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The objective of this thesis is to examine the photophysical and structural properties of Ru(II)/Re(I) based bimetallic complexes based on p-[N-2-(2’-pyridyl)benzimidazolyl]-[N-2-(2’-pyridyl)indolyl]-benzene (L1) ligand, as well as the photophysical and photochemical properties of N^C-chelate 4-coordinate organoboron compounds that contain a metal acetylide group. Ligand L1 was synthesized and fully characterized. Due to the incorporation of two distinct chelating sites, an N^N-chelate site and an N^C-chelate site, L1 has been found to be very effective in selective binding to two different metal ions. Two new heterobimetallic complexes Ru(II)-Pt(II) and Ru(II)-Pd(II) using L1 as the bridging ligand were prepared and fully characterized. All Ru(II)-containing complexes have been found to be luminescent. The Pt(II) unit appears to enhance phosphorescent efficiency of the Ru(II) unit while the Pd(II) unit has little influence. Using L1 as the bridging unit, two new Re(I) based heterobimetallic complexes Re(I)-Pt(II) and Re(I)-Pd(II) were also successfully synthesized. Results indicate that there is communication between the two different metal centers. The preliminary results indicated that the mononuclear Re(I) complex based on L1 is a promising candidate for the electrocatalytic CO2 reduction. Pd(II) and Pt(II) complexes were synthesized with an atropisomeric bis-pyridyl chelate ligand bis{3,3’-[N-Ph-2-(2’-py) indolyl]} (L4). To examine the potential use of the trans-chelate L4 ligand in oxidative coupling reactions catalyzed by Pd(II) compounds, acetoxylation of arenes by PhI(OAc)2 using PhI(OAc)2/L4 (2:1) as the catalyst was examined and found to accelerate the reaction, but lower the overall yield. Finally, to examine the impact of metal ions on photochromic properties of N^C-chelate organoboron compounds, three metal acetylide compounds that contain a photo-active N^C-chelate BMes2 unit (B(ppy)Mes2) were prepared and fully characterized. The studies indicated that by taking advantage of different heavy metals the photoisomerization quantum efficiency of the boron chromophores can be readily tuned through the adjustment of 3LC state localized on the chelate backbone or the involvement of MLCT state in the lowest energy electronic transition. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-01-07 15:20:45.675

A new polymeric material with a polyoxanorbornene backbone and carbamoylmethylphosphine oxide, CMPO, ligand pendant groups has been synthesized, characterized, and studied. The ability of the material to selectively partition actinides utilizing a biphasic extraction strategy was tested. The polymeric materials had significantly higher (> 5-25 times) ability to extract Th4+ than the monomeric system. The molecular weight of the material affected the extraction and separation abilities. The lower molecular weight material extracted more ions, but was less discriminate for thorium(IV) over cerium(III), lanthanum(III), and europium(III), than the higher molecular weight material. Structural modifications to this system were made by creating block copolymers. The influence of additional functionalities, created by the addition of new polymeric blocks, was investigated. The ability of the material to selectively partition actinides utilizing both solid-liquid and liquid-liquid extraction strategies was tested. Extraction efficiencies comparable to liquid-liquid extractions were achieved in the solid-liquid extractions. The extraction behavior of the materials was significantly altered by the incorporation of new blocks. The incorporation of glycol chains into the system caused an increase in the uptake of thorium(IV) over the homopolymers. The incorporation of blocks of glycol chains and blocks of cross-linked hydroxcoumarian increased the selectivity significantly (XTh/Eu 2.3 – 4.5 times higher) over the homopolymer. These materials show tremendous promise as modular polymeric scaffolds. A novel emissive tetradentate platinum complex with electropolymerizable ethylenedioxythiophene groups has been synthesized and characterized. This material has been developed for use as the active layer in polymer light-emitting diodes. Electropolymerization offers ease of processing by depositing thin films directly onto an electrode during the polymerization process. Additionally because the emitter is covalently bound in the polymer, it cannot aggregate as is the case with some small molecule emitters. The platinum complex displayed emission peaks at 510 nm and 544 nm. Electropolymerization resulted in a conductive and emissive thin film, with an emission maximum at 453 nm.

