Chemistry Commons^™

Dual-Action Hygienic Coatings: Benefits Of Hydrophobicity And Silver Ion Release And Surface Analysis, Niall Stobie, Brendan Duffy, John Colreavy, Patrick Mchale, Steven Hinder, Declan Mccormack

Articles

Coatings that demonstrate reduced attachment of crystalline precipitates and the medical device colonising Staphylococcus epidermidis were prepared by the immobilisation of silver doped perfluoropolyether–urethane siloxane thin films on glass substrates. The presence of stratified hydrophobic perfluoropolyether groups protects the coating surface from the attachment of crystalline hydrophilic species such as chlorides and phosphates, whilst silver ion release inhibited attachment of S. epidermidis and subsequent biofilm formation in vitro. The release of silver ions protects the perfluoro groups from the hydrophobic interactions of S. epidermidis cells, which can reduce the hydrophobicity of the protective coating. These coatings also exhibited significant antibacterial …

Structure-Reactivity Relationships Of L-Proline Derived Spirolactams And A-Methyl Prolinamide Organocatalysts In The Asymmetric Michael Addition Reaction Of Aldehydes To Nitroolefins., Fintan Kelleher, Sinead Kelly, John Watts, Vickie Mckee

Articles

L-Proline derived spirolactams and a-methyl prolinamides act as organocatalysts for the asymmetric conjugate addition of aldehydes to nitroolefins in excellent yields, with good diastereoselectivity and enantioselectivity. Furthermore, low catalyst loadings (5 mol%) and a low aldehyde molar excess (1.5 molar equivalents) were achieved.

Single Step Morphology-Controlled Synthesis Of Silver Nanoparticles, Vinodkumar Etacheri, Reenamole Georgekutty, Michael Seery, Suresh Pillai

Articles

Silver nanoparticles having different size and plasmon resonances were synthesized through a single step aqueous based method. The current procedure was based on the reduction of silver ions by ascorbic acid in the presence of sodiumborohydride and trisodium citrate. Triangular colloidal nanoparticles having different plasmon resonances (and hence different size and colours) were synthesized by varying only the concentration of ascorbic acid. These nanoparticles were found to be stable without using any surfactants or polymers. This study revealed a strong correlation between particle growth and concentration of constituent chemicals. Crystallinity and phase purity of the silver samples were investigated through …

Interaction Between Langmuir And Langmuir- Blodgett Films Of 5,11,17,23-Tetra-Tert-Butyl-25,27-Diethoxycarbonyl Methyleneoxy-26,28,Dihydroxycalix[4]Arene And 5,17-(9h-Fluoren-2-Yl)Methyleneamino)-11,23-Di-Tert-Butyl-25,27-Diethoxycarbonyl Methyleneoxy-26,28-Dihydroxycalix[4]Arene With Aqueous Copper And Lithium Ions., Mary Deasy, Fintan Kelleher, Faridah L. Supian, Tim H. Richardson, James P. Ward, Vickie Mckee

Articles

The binding interactions between aqueous copper (Cu2þ ) and lithium (Li þ ) ions and Langmuir monolayers and Langmuir-Blodgett (LB) multilayers have been investigated by studying surface pressure-area (Π-A) isotherms and surface potential-area (ΔV-A) behavior in order to find the effective dipole moment, μ^, of the calixarene molecules in the uncomplexed and complexed states. The orientation of both calix[4]arenes, namely, 5,11,17,23-tetra-tert-butyl- 25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene and 5,17-(9H-fluoren-2-yl)methyleneamino)- 11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene, is such that the plane of the calix ring is parallel with the plane of the water surface regardless of the ion content of the subphase. The Gibbs equation was used to interpret …

Corrosion Protection Properties Of Various Ligand Modified Organic Inorganic Hybrid Coating On Aa 2024-T3, Rajath Varma, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, John Colreavy, Brendan Duffy

