Molecular structures and vibrational frequencies for [PdX2(tdmPz)] (X = Cl-, SCN-): A DFT study

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Molecular structures and vibrational frequencies for cis-[PdCl2(tmen)] and cis-[Pd(N-3)(2)(tmen)]: A DFT study

Theoretical molecular structures of the complexes cis-[PdCl2(tmen)] and cis-[Pd(N-3)(2)(tmen)] (tmen = N,N,N',N'-tetramethylethylenediamine) were investigated using B3LYP/DFT method. The calculated molecular parameters, bond distances and angles, revealed a square-planar geometry around the metallic center for both compounds with the azide being linear. The theoretical infrared spectra of C, symmetry (electronic state (1)A) of the compounds are in agreement with the experimental data. (C) 2007 Elsevier B.V. All rights reserved.

THEORY OF ELECTRICAL CHARACTERISTICS OF A SCHOTTKY-BARRIER HAVING EXPONENTIALLY DISTRIBUTED IMPURITY STATES AND METAL-INSULATOR METAL STRUCTURES

The metal-insulator or metal-amorphous semiconductor blocking contact is still not well understood. Here, we discuss the steady state characteristics of a non-intimate metal-insulator Schottky barrier. We consider an exponential distribution (in energy) of impurity states in addition to impurity states at a single energy level within the depletion region. We present analytical expressions for the electrical potential, field, thickness of depletion region, capacitance, and charge accumulated in the depletion region. We also discuss ln I versus V(ap) data. Finally, we compare the characteristics in three cases: (i) impurity states at only a single energy level; (ii) uniform energy distribution of impurity states; and (iii) exponential energy distribution of impurity states.In general, the electrical characteristics of Schottky barriers and metal-insulator-metal structures with Schottky barriers depend strongly on the energy distribution of impurity states.

Crystal structures and luminescence properties of La3Zr4F25 and alpha-LaZr3F15

During a study of the LaF3-ZrF4 system, both La3Zr4F25 and alpha-LaZr3F15 compounds have been evidenced. Their crystal structures have been determined from single-crystal X-ray diffraction data. La3Zr4F25 crystallises in the cubic system with a= 12.384 Angstrom and I (4) over bar 3d space group (no. 220). Its crystal structure is built up of (ZrF6)(2-) octahedra and (LaF8)(5-) dodecahedra sharing corners. The low temperature form, alpha, of LaZr3F15 is orthorhombic (space group Pmmn, no. 59) with a = 15.721 Angstrom, b = 16.299 Angstrom, c= 8.438 Angstrom. Its structure is built of corner-sharing tricaped trigonal prisms surrounding the La3+ ions and both octahedra and monocapped trigonal prisms encompassing the Zr4+ ions. This structure is characterised by dynamically disordered (ZrF6)(2-) complex anions.The Eu3+ luminescence properties of these phases have been investigated and are discussed in relationship with their crystal structures.

Cleavage of the dimeric cyclopalladated [Pd(N,C-dmba)(mu-X)](2), (dmba = N,N-dimethylbenzylamine; X = SCN and NCO) by diphosphines. Palladium(II) compounds with distinct structures in the solid-state and in solution

The reactions of the pseudohalide-bridged dimer [Pd(N,C-dmba)(mu -SCN)](2) (1) (dmba = N,N-dimethylbenzylamine) with cis-Ph2PCH=CHPPh2 (cis-dppet) (1:1 molar ratio) and of [Pd(N,C-dmba)(mu -NCO)](2) (2) with Ph2PCH2CH2PPh2 (dppe) (1:2 molar ratio) gave mononuclear [Pd(C-dmba)(SCN)(cis-dppet)].H2O (1a) and [Pd(C-dmba)(NCO)(dppe)] (2a), respectively, with the diphosphines acting as chelating ligands. Reaction of (2) with Fe(C5H4PPh2)(2) (dppf) (1:1 molar ratio) yielded [{Pd(N,C-dmba)(NCO)}(2)(mu -dppf)] (2b), a bimetallic species containing two palladium atoms bridged by the diphosphine, whereas reaction in a 1:2 molar ratio gave the mononuclear [Pd(N,C-dmba)(dppf)][NCO]. CH2Cl2 (2c), with the diphosphine acting as a chelating ligand. The compounds have been characterized by elemental analysis, i.r., P-31{H-1}, C-13- and H-1-n.m.r. spectroscopies. Conductivity measurements together with spectroscopic data showed that (1a) and (2a) do not have the same structure in the solid state and in MeCl solution, whereas for compounds (2b) and (2c) no structural changes were observed when the solids were dissolved in MeCl.

