary) species were found in
all ternary systems. In
more basic medium, the ternary species were fragmented,
therefore generating
ML(OH)3 and ML(OH)4 hydrolyzed binary species, which have
in turn greater
stability.
24
Flynn, Elizabeth. "The catalysed decomposition of chlorosulfides." Thesis, Queen Mary, University of London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.336343.
Full text
25
Lin, Yongyue, and 林勇躍. "Luminescent platinum(II), copper(I), silver(I) and zinc(II) complexes with functional pyridyl and arylacetylide ligands: structures, spectroscopic properties and applications." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2001. http://hub.hku.hk/bib/B31243381.
Full text
26
Lin, Yongyue. "Luminescent platinum(II), copper(I), silver(I) and zinc(II) complexes with functional pyridyl and arylacetylide ligands : structures, spectroscopic properties and applications /." Hong Kong : University of Hong Kong, 2001. http://sunzi.lib.hku.hk/hkuto/record.jsp?B25155325.
Full text
27
Chen, Tianyu. "Study on the Copper(II)-Lactate Complexes in Cu₂O Electrodeposition Baths：From Determination to Application." Kyoto University, 2020. http://hdl.handle.net/2433/259043.
Full text
28
Ezenwa, Emmanuel. "N,N-diethyl-N'-naphthoylacylchalcogourea to metal (II)complexes as precursors for ternary metal chalcogenide thin films via AACVD." Thesis, University of Manchester, 2016. https://www.research.manchester.ac.uk/portal/en/theses/nndiethylnnaphthoylacylchalcogoureatometal-iicomplexes-as-precursors-for-ternary-metal-chalcogenide-thin-films-via-aacvd(85420a4c-89d4-4465-9734-ca40a75ba924).html.
Full textAbstract:
In this thesis complexes of acylchalcogoureas with cadmium (II), lead (II) and nickel (II) have been synthesised and investigated as single source precursors for the formation of metal chalcogenide thin films viaaerosol assisted chemical vapour deposition (AACVD). Routes to binary thin films have been explored using homoleptic complexes of the general structure bis(N,N-diethyl-N'-naphthoylchalcogoureato)metal(II). Analysis of the thin films produced showed the successful deposition of the binary materials from the synthesised complexes when characterised by powder XRD, ICP-OES, SEM and EDX. Routes to ternary thin films with the general structure MExE'1-x, where M represents a metal (Cd, Ni and Pb); and E chalcogen (S or Se) have been investigated using heteroleptic metal complexes of cadmium, nickel or lead including different chalcogen containing N,N-diethyl-N'-naphthoylchalcogoureato ligands and diethyldithiocarbamate. The precursors were fully characterised and novel compounds had their crystal structures determined. The heteroleptic complexes were thermolysed by AACVD forming the MExE'1-x thin films. In the cases of lead, nickel and cadmium the thin films produced showed that the composition of the film tended heavily towards the metal selenide. Ternary films of type MS1-xSex was prepared by mixing their binary precursors of type bis(N,N-diethyl-N'-naphthoylselenoureato)metal(II) and bis(N,N-diethyl-N'-naphthoylthioureato)metal(II) [metal = Cd, Ni and Pb]. In the case of lead and cadmium chalcogenide films variation of the ratio of sulphur and selenium containing precursors allowed for the full transition in composition between metal sulphide and metal selenide. In the case of CdS1-xSexthe band gap of the films was determined from UV-visible spectroscopy to vary from 2.4 eV (CdS) to 1.7 eV(CdSe). In the case of NiS1-xSex the movement from sulphide to selenide was less simple with multiple phases of nickel chalcogenides produced.
29
HOTTES, SUMAIA. "NEW PLATINUM(II) AND COPPER(II) COMPLEXES DERIVED FROM 1,2,3-TRIAZOLIC OXIMES AS POTENTIAL ANTITUMOR AGENTS AND PROTOTYPES OF BIOREDUCTIVE PRODRUGS." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2013. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=24950@1.
Full textAbstract:
PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO<br>COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR<br>CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO<br>O câncer constitui patologia de grande importância, visto que já corresponde à segunda maior causa de mortes em todo o mundo, havendo perspectiva de crescimento em número de casos para os próximos anos. Os tratamentos quimioterápicos atuais caracterizam-se por um elevado custo e índice terapêutico relativamente reduzido, estando associados a diversos efeitos colaterais e de resistência do tumor. Diante disso, muitos esforços têm sido direcionados na busca por novas drogas com melhor perfil farmacológico e com atividade frente a linhagens resistentes de tumor, bem como na viabilização de novas vias de administração. Neste sentido, diferentes abordagens têm sido empregadas para o desenho de drogas anticâncer baseadas em metais, como o desenvolvimento de novos complexos análogos à cisplatina, assim como de complexos que se mostrem mais seletivos ao ambiente tumoral. Uma estratégia bastante promissora compreende a preparação de complexos de metais inertes em elevados estados de oxidação, que possam atuar como pró-drogas, atingindo o tumor alvo sem redução prévia nem grandes transformações. Apenas no interior da massa tumoral, devido à condição de hipóxia (baixa oxigenação), normalmente não encontrada em tecidos normais, estes compostos seriam reduzidos, originando então as espécies ativas, que atacariam o alvo mais facilmente. O cobre, por apresentar dois estados de oxidação cujo potencial de redução é acessível dentro da faixa do potencial redox celular, é um elemento promissor. Nesse contexto, foram sintetizados neste trabalho dois complexos de cobre(II) e dois complexos de platina(II) dos ligantes isoméricos 1- e 2-fenil-1,2,3-triazol-4-carboxaldeído-oxima, nunca antes explorados no contexto da Química de Coordenação, sendo que apenas os complexos de cobre poderiam, a princípio, atuar como pró-drogas biorredutíveis. Os complexos foram caracterizados por análise elementar (CHN e AAS), espectroscopia vibracional e termogravimetria. Estudos de EPR no estado sólido foram realizados para os complexos de cobre(II); já os complexos de platina(II) foram também caracterizados por RMN de 195Pt. A modelagem computacional foi utilizada como recurso complementar à proposição estrutural e atribuição das bandas vibracionais dos complexos, com exceção do composto [Cu2(mu-L1)2(HL1)(ClO4)2(OH2)]·2H2O (1), cuja estrutura foi determinada por difração de