Articles

The inclusion of zirconium precursors to prepare organosilane solgel coatings improves the corrosion protection performance of the coatings on aluminium and steel. The inherent differences in the hydrolysis rates of the silane and zirconium precursors, various ligands were used to control the hydrolysis by decreasing the number of reactive alkoxide group. Hybrid sols were synthesised using 3-(trimethoxysilyl) propylmethacrylate (MAPTMS) and zirconium n-propoxide chelated with organic ligands including different organic acids, acetyl acetone and 2 2’ bipyridyl. The effects of zirconia inclusion on the properties of the coatings were compared on the aerospace alloy AA 2024-T3. Electrochemical analysis and salt spray …

Corrosion Protection Of Aa 2024-T3 Aluminium Alloys Using 3, 4-Diaminobenzoic Acid Chelated Zirconium-Silane Hybrid Sol-Gels, P.C. Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Organic-inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, such as organically modified silanes (Ormosils) have found applications as electronic, optical and protective coatings. Such coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol-gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acid or acetyl acetonate prior to hydrolysis, …

Silver Nanoparticle Polymer Composite Based Humidity Sensor, Aoife Power, Tony Betts, John Cassidy

Articles

Silver nanoparticles were synthesised by a chemical reduction process in order to produce an aqueous colloidal dispersion. The resulting colloids were then characterised by a combination of UV-Vis spectroscopy, dynamic light scattering, X-ray diffraction and transmission electron microscopy and the nanoparticles were found to have an average diameter of 20–22 nm. The Ag/polymer nanocomposites were then applied to platinum interdigital electrodes as sensor coatings and the capability of the resulting sensor as a humidity detector investigated. With the application of 1 V, a current developed which was found to be directly proportional to humidity levels. The sensor gives a reversible, …

Rapid Microwave Synthesis Of Mesoporous Tio2 For Electrochromic Displays, Suresh Pillai, Declan Mccormack, Pradeepan Periyat, Nigel Leyland, David Corr, John Colreavy

Articles

No abstract provided.

The Antioxidant Properties Of Whey Permeate Treated Fresh-Cut Tomatoes, Lubna Ahmed, Ana Belen Martin-Diana, Daniel Rico, Catherine Barry-Ryan

Articles

The aim of this research was to analyse the effects of three types of cheese whey permeate treatment on the antioxidant properties of fresh-cut tomatoes. Tomatoes were treated with whey permeate concentrate (PC), delactosed permeate (DP) and delactosed concentrate (DC), stored at 4 C for 10 days and compared to samples treated with the industry standard, chlorine (120 ppm). Samples treated with DP retained significantly higher antioxidant activity (FRAP) and total phenols (TP), when compared with those treated with PC and DC. DP showed significantly higher results than chlorine for DPPH, FRAP and TP. In DPPH assay, all whey permeate-treated …

Spectroscopic Analysis Of Therapeutic Drugs., Laura Perdisatt, Christine O'Connor, Samar Moqadasi, Luke O'Neill

Conference Papers

The aim of this project was to investigate the photochemistry of three new Ruthenium (II) complexes as possible therapeutics and their associated ligands. The objectives were to use the following spectroscopic techniques: Absorption, Emission and Raman spectroscopy. Luminescent lifetime measurements were obtained by laser studies (Nd:YAG laser and Time coupled single photon counting (TCSPC) ).

Spectroscopic Investigation Of The Anatase-To-Rutile Transformation Of Sol-Gel Synthesised Tio2 Photocatalysts, Nicholas Nolan, Suresh Pillai, Michael Seery

Articles

Among the three major phases in titania, anatase is reported to be a better photocatalytically active phase. Anatase to rutile transformations, under normal conditions, usually occurs at a temperatue range of 600- 700 °C. Various chemical additives have previously been employed to extend the anatase transition to higher temperatures. Effect of employing various concentrations of formic acid and water on phase transition has systematically been studied by XRD, FTIR and Raman spectroscopy. A considerably higher anatase phase (41%) has been obtained at 800 ºC and 10% anatase composition is retained after annealing the materials at 900 ºC for the optimised …

Synthesis And Spectroscopic Analysis Of Therapeutic Ru(Ii) Complexes, Samar Moqadasi, Laura Perdisatt, Christine O'Connor, Luke O'Neill

