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Displaying Results 226 - 250 of 3821 on page 10 of 153
Marked
Mark
Ligand design for controlling dimensionality and chirality in novel lanthanide-organic hybrid materials with tuneable optoelectronic properties
(2015)
Patterson, Adam Ross
Ligand design for controlling dimensionality and chirality in novel lanthanide-organic hybrid materials with tuneable optoelectronic properties
(2015)
Patterson, Adam Ross
Abstract:
THESIS 10659
The research presented in this thesis looks into the development of novel inorganic-organic hybrid materials with a particular focus on exploiting lanthanide(III) ions. The project considers the synthesis and structural characterisation of these materials and investigates their photoluminescence properties.
http://hdl.handle.net/2262/80462
Marked
Mark
Teaching old dogs new tricks : transition metal-catalysed reactions for generation of rigid cubane and designer porphyrin scaffolds
(2015)
Plunkett, Shane
Teaching old dogs new tricks : transition metal-catalysed reactions for generation of rigid cubane and designer porphyrin scaffolds
(2015)
Plunkett, Shane
Abstract:
THESIS 10660
The aim of this work was to use Pd-catalysis in the pursuit of novel, synthetically interesting, structural scaffolds based around either the rigid cubane framework or the optically active porphyrinoid core. In both cases, focus was on the application of the most modern chemical techniques to historically under-exploited or synthetically inaccessible organic scaffolds.
http://hdl.handle.net/2262/80467
Marked
Mark
Fiat Lux : the synthesis and manipulation of molecular scaffolds for photodynamic therapy and light-harvesting arrays
(2014)
Rogers, Luke
Fiat Lux : the synthesis and manipulation of molecular scaffolds for photodynamic therapy and light-harvesting arrays
(2014)
Rogers, Luke
Abstract:
THESIS 10870
Molecular scaffolds are an emerging paradigm that offers chemists the use of preformed chemical structures that can be manipulated structurally and synthetically for use in a plethora of applications. The goal of the research discussed herein was to develop new methodologies for the synthesis and manipulation of either new or preformed molecular scaffolds for PDT and light-harvesting technologies. It was hoped to implement techniques and synthetic strategies previously developed in house in the Senge lab, in concert with the development of new pathways for the installation of biologically and photophysically interesting molecules.
http://hdl.handle.net/2262/80487
Marked
Mark
Synthetic routes towards guanidines of biological interest
(2014)
Shaw, Julian W.
Synthetic routes towards guanidines of biological interest
(2014)
Shaw, Julian W.
Abstract:
THESIS 10430
The Rozas laboratory has been interested in the synthesis and biological evaluation of guanidine containing molecules for the past ten years. The application of guanidines as both minor groove binders (MGB) and a2-adrenoceptor (a2-AR) antagonists has been the focus of much of the research conducted. A number of promising results have been discovered in targeting the a2-AR. with a number of effective agonists and antagonists having been synthesised. a2-AR antagonists have proven to be a valid target for the alleviation of symptoms of Major Depressive Order. Historically these guanidines have been prepared by reacting the prerequisite anilines with N,N-bis-tert-butoxycarbonyl-thiourea in the presence of HgCl2 to form the protected aryl guanidines. The use of mercury in such reactions is an obvious drawback and it was decided that its use should be eliminated from the synthesis of biologically active guanidines in Rozas group. The overlying aim of this PhD project was...
http://hdl.handle.net/2262/80504
Marked
Mark
Synthesis and structural characterisation of metal-organic frameworks composed of transition or lanthanide metal cations linded via tritopic ligands
(2014)
Tobin, Gerard Martin
Synthesis and structural characterisation of metal-organic frameworks composed of transition or lanthanide metal cations linded via tritopic ligands
(2014)
Tobin, Gerard Martin
Abstract:
THESIS 10405
The work presented in this thesis is concerned with the design and synthesis of metal- organic frameworks (MOFs). MOFs are a class of hybrid inorganic-organic material composed of metal-ions or clusters of metal-ions linked via organic linkers into high dimensional frameworks. Interest in MOFs arises from their advantageous physicochemical properties such as porosity and ease of functionalisation, which facilitate their use in a diverse range of potential applications such as energy storage, drug delivery and catalysis.