The study of biological analytes in their native environment is a major challenge for biochemistry and molecular biology.  Luminesce spectroscopy is well suited for this task due to its non-invasiveness, high spatial and temporal resolution, and high signal to noise ratio. This thesis describes the development and applications of Ln-based luminescent probes for detecting small molecules and enzymes.  Specifically the probes presented are based on coumarin sensitizers coupled to a DO3A chelated LnIII center. The 1st generation of these probes employ 7-OH coumarins, caged at the 7-O position (Chapter 2). By use of p-pinacolatoboron benzyl or p-methoxybenzyl cages, this design allowed the construction of ratiometric EuIII-based probes capable of detecting the reactive oxygen species H2O2, NO and ONOO−. The second and third part of the thesis describes a further improvement of the design (Chapters 3 and 4). By employing caged coumarin precursors EuIII and TbIII-based probes were developed for a variety of different analytes (F−, Pd0, H2O2, β-galactosidase, β-glucosidase, α-mannosidase and phosphatase). Most of these probes displayed excellent turn-on responses when treated with their respective analytes. Furthermore they could be used for detecting multiple analytes simultaneously (Chapter 4). By use of one Eu-based and another Tb-based probe, the simultaneous detection of two analytes was possible. This could further be extended to simultaneous three analyte detection by the additional employment of an organic coumarin-based probe. The last part of the thesis (Chapter 5) describes protocols for the rapid and efficient access to triazole-linked lanthanide-antenna complexes by use of the copper-catalyzed azide-alkyne cycloaddition reaction. For robust substrates, microwave heating at 100 °C enabled rapid (15-60 min) access to various lanthanide complexes, which could be isolated via simple precipitation. Using these conditions pure bi- and tri-homometallic lanthanide complexes could be prepared. A second protocol, for substrates carrying sensitive functionalities was also developed. The application of catalytic amounts of CuOAc, BimPy2 ligand, and a large excess of NaAsc afforded a variety of lanthanide complexes, among them caged responsive probes, in moderate to good yields.

Nanotechnology has been increasingly employed in forensic science for the detection of latent fingerprints, using multiple techniques from new aluminium nanomaterials for dusting to quantum dot dispersions, to try to increase and enhance areas where prints are likely to be found at scenes of crime. Different substrates use a diverse range of methods to develop prints when they are found and each method has its own drawbacks. It is not viable to use many of these techniques in conditions other than in a laboratory due to the harmful environmental effects they can cause over long term use. With this in mind a new easier to use technique that can be used on any substrate from wood to glass to paper was looked into. A range of nano-sized rare earth phosphor precursors were synthesised using homogeneous precipitation and solid state methods which were then converted to phosphors by firing at 980oC. Eu3+ and Tb3+ doped Y2O3, YVO4 and Y2O2S were chosen for their luminescent intensity. Analysis of each of the phosphors was carried out using multiple techniques and a single host lattice chosen for continuation. Y2O3:Eu3+ and Y2O3:Tb3+ were coated using a modified Stöber process to try and decrease the agglomeration of particles as well as allowing for surface modification to take place. Modifications of the surface were prepared and analysed, and these particles were then used in multiple fingerprint examinations to examine the adherence on fingerprints of different ages. The surface modifications manifested great adherence to the fingerprint residue even after two weeks elapsed and showed great promise after a two year period.