Conference Papers

The aim of this study is to synthesise and characterise new ligands based on a 1,10-Phenanthroline-5,6-dione backbone and their respective Ru(II) complexes; Ru(bpy)2mfmp, Ru(bpy)2fmp and Ru(bpy)2NO2-mp as shown in figure 1.The synthesis of the ligands will be discussed and a variety of Ru(II) complexes. A brief insight of the electronic and NMR spectroscopy will be presented along with preliminary photochemical results such as extinction coefficients, quantum yields and luminescence lifetimes. Ruthenium complexes have well established synthetic and photochemical properties.1The objective of this work is to synthesise Ru(II) complexes for the applications of potential therapeutics. In order to establish their uses …

Online Support And Online Assessment For Teaching And Learning Chemistry, Claire M. Mcdonnell, Natasa Brouwer

Books/Book chapters

In this chapter, examples of innovative approaches that use educational technology to support active learning in chemistry lectures, tutorials and laboratory sessions are considered. The scope of the chapter is limited to blended learning. The strengths and weaknesses of e-learning are examined and the options available for online assessment using electronic tests and e-portfolios are discussed. In addition to the literature references provided in the chapter, several examples of good practice involving the implementation of information and communication technology for chemistry teaching in higher education are incorporated. A list of online resources for lecturers is also included.

One-Pot Synthesis Of Anionic (Nitrogen) And Cationic (Sulfur) Codoped High-Temperature Stable, Visible Light Active, Anatase Photocatalysts, Suresh Pillai, Declan Mccormack, Steven Hinder, Pradeepan Periyat

Articles

No abstract provided.

Influence Of Magnesium Nitrate On The Corrosion Performance Of Sol-Gel Coated Aa2024-T3 Aluminium Alloy, Rajath Varma, Brendan Duffy, John Cassidy

Articles

Traditional anti-corrosion technology has relied heavily on using reducible metal species, predominantly hexavalent chromium (Cr(VI)), for protecting reactive metal alloys such as aluminium which is extensively used in the aerospace sector. However, the impending changes in the use of Cr(VI) in Europe and the United States have forced aerospace manufacturers to examine alternative materials for protecting aluminium. One of the most promising alternatives being investigated are organosilane based sol-gels containing anticorrosion additives. In this work the anti-corrosion properties of magnesium (II) nitrate (Mg(NO3)2) as a inhibitor was investigated at different concentrations (0.1% - 1.0 wt %) in a methyltriethoxysilane (MTEOS) …

Silver Doped Perfluoropolyether-Urethane Coatings: Antibacterial Activity And Surface Analysis, Niall Stobie, Brendan Duffy, Steven Hinder, Patrick Mchale, Declan Mccormack

Articles

The colonisation of clinical and industrial surfaces with pathogenic microorganisms has prompted increased research into the development of effective antibacterial and antifouling coatings. There is evidence that implanted biomedical surfaces coated with metallic silver can be inactivated by hysiological fluids, thus reducing the bioactivity of the coating. In this work, we report the biofilm inhibition of Staphylococcus epidermidis using a roomtemperatureprocessedsilver dopedperfluoropolyether-urethane coating. The release of silver ions from these fluoropolymers over a six-day period inhibited bacterial encrustation – as observed by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) analysis indicated differences in carbon, fluorine and sodium surface composition …

Effect Of Organic Chelates On The Performance Of Hybrid Sol–Gel Coated Aa2024-T3 Aluminium Alloys, Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Sol–gels are organic–inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, primarily silanes, which have found applications as electronic, optical and protective coatings. These coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol–gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acids, prior to hydrolysis, to lower the hydrolysis …

One-Pot Synthesis Of Anionic (Nitrogen) And Cationic (Sulfur) Codoped High-Temperature Stable, Visible Light Active, Anatase Photocatalysts, Suresh Pillai, Declan Mccormack, Steven Hinder, Pradeepan Periyat

Articles

No abstract provided.