http://hdl.handle.net/2262/80527
Marked
Mark
Photodynamic therapy against oesophageal cancer : In vitro testing of potential new agents
(2014)
Vaz, Gisela
Photodynamic therapy against oesophageal cancer : In vitro testing of potential new agents
(2014)
Vaz, Gisela
Abstract:
THESIS 10742
Oesophageal malignancies are one of the leading causes of death in the Western World. The incidence of these diseases is currently on the rise alternative but powerful therapies are being developed against them, an example of these is photodynamic therapy (PDT) which is an emerging treatment against oesophageal cancer. However, it is still a long way from being widely used as an alternative to the more conventional therapies. The most commonly used photosensitisers are based on porphyrins and their derivatives yet those in clinical use still show many side effects and issues such as prolonged patient phototoxicity.
http://hdl.handle.net/2262/80534
Marked
Mark
Functionalising and nitrogen-doping molecular graphenes : the chemical, optical and electronic consequences
(2014)
Wijesinghe, Lankani Priyangika
Functionalising and nitrogen-doping molecular graphenes : the chemical, optical and electronic consequences
(2014)
Wijesinghe, Lankani Priyangika
Abstract:
THESIS 10474
Chapter 1: This chapter gives a comprehensive literature review to the field of graphitic materials with particular focus on polyaromatic hydrocarbons (PAHs). The latter section will focus on the key oxidative cyclodehydrogenation reaction. Chapter 2: This chapter details the synthesis and characterisation of a novel family of 2N-doped heterosuperbenzenes [diazasuperbenzenes (DASB)] with varying peripheral functionalisation ... Chapter 3: This chapter outlines the synthesis and characterisation of a novel family of 6N-doped heterosuperbenzenes [hexaazasuperbenzenes (HASB)] which vary in their peripheral functionalisation. ... Chapter 4: provides a full account of the experimental work carried out in this research.
http://hdl.handle.net/2262/80544
Marked
Mark
Investigation of vertically stacked hybrid devices
(2015)
Yim, Chanyoung
Investigation of vertically stacked hybrid devices
(2015)
Yim, Chanyoung
Abstract:
THESIS 10587
Conductive carbon thin films are known to be promising candidates for future electrode materials for micro/nano-electronic device applications due to their favourable electrical properties and diversity of formation. In particular, recent enormous interest in graphene, a two-dimensional carbon material, has triggered many broad and comprehensive studies not only on graphene itself, but also on other two-dimensional layered materials such as transition metal dichalcogenides. The introduction of such materials to real electronic device applications can be effectively achieved by making hybrid devices where these materials are combined with conventional semiconductors in device fabrication. Therefore, it is very important to understand and define the electrical characteristics of such hybrid devices thoroughly in the initial stages of research.
http://hdl.handle.net/2262/80550
Marked
Mark
A study on novel pyrazine-substituted dithiolene complexes as synthetic models for molybdenum cofactor and facile molybdenum mediated unexpected formation of pentathiepins
(2014)
Zubair, Muhammad
A study on novel pyrazine-substituted dithiolene complexes as synthetic models for molybdenum cofactor and facile molybdenum mediated unexpected formation of pentathiepins
(2014)
Zubair, Muhammad
Abstract:
THESIS 10522
In the present study, pyrazine (3 and 12) and quinoxaline (4 and 9-11) based compounds were synthesised as precursors for the synthetic analogues of MPT in MoCo. During the attempts to synthesise target model complexes, an unexpected formation of quinoxaline-derived pentathiepin (15) was observed. This by chance invented method for preparation of pentathiepin was optimised and then used to synthesise a series of other pentathiepin derivatives (16-18). Further on, a study has been made with regard to evaluate the influence of different substituents on the biological properties of these compounds. All pentathiepin derivatives (15-18) exhibited promising DNA binding properties as a minor groove binding agents and remarkable therapeutic activities.