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structures of the noncovalent complexes of human and bovine prothrombin fragment 2 with human PPACK-thrombin

Both human and bovine prothrombin fragment 2 (the second kringle) have been cocrystallized separately with human PPACK (D-Phe-Pro-Arg)-thrombin, and the structures of these noncovalent complexes have been determined and refined (R = 0.155 and 0.157, respectively) at 3.3-Å resolution using X-ray crystallographic methods. The kringles interact with thrombin at a site that has previously been proposed to be the heparin binding region. The latter is a highly electropositive surface near the C-terminal helix of thrombin abundant in arginine and lysine residues. These form salt bridges with acidic side chains of kringle 2. Somewhat unexpectedly, the negative groups of the kringle correspond to an enlarged anionic center of the lysine binding site of lysine binding kringles such as plasminogens K1 and K4 and TPA K2. The anionic motif is DGDEE in prothrombin kringle 2. The corresponding cationic center of the lysine binding site region has an unfavorable Arg70Asp substitution, but Lys35 is conserved. However, the folding of fragment 2 is different from that of prothrombin kringle 1 and other kringles: the second outer loop possesses a distorted two-turn helix, and the hairpin β-turn of the second inner loop pivots at Val64 and Asp70 by 60°. Lys35 is located on a turn of the helix, which causes it to project into solvent space in the fragment 2-thrombin complex, thereby devastating any vestige of the cationic center of the lysine binding site. Since fragment 2 has not been reported to bind lysine, it most likely has a different inherent folding conformation for the second outer loop, as has also been observed to be the case with TPA K2 and the urokinase kringle. The movement of the Val64-Asp70 β-turn is most likely a conformational change accompanying complexation, which reveals a new heretofore unsuspected flexibility in kringles. The fragment 2-thrombin complex is only the second cassette module-catalytic domain structure to be determined for a multidomain blood protein and only the third domain-domain interaction to be described among such proteins, the others being factor Xa without a Gla domain and Ca2+ prothrombin fragment 1 with a Gla domain and a kringle. © 1993 American Chemical Society.

Application of a model updating technique for health condition monitoring and damage detection of flexible structures

This paper discusses the application of a damage detection methodology to monitor the location and extent of partial structural damage. The methodology combines, in an iterative way, the model updating technique based on frequency response functions (FRF) with monitoring data aiming at identifying the damage area of the structure. After the updating procedure reaches a good correlation between the models, it compares the parameters of the damage structure with those of the undamaged one to find the deteriorated area. The influence of the FEM mesh size on the evaluation of the extent of the damage has also been discussed. The methodology is applied using real experimental data from a spatial frame structure.

Synthesis, characterization and molecular structures of the pyridinium trans-bis(pyridine)tetrachlororuthenate(III) and pyridinium trans-(carbonyl)(pyridine)tetrachlororuthenate(III)