Enhanced Absorption Metal Oxides For Photocatalytic Applications, Reenamole Georgekutty

Doctoral

Environmental pollution and industrialization on a global scale has drawn attention to the vital need for developing new hygienic and environmentally friendly purification technologies. The most common indoor and outdoor purification process have their corresponding limitations of electricity and/or other energy sources. To address such enormous tasks, advance oxidation technology like heterogeneous photocatalytic systems via metal oxide semiconductors such as TiO2, ZnO, that are capable to operate effectively and efficiently under UV and visible light must be established. Due to the wide band gap of semiconductors, they are unable to absorb visible light. Hence, numerous research efforts have been done …

Development Of A Novel Humidity Sensor Based On A Polymer Silver Nanoparticle Composite, Aoife Power, John Cassidy, Tony Betts

Conference Papers

Humidity sensing is of particular concern for many industrial applications. Humidity sensors have typically been based on a reversible interaction between a polymer and water vapour. There is work published on gas sensors based on polymer gold nanoparticle composites, where the conductivity of the composite decreases on interaction with the gas. This happens because the swelling of the polymer which increases the electron hopping distance between the gold nanoparticles. The device in this work is a poly vinyl alcohol silver nanoparticle composite cast on an interdigital electrode array. On application of a dc bias, a current develops which is proportional …

Folate-Cyclodextrin Conjugate For Targeted Chemotherapy, Zlata Tofzikovskaya, Orla L. Howe, Mary Mcnamara, Christine O'Connor

Conference Papers

A general disadvantage of chemotherapy is that the drugs cannot discriminate between fast-growing cancer cells and normal healthy cells which causes many side-effects such as hair loss. An ideal solution to current methods of chemotherapy would be the development of a carrier for an anticancer drug which would be able to transport the drug and therefore target only cancer cells and release the drug molecules inside the cells. In this work folic acid (FA) is attached to an aminoalkane derivative of b-cyclodextrin (CDEn) with a view to developing novel drug delivery systems for therapeutic purposes. Cytotoxisity of folate-conjugate (CDEnFA) is …

Localised Galvanic Corrosion Processes In Thermal Spray Coated/Cast Aluminium Alloy Systems, David Culliton, Tony Betts, David Kennedy

Conference Papers

Cast Aluminium Alloys, because of the propensity of aluminium to react with impurities and alloying elements, are prone to developing IM impurities during the solidification process. These IM phases can act, in some fluids, as initiation sites for localised corrosion processes, resulting in degradation phenomena, such as pitting. Whilst Thermal Spray coatings can improve the wear resistance of Cast Aluminium Alloys, their corrosion performance may be hampered by the presence of through porosity within the coating.

The present work details some preliminary studies of the localised corrosion processes occurring at the interface area between a Thermal Spray coating and a …

An Integrated Approach To The Toxicity Evaluation Of Irish Marine Sediment - Chemical Assessment, Michelle Giltrap

Doctoral

This project was a collaborative project between the Marine Institute (MI) in Galway and Radiation and Environmental Science Centre (RESC) in the Technological University Dublin (DIT). In Ireland, at present, sediment quality assessments are generally reliant on chemical analysis alone with limited bioassay techniques available to further characterise the sediment. Some causative agents of toxicity to biological organisms are below analytical detection limits. Integration of bioassay data with chemical analysis is essential in order to complete a full ecotoxicological assessment of the quality of the marine environment. This project describes the chemical analysis of marine sediment for persistent pollutants from …

Working Report On The Status Quo Of Nanomaterials Impact On Health And Environment, Harald Krug, Margarita Apostolova, Marite Arija Bake, Gordon Chambers, Horia Chiriac, Eva Herzog, Victoria Hand, Jürgen Höck, Peter Hoet, Nicoleta Lupu, Declan Mccormack, Maja Remskar, George Robillard, Jamila Smisterova, Jan Stetkiewicz, Speranta Tanasescu, Aris Tsatsakis, David Vaughn, Peter Wick, Jörg Wörle-Knirsch

Articles

Nanotechnology is regarded as one of the key technologies of the future and associated with high expectations by politics, science and economy. Artificially produced nanosized particles and nanoscale system components have new properties which are of importance for the development of new products and applications. Such new properties of materials and substances result from the special properties of surfaces and interfaces and in part, from the geometric shape of the material. In theory nanoparticles (NPs) can be produced from nearly any chemical; however, most NPs that are currently in use today have been made from transition metals, silicon, carbon (single-walled …