http://hdl.handle.net/2262/80553
Marked
Mark
Studies towards oligodeoxynucleotide conjugates as potential photoactive antisense agents in chronic myeloid leukaemia
(2002)
Crean, Conor
Studies towards oligodeoxynucleotide conjugates as potential photoactive antisense agents in chronic myeloid leukaemia
(2002)
Crean, Conor
Abstract:
THESIS 6542
The research presented in this thesis concerns the synthesis of oligodeoxynucleotide (ODN) conjugates and their use in the photochemical induction of oxidative damage to specific nucleic acid bases in a complementary ODN target strand as shown below: 5`T G A C C A T C A A T A A G G A A G A A G C C C T T C A G C G G C C3`, 3`G G T A G T T A T T C C T T C T T ?sensitiser. The target strand used is an ODN model of the bcr/abl oncogenic mRNA present in chronic myeloid leukaemia (CML). As such, the aim of this research is the development of potential photoactive antisense agents, which could be used in future experiments to hinder expression of the oncogenic mRNA and be used in the development of therapeutic agents to treat CML. ODN conjugates were synthesised with photosensitising molecules, which were derivatives of a ruthenium polypyridyl complex and pteridinone derivatives. Thus, molecules were synthesised with functional groups that could be activated towards couplin...
http://hdl.handle.net/2262/81819
Marked
Mark
Enhancing the oxygen vacancy formation and migration in bulk chromium(iii) oxide by alkali metal doping: a change from isotropic to anisotropic oxygen diffusion
(2017)
Carey, John J.; Nolan, Michael
Enhancing the oxygen vacancy formation and migration in bulk chromium(iii) oxide by alkali metal doping: a change from isotropic to anisotropic oxygen diffusion
(2017)
Carey, John J.; Nolan, Michael
Abstract:
Oxygen vacancy formation and migration are vital properties for reducible oxides such as TiO2, CeO2 and Cr2O3 as the oxygen storage capacity (OSC) of these materials are important for a wide range of applications in photovoltaics, oxidative catalysis and solid oxide fuel cells. Substitutional doping these transition metal oxides enhances their OSC potential, in particular for oxygenation and surface reaction chemistry. This study uses density functional theory with on-site Coulomb interactions (PBE+U) for Cr 3d states (+U = 5 eV) and O 2p states (+U = 5.5 eV) to calculate the oxygen vacancy formation energy and oxygen diffusion pathways for alkali metal (Li, K, Na, Rb) doping of bulk chromium(III) oxide (α-Cr2O3). Substitutional doping of the lattice Cr3+ cations with alkali metals that have a +1 oxidation state, creates two hole states on the neighbouring lattice O atoms, and removal of a lattice oxygen charge compensates the dopants by filling the holes. The removal of the next ox...
http://hdl.handle.net/10468/4948
Marked
Mark
Mediated water electrolysis in biphasic systems
(2017)
Scanlon, Micheál D.; Peljo, Pekka; Rivier, Lucie; Vrubel, Heron; Girault, Hubert H
Mediated water electrolysis in biphasic systems
(2017)
Scanlon, Micheál D.; Peljo, Pekka; Rivier, Lucie; Vrubel, Heron; Girault, Hubert H
Abstract:
The concept of efficient electrolysis by linking photoelectrochemical biphasic H2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp2*Fe(III)]+) to neutral decamethylferrocene (Cp2*Fe(II)) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp2*Fe(II) to form the corresponding hydride species, [Cp2*Fe...
http://hdl.handle.net/10344/6234
Marked
Mark
Application of ionic liquid materials in microfluidic devices
(2017)
Akyazi, Tuğçe; Saez, Janire; Tudor, Alexandru; Delaney, Colm; Francis, Wayne; Diamond...
