ORBITAL MIXING IN CO CHEMISORPTION ON TRANSITION-METAL SURFACES

The chemisorption of CO on metal surfaces is widely accepted as a model for understanding chemical bonding between molecules and solid surfaces, but is nevertheless still a controversial subject. Ab initio total energy calculations using density functional theory with gradient corrections for CO chemisorption on an extended Pd{110} slab yield good agreement with experimental adsorption energies. Examination of the spatial distribution of individual Bloch states demonstrates that the conventional model for CO chemisorption involving charge donation from CO 5 sigma states to metal states and back-donation from metal states into CO 2 pi states is too simplistic, but the computational results provide direct insight into the chemical bonding within the framework of orbital mixing (or hybridisation). The results provide a sound basis for understanding the bonding between molecules and metal surfaces.

A DFT Guided/Experimental Approach to Asymmetric Allylation and Phase-Transfer Catalysis

The Dudding group is interested in the application of Density Functional Theory (DFT) in developing asymmetric methodologies, and thus the focus of this dissertation will be on the integration of these approaches. Several interrelated subsets of computer aided design and implementation in catalysis have been addressed during the course of these studies. The first of the aims rested upon the advancement of methodologies for the synthesis of biological active C(1)-chiral 3-methylene-indan-1-ols, which in practice lead to the use of a sequential asymmetric Yamamoto-Sakurai-Hosomi allylation/Mizoroki Heck reaction sequence. An important aspect of this work was the utilization of ortho-substituted arylaldehyde reagents which are known to be a problematic class of substrates for existing asymmetric allylation approaches. The second phase of my research program lead to the further development of asymmetric allylation methods using o-arylaldehyde substrates for synthesis of chiral C(3)-substituted phthalides. Apart from the de novo design of these chemistries in silico, which notably utilized water-tolerant, inexpensive, and relatively environmental benign indium metal, this work represented the first computational study of a stereoselective indium-mediated process. Following from these discoveries was the advent of a related, yet catalytic, Ag(I)-catalyzed approach for preparing C(3)-substituted phthalides that from a practical standpoint was complementary in many ways. Not only did this new methodology build upon my earlier work with the integrated (experimental/computational) use of the Ag(I)-catalyzed asymmetric methods in synthesis, it provided fundamental insight arrived at through DFT calculations, regarding the Yamamoto-Sakurai-Hosomi allylation. The development of ligands for unprecedented asymmetric Lewis base catalysis, especially asymmetric allylations using silver and indium metals, followed as a natural extension from these earlier discoveries. To this end, forthcoming as well was the advancement of a family of disubstituted (N-cyclopropenium guanidine/N-imidazoliumyl substituted cyclopropenylimine) nitrogen adducts that has provided fundamental insight into chemical bonding and offered an unprecedented class of phase transfer catalysts (PTC) having far-reaching potential. Salient features of these disubstituted nitrogen species is unprecedented finding of a cyclopropenium based C-H•••πaryl interaction, as well, the presence of a highly dissociated anion projected them to serve as a catalyst promoting fluorination reactions. Attracted by the timely development of these disubstituted nitrogen adducts my last studies as a PhD scholar has addressed the utility of one of the synthesized disubstituted nitrogen adducts as a valuable catalyst for benzylation of the Schiff base N-diphenyl methylene glycine ethyl ester. Additionally, the catalyst was applied for benzylic fluorination, emerging from this exploration was successful fluorination of benzyl bromide and its derivatives in high yields. A notable feature of this protocol is column-free purification of the product and recovery of the catalyst to use in a further reaction sequence.