raios X em monocristal. O outro complexo de cobre(II) é mononuclear: cis-[Cu(HL2)2Cl2] (2). Já os compostos de platina(II) são mononucleares e, como esperado, quadráticos, obedecendo às fórmulas: cis-[Pt(HL1)2Cl2]1 H2O (3) e cis-[Pt(HL2)2Cl2] (4). Os complexos de cobre foram testados nas linhagens de células leucêmicas U937 e THP-1, sendo o complexo 1 e HL1 ainda testados em células normais do sangue do tipo PBMC. Nas linhagens tumorais testadas ambos os complexos reduziram a viabilidade celular de maneira concentração-dependente. O perfil de atividade frente às células U937 foi semelhante para 1 e 2. Entretanto, o composto 1 foi duas vezes mais ativo que 2 contra a linhagem celular THP-1. Cabe ressaltar que 1 foi 23 porcento mais tóxico para a linhagem leucêmica THP-1 do que para as células normais PBMC. HL1 foi capaz de reduzir a viabilidade celular das linhagens tumorais em aproximadamente 30 porcento, não se mostrando tóxico para as PBMC. Os complexos de platina, por sua vez, foram testados na linhagem K562, de leucemia mielóide crônica, tendo ambos demonstrando toxicidade similar e cerca de 5x maior que a droga carboplatina.<br>Cancer pathology is of great importance, since it is the second leading cause of death worldwide, with a prospect of growth in the number of cases for the next decades. Current chemotherapy treatments are characterized by high cost and a relatively low therapeutic index and are associated with several side effects and tumor resistance. Therefore, many efforts have been focused on the search for new drugs with an improved pharmacological profile and tumor-resistant lineage activity, as well as the feasibility of new administration routes. In this regard, different approaches have been employed for the design of metal-based anticancer drugs, such as the development of new cisplatin analogue complexes, as well as complexes that may be more selective to the tumor environment. A very promising strategy involves the preparation of high oxidation state inert metal complexes, which may act as prodrugs, reaching the tumor target without prior reduction or significant transformations. Only inside the tumor mass, due to hypoxia conditions (low oxygen) not normally found in normal tissues, these compounds would be reduced, originating the active species which would then attack the target more easily. Copper, by presenting two oxidation states whose reduction potential is accessible within the range of the cellular redox potential, is a promising element. In this context, two copper(II) complexes and two platinum(II) complexes with the isomeric ligands 1- and 2-phenyl-1,2,3-triazole-4-carboxaldehyde oxime were synthesized in the present study, which have never before been explored in the context of Coordination Chemistry, with only the copper complexes, in theory, demonstrating the potential to act as bioreductive prodrugs. The complexes were characterized by elemental analysis (CHN and AAS), vibrational spectroscopy and thermogravimetry. EPR studies in solid state were performed for the copper(II) complexes, while the platinum(II) complexes were also characterized by 195Pt NMR. Computer modeling was used as a complementary resource for structural propositions and assignment of the vibrational bands of the complexes, with the exception of coordination compound [Cu2(mu-L1)2(HL1)(ClO4)2(OH2)]·2H2O (1), whose structure was determined by single crystal X-ray diffraction. The other mononuclear copper(II) complex is cis-[Cu(HL2)2Cl2] (2). On the other hand, the platinum(II) compounds are mononuclear and as expected, quadratic, according to the formulae cis-[Pt(HL1)2Cl2]1 H2O (3) and cis-[Pt(HL2)2Cl2] (4). The copper complexes were tested against the leukemic cell lines U937 and THP-1, with complex 1 and HL1 also being tested on normal PBMC blood cells. Both complexes reduced cell viability in a concentration-dependent manner in the tested tumor lines; The activity profile towards U937 cells was similar for 1 and 2. However, compound 1 was twice as active as 2 against cell line THP-1. It is worth noting that 1 was 23 percent more toxic against the leukemic cell line THP-1 when compared to normal PBMC cells. The platinum complexes, alternatively, were tested against the K562 cell line, chronic myeloid leukemia, and both demonstrated similar toxicity, approximately 5x higher than carboplatin.
30
Lingga, Novalina. "Syntheses and structural studies of polynuclear copper (II) complexes of Schiff-base macrocycles and related ligands." Thesis, University of Canterbury. Chemistry, 1996. http://hdl.handle.net/10092/7315.
Full textAbstract:
Two diimine-diamine ligands derived from the [2+1] template condensation of 1,3-diaminopropane with 2,6-diformyl-4-R-phenol [R = Me, (L¹)-; R = tBu, (L⁸)-], have been isolated as their dicopper(II) hydroxo-bridged complex cations. The ring-closure condensation reaction of the dicopper complex cation of (L¹)- with 2,5-diformylfuran produced a new asymmetric tetraimine macrocycle, (L³)- as the methoxo-, hydroxo- and
ethoxo-bridged dicopper(II) complexes. The hydroxo- and ethoxo-bridged dicopper(II) complexes of (L³)- were isolated from the recrystallisation of the methoxo-bridged analogue using N,N-dimethylformamide, in the absence or presence of ethanol, respectively. The structures of the dicopper(II) acyclic complexes of (L¹)- and of the
ethoxo-bridged complex of (L³)- have been determined by X-ray crystallography.
Two hexacopper(II) complexes of a new acyclic Schiff-base ligand, derived from the [3+2] condensation of 1,3-diamino-2-hydroxypropane with 4-t-butyl-2,6-
diformylphenol, were isolated. Preliminary X-ray crystallographic investigations on these hexacopper(II) complexes revealed a CU₆ ring templating the ligand such that the primary amine groups are held in an appropriate orientation and separation for ring-closure with a dicarbonyl compound.
Two tetracopper(II) macro cyclic complexes were obtained from the [2+2] template condensation of 1,5-diarnino-3-hydroxypentane and 2,6-diformyl-4-
Methylphenol. One of the complexes was isolated as a tetrafluoroborate complex, while the other as a formate complex. The formate complex, whose crystal structure has been determined, is believed to have been generated by the hydrolysis of N,N-dimethylformamide at room temperature, promoted by the tetrafluoroborate complex. The tetrafluoroborate complex underwent dimerisation to give an octacopper(II) complex.