Application of ionic liquid materials in microfluidic devices
(2017)
Akyazi, Tuğçe; Saez, Janire; Tudor, Alexandru; Delaney, Colm; Francis, Wayne; Diamond, Dermot; Basabe-Desmonts, Lourdes; Florea, Larisa; Benito-Lopez, Fernando
http://doras.dcu.ie/21789/
Marked
Mark
Physico-chemical characterisation of hydrogels from chemistry to function
(2016)
Wu, Bing
Physico-chemical characterisation of hydrogels from chemistry to function
(2016)
Wu, Bing
Abstract:
Hydrogels in industrial applications have received increased attention due to potential in drug eluting contact lenses and in the pharmaceutical field because of the anticipated biocompatibility of this class of materials. As one of most common commercial hydrogels, Polyethylene glycol (PEG)-based polyacrylate gels are widely used in tissue engineering and coating applications. In many cases photopolymerization is the preferred route to preparing these crosslinked networks. Hence, a thorough understanding of these photo-cured PEG-based polyacrylate network is of great interest in the further understanding of industrial applications of these materials. In this work, we probed the detailed polymer dynamics inside these photo-cured networks by using a series of analytical tools, like Nuclear Magnetic Resonances (NMR) techniques, while these bulky characters (mechanic properties, thermal properties, etc.) were also measured correspondingly. By correlating these data, several effects cau...
http://doras.dcu.ie/21410/
Marked
Mark
Strategic design of conjugated polymer materials for sensors and solid-state lighting
(2016)
Fox, Niamh Willis
Strategic design of conjugated polymer materials for sensors and solid-state lighting
(2016)
Fox, Niamh Willis
Abstract:
THESIS 10936
Conjugated polymers (CPs) have shown extreme promise in a range of applications such as optical sensors and light-emitting devices due to their exceptional optoelectronic properties, low cost and solution processability. CPs are particularly sought after as sensory materials due to their property of amplified quenching, which can facilitate analyte detection at nanomolar concentrations. This work begins by examining the use of a polyfluorene (blue-emitting)- polythiophene (red-emitting) diblock CP with complementary optoelectronic properties attributed to both blocks, which enables fluorimetric and colorimetric detection of biologically important nucleotides. The magnitude of the optical response is sensitive to both nucleotide geometry and charge. The proposed mechanism behind this process involves electron transfer from the nucleobase to the polythiophene block, mediated by the CP triplet state. Although the vast majority of CP-based sensing schemes involve the de...
http://hdl.handle.net/2262/83127
Marked
Mark
N-Heterocyclic carbene-catalysed transformations : the crossed benzoin condensation and oxidative aldehyde esterifications
(2016)
Delany, Eoghan
N-Heterocyclic carbene-catalysed transformations : the crossed benzoin condensation and oxidative aldehyde esterifications
(2016)
Delany, Eoghan
Abstract:
THESIS 11267
The focus of this thesis is the development of a suite of heteroazolium ion-based salts as precursors to N-heterocyclic carbene (NHC) catalysts for a range of transformations involving aldehyde substrates. It has been demonstrated that, under basic conditions, a novel triazolium ion-based precatalyst can promote the chemoselective crossed benzoin condensation between ortho-substituted benzaldehydes and a range of aromatic aldehyde coupling partners in excellent yield. The chemoselectivity of the methodology was found to be reliant on a careful balance of catalyst and substrate control, with an ortho-bromine atom serving as a temporary directing group to aid the catalyst in differentiating between the two aromatic aldehydes. It has then been shown how this ortho-bromine atom can be conveniently and quickly removed via transition metal-catalysed reduction (to allow access to a further range of cross-benzoin adducts) or utilised as a functional handle for further trans...
http://hdl.handle.net/2262/83121
Marked
Mark
Single-walled carbon nanotubes as novel NIR fluorescent probes for biomedical optical imaging
(2011)
Movia, Dania
Single-walled carbon nanotubes as novel NIR fluorescent probes for biomedical optical imaging
(2011)
Movia, Dania
Abstract:
THESIS 9503
http://hdl.handle.net/2262/83171
Marked
Mark
Computational screening of structural and compositional factors for electrically conductive coordination polymers
(2014)
Tiana, Davide; Hendon, Christopher H.; Walsh, Aron; Vaid, Thomas P.
Computational screening of structural and compositional factors for electrically conductive coordination polymers
(2014)
Tiana, Davide; Hendon, Christopher H.; Walsh, Aron; Vaid, Thomas P.