Quantum dots (QDs) CdS and CdSe were synthesized in three different media including reverse micelles, aqueous solution, and trioctylphosphine oxide/trioctylphosphine (TOPO/TOP). Transmission electron microscope (TEM), X-ray diffraction (XRD), UV-VIS, fluorescence spectroscopy and microscopy were used to characterize the QDs and their nanoassemblies. CdS QDs synthesized in reverse micelles showed broad emission spectra. CdSe-CdS QDs with core shell structure synthesized in aqueous solution showed more than 30% emission quantum yield. CdSe-CdS QDs of different emission colors were prepared. CdSe and CdSe-ZnS QDs were also synthesized in TOPO/TOP media. This synthesis route produced highly luminescent CdSe QDs with over 50% emission quantum yield. The application of QDs as ions probes and methods to encapsulate QDs in nanospheres including micelles, glyconanospheres and silica nanospheres and the use of these nanospheres in bioassays are described. CdS QDs capped with different ligands such as thioglycerol, cysteine and polyphosphate showed different responses to biological relevant ions. The emission intensity of polyphosphate capped CdS QDs was affected by all the tested ions and did not show a selective response. On the other hand, the emission of thioglycerol capped CdS QDs was selectively quenched by copper ions while the emission of cysteine capped CdS QDs was selectively enhanced by zinc ions. Stern-Volmer equation was applied to correlate the emission intensity of the CdS QDs and the copper ion concentration. A Lagmuir isotherm binding equation was used to describe the relation between the emission intensity of cysteine capped CdS QDs and zinc ion concentration. The possible mechanism to explain the effects of capping ligands on CdS QDs responses to ions is also discussed. CdSe QDs synthesized in TOPO/TOP media were encapsulated in nanospheres for bioassay applications. The glyconanospheres contained a large number of glucose residues on their surface and showed high binding activity towards the lectinic protein Concanavalin A (Con A). Silica nanospheres containing hundreds of CdSe QDs were functionalized with thiol groups to enable the conjugation of streptavidin to the nanospheres. The streptavidin modified silica nanospheres were used as luminescent indicators in a sandwich immunoassay for the detection of antiprotein A antibody. The advantages and disadvantages of the nanospheres based bioassay are discussed.

Inspired by nature’s use of self-assembled systems to carry out virtually all biological processes, chemists have taken to building simplified synthetic systems that mimic the biotic world. Although transition metal-ligand interactions are rarely used for the purpose of biological self-assembly, they have several advantages over other weak noncovalent interactions, such as pronounced directionality and significant strength. These particular attributes have allowed chemists to construct a comprehensive library of self-assembled polygons and polyhedra, using different transition metal-ligand motifs. Many of these supramolecular assemblies possess cavities of defined shape and size, which are able to accommodate guest molecules. It has further been realised that isolation of guest species from the bulk phase can lead to many interesting functions, such as containment, sensing and catalysis. Herein, a new self-assembly strategy has been used to construct novel cyclometalated Pt cages and assembly of the first known [Ir(ppy)2]-based capsule has also been achieved. Chapter 1 includes an introduction to metallosupramolecular assemblies, followed by a comprehensive review of three-dimensional architectures with accessible cavities, their synthetic strategies and applications. Chapter 2 reports on the construction of novel Pt(II)-based trigonal prisms using an unusual, kinetically controlled protocol. By exploiting asymmetric cyclometalated 2-phenylatopyridine based platinum corner units that possess both labile and non-labile cis-coordination sites, trigonal prismatic stereoisomeric architectures have been selectively prepared by altering the sequence of addition of ditopic 4,4′-bipy (4,4′-bipyridine) and tritopic tpt (2,4,6-tris(4-pyridyl)-1,3,5-triazine) molecular structural components using a template free method. Collision-induced-dissociation mass spectrometry experiments were used to differentiate between the structural isomers due to their significantly different fragmentation profiles. Chapter 3 describes the synthesis and characterisation of the first molecular capsule based on an [Ir(ppy)2]+ 90° metallosupramolecular acceptor unit. Initial work focused on pyridine-based donor ligands from which an Ir2L2 metallamacrocycle was assembled. However, when the highly conjugated tpt “panels” were used, due to postulated constraints in the dihedral angle, self-assembly of the Ir6tpt4 octahedral was unsuccessful. The constraints in the dihedral angle were eliminated by swapping pyridine for nitrile-based ligands and following the development of a method to resolve rac-[(Ir(ppy)2Cl)2] into its enantiopure forms, homochiral Ir6tcb4 (tcb = 1,3,5-tricyanobenzene) octahedral capsules where realised. Photophysical studies on the Ircapsules have shown that the ensemble of cooperative, weakly coordinating ligands can lead to luminescence not present in the comparative mononuclear analogues. X-ray crystallographic analysis revealed that the Ir capsules possess cavities large enough to accommodate 4 triflate counterions. Through a series of titration experiments the ability of the capsules to act as anion sensors was also exposed. Further exploration into the host-guest chemistry of the Ir6tcb4 capsule is reported in Chapter 4. Subsequent experiments have shown that self-assembly is highly dependent on the counterions associated with the system. While a number of different anions (OTf-, BF4 -, ClO4 -, PF6 -) facilitate the formation of the same octahedral scaffold, when triflimide was employed as a bulkier counterion, no capsule was observed. On subsequent addition of smaller counterions, such as triflate, the same Ir6tcb4 cage assembles, demonstrating that the anions also act as templates. Kinetic stability experiments, undertook by monitoring the rate of scrambling of the Δ and Λ-[Ir(ppy)2]+ components within the preformed ensembles, show that the Ir capsules are up to 1.4×104 times more stable than their mononuclear analogues. The counter anions were also observed to play a crucial role in the capsule’s stability with measured scrambling half-lives ranging from 4.7 mins with tetrafluoroborate to as long as 4.5 days with triflate. In contrast, the rate of ligand exchange in simple mononuclear complexes, as ascertained using EXSY NMR experiments, was found to be approximately independent of the associated anion.

