A Computational Study of Tetrafluoro-[2.2]Cyclophanes

A computational study of the isomers of tetrafluorinated [2.2]cyclophanes persubstituted in one ring, namely F-4-[2.2]paracyclophane (4), F-4-anti-[2.2]metacyclophane (5a), F-4-syn-[2.2]metacyclophane (5b), and F-4-[2.2]metaparacyclophane (6a and 6b), was carried out. The effects of fluorination on the geometries, relative energies, local and global aromaticity, and strain energies of the bridges and rings were investigated. An analysis of the electron density by B3PW91/6-31+G(d,p), B3LYP/6-31+G(d,p), and MP2/6-31+G(d,p) was carried out using the natural bond orbitals (NBO), natural steric analysis (NSA), and atoms in molecules (AIM) methods. The analysis of frontier molecular orbitals (MOs) was also employed. The results indicated that the molecular structure of [2.2]paracyclophane is the most affected by the fluorination. Isodesmic reactions showed that the fluorinated rings are more strained than the nonfluorinated ones. The NICS, HOMA, and PDI criteria evidenced that the fluorination affects the aromaticity of both the fluorinated and the nonfluorinated rings. The NBO and NSA analyses gave an indication that the fluorination increases not only the number of through-space interactions but also their magnitude. The AIM analysis suggested that the through-space interactions are restricted to the F-4-[2.2]metacyclophanes. In addition, the atomic properties, computed over the atomic basins, shave evidence that not only the substitution, but also the position of the bridges could affect the atomic charges. the first atomic moments, and the atomic volumes.

Ideal soliton environment using parametric band gaps

Simultaneous solitary wave solutions for laser propagation in nonlinear parametric media with up to (3 + 1) dimensions are proved to exist. The combination of the large dispersion of a Bragg grating and the strong nonlinearity of chi((2)) optical material results in stable behavior with short interaction distances and low power requirements. The solutions are obtained by using the effective mass approximation to reduce the coupled propagation equations to those describing a dispersive parametric nonlinear waveguide, and are verified by solving the complete set of coupled band-gap equations numerically.

Spatiotemporal solitons in multidimensional optical media with a quadratic nonlinearity

We consider solutions to the second-harmonic generation equations in two-and three-dimensional dispersive media in the form of solitons localized in space and time. As is known, collapse does not take place in these models, which is why the solitons may be stable. The general solution is obtained in an approximate analytical form by means of a variational approach, which also allows the stability of the solutions to be predicted. Then, we directly simulate the two-dimensional case, taking the initial configuration as suggested by the variational approximation. We thus demonstrate that spatiotemporal solitons indeed exist and are stable. Furthermore, they are not, in the general case, equivalent to the previously known cylindrical spatial solitons. Direct simulations generate solitons with some internal oscillations. However, these oscillations neither grow nor do they exhibit any significant radiative damping. Numerical solutions of the stationary version of the equations produce the same solitons in their unperturbed form, i.e., without internal oscillations. Strictly stable solitons exist only if the system has anomalous dispersion at both the fundamental harmonic and second harmonic (SH), including the case of zero dispersion at SH. Quasistationary solitons, decaying extremely slowly into radiation, are found in the presence of weak normal dispersion at the second-harmonic frequency.

Quantitative analysis of the time courses of enzyme-catalyzed reactions

The catalytic properties of enzymes are usually evaluated by measuring and analyzing reaction rates. However, analyzing the complete time course can be advantageous because it contains additional information about the properties of the enzyme. Moreover, for systems that are not at steady state, the analysis of time courses is the preferred method. One of the major barriers to the wide application of time courses is that it may be computationally more difficult to extract information from these experiments. Here the basic approach to analyzing time courses is described, together with some examples of the essential computer code to implement these analyses. A general method that can be applied to both steady state and non-steady-state systems is recommended. (C) 2001 academic Press.