Abstract:
The combination of organic and inorganic chemical building blocks to form metal-organic frameworks (MOFs) offers opportunities for producing functional materials suitable for energy generation, storage and conversion. However, such applications rely on robust electron transport and the design of conductive hybrid materials is still in its infancy. Here we apply density functional theory to assess the important structural and compositional factors for forming conducting MOFs. We focus on 1D metal-organic polymers as a model system and assess the choice of organic, inorganic and linking units. The results demonstrate that electronic communication is sensitive to the energy and symmetry of the frontier orbitals associated with the organic and inorganic building blocks and offers guidance on how to optimise electrical conduction in hybrid materials.
http://hdl.handle.net/10468/6417
Marked
Mark
Covalent functionalization of few-layer black phosphorus using iodonium salts and comparison to diazonium modified black phosphorus
(2018)
van Druenen, Maart; Davitt, Fionán; Collins, Timothy W.; Glynn, Colm; O'Dwyer, Col...
Covalent functionalization of few-layer black phosphorus using iodonium salts and comparison to diazonium modified black phosphorus
(2018)
van Druenen, Maart; Davitt, Fionán; Collins, Timothy W.; Glynn, Colm; O'Dwyer, Colm; Holmes, Justin D.; Collins, Jillian
Abstract:
Since the isolation of two-dimensional (2D) phosphorene, black phosphorus (BP) has gained popularity due to its high carrier mobility and tunable bandgap. Poor ambient stability of BP remains a key issue and impedes its use in electronic applications. Here we report a new stabilization strategy based on covalent functionalization of liquid exfoliated few-layer BP using aryl iodonium salts. Arylation of BP using iodonium salts enables covalent modification without inducing oxidation and alters the degradation chemistry of BP by inhibiting bridged oxygen formation through attachment to surface oxygen sites. In comparison, functionalization using aryl diazonium salts results in oxidation and aryl multilayer formation and does not adequately disrupt noncovalent solvent passivation. Aryl functionalization of BP using iodonium salts displays superior ambient stability compared to arylation using diazonium salts associated with greater covalent functionalization as characterized using X-ra...
http://hdl.handle.net/10468/6561
Marked
Mark
Guanidine-based DNA binders and strategies toward their platinum complexes as anticancer dual agents
(2016)
O'Sullivan, Patrick
Guanidine-based DNA binders and strategies toward their platinum complexes as anticancer dual agents
(2016)
O'Sullivan, Patrick
Abstract:
THESIS 11094
One in three people will be diagnosed with cancer in their lifetime. One of the main targets of chemotherapy is DNA. Platinum-based anti-cancer agents form covalent bonds with bases in the major groove of DNA in cancer cells, causing death of these cells. The platinum-based coordination compound cisplatin (Platinol?) and its derivatives carboplatin (Paraplatin?) and oxaliplatin (Eloxatin?) are used in 50% of chemotherapies and are especially efficacious against testicular cancer, where platinum-based drugs have increased the five-year survival rate from 10% in the 1960s to 98% today. One of the most recent chemotherapies to gain approval for cancer treatment is trabectedin (Yondelis?), a natural product that works as a DNA minor groove binder (MGB) and specifically treats liposarcomas by binding covalently to the minor groove of DNA. Over the past 10 years, Rozas? group has developed dicationic guanidinium-like DNA MGBs that strongly bind to AT-rich DNA sequences a...
http://hdl.handle.net/2262/83447
Marked
Mark
Enantioselective receptors for anionic species
(2001)
Hurley, Fionn Christopher
Enantioselective receptors for anionic species
(2001)
Hurley, Fionn Christopher
Abstract:
THESIS 6345
This project aimed to design, synthesise and test neutral, tripodal steroid receptors based on cholic acid 1 that were capable of binding to carboxylates (especially N-acyl-a-aminoacid carboxylates), and differentiating between their enantiomers.
http://hdl.handle.net/2262/85476
Marked
Mark
A study of Hydrogen-Deuterium exchange on the photophysical properties of Ruthenium (II) Polypyridyl complexes
(2002)
Higgins, Michelle E.