Another tetracopper(II) complex was synthesised by the template condensation of 1,5-diamino-3-hydroxypentane and 2,6-diformyl-methylphenol. X-ray structure determination of this complex revealed that it is a dimer of two dinuclear macro cyclic complexes. The two copper(II) ions in one unit of the dimer are bound inside the macro cycle "laterally". In contrast, two copper(II) ions are found to be held "diagonally" within the cavity of another Schiff-base macrocycle, derived from the [2+2] template condensation of 2,6-diformyl-4-methylphenol with triethylenetetramine.
31
INCIO, JIMMY LLONTOP. "SPECTROSCOPIC STUDIES OF FLUOROQUINOLONES AND THEIR COPPER(II) COMPLEXES: INTERACTION WITH MICELLES, LIPOSOMES AND GOLD NANOCOMPOSITES." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2018. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=36043@1.
Full textAbstract:
PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO<br>COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR<br>CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO<br>PROGRAMA DE EXCELENCIA ACADEMICA<br>Norfloxacina (NFX) é um antibiótico fluorescente de amplo espectro bacteriológico, membro da família das fluorquinolonas (FQs). A interação das FQs com íons metálicos pode incrementar a ação bactericida e agir contra a resistência das bactérias frente aos antibióticos. Diversos exemplos de complexos mistos de norfloxacina e Cu(II) podem ser encontrados na literatura. A compreensão dos mecanismos moleculares de interação desses antibióticos com os diferentes componentes das células e com nanopartículas de ouro, como transportadores do fármaco, é extremamente importante. Para entender essas interações, neste trabalho utilizamos diferentes técnicas espectroscópicas, como espectroscopia de fluorescência estacionária e resolvida no tempo, absorção de luz UV-Visível e ressonância paramagnética eletrônica (RPE). A interação de NFX e do complexo ternário Cu(II):L:NFX, onde o ligante L é a 1,10-fenantrolina (Phen) ou 2,2-bipiridina (Bipy), com micelas e lipossomas unilamelares pequenos de fosfatidilcolina de ovo (PC) foi estudada usando espectroscopia de fluorescência em estado estacionário e resolvida no tempo. Foi estudada a estabilidade dos complexos ternários formados em micelas. Foram obtidas constantes de estabilidade no interior de micelas de SDS, as quais mostraram valores muito maiores do que em tampão. Já os espectros de RPE deram maiores detalhes sobre a estrutura dos complexos e confirmaram a formação do complexo ternário dentro das micelas. Foram estudadas as interações de FQs e seus complexos de cobre com lipossomas de PC preparados com diferentes densidades superficiais de carga elétrica negativa. No estudo da interação de FQs com nanopartículas de ouro sintetizadas por ablação a laser (nanocompósitos, AuNCs), NFX mostrou maiores mudanças, tanto na absorbância como na fluorescência, do que as FQs ciprofloxacina (CFX) e levofloxacina (LFX). Os resultados sugerem mudanças no índice de refração na superfície dos AuNCs, por associação com o fármaco e/ou formação de aglomerados como resultado da interação. Observou-se também uma supressão lenta, porém significativa, na fluorescência da NFX, sem mudança na posição do pico, indicando que NFX mantém o seu estado inicial de protonação ligando-se à superfície dos AuNCs. Também foi observada a liberação de FQs ligadas à superfície de AuNPs mediante substituição por tióis, que ocasiona recuperação parcial da fluorescência da fluorquinolona. Por último, como o surfactante aniônico SDS se mostrou promissor na interação com NFX, em comparação com surfactantes catiônicos e neutros, e como os AuNCs são estáveis em SDS, estudamos a interação de NFX com AuNCs sintetizados em presença de SDS e, para comparação, com AuNCs colocados em solução de SDS após a síntese.<br>Norfloxacin (NFX) is a fluorescent antibiotic of broad bacteriological spectrum, member of the fluoroquinolone (FQ) family. The interaction of FQs with metal ions can increase the bactericidal action and act against antibiotics bacterial resistance. Several examples of mixed-ligand norfloxacin Cu (II) complexes can be found in the literature. Understanding the molecular mechanisms of interaction of these antibiotics with different cell components and with gold nanoparticles as drug transporters is extremely important. To clarify these interactions, we used different spectroscopic techniques, such as steady-state and time-resolved fluorescence spectroscopy, UV-Visible light absorption, and electron paramagnetic resonance (EPR). The interaction of NFX and the ternary complex Cu(II):L:NFX, where the L is the ligand 1,10-phenanthroline (Phen) or 2,2-bipyridine (Bipy), with micelles and small unilamellar liposomes of egg phosphatidylcholine (PC) was studied using steady-state and time-resolved fluorescence spectroscopy. The stability of the ternary complexes formed in micelles was studied, and stability constants were obtained inside SDS micelles, which showed values much larger than in buffer. The EPR spectra gave further details on the structure of the complexes, and confirmed the formation of the ternary complex inside the micelles. The interactions of FQs and their copper complexes with PC liposomes prepared with different surface densities of negative electrical charge were studied. In the study of the interaction of FQs with gold nanoparticles synthesized by laser ablation (nanocomposites, AuNCs), NFX showed greater changes than FQs ciprofloxacin (CFX) and levofloxacin (LFX) in both absorbance and fluorescence. The results suggest changes in the surface refractive index of the AuNCs and/or cluster formation, as result of the interaction with the drug. A slow but significant quenching of NFX fluorescence was also observed, with no change in peak position, indicating that NFX maintains its initial state of protonation by binding to the surface of the AuNCs. Release of FQs attached to the surface of AuNCs by thiols has also been observed, which causes partial recovery of FQ fluorescence. Finally, as the anionic surfactant SDS showed to be promising in the interaction with NFX, compared to cationic and neutral surfactants, and because the AuNCs are stable in SDS, we studied the interaction of NFX with AuNCs synthesized in the presence of SDS and, for comparison, with AuNCs placed in SDS solution after synthesis.
32
Patra, Ashis Kumar. "Studies On The Photo-induced DNA Cleavage Activity Of α-Amino Acid Copper Complexes Having Phenanthroline Bases". Thesis, 2007. https://etd.iisc.ac.in/handle/2005/610.
Full textAbstract:
Photo sensitizers showing visible light induced DNA cleavage activity are of current importance for medicinal applications related to photodynamic therapy (PTD) considering greater skin penetration of light near 700 nm. While organic molecules and complexes of 4d-5d metal ions are extensively studied for their DNA photo-damage properties in UV and visible light, the chemistry of 3D metal complexes showing visible light-induced DNA cleavage activity is relatively unexplored efforts have been made in this thesis work to design new ternary copper (II) complexes having a-amino acids Such copper (II) complexes with tunable coordination geometry could find potential applications in PDT.