Electron localization function at the correlated level

The electron localization function (ELF) has been proven so far a valuable tool to determine the location of electron pairs. Because of that, the ELF has been widely used to understand the nature of the chemical bonding and to discuss the mechanism of chemical reactions. Up to now, most applications of the ELF have been performed with monodeterminantal methods and only few attempts to calculate this function for correlated wave functions have been carried out. Here, a formulation of ELF valid for mono- and multiconfigurational wave functions is given and compared with previous recently reported approaches. The method described does not require the use of the homogeneous electron gas to define the ELF, at variance with the ELF definition given by Becke. The effect of the electron correlation in the ELF, introduced by means of configuration interaction with singles and doubles calculations, is discussed in the light of the results derived from a set of atomic and molecular systems

Selective biodegradation of keratin matrix in feather rachis reveals classic bioengineering

Flight necessitates that the feather rachis is extremely tough and light. Yet, the crucial filamentous hierarchy of the rachis is unknown—study hindered by the tight chemical bonding between the filaments and matrix. We used novel microbial biodegradation to delineate the fibres of the rachidial cortex in situ. It revealed the thickest keratin filaments known to date (factor >10), approximately 6 µm thick, extending predominantly axially but with a small outer circumferential component. Near-periodic thickened nodes of the fibres are staggered with those in adjacent fibres in two- and three-dimensional planes, creating a fibre–matrix texture with high attributes for crack stopping and resistance to transverse cutting. Close association of the fibre layer with the underlying ‘spongy’ medulloid pith indicates the potential for higher buckling loads and greater elastic recoil. Strikingly, the fibres are similar in dimensions and form to the free filaments of the feather vane and plumulaceous and embryonic down, the syncitial barbules, but, identified for the first time in 140+ years of study in a new location—as a major structural component of the rachis. Early in feather evolution, syncitial barbules were consolidated in a robust central rachis, definitively characterizing the avian lineage of keratin.

Low-lying singlet and triplet electronic states of RhB

The low-lying X-1 Sigma(+), a(3)Delta, A(1)Delta, b(3)Sigma(+), B-1 Pi, c(3)Pi, C-1 Phi, D-1 Sigma(+), E-1 Pi, d(1)Phi, and e(3)Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X-1 Sigma(+), D-1 Sigma(+), and E-1 Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Análise das avaliações realizadas na disciplina de arquitetura atômica e molecular no curso de química, modalidade a distância da UFRN

The field of education is very rich and allows us to research in various aspects. The area of chemical education has been growing more and more, and an important aspect that has been researching this area is about the learning difficulties of students. The approach of the themes atomic structure and chemical bonds are developed in high school and have many problems that are often brought to higher education becoming an obstacle to the advancement of learning. It is necessary for these initial themes - the atomic structure and chemical bonds - are well understood by the student to the other contents of Chemistry will be understood more easily. This paper aims to describe, analyze errors and difficulties presented in the assessments of the discipline Atomic and Molecular Architecture, the students of the degree course in Chemistry - EAD, with respect to the contents of " Atomic Structure and Chemical Bonding ", by of the assessments made by the students and the Virtual Learning Environment (VLE), taking into account the activities , discussion forum and access to materials . AVA allows obtaining reports which were used to analyze regarding access / participation to assess their contribution to learning and its relation to the final result (pass / fail). It was observed that the most frequent errors in the assessments are related to the early part of the chemistry that is the understanding of atomic structure and evolution models. Students who accessed the extra material and participated in the activities and forums were students who achieved success in the course. Ie, the difficulties were emerging and the use of available teaching strategies, students could minimize such difficulties, making their performance in activities and assessments were better. Was also observed by attending the AVA, the discipline began with a large withdrawal from the page access as well as the frequency of face- evidence from observation in Listing presence of classroom assessments

Effect of microwave disinfection on the bond strength of denture teeth to acrylic resins

During microwave disinfection, the dentures are exposed to water at high temperature and this may affect the bond between the denture teeth and the acrylic resin from which dentures are made. In this study, a shear test was used to evaluate the effect of microwave disinfection (650W/6 min) on the bond strength of two types of denture teeth to three acrylic resins, with different polymerization methods. The specimens were submitted to the shear tests (0.5 mm/min) after: immersion in water (37 degrees C) for 48 h or 8 days (controls); two or seven cycles of microwave disinfection (test groups). Data (MPa) were analyzed using three-way ANOVA and Tukey HSD test (alpha = 0.05). Microwave disinfection did not adversely affect the bond strength of all tested materials with the exception of QC-20 bonded to SR Vivodent PE, for which a significant reduction was recorded after seven cycles of irradiation. (C) 2007 Elsevier Ltd. All rights reserved.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. All rights reserved.