Photoactive Supramolecular Cyclodextrin Assemblies, Muath Atmeh

Doctoral

Ligands with a macrocyclic host unit attached to a photoactive metal core are of interest across a range of applications from luminescent or electrochemical sensors, light harvesting and energy-collection purposes. Their versatile properties and possibility of associating cyclodextrins with other molecules both covalently and non-covalently mean that these macrocyclic ligands can be employed in the design and the formation of supramolecular complexes. A particularly attractive proposition is to combine the selective inclusion capabilities of CD with luminophores which may act as reporters of binding or other interactions at the cyclodextrin cavity. Ruthenium, osmium, and iridium polypyridyl complexes are particularly attractive …

Targeted Drug Delivery Systems For Cancer Therapy, Antonio Clementi, Christine O'Connor, Mary Mcnamara, A. Mazzaglia, M. C. Aversa, A. Giuffrida

Conference Papers

The role of cyclodextrin’s (CD) in drug delivery has advanced in recent years and this may be attributed to its biocompatibility and well established synthesis. Chemical modification of CDs has shown to extend the physicochemical properties and the host capacity for a variety of drugs. β-CD has been widely used in the early stages of pharmaceutical applications because of its ready availability and its cavity size suitability for a wide range of drugs. Chemical modification of β-CD has proven to enhance aqueous solubilisation, microbiological stability and reduced toxicity in previous studies.1 Folate Receptors are over-expressed in several human cancers including …

Real-Time Plasma Controlled Chemistry In A Two-Frequency, Confined Plasma Etcher, Vladimir Milosavljevic, Albert R. Ellingboe, Cezar Gaman, John V. Ringwood

Articles

The physics issues of developing model-based control of plasma etching are presented. A novel methodology for incorporating real-time model-based control of plasma processing systems is developed. The methodology is developed for control of two dependent variables (ion flux and chemical densities) by two independent controls (27 MHz power and O2flow). A phenomenological physics model of the nonlinear coupling between the independent controls and the dependent variables of the plasma is presented. By using a design of experiment, the functional dependencies of the response surface are determined. In conjunction with the physical model, the dependencies are used to deconvolve the sensor …

Metal Coordination And Cis-Trans Isomerisation Of Benzene Dihydrodiols, Catriona O'Meara

Masters

Abstract In this thesis, a viable route for conversion of arene cis-dihydrodiols to their trans isomers was investigated. The cis-dihydrodiols can be produced by large scale fermentation but their trans analogues are not accessible using this approach. The trans dihydrodiols are potentially important chiral building blocks in synthetic chemistry particularly because they have the advantage that they are more stable than the cis-isomers. The principal aim of this work was to carry out parallel studies to inform the development of the synthetic pathway under study by; (a) synthesis of organometallic and organic intermediates and products and, (b) investigation of the …

Novel Calixarene-Schiff Bases That Bind Silver(I) Ion, Mary Deasy, Bernadette Creaven, Brian A. Murray, John Mcginley, Paul M. Flood

Articles

Two novel calix[4]arene-Schiff base receptors have been synthesized. One of the new compounds has two pendant aldimines, while the second has been prepared by two-point attachment of a calixarene-dialdehyde onto a calixarene-diamine to form a “calix-tube”. Preliminary binding studies with AgClO₄ show large complexation-induced shifts in ¹H NMR positions.

Photochemical Studies Of Nutraceuticals In The Presence Of Cyclodextrins, Zlata Tofzikovskaya, Christine O'Connor, Mary Mcnamara

Conference Papers

The photostability studies of Folic acid and Menadione Sodium Bisulfite, also known as vitamin K3, were carried out in their aqueous solutions at room temperature. Solutions of Folic acid ( 4.8 x 10-5 M) and Menadione Sodium Bisulfite (4.0 x 10-4 M) were exposed to ultraviolet radiation at a wavelength of 365 nm. During exposure absorbance of both solutions was measured using a Perkin Elmer Lamda 900 UV/VIS/NIR Spectrometer. During the stability tests it was noted that addition of β Cyclodextrin (1:1 ratio) to aqueous solutions containing the vitamin slowed down the photodegradation process. The unique shape of Cyclodextrins allows …