2-pyrazinylnitrene and 4-pyrimidylnitrene. Ring expansion to 1,3,5-triazacyclohepta-1,2,4,6-tetraene and ring opening to (2-isocyanovinyl)carbodiimide

Tetrazolo[1,5-a]pyrazine/2-azidopyrazine 9T/9A undergo photolysis in Ar matrix at cryogenic temperatures to yield 1,3,5-triazacyclohepta-1,2,4,6-tetraene 21 as the first observable intermediate, and 1-cyanoimidazole 11 and (2-isocyanovinyl)carbodiimide 22 as the final products. The latter tautomerizes to 2-(isocyanovinyl)cyanamide 23 on warming to 40 K. The same intermediate 21 and the same final products are obtained on matrix photolysis of the isomeric tetrazolo[1,5-c]pyrimidine/4-azidopyrimidine 24T/24A. These photolysis results as well as those of the previously reported thermal ring contraction of N-15-labeled 2-pyrazinyl- and 4-pyrimidylnitrenes to 1-cyanoimidazoles can all be rationalized in terms of selective ring opening of 21 or nitrine 10 to a nitrile ylide zwitterion 28 prior to formation of the final products, 11 and 22. The results are supported by high-level ab initio and DFT calculations (CASPT2-CASSCF(6,6), G3(MP2), and B3LYP/6-31+G*) of the energies and IR spectra of the intermediates and products.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Computing the phase diagram of binary mixtures: A patchy particle case study

We investigate the phase behaviour of 2D mixtures of bi-functional and three-functional patchy particles and 3D mixtures of bi-functional and tetra-functional patchy particles by means of Monte Carlo simulations and Wertheim theory. We start by computing the critical points of the pure systems and then we investigate how the critical parameters change upon lowering the temperature. We extend the successive umbrella sampling method to mixtures to make it possible to extract information about the phase behaviour of the system at a fixed temperature for the whole range of densities and compositions of interest. (C) 2013 AIP Publishing LLC.

Efficient Implementation Of A Single-Precision Floating-Point Arithmetic Unit on FPGA

This paper presents a single precision floating point arithmetic unit with support for multiplication, addition, fused multiply-add, reciprocal, square-root and inverse squareroot with high-performance and low resource usage. The design uses a piecewise 2nd order polynomial approximation to implement reciprocal, square-root and inverse square-root. The unit can be configured with any number of operations and is capable to calculate any function with a throughput of one operation per cycle. The floatingpoint multiplier of the unit is also used to implement the polynomial approximation and the fused multiply-add operation. We have compared our implementation with other state-of-the-art proposals, including the Xilinx Core-Gen operators, and conclude that the approach has a high relative performance/area efficiency. © 2014 Technical University of Munich (TUM).

Hierarchical wrinkling on elastometric Janus spheres

Hierarchical wrinkling on elastomeric Janus spheres is permanently imprinted by swelling, for different lengths of time, followed by drying the particles in an appropriate solvent. First-order buckling with a spatial periodicity (lambda(11)) of the order of a few microns and hierarchical structures comprising of 2nd order buckling with a spatial periodicity (lambda(12)) of the order of hundreds of nanometers have been obtained. The 2nd order buckling features result from a Grinfeld surface instability due to the diffusion of the solvent and the presence of sol molecules.

Quantitative description of the self-assembly of patchy particles into chains and rings

We numerically study a simple fluid composed of particles having a hard-core repulsion complemented by two patchy attractive sites on the particle poles. An appropriate choice of the patch angular width allows for the formation of ring structures which, at low temperatures and low densities, compete with the growth of linear aggregates. The simplicity of the model makes it possible to compare simulation results and theoretical predictions based on the Wertheim perturbation theory, specialized to the case in which ring formation is allowed. Such a comparison offers a unique framework for establishing the quality of the analytic predictions. We find that the Wertheim theory describes remarkably well the simulation results.