Ternary Copper (II) complexes containing L-methionine, S-methy1-L-cysteine and phenanthroline bases are prepared and characterized. They display DNA binding and visible light induced DNA cleavage activity. An enhancement of the DNA cleavage activity is observed for analogous ternary copper (II) complexes contained L-lysine with a pendant cationic amine moiety as a photo-induced DNA Cleavage activity using binary and ternary copper (II) complexes of L-arginine and phenanthroline bases. We have observed AT selective DNA binding and visible light –induced DNA cleavage activity. The crescent-shaped bis-arginine Copper (II) complex mimics the natural antiviral antibiotic netropsin. T o investigate the role of the pendant groups of the amino acids, we have explored the DNA binding and DNA cleavage activity of analogues L-glutamine and L-asparagine complexes. We have prepared ternary copper (II) complexes containing two photosensitizers, viz., L-tryptophan (L-trp) and dipyridoquininoxaline/dipyridophenazine to achieve double strand breaks forming linear DNA. Complex [Cu(L-trp)(dppz)(H2O)+ shows a stacking arrangement of the indole and dppz rings giving a separation that fits with the base pair separation of ds-DNA. Photosensitizes in these complexes approach two different complementary stands of the ds-DNA, leading to double strand breaks and formation of linear DNA.
Mechanistic studies on the DNA photocleavage reactions reveal the formation of singlet oxygen(1O2)species by a type-II pathway in preference to the hydroxyl radical generation. A process leading to an efficient DNA cleavage activity on visible light irradiation. The observation of sequence selectivity and double strand DNA cleavage on red light exposure by national design of the complexes is significant considering importance of the results in the chemistry of photodynamic therapy of cancer. The results of this dissertation open up new avenues for designing and developing 3d metal-based photosensitizers with potential utility in nulcleic acid chemistry.
33
Patra, Ashis Kumar. "Studies On The Photo-induced DNA Cleavage Activity Of α-Amino Acid Copper Complexes Having Phenanthroline Bases". Thesis, 2007. http://hdl.handle.net/2005/610.
Full textAbstract:
Photo sensitizers showing visible light induced DNA cleavage activity are of current importance for medicinal applications related to photodynamic therapy (PTD) considering greater skin penetration of light near 700 nm. While organic molecules and complexes of 4d-5d metal ions are extensively studied for their DNA photo-damage properties in UV and visible light, the chemistry of 3D metal complexes showing visible light-induced DNA cleavage activity is relatively unexplored efforts have been made in this thesis work to design new ternary copper (II) complexes having a-amino acids Such copper (II) complexes with tunable coordination geometry could find potential applications in PDT.
Ternary Copper (II) complexes containing L-methionine, S-methy1-L-cysteine and phenanthroline bases are prepared and characterized. They display DNA binding and visible light induced DNA cleavage activity. An enhancement of the DNA cleavage activity is observed for analogous ternary copper (II) complexes contained L-lysine with a pendant cationic amine moiety as a photo-induced DNA Cleavage activity using binary and ternary copper (II) complexes of L-arginine and phenanthroline bases. We have observed AT selective DNA binding and visible light –induced DNA cleavage activity. The crescent-shaped bis-arginine Copper (II) complex mimics the natural antiviral antibiotic netropsin. T o investigate the role of the pendant groups of the amino acids, we have explored the DNA binding and DNA cleavage activity of analogues L-glutamine and L-asparagine complexes. We have prepared ternary copper (II) complexes containing two photosensitizers, viz., L-tryptophan (L-trp) and dipyridoquininoxaline/dipyridophenazine to achieve double strand breaks forming linear DNA. Complex [Cu(L-trp)(dppz)(H2O)+ shows a stacking arrangement of the indole and dppz rings giving a separation that fits with the base pair separation of ds-DNA. Photosensitizes in these complexes approach two different complementary stands of the ds-DNA, leading to double strand breaks and formation of linear DNA.
Mechanistic studies on the DNA photocleavage reactions reveal the formation of singlet oxygen(1O2)species by a type-II pathway in preference to the hydroxyl radical generation. A process leading to an efficient DNA cleavage activity on visible light irradiation. The observation of sequence selectivity and double strand DNA cleavage on red light exposure by national design of the complexes is significant considering importance of the results in the chemistry of photodynamic therapy of cancer. The results of this dissertation open up new avenues for designing and developing 3d metal-based photosensitizers with potential utility in nulcleic acid chemistry.
34
Chen, Li-Hsuan, and 陳立軒. "Coordination Chemistry of Nickel(II) Ternary Complexes." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/78937714821448572345.
Full text
35
Cheng, Sheng-Chuan, and 鄭勝權. "Studies of Catecholase-like Model Copper( II ) Complexes." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/38523503391867508457.
Full textAbstract:
碩士<br>淡江大學<br>化學學系<br>88<br>Title of Thesis: Studies of Catecholase-like Model Copper( II ) Complexes
Key word: Copper(II) complex,Magnetic properties, Catecholase-like
Name of Institute:Graduate Institute of Chemistry Tamkang University
Graduate date: June, 2000 Degree conferred: Master
Name of student: Sheng-Chuan Cheng Advisor:Dr. Ho-Hsiang Wei
鄭 勝 權
Abstract:
This thesis essentially has been separated into two parts : Ⅰ. The synthesis of dinuclear copper(II) complexes and the correlation between their structures and magneticbehavior；Ⅱ.The reactive activities of catecholase-like.Part Ⅰ.: The simplified formula for dinuclear copper(II) complexes are represented as follows: 1.{Cu2[-C5H4NCH2O]2(NCS)2} 2.{Cu2[-C5H3CH3NCH2O]2(CH3COO)2}．2H2O 3.{Cu2[-C5H4NCH2CH2O]2(NCO)2} 4.{Cu2[-(CH3)2NC(CH3)2CH2O]2(NCS)2} 5.{Cu2[-(CH3)2NCH2CH(CH3)O]2(NCS)2} 6.{Cu2[-(CH3)2NC(CH3)2CH2O]2(Cl)2} The theoretical fitting has been simulated to obtain the values of exchange integral 2J by using Bleaney-Blowers equation. The magnetic behaviors of these dinuclear copper(II) complexes all show antiferromagnetic interaction. Part Ⅱ.:Reactive activities of catecholase-like studies Dinuclear copper(II) complexes were found to be readily reduced to copper(Ⅰ) complexes by 3,5-di-tert-butylcatechol(dtbc). The reaction of copper(II) complexes in MeOH has been studied. The dtbc has been oxidized to quinone, and characetrized by absorption band at 400nm of UV-visible spectra. The reactive activity of these oxo-bridged catecholase-like reactions is correlated to the Cu-Cu distances in the complexes. Temperature dependence of magnetic susceptibility and Mőssbauer measurements for these complexes revealed that the style of spin transition s=5/2 ↔ s=1/2 of Iron(Ⅲ ) atom in complexes is dependent on the chemical enviromment. All these form complexe 1-4 exhihit catalase- like activity toward H2O2 disproportionation.
