Dependência estrutural da capacidade de rotação plástic em vigas de concreto armado

Summary In this work the structural dependence of plastic rotation capacity in RC beams is evaluated using the Finite Element Method. The objective is to achieve a better understanding of the non-linear behavior of reinforced concrete members and perform extensive parameter studies, using a rational model developed by Bigaj [1] to analyze the phenomenon of plastic rotation capacity in reinforced concrete members. It is assumed that only bending failure is relevant due to sufficient member resistance against shear and torsion. The paper begins with the physical and theoretical background of the phenomenon of plastic hinge development in RC structures. Special emphasis is laid on the issue of structural dependence of deformation capacity of plastic hinges in RC members. Member size dependence and influence of properties of construction materials were emphasized as well. The essential components of the Bigajs model for calculating the plastic rotation capacity are discussed. The behaviour of the plastic hinge is analysed taking into account the strain localisation in the damage zones of the hinge region. The Fictitious Crack Model (FCM) and the Compressive Damage Zone Model (CDZ) are adopted in a Fracture Mechanics approach to model the behaviour of concrete in tension and compression, respectively. The approach is implemented in FEMOOP, a FEM in-house solver under development, and applied to evaluate ductility in 2D beams. The models were generated with GiD, a pre-processor and post-processor developed by CIMNE, and analyzed with the capabilities implemented in FEMOOP. © Universitat Politècnica de Catalunya, Barcelona, España 2010.

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

A Study on the Origin of Banded Agate

Agate in any of its varieties presents numerous problems in regard to its origin. Many types have been described and their beauty elaborated upon, but little has been written concerning their formation and the problems involved. The genesis of agate implicates an amazing complexity of physical and colloid­al chemistry, as well as, various principles of geology.

Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Chemical abstracts.

"A publication of the Chemical Abstracts Service."

Chemical abstracts.

"A publication of the Chemical Abstracts Service."

Quantities, units and symbols in physical chemistry, 3rd edition

The first IUPAC Manual of Symbols and Terminology for Physicochemical Quantities and Units (the Green Book) of which this is the direct successor, was published in 1969, with the object of 'securing clarity and precision, and wider agreement in the use of symbols, by chemists in different countries, among physicists, chemists and engineers, and by editors of scientific journals'. Subsequent revisions have taken account of many developments in the field, culminating in the major extension and revision represented by the 1988 edition under the simplified title Quantities, Units and Symbols in Physical Chemistry. This 2007, third edition, is a further revision of the material which reflects the experience of the contributors with the previous editions. The book has been systematically brought up to date and new sections have been added. It strives to improve the exchange of scientific information among the readers in different disciplines and across different nations. In a rapidly expanding volume of scientific literature where each discipline has a tendency to retreat into its own jargon this book attempts to provide a readable compilation of widely used terms and symbols from many sources together with brief understandable definitions. This is the definitive guide for scientists and organizations working across a multitude of disciplines requiring internationally approved nomenclature.

Centesimal composition and physical-chemistry analysis of the edible mushroom Lentinus strigosus occurring in the Brazilian Amazon

Avaliou-se a composição centesimal e análise físico-química do Lentinus strigosus, um cogumelo comestível de ocorrência na Amazônia brasileira, produzidos em substratos alternativos à base de resíduos madeireiros e agroindustriais. Com este objetivo, determinou-se C, N, pH, sólidos solúveis, atividade de água, proteína, lipídios, fibra total, cinzas, carboidratos e energia. Os substratos foram formulados a partir de serragem de Simarouba amara Aubl. (marupá), Ochroma piramidale Cav. ex. Lam. (pau-de-balsa) e Anacardium giganteum (cajuí); e do estipe de Bactris gasipaes Kunth (pupunheira) e de Saccharum officinarum (cana-de-açúcar). Os resultados demonstraram que: a composição nutricional do L. strigosus variou com o substrato de cultivo; os valores de proteína encontrados nos cogumelos cultivados nos diferentes substratos (18 - 21,5%) variaram de acordo com o substrato, sendo considerados elevados; os sólidos solúveis presentes nos cogumelos podem ter relação com vitaminas hidrossolúveis do complexo B; o L. strigosus pode ser considerado um importante alimento devido suas características nutricionais: alto teor de proteína, carboidratos metabolizáveis e fibras; baixos teores de lipídios e de calorias.

Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

Correlation Between Molecular Conformation, Packing, and Dynamics in Oligofluorenes: A Theoretical/Experimental Study

Fluorene-based systems have shown great potential as components in organic electronics and optoelectronics (organic photovoltaics, OPVs, organic light emitting diodes, OLEDs, and organic transistors, OTFTs). These systems have drawn attention primarily because they exhibit strong blue emission associated with relatively good thermal stability. It is well-known that the electronic properties of polymers are directly related to the molecular conformations and chain packing of polymers. Here, we used three oligofluorenes (trimer, pentamer, and heptamer) as model systems to theoretically investigate the conformational properties of fluorene molecules, starting with the identification of preferred conformations. The hybrid exchange correlation functional, OPBE, and ZINDO/S-CI showed that each oligomer exhibits a tendency to adopt a specific chain arrangement, which could be distinguished by comparing their UV/vis electronic absorption and C-13 NMR spectra. This feature was used to identify the preferred conformation of the oligomer chains in chloroform-cast films by comparing experimental and theoretical UV/vis and C-13 NMR spectra. Moreover, the oligomer chain packing and dynamics in the films were studied by DSC and several solid state NMR techniques, which indicated that the phase behavior of the films may be influenced by the tendency that each oligomeric chain has to adopt a given conformation.

Synthesis, NMR studies and conformational analysis of oxazolidine derivatives of the beta-adrenoreceptor antagonists metoprolol, atenolol and timolol

Formaldehyde-derived oxazolidine derivatives 4-7 of the beta-adrenoreceptor antagonists metoprolol 1, atenolol 2 and timolol 3 have been synthesised. Conformational analysis of 1-3 and the oxazolidine derivatives 4-7 has been performed using H-1 NMR spectroscopy and computational methods. The H-1 NMR studies show that for the aryloxypropanolamine beta-adrenoreceptor antagonists there is a predominance of the conformer in which the amine group is approximately antiperiplanar or trans to the aryloxymethylene group. Both H-1 NMR data and theoretical studies indicate that the oxazolidine derivatives 4-7 and the aryloxypropanolamine beta-adrenoreceptor antagonists 1-3 adopt similar conformations around the beta-amino alcohol moiety. Thus, oxazolidine ring formation does not dramatically alter the preferred conformation adopted by the beta-amino alcohol moiety of 1-3. Oxazolidine derivatives of aryloxypropanolamine beta-adrenoreceptor antagonists may therefore be appropriate as prodrugs, or semi-rigid analogues, when greater lipophilicity is required for drug delivery.

Mesoionic pyridopyrimidinylium and pyridooxazinylium olates and non-mesoionic pyridopyrimidinones. Structures in the solid state, solution, and matrices

X-Ray crystal structures, C-13 NMR spectra and theoretical calculations (B3LYP/6-31G*) are reported for the mesoionic (zwitterionic) pyridopyrimidinylium- and pyridooxazinyliumolates 2a, 3a and 5a,b as well as the enol ether 11b and the enamine 11c. The 1-NH compounds like 1a, 2a and 3a exist in the mesoionic form in the crystal and in solution, but the OH tautomers such as 1b and 2b dominate in the gas phase as revealed by the Ar matrix IR spectra in conjunction with DFT calculations. All data indicate that the mesoionic compounds can be regarded as intramolecular pyridine-ketene zwitterions (cf. 16 --> 17) with a high degree of positive charge on the pyridinium nitrogen, a long pyridinium N-CO bond (ca. 1.44-1.49 Angstrom), and normal C=O double bonds (ca. 1.22 Angstrom). All mesoionic compounds exhibit a pronounced tilting of the olate C=O groups (the C=O groups formally derived from a ketene) towards the pyridinium nitrogen, giving NCO angles of 110-118 degrees. Calculations reveal a hydrogen bond with 6-CH, analogous to what is found in ketene-pyridine zwitterions and the C3O2-pyridine complex. The 2-OH tautomers of type 1b, 2b, and 11 also show a high degree of zwitterionic character as indicated by the canonical structures 11 12.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

A comparison of low-storage strategies for spectral analysis in dissipative systems: filter diagonalisation in the Lanczos representation and harmonic inversion of the Chebychev-order-domain autocorrelation function

We compare the performance of two different low-storage filter diagonalisation (LSFD) strategies in the calculation of complex resonance energies of the HO2, radical. The first is carried out within a complex-symmetric Lanczos subspace representation [H. Zhang, S.C. Smith, Phys. Chem. Chem. Phys. 3 (2001) 2281]. The second involves harmonic inversion of a real autocorrelation function obtained via a damped Chebychev recursion [V.A. Mandelshtam, H.S. Taylor, J. Chem. Phys. 107 (1997) 6756]. We find that while the Chebychev approach has the advantage of utilizing real algebra in the time-consuming process of generating the vector recursion, the Lanczos, method (using complex vectors) requires fewer iterations, especially for low-energy part of the spectrum. The overall efficiency in calculating resonances for these two methods is comparable for this challenging system. (C) 2001 Elsevier Science B.V. All rights reserved.