The three main marine depositional cycles of the Neogene of Portugal

The present work follows a stratigraphic model for the marine Neogene of Portugal based on the definition of three main marine sedimentary cycles. Conceptually the I, II and III Neogene Cycles can be defined as 2nd order sedimentary sequences with duration ranging from 5 to 8 Ma. The I Neogene Cycle is fully represented only in the Lower Tagus Basin. Ranging from the Early Aquitanian to the Late Burdigalian the I Neogene Cycle testify a transgressive episode in the region of Lisbon and Setúbal Peninsula. Rapid lateral facies variations suggest a shallowmarine basin. This cycle ends with an important Late Burdigalian tectonic compressive event expressed by uplift of the surrounding areas and deformation affecting the Early Miocene deposits of the Arrábida Chain. The II Neogene Cycle includes thick sedimentary sequences covering Paleozoic and Mesozoic formations in the Algarve and Alvalade-Melides regions and it extends as far north as Santarém in the Lower Tagus Basin. Mainly controlled by global eustasy, it was generated by the important positive eustatic trend that characterized the Middle Miocene worldwide to which the Portuguese continental margin acted more or less passively. This cycle ended with a second and the most important compression event starting after the end of the Serravallian affecting the entire Portuguese onshore and shelf areas. This led to an important depositional hiatus of marine sediments for more than 2.5 Ma. During the Early and the Middle Tortonian occurred the clockwise rotation of the Guadalquivir Basin. The thickmarine units deposited afterwards in this basin produced a litostatic load, which seems to have induced subsidence farther west resuming the Neogene marine sedimentation in the Cacela region (Eastern Algarve), during the Late Tortonian. This marks the beginning of the III Neogene Cycle. To the north, in the Sado Basin (Alvalade-Melides region), a similar depositional sequence starts its sedimentation during the Messinian. Further north, in the Pombal-Caldas da Rainha region, marine sedimentation started during the Late Pliocene (Piacenzian). The migration in time, from south to north for the beginning of the marine sedimentation of this cycle is interpreted as reflecting a visco-elastic propagation of the deformation from the Betic chain northwards.

An RF LC Q-enhanced CMOS iter using integrated inductors with layout optimization

Dissertação apresentada para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Inventário de Medos III : Avaliação das qualidades psicométricas em uma amostra portuguesa

Este estudo teve como objetivo avaliar as qualidades psicométricas do Fear Survey Schedule-III, em uma amostra portuguesa. Participaram 1.980 sujeitos selecionados por conveniência a partir de uma população adulta normativa. As idades dos participantes estavam compreendidas entre os 18 e os 80 anos (M = 39,5, DP = 8,5), sendo 59% do sexo feminino. As qualidades psicométricas da escala foram avaliadas em suas facetas de sensibilidade psicométrica, validade de construto e confi abilidade. A validade externa de construto foi avaliada com análise multigrupos em amostra aleatória e independente da amostra de validação inicial. O modelo fatorial original proposto apresentou um ajustamento inaceitável à amostra de validação. Procedeu-se ao refi namento do modelo de medida em uma parte da amostra, selecionada aleatoriamente. Em conclusão, o modelo de medida simplifi cado apresentou uma boa qualidade de ajustamento fatorial e foi invariante em uma segunda amostra independente da primeira. Propôs-se uma nova estrutura hierárquica, com fator de 2ª ordem designado por “Medos”, que revelou boas qualidades psicométricas (sensibilidade, validade de construto e confi abilidade).

Assessment of fish assemblages in streams of different orders in the Upper Paraná River basin, Central Brazil

The aim of this study was to test whether the richness observed and the biomass per trophic group of fish assemblages vary depending on the order (1st and 2nd) of the streams located in three different basins of the Upper Paraná River Basin, Central Brazil. Samples were collected between April and September, 2009, in 27 streams of the Meia Ponte, Piracanjuba and Santa Maria River basins. A total of 4,879 specimens were collected distributed in 59 species and 19 families. The statistical analyses carried out indicate that the observed richness and biomass of omnivore fish were influenced by the interaction of two factors: stream order and basin. The 2nd order streams located in the Santa Maria basin presented significant differences in the observed richness and omnivore biomass when compared to i) 1st order streams in the same basin (only richness) or in the Piracanjuba and Meia Ponte basin; ii) 2nd order streams in the Piracanjuba (only omnivore biomass) and Meia Ponte Rivers basins. Results are discussed considering the influence of geomorphic processes on fish assemblages and food availability.

Formulació matricial de la teoria de pertorbacions de Rayleigh-Schrödringer: monodimensional

Es repassa la formulació de la Teoria de Pertorbacions en notació matricial i s'exposa una aplicació senzilla com és la solució del problema de la partícula sotmesa a un potencial d'atracció dins la caixa quàntica monodimensional