36
YU, LIN, and 俞琳. "Electrochemistry of copper (II) complexes of diamino diamides." Thesis, 1990. http://ndltd.ncl.edu.tw/handle/96036039770267042153.
Full text
37
Lin, Yung-Chan, and 林永展. "Structures and Kinetics of Nickel(II) and Copper(II) Macrocyclic Complexes." Thesis, 2004. http://ndltd.ncl.edu.tw/handle/946je8.
Full textAbstract:
博士<br>國立清華大學<br>化學系<br>92<br>The tetraaza-macrocyclic ligands were synthesized by two methods. (1) The protecting group method reported by Richman and Atkins was used for the synthesis of isocyclam. (2) The general organic method with Michael addition reaction was employed to prepare 3-10-C-meso-Me8[14]dieneN4.2HClO4. The structures and components of these ligands were analyzed and identified by NMR, IR, UV-vis, mass, and X-ray studies. The complexes of Ni(II) and Cu(II) were synthesized by using Ni(ClO4)2.6H2O, Ni(OAc)2.4H2O, or Cu(ClO4)2.6H2O in hot methanol solution and recrystallized from water or acetonitrile.
According to the results of NMR and X-ray studies, the structures of isomers, LB and LC, from reduction of 3-10-C-meso- Me8[14]dieneN4·2HClO4 and their complexes of Ni(II) and Cu(II) are indeed different from literature reports. We could not get the isomer LA following the experimental methods described in the published paper and in our work. The melting point of LB is greater than that of LC and the melting point of LA is anticipated to be higher than that of LB. The solubility of LB in organic solvent is less than that of LC, while that of LA is expected to be lower compared to LB.
The 1H NMR spectrum of LB shows four methyl resonances for eight methyl groups suggesting that LB is a symmetric molecule whereas the isomer LC shows eight methyl resonances indicating that LC is an asymmetric molecule. The 13C NMR spectrum of LB displayed only nine peaks due to pairwise equivalence of carbon atoms. In contrast, isomer LC displayed eighteen peaks of corresponding to eighteen nonequivalent carbon atoms indicating the absence of symmetry in the molecule.
We have studied the X-ray diffractional analysis of isomeric LB, LC and their transition metal complexes.
(1) Crystal structure of 3,10-C-meso-5,12-C-meso-Me8[14]aneN4 (LB).
The molecule is located at an inversion. This determination indicates that the ring lies in a chair form with tetramine equatorial positions. The configurations of the four chiral carbon centers are 3S, 5S, 10R and 12R. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, and have an axial orientation. In addition, the methyl groups in 5S and 12R are also disposed on opposite sides of the macrocyclic plane, and have an equatorial orientation.
(2) Crystal structure of 3,10-C-meso-5,12-C-rac-Me8[14]aneN4 (LC)
The compound has a butterfly structure. The configurations of the four chiral carbon centers are 3S, 5S, 10R and 12S. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, and have an axial orientation. On the other side, the methyl groups in 5S and 12S are disposed on the same sides of the macrocyclic plane, and have an equatorial orientation.
(3) Crystal structure of [CuLB(H2O)2](ClO4)2
The molecule is located at an inversion. The compound is a six-coordinated octahedral complex with four N atoms of the macrocyclic ligand in the equatorial positions and two axial water O atoms in the trans axial positions; it belongs to the “4 + 2” type with four stronger Ni-N and two weaker Ni-O. The ligand is in its most stable, planar configuration with both the six-membered rings in chair forms and both the five-membered rings in gauche forms. The configurations of the four chiral nitrogen centers are 1R, 4S, 8S and 11R. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, and have an axial orientation. The methyl groups in 5S and 12S are also disposed on opposite sides of the macrocyclic plane, and have an equatorial orientation.
(4) Crystal structure of [CuLC(ClO4)2]
The compound is a six-coordinated octahedral complex with four N atoms of the macrocyclic ligand in the equatorial positions and two axial perchlorate O atoms in the trans axial positions; it belongs to the “5 + 1” type with four stronger Ni-N bounds, one stronger Cu(1)-O(3) and one weaker Cu(1)-O(6). The ligand consists of both the six-membered rings in chair forms and both the five-membered rings in gauche forms. The configurations of the four chiral nitrogen centers are 1S, 4R, 8R and 11S. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, and have an axial orientation. On the other hand, the methyl groups in 5S and 12S are disposed on the same sides of the macrocyclic plane, which the methyl group in 5S has an equatorial orientation and the methyl group in 12S has an axial orientation.
(5) Crystal structure of [NiLB](ClO4)2
The compound is a four-coordinated square planar complex with both the six-membered rings in chair forms and both the five-membered rings in gauche forms. The configurations of the four chiral nitrogen centers are 1R, 4S, 8S and 11R. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, and have an axial orientation. The methyl groups in 5S and 12S are also disposed on opposite sides of the macrocyclic plane, and have an equatorial orientation.
(6) Crystal structure of [NiLC](ClO4)2
The compound is a four-coordinated distorted planar complex with two six-membered rings-one in a chair form and the other in a twist-boat form, and two five-membered rings-one of which is in a gauche form and the other in an eclipsed form. The configurations of the four chiral nitrogen centers are 1S, 4R, 8S and 11S. The methyl groups in 3S and 10R are disposed on opposite sides of the macrocyclic plane, in which the methyl group in 3S has an equatorial orientation and the methyl group in 5S has an axial orientation. On the other side, the methyl groups in 5S and 12S are disposed on the same sides of the macrocyclic plane, in which the methyl group in 5S has an axial orientation and the methyl group in 12S has an equatorial orientation.