Orientador: Ana Maria Pires / Banca: Luiz Humberto Marcolino Júnior / Banca: Sergio Antônio Marques de Lima / Resumo: O objetivo deste trabalho foi a investigação da potencialidade de sistemas luminescentes de matrizes à base de silicatos contendo Ba 2+ dopados com Eu 3+ , de serem aplicados na elaboração de eletrodos de pasta de carbono modificados (EPCM) para atuarem como sensores eletroquímicos. Para obtenção do material modificador do eletrodo foi desenvolvida uma rota de síntese sol-gel a qual tem como precursor o acetato de bário, Ba(CH3COO)2, o tetraetoxissilano, TEOS, como alcóxido para formação da cadeia polimérica e o ácido acético, CH3COOH, como solvente para dissolução do sal de bário, além de servir como catalisador da reação. Após a obtenção do material na sua forma gel e xerogel (aquecida a 100°C) essas formas foram caracterizadas por análise térmica, difração de raios X, espectroscopia no infravermelho e espectroscopia de luminescência. A partir dos resultados, verificou-se que quando o gel produzido é aquecido a 450°C e a 1100°C as fases formadas são o carbonato e silicato de bário, respectivamente. O material na sua fase silicato, aquecido a 1100°C, apresentou melhores propriedades luminescentes quando comparado ao material xerogel, sendo possível detectar na fase silicato um maior número de transições eletrônicas do európio. Conhecendo a estrutura do material em diferentes temperaturas ele foi utilizado para a elaboração de EPCMs, preparados a base de grafite e óleo mineral como aglutinante, no qual uma porcentagem do material modificador desenvolvido foi adicionada. Os modificadores testados foram os materiais na fase xerogel contendo 0,5, 1, 5 e 10% em mol de európio, além dos materiais calcinados a 450°C dopado com 1% de európio. Aquele que apresentou melhor resposta eletroquímica foi o xerogel da amostra dopada a 1% de európio e, a partir desse... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this study was to investigate the potential of luminescent systems, based on silicate matrices containing Ba 2+ and doped with Eu 3+ to be applied in the preparation of carbon paste electrode modified (CPEM) to act as electrochemical sensors. To obtain the modifier material of the electrode a sol-gel synthetic route was developed whereas it uses barium acetate, Ba(CH3COO)2 as precursor, tetraethoxysilane, TEOS as alkoxide to form the polymer chain and acetic acid, CH3COOH, as a solvent for dissolving the barium salt, as well as to act as a catalyst for the reaction. After obtaining the material in its gel and xerogel forms (heated to 100 ° C), they were characterized by thermal analysis, X-ray diffraction, infrared spectroscopy and luminescence spectroscopy. From the results, it was found that when the gel is heated to 450 ° C and 1100 ° C it is formed barium carbonate and silicate phases, respectively. The material in its silicate phase, heated to 1100 ° C, showed better luminescent properties when compared to the xerogel material and, exhibits a larger number of electronic transitions of europium. Knowing the structure of this material at different temperatures, it was used to prepare CPEMs, based on graphite and mineral oil as a binder, where a percentage of the modifier material developed was added. The modifiers were tested in phase xerogel materials containing 0.5, 1, 5 and 10% of europium, besides, the material calcined at 450 ° C doped with 1% of europium. The one that showed the best electrochemical response was the xerogel sample doped at 1% europium and from this modifier, different tests were carried out by using cyclic voltammetry to establish the best conditions, such as europium concentration and calcination temperature of the material modifier. Parameters such as pH and electrolyte... (Complete abstract click electronic access below) / Mestre