The pyH[trans-RuCl4(py)2](1) and pyH[trans-RuCl4(CO)(py)](2) complexes were synthesized and found to crystallize in space group P21/n, Z = 4 with a = 8.080(7), b = 22.503(7), c = 10.125(6) Å, β = 93.19(6)° for (1) and a = 7.821(1), b = 10.337(3), c = 19.763(3) Å, β = 93.07(1)° for (2). The structures were solved by Patterson and difference Fourier techniques and refined to R = 0.062 for (1) and R = 0.038 for (2). In both cases the Ru(III) ion is octahedrally coordinated to four co-planar chlorine atoms, the nitrogen of the pyridine rings or carbon from the carbon monoxide. Another protonated pyridine group, which forms the counter-cation completes the crystal structures. The UV-Vis absorption spectra show three bands: (1) 360 (ε = 1180 M-1 cm-1), 441 (ε = 3200 M-1 cm-1) and 532 nm (ε = 400 M-1 cm-1); (2) 315(ε = 1150 M-1 cm-1), 442 (ε = 3170 M-1 cm-1) and 530 nm (ε = 390 M-1 cm-1). The two higher energy bands were associated with ligand-to-metal charge transfer transitions and a third band at lower energy was assigned to a d-d transition. Low temperature EPR data confirmed the presence of the paramagnetically active Ru(III) and it is consistent with axial symmetry of the complexes. The position of the stretching CO band in complex (2) is discussed in terms of metal-CO backbonding.

Gravity Data and Crustal Structure of North-Central Brazil

The Bouguer gravity anomaly of the northwest Ceará state in north-central Brazil was separated into its regional and residual components which were interpreted separately. By assuming that the sources of the regional anomalies are the depth variations of the crust-mantle interface, the mapping of these variations permited identifying crustal thickening zones which may be related to regional structures. The gravity residual sources coincide with occurrences of high-grade rocks (granulites) associated to medium-grade gneisses. Besides, the major strike-slip zones present significant signatures in the gravity data. This geophysical interpretation is compatible with the interpretation that the tectonic framework of the area is related to two crustal blocks conjoined by an A-type suture. The blocks are displaced along an oblique ramp with dextral movement, which played an important role in uplifting high-grade rocks from the lower crust to upper crustal levels. The suture zone corresponds to an imbricated compressive system dipping to the east and complicated by late dextral strike-slip shear zones.

Crystal structures and luminescence properties of La3Zr4F25 and α-LaZr3F15

During a study of the LaF3-ZrF4 system, both La3Zr4F25 and α-LaZr3F15 compounds have been evidenced. Their crystal structures have been determined from single-crystal X-ray diffraction data. La3Zr4F25 crystallises in the cubic system with a = 12.384 Å and 143d space group (no. 220). Its crystal structure is built up of (ZrF6)2- octahedra and (LaF8)5- dodecahedra sharing corners. The low temperature form, α, of LaZr3F15 is orthorhombic (space group Pmmn, no. 59) with a = 15.721 Å, b = 16.299 Å, c = 8.438 Å. Its structure is built of corner-sharing tricaped trigonal prisms surrounding the La3+ ions and both octahedra and monocapped trigonal prisms encompassing the Zr4+ ions. This structure is characterised by dynamically disordered (ZrF6)2- complex anions. The Eu3+ luminescence properties of these phases have been investigated and are discussed in relationship with their crystal structures.

Crystal structures and magnetic properties of CuX2(pdmp)2 complexes (X = Br, Cl)

We report the synthesis and the structural and magnetic characterization of two new compounds: dibromobis-(pdmp)copper(II), CuBr2C22H24N4 (1), and dichlorobis(pdmp)copper(II), CuCl2C22H24N4 (2), where pdmp = 1-phenyl-3,5-dimethylpyrazole. The structures were refined by full-matrix least-squares techniques to R1 = 0.0620 and 0.0777, respectively. Compound 1 belongs to the space group P21/n with a = 8.165(5) Å, b = 10.432(3) Å, c = 13.385(4) Å, β = 100.12(4)̊, and Z = 2. Compound 2 belongs to the space group P21/c with a = 8.379(2) Å, b = 22.630(2) Å, c = 12.256(2) Å, β= 98.43(3)°, and Z = 4. It has the same molecular formula as a compound reported previously but a different crystal structure. Detailed single-crystal EPR measurements were performed for single-crystal samples of 1 and 2 at 9 and 35 GHz and at room temperature. The positions and line widths of the EPR lines were measured as a function of the magnetic field orientation in three orthogonal planes. The data were used to study the electronic properties of the copper ions and to evaluate the exchange interactions between them. Our results are discussed in terms of the electronic pathways for superexchange between copper ions, which are provided by the stacking of pyrazole and phenyl rings of neighboring molecules and by hydrogen-halogen bonds. © 1999 American Chemical Society.