Ni(II) complexes with the tetraaza-macrocyclic ligands exist in aqueous solution as an equilibrium mixture of cis, trans, and planar species. The distribution ratios of the three species are related to temperature, ionic strength, pH value, and steric effect, etc. The blue-to-yellow reactions were carried out with a UV-vis spectrophotometer. The results of spectrophotometric studies indicate that the proportion of planar species increases by either an increase in temperature or by an increase of ionic strength. In addition, the proportion of planar species also increases by an increase of the number of methyl groups on the macrocyclic ligand. Furthermore, the axial methyl groups contribute to raise the standard equilibrium constant, ΔHo and ΔSo. This may be due to the steric effect and the distorted structure. In conclusion, [13]aneN4 provide the best fit cavity size for a square-planar Ni(II) complex. The order of the values of V (d-d) for square-planar Ni(I1) complexes is [13]aneN4 > [12]aneN4 > [14]aneN4 > [15]aneN4.
In order to examine the effects of coordinated hydroxide ion and free hydroxide ion in configurational conversion of a tetramine macrocyclic ligand complex, the kinetics of the cis-to-planar interconversion of cis-[Ni(isocyclam)(H2O)2]2+ (isocyclam, 1,4,7,11- tetraazacyclotetradecane) has been studied spectrophotometrically in basic aqueous solution. The interconversion requires the inversion of one sec-NH center of the folded cis-complex to have the planar species. The proposed mechanism is a free-base catalyzed pathway because the metal-bound hydroxide ion cannot form a hydrogen-bonded chelate ring with the adjacent sec-NH。Furthermore, the kinetic data satisfactorily fits as the rate law, R = kOH[OH-][cis-[Ni(isocyclam)(H2O)2]2+], where kOH = 3.84 ´ 103 dm3 mol-1 s-1 at 25.0 ± 0.1 oC with I = 0.10 mol dm-3 (NaClO4). The large ΔH¹, 61.7 ± 3.2 kJ mol-1, and the large positive ΔS¹, 30.2 ± 10.8 J K-1 mol-1, strongly support a free-base-catalyzed mechanism for the reaction. On the other hand, the coordinated-base-catalyzed pathway results in a small ΔH¹ and a large negative ΔS¹ for cis-folded Ni(II) complexes of [13]aneN4, cyclam, C-meso-5,12-Me2cyclam, and C-rac-5,12-Me2cyclam. In higher base media, the kinetic studies were carried out by using a stopped-flow spectrophotometer and the resulting kinetic data provide different rate constants which are functions of ionic strength. This phenomenon gives good evidence for a free-base-catalyzed mechanism.
38
WANG, YUN-MING, and 王雲銘. "COORDINATION CHEMISTRY OF COPPER(II) AND NICKEL(II) COMPLEXES OF DIAZADIOXIMES." Thesis, 1990. http://ndltd.ncl.edu.tw/handle/69153478402852757506.
Full text
39
Kuo-Shen, Chuang, and 莊國昇. "Synthesis and Characterization of Hexaazamacrocyclophane and Cobalt(II),Nickel(II),Copper(II) Complexes." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/07616080849513435027.
Full textAbstract:
博士<br>淡江大學<br>化學學系<br>87<br>We synthesize a new hexaazamacrocyclic ligand(H2HAPP) and their cobalt(II)、nickel(II)、copper(II) complexes, and the N-substituted methyl derivative(DMHAPP)
was also obtained by reactng with methyl iodide. The X-ray stacking structures of i-H2HAPP and H4HAPP(CF3COO)2 show that both ligands exist a type of face-to-face aggregates between macrocyclic molecules and a strong interaction exists in aggregates according to the distance of plane-to-plane in the aggregates(3.28~3.29 ). The study of aggregate behavior in solution proved the formation of face-to-face dimer in both i-H2HAPP and [CoII(H2HAPP)(TFA)2]. Two stable tautomers of H2HAPP,i-H2HAPP and o-H2HAPP respectively, was found to exist in crystal structures of the complexes and ligand. We also observed their tautomerism occurred in the solution by using UV/VIS spectrum of model compound DMHAPP. The electrochemistry in H2HAPP、nickel and copper complexes shows one electron reduction on ligand, but the cobalt complex shows metal-centered redox reaction. The chemical oxidation of H2HAPP and [NiII(HAPP)] by (Thian+.)ClO4 and (Phenox+.)SbCl6 oxidants shows the formation of cation radical species, but the nickel cation radical complex at room temperature is transformed into [NiIII(HAPP)(Cl)2] complex at liquild nitrogen temperature by intramolecular electron transfer mechanism. [CoII(H2HAPP)(TFA)2] complex will react with O2 and formate irreversible oxygen-carrier complex in the presence of axial bases. Two oxygenation adducts, mononuclear superoxide and dinuclear -peroxide complex, are observed in oxygenation reaction. We proposed that a CoIII-hydroperoxyl intermediate is produced by protonation of superoxide ion of mononuclear superoxide complex or is stablized by hydrogen-bonding interaction of methanol molecule, but the deprotonation reaction of the species will lead to the formation of the dinuclear -peroxide complex. All the factors affecting the oxygenation adducts will be related to the CoIII-hydroperoxyl intermediate. The catalytic oxidation of di-tert-butyl pheno by using [CoII(H2HAPP)(TFA)2] complex indicates that the major product is DPQ dimer and the sub-product is DTBQ monomer. We proposed that the activity of the dinuclear -peroxide complex determines the distribution of catalytic products. The homogeneous electrochemical catalytic reduction of oxygen by using [CoII(H2HAPP)(TFA)2] complex is proved to formate two-electron reduction product, H2O2. The electrocatalytic mechanism indicates that hydrogen peroxide is produced by one-step two electrons reduction in pH<4.3, and by two-step one electron reduction in pH>4.3. The study of H2HAPP monomer luminescence displayed the E-type delayed fluorescence and triplet phosphorescece properties and H2HAPP will formate the excimer in very low concentration(10-7 M).
40
Lee, Chen-Shiang, and 李成祥. "Palladium (II), Copper (I), Ruthenium (II) and Platinum (II) N-Heterocyclic Carbene Complexes." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/50020053295025232657.