A study of Hydrogen-Deuterium exchange on the photophysical properties of Ruthenium (II) Polypyridyl complexes
(2002)
Higgins, Michelle E.
Abstract:
THESIS 6720
This main aim of the present study is to investigate the effect of protium-deuterium exchange on the photophysical and excited state energetics of Ru(ll) complexes by UV-Vis absorption, both steady-state and time-resolved emission spectroscopies. The three main complexes synthesised, characterised and studied are [Ru(phen)2 dppz]2+ 4, [Ru(phen)2diMedppz]2+ 8, and [Ru(phen)2 diFdppz]2+ 9. For each of these complexes, a series of partially deuterated analogues were successfully synthesised. For example, for 4, a series of complexes of the form, [Ru(dx-phen)2dy-dppz]2+, where x = 0 and 8, and y = 0, 4, 6, and 10 were prepared. These species could be used to probe: (i) the nature of the excited state and (ii) in which part of the dppz ligand (i.e. 1,10-phenanthroline (phen) or phenazine (phz)) the excited state electron is located.
http://hdl.handle.net/2262/85472
Marked
Mark
Formation of an ordered porous polymer microstructure by water droplet templating
(2010)
Daly, Ronan
Formation of an ordered porous polymer microstructure by water droplet templating
(2010)
Daly, Ronan
Abstract:
THESIS 9414
This thesis examines the complex system of competing mechanisms involved when evaporation of a polymer solution induces sufficient cooling to drive condensation of water droplets onto the solution surface, where they pack, order and are ultimately captured in a polymeric matrix as the solvent leaves. This use of rafts of water droplets to template a polymer solution leaves behind an ordered porous microstructured film of the polymer, upon evaporation of the water. The dynamic mechanism, rather than studied as a whole, was broken down into an examination of (i) the equilibrium force balance of droplets on the solvent surface and (ii) the dynamical behaviour associated with solvent evaporation, water condensation and the evolution of polymer solution concentration. The first section examines the interfacial energy balances that can ensure or prohibit stability of the water droplets at the solvent/air boundary. A theoretical model and a novel experimental approach are e...
http://hdl.handle.net/2262/85519
Marked
Mark
Transmission electron microscopy and spectroscopy of carbon-based nanomaterials
(2016)
Rezvani, Ehsan
Transmission electron microscopy and spectroscopy of carbon-based nanomaterials
(2016)
Rezvani, Ehsan
Abstract:
Carbon-based nanomaterials, such as graphene, Carbon Nanotubes and fullerenes, have attracted a great deal of interest from the materials research community; especially in electronic and sensing applications. Despite all these outstanding properties, these materials pose significant challenges to the established characterisation techniques. Transmission electron microscopy (TEM) is considered as a powerful tool to tackle this challenge due to its capability to achieve images of atomic-scale resolution. Nonetheless, a key requirement for efficient application of TEM, is sample quality. To meet this need, in the first part of this work, modification of the CVD growth of graphene via catalyst optimisation was investigated and is reported in a dedicated chapter. We show that chromium can be used to successfully obtain entirely monolayer graphene films. The second part of this study, comprises HRTEM/EELS investigation of plasma-functionalised graphene; where we propose application of the...
http://hdl.handle.net/2262/85528
Marked
Mark
Directing the mechanism of CO2 reduction by a Mn catalyst through surface immobilization
(2018)
Walsh, James J.; Forster, Mark; Smith, Charlotte L.; Neri, Gaia; Potter, Richard J.; Co...
Directing the mechanism of CO2 reduction by a Mn catalyst through surface immobilization
(2018)
Walsh, James J.; Forster, Mark; Smith, Charlotte L.; Neri, Gaia; Potter, Richard J.; Cowan, Alexander J.
Abstract:
Immobilization of a Mn polypyridyl CO2 reduction electrocatalyst on nanocrystalline TiO2 electrodes yields an active heterogeneous system and also significantly triggers a change in voltammetric and catalytic behaviour, relative to in solution. A combination of spectroelectrochemical techniques are presented here to elucidate the mechanism of the immobilised catalyst in-situ.
http://doras.dcu.ie/22923/
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