Identification of structural damage in flexible structures using system norm and neural networks

Nowadays there is great interest in damage identification using non destructive tests. Predictive maintenance is one of the most important techniques that are based on analysis of vibrations and it consists basically of monitoring the condition of structures or machines. A complete procedure should be able to detect the damage, to foresee the probable time of occurrence and to diagnosis the type of fault in order to plan the maintenance operation in a convenient form and occasion. In practical problems, it is frequent the necessity of getting the solution of non linear equations. These processes have been studied for a long time due to its great utility. Among the methods, there are different approaches, as for instance numerical methods (classic), intelligent methods (artificial neural networks), evolutions methods (genetic algorithms), and others. The characterization of damages, for better agreement, can be classified by levels. A new one uses seven levels of classification: detect the existence of the damage; detect and locate the damage; detect, locate and quantify the damages; predict the equipment's working life; auto-diagnoses; control for auto structural repair; and system of simultaneous control and monitoring. The neural networks are computational models or systems for information processing that, in a general way, can be thought as a device black box that accepts an input and produces an output. Artificial neural nets (ANN) are based on the biological neural nets and possess habilities for identification of functions and classification of standards. In this paper a methodology for structural damages location is presented. This procedure can be divided on two phases. The first one uses norms of systems to localize the damage positions. The second one uses ANN to quantify the severity of the damage. The paper concludes with a numerical application in a beam like structure with five cases of structural damages with different levels of severities. The results show the applicability of the presented methodology. A great advantage is the possibility of to apply this approach for identification of simultaneous damages.

Homologies of floral structures in velloziaceae with particular reference to the corona

New data on floral morphology, development, and vasculature in two Brazilian genera of the monocot family Velloziaceae (Pandanales) are used to explore the homologies of their unusual floral structures, especially the corona of Barbacenia and the corona-like appendages and multiple stamens of some Vellozia species. All Velloziaceae have epigynous flowers. Some species of Vellozia are polyandrous, and stamen number can be variable within species. In Vellozia jolyi, there is a single stamen opposite each sepal and a stamen fascicle (of three secondary stamens) opposite each petal. Each stamen possesses a single vascular bundle, and these are united into a single aggregate bundle in proximal regions of the fascicle. Stamens mature centripetally within each fascicle. The coronal appendages of both genera are closely associated with the stamens, but they share some vasculature with the tepals and develop late in ontogeny. The coronal organs cannot readily be homologized with any of the typical floral organs, but they show partial homology with both tepals and stamens. They are most readily interpreted as a late elaboration of the region between the petals and stamens associated with epigyny and the hypanthium. © 2010 by The University of Chicago. All rights reserved.

Morphological Variation of Primary Reproductive Structures in Males of Five Families of Neotropical Bats

Bats present unique features among mammals with respect to reproduction, and although neotropical bats do not have a hibernation period, many of their reproductive characteristics vary seasonally and interspecifically. Thus, this work aimed to examine the reproductive structures of 18 species belonging to five families of Brazilian bats. The gross anatomy of the testes varied little; however, the epididymis of Emballonuridae and Vespertilionidae showed exceptional structures with a large elongation of the caudal region. We observed a wide variation in the positioning of the testes: Phyllostomidae and Noctilionidae presented external testes; Emballonuridae and Molossidae presented migratory testes that may be in intra-abdominal or external positions; and Vespertilionidae displayed scrotal testes. In the histological evaluation, we observed a different pattern in vespertilionid species, with testicular regression and sperm retention/storage in the cauda epididymis in the five species analyzed. Similar testicular regression was observed in Molossops temminckii; however, sperm retention/storage was not observed in this species. These data suggest that although the species analyzed are tropical species that do not present a prolonged period of torpor (hibernation), they still maintain a period of seminiferous tubule regression and sperm storage very similar to that observed in hibernating bats. © 2012 Wiley Periodicals, Inc.