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Full-Text Articles in Chemistry

Solid State And Solution Dynamics Of Pyridine Based Tetraaza- Macrocyclic Lanthanide Chelates Possessing Phosphonate Ligating Functionality (Ln-Pctmb): Effect On Relaxometry And Optical Properties, Garry Kiefer, Mark Woods Dec 2009

Solid State And Solution Dynamics Of Pyridine Based Tetraaza- Macrocyclic Lanthanide Chelates Possessing Phosphonate Ligating Functionality (Ln-Pctmb): Effect On Relaxometry And Optical Properties, Garry Kiefer, Mark Woods

Chemistry Faculty Publications and Presentations

The macrocyclic ligand 3,6,9-tris(methylenebutyl phosphonic acid)-3,6,9−15-tetraazabicyclo [9.3.1]pentadeca-1(15),11,13-triene (PCTMB) was synthesized and complexes of Eu3+, Tb3+, and Gd3+ studied by X-ray crystallography, luminescence, and relaxometry. In the crystal these complexes are dimeric and possess 8-coordinate Ln3+ centers that are linked by bridging phosphonates. The rigidity introduced by the pyridyl nucleus forces the EuPCTMB and TbPCTMB to adopt a twisted snub disphenoid (TSD) coordination geometry. Examination of the 5D07F0 luminescent transition of EuPCTMB in the solid state confirmed the existence of a single distinct Eu3+ coordination environment, whereas two …


Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold Aug 2009

Distance Dependence Of Electron Transfer Kinetics For Azurin Protein Adsorbed To Monolayer Protected Nanoparticle Film Assemblies, Morgan Lynn Vargo, Chris P. Gulka, John K. Gerig, Christopher M. Manieri, Jonathan D. Dattelbaum, Carolyn B. Marks, Nathaniel T. Lawrence, Matthew L. Trawick, Michael C. Leopold

Chemistry Faculty Publications

The distance dependence and kinetics of the heterogeneous electron transfer (ET) reaction for the redox protein azurin adsorbed to an electrode modified with a gold nanoparticle film are investigated using cyclic voltammetry. The nanoparticle films are comprised of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), which are covalently networked with dithiol linkers. The MPC film assembly serves as an alternative adsorption platform to the traditional alkanethiolate self-assembled monolayer (SAM) modified electrodes that are commonly employed to study the ET kinetics of immobilized redox proteins, a strategy known as protein monolayer electrochemistry. Voltammetric analysis of the ET kinetics for azurin adsorbed …


Synthesis And Characterization Of Bis-Phosphine Complexes With Transition Metals, Alicia L. Mcdaniel Aug 2009

Synthesis And Characterization Of Bis-Phosphine Complexes With Transition Metals, Alicia L. Mcdaniel

Masters Theses & Specialist Projects

Extractants and extraction methodologies play a vital role in many industrial processes, from the concentration of precious metals from ores to the separation of longlived nuclei from radioactive waste as well as the removal of heavy metals from soils and water for remediation. The vast majority of extractants rely on the use of nitrogen, oxygen, sulfur or selenium as Lewis base donor atoms to form coordination complexes with the metal ions of interest. These extractants often make use of the chelate effect and/or the macrocyclic effect in order to form stable complexes. Some of the best known types of chelate …


Metallophilic Interactions In Closed-Shell Metal-Metal Bonded Luminescent Systems And Their Tunability For Excited State Energy Transfer, Howard H. Patterson Apr 2009

Metallophilic Interactions In Closed-Shell Metal-Metal Bonded Luminescent Systems And Their Tunability For Excited State Energy Transfer, Howard H. Patterson

University of Maine Office of Research Administration: Grant Reports

Howard Patterson, University of Maine, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for photochemical studies of metal-metal bonded excimers and exciplexes. In solution or in the solid state, dicyanoaurate(I) and dicyanoargentate(I) ions oligomerize. The oligomers show complex photochemistry, including luminescence caused by metallophilic interactions. These systems can be tuned over 18,000 wavenumbers by doping or by adding various donor ions. This research project will look in detail at lifetime and time-resolved studies, vibrational analysis by Raman scattering and infrared, structural studies by x-ray and neutron diffraction, and theoretical analyses. The research will provide insight into metallophilic interactions …


Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold Mar 2009

Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell …


Synthesis And Evaluation Of Lanthanide Ion Dota-Tetraamide Complexes Bearing Peripheral Hydroxyl Groups, Azhar Pasha, Mai Lin, Gyula Tircso, Cynthia L. Rostollan, Mark Woods, Garry Kiefer, A. Dean Sherry, Xiankai Sun Mar 2009

Synthesis And Evaluation Of Lanthanide Ion Dota-Tetraamide Complexes Bearing Peripheral Hydroxyl Groups, Azhar Pasha, Mai Lin, Gyula Tircso, Cynthia L. Rostollan, Mark Woods, Garry Kiefer, A. Dean Sherry, Xiankai Sun

Chemistry Faculty Publications and Presentations

The use of lanthanide-based contrast agents for magnetic resonance imaging has become an integral component of this important diagnostic modality. These inert chelates typically possess high thermodynamic stability constants that serve as a predictor for in vivo stability and low toxicity. Recently, a new class of contrast agents was reported having a significantly lower degree of thermodynamic stability while exhibiting biodistribution profiles indicative of high stability under biological conditions. These observations are suggestive that the nature of contrast agent stability is also dependent upon the kinetics of complex dissociation, a feature of potential importance when contemplating the design of new …


Silver Doped Perfluoropolyether-Urethane Coatings: Antibacterial Activity And Surface Analysis, Niall Stobie, Brendan Duffy, Steven Hinder, Patrick Mchale, Declan Mccormack Jan 2009

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 …


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 Jan 2009

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.


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 Jan 2009

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.


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 Jan 2009

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 …


Influence Of Magnesium Nitrate On The Corrosion Performance Of Sol-Gel Coated Aa2024-T3 Aluminium Alloy, Rajath Varma, Brendan Duffy, John Cassidy Jan 2009

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) …


Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin Jan 2009

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.


Come For The Content, Stay For The Community, Hilary J. Eppley Jan 2009

Come For The Content, Stay For The Community, Hilary J. Eppley

Chemistry & Biochemistry Faculty Publications

No abstract provided.