Aptamers have shown a great potential due to their cheaper synthesis and easy chemical modification compared to antibodies, and have been employed in various biological assays and applications throughout the last two decades. Despite of their limitations, such as non-specific binding and low nuclease resistance, aptamers could be successfully used in the biomarker discovery and for the development of the aptamer-based imaging probes for in vitro assays. In this thesis, luminescent aptamer-conjugated nanoparticles were developed and utilized for leukemia cell detection with fluorescent microscopy. It was shown that for the bioconjugation of an aptamer with luminescent nanoparticles it is more beneficial to use carboxyl-modified nanoparticles, which results in a stable luminescence after the conjugation and the absence of unsaturated and unstable conjugates, unlike with amino-modified nanoparticles. Moreover, a cell viability assay was performed and it was revealed that aptamer-conjugated nanoparticles did not induce spontaneous apoptosis and necrosis of leukemia cells, which can be further explored with additional cytotoxicity tests, whether the aptamer-conjugated nanoparticles are biocompatible, or not. Aptamer-based biomarker discovery implies disease biomarker identification, and most commonly used methods are tedious and require a relatively high concentration of captured aptamer-target complexes. For that, AptaBiD was used in order to optimize aptamer-target identification method. Using Sgc8-aptamer, it was first shown with flow cytometry that it binds to both, healthy and malignant T lymphocytes, which requires further improvements for this aptamer to be used for leukemia detection. Among three tested detergents for the aptamer-target purification, DDM happened to be the most suitable one, due to its gentle cell lysis and solubilization properties. However, the cross-linking with formaldehyde has not positively affected the results obtained and could be replaced with photocross-linking in future experiments, which would allow to selectively cross-link an aptamer with a photomodified nucleobase with its target. Lastly, a high number of intracellular proteins identified within samples could be associated with the aptamer non-specific binding and internalization, which could be improved in future with an alternative cell fractionation with a membrane isolation approach used for the identification of transmembrane target protein.

Fluorescent labeling of biological materials using small organic dyes is widely employed in the life sciences and have been used in a variety of applications that include diagnostics and imaging. Quantum dots have the potential to overcome problems encountered by organic molecules and have been exploited for applications in biological imaging and in single particle tracking studies. The dithiolane ring can be exploited to attach a diversity of organic compounds to CdSe–ZnS core–shell nanoparticles. The introduction of spectroscopic labels as trans-azobenzene chromophores offers the opportunity to quantify the average number of dithiolane anchoring groups attached to each quantum dot. The transition from monomeric ligands with a single dithiolane anchor to polymeric ligands with multiple dithiolane anchoring groups can be exploited to raise the number of chromophoric labels adsorbed on each quantum dot. Systems showing FRET have been developed on the basis of supramolecular association of BODIPY based dyes or quantum dots as donors and organic chromophores as acceptors. Amino - terminated dyes and quantum dots associate with the chromophores through an ammonium moiety on addition of acid, thereby bringing them closer. Addition of base increases back the fluorescence intensity of the donor completely because of the dissociation. However a similar system with quantum dots as donor, show a very small restoration of fluorescence possibly due to non-specific interaction. In the next project, introduction of spectroscopic labels, in the form of BODIPY dye within the ligands offered the opportunity to quantify the average number of dithiolane anchoring groups attached to each quantum dot. Both fluorescence resonance energy transfer and electron transfer mechanisms are responsible for the quenching of quantum dot fluorescence and unfortunately does not make the system suitable for pH sensing. In the final project, BODIPY-oxazine based fluorophore – photochrome dyad has been assembled by a connecting triazole ring, such that the emission of the former can be modulated by the electronic and structural changes caused by the photoinduced transformations of the later. Further experiments need to be conducted on the fluorophore – photochrome dyads to switch the luminescence of the former with optical inputs.