Inorganic Chemistry Commons^™

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) …

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 …

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.

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.

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …

Equation Of State Of Gallium Oxide To 70 Gpa: Comparison Of Quasihydrostatic And Nonhydrostatic Compression, Kristina E. Lipinska-Kalita, Patricia Kalita, Oliver Hemmers, Thomas Hartmann

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond-anvil cell techniques were used to characterize pressure induced structural modifications in gallium oxide. Gallium oxide was studied on compression up to 70 GPa and on the following decompression. The effect of the pressure-transmitting medium on the structural transformations was investigated in two sets of compression and decompression runs, one with nitrogen as a quasihydrostatic pressure-transmitting medium and the other in nonhydrostatic pressure conditions. The x-ray diffraction data showed gradual phase transition from a low-density, monoclinic β-Ga₂O₃ to a high-density, rhombohedral α-Ga₂O₃. With the use of nitrogen as a …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.

Synthesis Of Novel Alkaline Earth Metal Acetylides, Eva Baker

Renée Crown University Honors Thesis Projects - All

Acetylide complexes of the heavy alkaline-earth metals were first introduced by our group. With our group being interested in how the ligand and donor affect the structural chemistry of the resulting complexes, my project was focused on the detailed analysis of past work and the extension towards new ligand and donor sets. The work required the analysis and development of synthetic procedures towards these highly reactive species.

Past synthetic work in our group had established several synthetic routes towards the target compounds including transamination and toluene elimination. Using toluene elimination, I was able to reproduce the synthesis of M(C≡CSiPh_{3 …}

Synthesis, Structural Studies And Desilylation Reactions Of Some N-2-(Trimethylsilyl)Ethyl-N-Nitrosocarbamates, Arpitha Thakkalapally, Vladimir Benin

Chemistry Faculty Publications

The present report describes the preparation and characterization of several N-2-(trimethylsilyl)ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an s-E orientation at the N–N bond. DFT calculations (B3LYP/6-31+G(d)) reproduce accurately the structural features of the title compounds and detailed conformational analysis at the same level of theory addresses the long-standing issue of preferred geometries for three classes of related structures: N-nitrosocarbamates, N-nitrosoureas and N-nitrosoamides. Desilylation studies demonstrate that both the …

Nearest-Neighbor-Atom Core-Hole Transfer In Isolated Molecules, Renaud Guillemin, Oliver Hemmers, D. Rolles, S. W. Yu, A. Wolska, I. Tran, A. C. Hudson, J. Baker, Dennis W. Lindle

Environmental Studies Faculty Publications

A new phenomenon sensitive only to next-door-neighbor atoms in isolated molecules is demonstrated using angle-resolved photoemission of site-selective core electrons. Evidence for this interatomic core-to-core electron interaction is observable only by measuring nondipolar angular distributions of photoelectrons. In essence, the phenomenon acts as a very fine atomic-scale sensor of nearest-neighbor elemental identity.

E1-E2 Interference In The Vuv Photoionization Of He, E. P. Kanter, B. Krassig, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, M. Ya Amusia, L. V. Chernysheva, N. L. S. Martin

Environmental Studies Faculty Publications

We have measured the forward-backward asymmetry of photoelectron angular distributions produced in the vacuum ultraviolet photoionization of helium. This asymmetry, a consequence of the breakdown of the dipole approximation, measures the real part of the ratio of the quadrupole and dipole matrix elements. In the autoionization region, the strong energy dependence of the asymmetry permits an experimental separation of the ratio of those magnitudes from their phase difference. We experimentally determined the Fano parameters of the 2p²¹D₂ quadrupole resonance, and report improved values of the width Γ and line profile parameter q from those previously available …

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N₂. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.

Effect Of Electron-Attracting Groups On The Thermal Stability Of Subtituted Copper (Ii) Benzoate, Fauziah Kamaruddin

Student Works (2000-2009)

Copper(II) benzoate, copper(II) 4-fluorobenzoate, copper(II) 4-chlorobenzoate, copper(II) 4-bromobenzoate, copper(II) 4-iodobenzoate, copper(II) pentafluoro benzoate, copper(II) 4-nitrobenzoate and copper(II) 3,5-dinitrobenzoate are potential low dimensional thermally stable molecular electronics. The them1al properties of these samples are investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA reveals that copper(II) benzoate (CB) slowly decomposed at 243.5°C, losing 67.7% of its weight at 515°C. The DSC shows two endotherms separated by an exotherm. The first endotherm at 224°C may due to the breaking of bridging bond to give benzoyloxy radicals. The exotherm at 231°C may due to the formation of volatiles from the decomposition …

3-Hydroxykynurenine And 3-Hydroxyanthranilic Acid Generate Hydrogen Peroxide And Promote Α-Crystallin Cross Linking By Metal Ion Reduction, Lee E. Goldstein, Michael C. Leopold, Xudong Huang, Craig S. Atwood, Aleister J. Saunders, Mariana Hartshorn, James T. Lim, Et Al.

Chemistry Faculty Publications

The kynurenine pathway catabolite 3-hydroxykynurenine (3HK) and redox-active metals such as copper and iron are implicated in cataractogenesis. Here we investigate the reaction of kynurenine pathway catabolites with copper and iron, as well as interactions with the major lenticular structural proteins, the R-crystallins. The o-aminophenol kynurenine catabolites 3HK and 3-hydroxyanthranilic acid (3HAA) reduced Cu(II)>Fe(III) to Cu(I) and Fe(II), respectively, whereas quinolinic acid and the nonphenolic kynurenine catabolites kynurenine and anthranilic acid did not reduce either metal. Both 3HK and 3HAA generated superoxide and hydrogen peroxide in a copper-dependent manner. In addition, 3HK and 3HAA fostered copper-dependent R-crystallin cross-linking. 3HK- …

On The Mechanism Of The Diels-Alder Reaction--Dimerization Of Trans-Phenylbutadiene, Michael Ward Mcnicholas

Dissertations and Theses

The Diels-Alder dimerization of trans-1-substituted butadienes is expected to yield a cyclohexene adduct with the substituents in the 3 and 4 positions cis to one another. This prediction is based on past observations of other Diels-Alder additions. The cis-isomer is the only one consistent with a two-stage mechanism proposed by Woodward and Katz.

In the case of trans-phenylbutadiene, the expected adduct is cis-3-phenyl 1-4-(trans-styry1) cyclohexene. Alder, Haydn and Vogt, however, reported that the corresponding trans-isomer is the dimerization product. There is reason to believe that the observation of the trans-isomer may have been the result of product isomerization during purification. …

A Study Of The Products Of The Reaction Between Stannous And Arsenate Ions In Silicic Acid Gels, Frank K. Thompson

University of the Pacific Theses and Dissertations

The fact that characteristic crystalline products result upon the diffusion of arsenate ions into silicic acid gel which has been impregnated with stannous ions has been known by the Pacific Chemistry Department for some time. The optimum conditions with regards to heat and hydrogen ion concentration have been determined. The purpose of this investigation was to study the products of the reaction. First to determine whether or not the silicic acid itself combined with the stannous and arsenate. ions in the formation of the crystalline product, and second to determine its chemical composition.