Full textAbstract:
博士<br>國立東華大學<br>化學系<br>98<br>This dissertation discusses the synthesis, structural characterizations, related
properties and further applications of N-heterocyclic carbene (NHC) complexes of
palladium (II), copper (I), ruthenium (II) and platinum (II).
In Chapter 1, the basic principles of N-heterocyclic carbene ligand and the
related background of their metal complexes are conceptually described. The
properties of metal complexes bearing chelate- or pincer-type NHC ligand are
introduced. The main ideas of each chapter in this dissertation are illustrated.
In Chapter 2, the homoleptic bis-chelate tetracarbene palladium(II) complex ,
[(BuCCmeth)2Pd][BF4]2, have been synthesized through Ag2O method and
characterized spectroscopically. Single crystal structure of resulting complex has been
studied. The dicarbene ligand is proposed to enhance the basic property on the Pd
center, and increase the stability of the active Pd species by chelating effect.
[(BuCCmeth)2Pd][BF4]2 shows excellent air and thermal stability at high temperature
and also exhibits good catalytic activity with full recyclability in DMF towards Heck
reaction. The dicarbene ligand is further modified by attaching pyridinum moiety on
the side arms of the NHC rings. The Pd(II) complexes of the pyridinum-tagged NHC
ligand, [(PyBuCCmeth)2Pd][PF6]6 and [(PyBuCCmeth)PdCl]2[PF6]6, are also applied and
compared with other type of Pd(II)-NHCs in Heck reaction under identical reaction
condition. Heck reaction in pure aqua phase using bis-chelate Pd(II)-NHCs is
performed as well.
In Chapter 3, the methylenebis(N-alkylimidazolium) chloride, [alkylCCMe-H]Cl2
(alkyl = methyl or n-butyl group), are converted to dialkyl-biimidazoles by cuprous
oxide with concurrent C-N bond cleavage and C-C bond formation. This unusual C-N
bond cleavage is proposed to involve a Cu(I)-NHC complex. The reaction is unique as
it involves C-N bond cleavage and C-C bond formation.
In Chapter 4, reaction of [RCPC-H]Cl2, where the RCPC is
2,6-bis(methylimidazol-2-ylidene)-pyrazine (R = me) or
2,6-bis(butylimidazol-2-ylidene)-pyrazine (R = Bu), with RuCl3 under high
temperature generated the [(RCPC)2Ru]Cl2 complexes. The anion-exchanged
products, [(RCPC)2Ru][PF6]2 were obtained by the reaction of NH4PF6 with
[(RCPC)2Ru]Cl2 in aqueous solution. The structural analyses of [(BuCPC)2Ru]Cl2,
[(meCPC)2Ru][PF6]2 and [(BuCPC)2Ru][PF6]2 showed that all three complexes are in
six-coordinated geometry with two tridentated ligands and one metal center, , and are
analogous to Ru(II)(terpy)2 system. Their absorption and emission spectra showed
dramatic variation upon addition of the acid, indicating a possible application on acid
detection. Introducing a methyl group on the nitrogen atom of the pyrazine of
[(BuCPC)2Ru][PF6]2 led to a similar UV-vis spectrum pattern to that of the protonated
[(BuCPC)2Ru][PF6]2.
In Chapter 5, a novel class of Pt(II) complexes with pyridine-based pincer-type
NHC ligand, denoted as RCNC, where R = Bu or Mestyl ring, was synthesized. The R
groups on the pincer ligand were found to be responsible for the formation of dimmer,
as evidenced by the single crystal X-ray analysis of the reported complexes. All
Pt(II)-NHCs in this work are emissive in solution at room temperature, which are
attributed to the incorporation of NHC moieties with strong σ-donating nature. The
dimeric Pt(II)-NHCs shows aquachromic photoluminescence in the solid state upon
hydration and dehydration.
41
Wu, Chiou-yeh, and 吳秋月. "Studies of Modelling Complexes of Copper Proteins:Syntheses, Structures and Bonding Properties of Tridentate Picolinamido Copper(II) Complexes." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/02297080253961804172.
Full textAbstract:
博士<br>國立臺灣師範大學<br>化學系<br>84<br>Four series of mixed ligand tridentate picolinamido
copper(II) complexeshave been prepared. They are :(1) Cu(pmpa)(
L)(X)(H2O)n type, where pmpa stands for N-(2-picolinyl)-
picolinamido, and L for imidazole(ImH), N-methylimidazole(NMIm),
4-methylimidazole(4MImH), pyridine(py), 2-methylpyridine(2Mpy),
3-methylpyridine(3Mpy), and 4-methylpyridine(4Mpy), and X for
ClO4-, or BF4-,and n = 0, 1 or 2.(2) Cu(pepa)(L)(X)(H2O)n type,
where pepa stands for (N-(2-(2''-pyridine)-aminoethyl)
picolinamido, and L for Imidazole(ImH), N-methylimidazole(NMIm),
2-methylimidazole(2MImH), 4-methylimidazole(4MImH),pyridine(py),
3-methylpyridine(3Mpy), and 4-methylpyridine(4Mpy) and X
forClO4-, or BF4-, n=0, 1 or 2. (3) Cu(depa)(L)(X)(H2O)n type,
where depa stands for N-(2-(N,N-dimethylaminoethyl)picolinamido
and L for 2-methylimidazole(2MImH), 4-methylpyridine(4Mpy), and
X for ClO4-, and n= 1. (4) Cu(L)(X)(H2O)n type, where L stands
for pepa, pmpa, depa, and X for Cl-ClO4-, or BF4-, and n= 0, 1,
2, 3, or 4. The mixed ligand copper(II) complexes have
been characterized byelemental analyses, and electronic,
vibrational, and EPR spectroscopicmeasurements. X-ray crystal
structures of the following complexes have beendetermined from
three-dimensional X-ray diffraction data.(1) [Cu(pmpa)(4MImH)(H2