XPS study on water corrosion of fluorzirconate glasses and their protection by a layer of surface modified tin dioxide nanoparticles

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, Z-BLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)), and the corrosion protection efficiency of a nanocrystalline transparent SnO2 layer were investigated by X-ray photoelectron spectroscopy. The tin oxide film was deposited by the sol-gel dip-coating process in the presence of Tiron(R) as particle surface modifier agent. The chemical bonding structure and composition of the surface region of coated and non-coated ZBLAN were studied before water contact and after different immersion periods (5-30 min). In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species inducing the formation of a new surface phase consisting of stable zirconium oxyfluoride, barium fluoride and lanthanum fluoride species, the results for the SnO2-coated glass showed that the hydrolytic attack induces a filling of the film nanopores by dissolved glass material and the formation of tin oxylluoride and zirconium oxyfluoride species. This process results in a modified film, which acts as a hermetic diffusion barrier protecting efficiently the glass surface. (C) 2006 Elsevier B.V. All rights reserved.

Morphological characterization of aqueous tin oxyhydroxide gel

Light scattering, electron microscopy and X-ray diffraction are used to determine the morphology and size of particles in diluted aqueous gel of tin (IV) oxyhydroxide. Data show that the gel is composed of spherical 2-3 nm sized crystalline particles aggregated as rigid branched chains. It is suggested that stiffness of chains results from dissolution-precipitation equilibria and chemical bonding between particles within the chains. © 1994.

Sintering and mass transport features of (Sn,Ti)O2 polycrystalline ceramics

Different (Sn,Ti)O2 compositions were sintered at 1450 °C for 2 h with the purpose of investigating their sintering and mass transport properties. Highly dense ceramics were obtained and their structural properties studied by X-ray diffraction and scanning electron microscopy. The changes in lattice parameters were analyzed by the Rietveld method and two mass transport mechanisms were observed during sintering in different temperature ranges, evidenced by the linear shrinkage rate as a function of temperature. The effect of the concentration of TiO2 on mass transport and densiffication during sintering was analyzed by considering the intrinsic defects. System densiffication was attributed to a mass transport mechanism in the SnO2 matrix, caused by the presence of TiO2, which formed a solid solution phase. The change in the mass transport mechanism was attributed to chemical bonding between SnO2 and TiO2, which improves ionic difusion as the concentration of TiO2 increased in (Sn,Ti)O2 compositions. © 2002 Elsevier Science Ltd. All rights reserved.

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Caracterização de superfície, adesiva e mecânica de uma zircônia parcialmente estabilizada por ítria em função da partícula ou do momento do jateamento

Pós-graduação em Reabilitação Oral - FOAR

Surface modification of polymeric materials by cold atmospheric plasma jet

In this work we report the surface modification of different engineering polymers, such as, polyethylene terephthalate (PET), polyethylene (PE) and polypropylene (PP) by an atmospheric pressure plasma jet (APPJ). It was operated with Ar gas using 10 kV, 37 kHz, sine wave as an excitation source. The aim of this study is to determine the optimal treatment conditions and also to compare the polymer surface modification induced by plasma jet with the one obtained by another atmospheric pressure plasma source the dielectric barrier discharge (DBD). The samples were exposed to the plasma jet effluent using a scanning procedure, which allowed achieving a uniform surface modification. The wettability assessments of all polymers reveal that the treatment leads to reduction of more than 40 degrees in the water contact angle (WCA). Changes in surface composition and chemical bonding were analyzed by x-ray photoelectron spectroscopy (XPS) and Fourier-Transformed Infrared spectroscopy (FTIR) that both detected incorporation of oxygen-related functional groups. Surface morphology of polymer samples was investigated by Atomic Force Microscopy (AFM) and an increase of polymer roughness after the APPJ treatment was found. The plasma-treated polymers exhibited hydrophobic recovery expressed in reduction of the O-content of the surface upon rinsing with water. This process was caused by the dissolution of low molecular weight oxidized materials (LMWOMs) formed on the surface as a result of the plasma exposure. (C) 2014 Elsevier B.V. All rights reserved.