O)](H2O)(ClO4), tirclinic, a = 7.536(1) A, b =10.269(1) A, c =
14.113(3) A,α = 75.09(1), β = 76.48(1), γ = 88.45(1) °, Z=
2, space group P1-, R = 0.056, Rw = 0.062.(2)[Cu(pmpa)(4Mpy)(H2
O)](H2O)(ClO4) tirclinic, a = 7.704(1) A, b = 10.457(4)A , c =
13.917(2) A, α = 79.98(2), β = 75.81(1), γ = 87.33(2) °, Z =
2, spacegroup P1-, R = 0.051, Rw = 0.55.(3) [Cu(pepa)(4MImH)(H2
O)](H2O)(ClO4), monoclinic, a = 7.337(2) A, b =12.294(1) A , c =
22.293(2) A, β = 98.37(2)°, Z = 4, space group P21/c, R
=0.070, Rw = 0.083.(4) [Cu(pepa)(3Mpy)(H2O)](ClO4), monoclinic,
a = 7.493(3) A, b = 12.591(2)A , c = 22.403(5) A, β =
98.38(2)°, Z = 4, space group P21/n, R = 0.046, Rw= 0.049.(5)
[Cu(pepa)(4Mpy)(H2O)](ClO4), monoclinic, a = 7.322(1) A, b =
24.426(2)A , c = 12.077(1) A, β = 96.38(2)°, Z = 4, space
group P21/c, R = 0.043, Rw =0.065.(6) [Cu(depa)(2MImH)(H2O)](
ClO4), monoclinic, a = 19.779(3) A, b =10.580(2) A , c =
18.919(4) A, β = 94.28(1)°, Z = 8, space group C2/c, R =0.045,
Rw = 0.049.(7) [Cu(pepa)(Cl)], monoclinic, a = 9.176(2) A, b =
11.993(2) A , c = 11.017(4)A, β = 93.41(2)°, Z = 4, space
group P21/n, R = 0.047, Rw = 0.069.(8) [Cu(pepa)(H2O)2](ClO4),
monoclinic, a = 7.175(2) A, b = 22.337(9) A , c =11.190(4) A, β
= 91.80(2)°, Z = 4, space group P21/n, R = 0.095, Rw =
0.104.(9) [Cu(pepa)(H2O)2](BF4), monoclinic, a = 7.163(1) A, b =
21.944(4) A , c =11.135(1) A, β = 91.99(1)°, Z = 4, space
group P21/n, R = 0.083, Rw =0.098. Comparing the
Gaussian component bands of electronic spectra, thesequences of
the d orbitals were assigned as dx2-y2 >> dz2 >dyz > dxy > dxz
forelongated square pyramidal complexes, and dx2-y2 >> dyz > dxy
> dxz >dz2 forsquare plannar complexes. It is obvious
that the energy of the dyz orbital of the mixed ligandcopper(II)
complexes was raised significantly, suggesting that the central
amidoN atom of the N-(2-picolinyl)picolinamido and the
(N-(2-(2''-pyridine)-aminoethyl)picolinamido are π-donor.
42
劉育良. "Structural and Kinetic Studies of Copper(II) and Nickel(II) Polyamine Complexes." Thesis, 1992. http://ndltd.ncl.edu.tw/handle/25005470719694984803.
Full text
43
Sheu, Shuenn Yih, and 許順益. "Ternary Complex Formation Kinetics Involving Nickel(II) Tetraamine Complexes and Bidentate Ligands." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/60714198699945929648.
Full text
44
Wu, Shu-Pao, and 吳淑褓. "The Copper(II) Complexes of Glycine and L-Alanine." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/37208790571201430373.
Full textAbstract:
碩士<br>國立臺灣師範大學<br>化學系<br>84<br>Copper(II) complexes of two types, Cu(A)(LL)(ClO4) and Cu(
pa)(L)(ClO4), where A = glycine(gly) and L-alanine(L-ala); pa =
N-picolyl-(L)-alanine; LL = 1,10-phenanthroline(phen),
2,2'-bipyridine(bipy), neocuproine(neoc) and ethylenediamine(
en); L = N-methylimidazole(NMIm), 4-methylimidazole(4MImH),
4-methylpyridine(4Mpy) and pyridine(py), have been synthesized
andcharacterized by elemental analyses, IR, UV-VIS, CD and EPR
spectroscopicmeasurements.
45
Chiu, Po-Lin, та 邱柏霖. "β-Diketiminato Copper(II)-nitrito Complexes As New Models For Copper Nitrite Reductases". Thesis, 2013. http://ndltd.ncl.edu.tw/handle/44963923225850910846.
Full textAbstract:
碩士<br>高雄醫學大學<br>醫藥暨應用化學研究所<br>101<br>Copper-containing nitrite reductases active site contains a type II copper catalytic center possessing a (His)3 coordination sphere. A new type asymmetry N,N-substituted ??-diketiminato ligand sets bearing different kinds of arms ( L1H、L2H、L3H、L4H ) are design for the type II coordination environment. The synthesis of lithium complexes ( L1Li、L2Li、L3Li、L4Li ) show the tridentate chelating nature. Asymmetry N,N-substituted ??-diketiminato copper(II) complexes ( L1CuCl、L2CuCl、L3CuCl、L4CuCl ) could be obtained by reaction of the corresponding lithium complex with CuCl2. Treatment of the L1CuCl、L2CuCl、L3CuCl and L4CuCl with NaNO2 leads to formation of the copper(II)-nitrito complexes containing asymmetry N,N-substituted ??-diketiminato ligand ( L1CuNO2、L2CuNO2、L3CuNO2 and L4CuNO2 ). All copper (II) complexes were characterized by routine spectroscopy and X-ray crystallography to confirm their formula and structure.
46
ZHONG, YI-ZHEN, and 鐘意鎮. "Kinetics of acid-catalyzed dissociation of copper (II) and nickel (II) hexaazamacrocyclic complexes." Thesis, 1992. http://ndltd.ncl.edu.tw/handle/98245993345245508376.
Full text
47
謝子逸. "The study of kinetics and mechanisms of reactions of nickel(II)ternary complexes." Thesis, 2000. http://ndltd.ncl.edu.tw/handle/63614237409818540012.
Full text
48
Torre, Lorente Laura. "Liquid crystalline copper(II) complexes of poly(propylene imine) dendrimers." 2007. http://opus.ub.uni-bayreuth.de/volltexte/2009/558/.
Full text
49
WU, DE-XIN, and 伍德馨. "The study of coordination chemistry of copper (II) macrocyclic complexes." Thesis, 1986. http://ndltd.ncl.edu.tw/handle/63640024981323501622.
Full text
50
Chen, Zhi-Wan, and 陳枝萬. "Stereochemistry of tetraamine macrocyclic complexes of nickel(II); kinetics and mechanisms of tetraamine macrocyclic complexes of copper(II) and nickel(II)." Thesis, 1986. http://ndltd.ncl.edu.tw/handle/63807275128724776095.
Full text