Ab initio studies of solvent effect on conformational equilibria and vibrational spectra of dipropionamide

Systematic ab initio molecular orbital studies of the conformational equilibria and vibrational spectra of dipropionamide using the basis sets 6-31g(d) and 6-31++G(d,p) have been carried out. The vibrational spectra of dipropionamide have been satisfactorily interpreted taking into account the agreement between the calculated frequencies, infrared and Raman band intensities and the shifts in the spectra of deuterated molecules with those observed. The previous assignments of most of the vibrational bands are well confirmed, a few bands need reassignment, however. The solvent effects were investigated by self-consistent reaction field theory using dipole and self-consistent isodensity polarized continuum model methods. The introduction of a dielectric medium has only a marginal effect on the conformational equilibria and vibrational spectra. However, the calculated changes in geometry and vibrational spectra on going from the gas phase to the solution phase are in accord with the increasing weight of the dipolar resonance structure in polar solvents. (C) 2002 Elsevier Science B.V. All rights reserved.

Density-matrix renormalization-group study of low-lying excitations of polyacene within a Pariser-Parr-Pople model

We have carried out symmetrized density-matrix renormalization-group calculations to study the nature of excited states of long polyacene oligomers within a Pariser-Parr-Pople Hamiltonian. We have used the C-2 symmetry, the electron-hole symmetry, and the spin parity of the system in our calculations. We find that there is a crossover in the lowest dipole forbidden two-photon state and the lowest dipole allowed excited state with size of the oligomer. In the long system limit, the two-photon state lies below the lowest dipole allowed excited state. The triplet state lies well below the two-photon state and energetically does not correspond to its description as being made up of two triplets. These results are in agreement with the general trends in linear conjugated polymers. However, unlike in linear polyenes wherein the two-photon state is a localized excitation, we find that in polyacenes, the two-photon excitation is spread out over the system. We have doped the systems with a hole and an electron and have calculated the charge excitation gap. Using the charge gap and the optical gap, we estimate the binding energy of the 1(1)B(-) exciton to be 2.09 eV. We have also studied doubly doped polyacenes and find that the bipolaron in these systems, to be composed of two separated polarons, as indicated by the calculated charge-density profile and charge-charge correlation function. We have studied bond orders in various states in order to get an idea of the excited state geometry of the system. We find that the ground state, the triplet state, the dipole allowed state, and the polaron excitations correspond to lengthening of the rung bonds in the interior of the oligomer while the two-photon excitation corresponds to the rung bond lengths having two maxima in the system.

Fuzzy logic intelligent system for gas turbine module and system fault isolation

A fuzzy logic intelligent system is developed for gas-turbine fault isolation. The gas path measurements used for fault isolation are exhaust gas temperature, low and high rotor speed, and fuel flow. These four measurements are also called the cockpit parameters and are typically found in almost all older and newer jet engines. The fuzzy logic system uses rules developed from a model of performance influence coefficients to isolate engine faults while accounting for uncertainty in gas path measurements. It automates the reasoning process of an experienced powerplant engineer. Tests with simulated data show that the fuzzy system isolates faults with an accuracy of 89% with only the four cockpit measurements. However, if additional pressure and temperature probes between the compressors and before the burner, which are often found in newer jet engines, are considered, the fault isolation accuracy rises to as high as 98%. In addition, the additional sensors are useful in keeping the fault isolation system robust as quality of the measured data deteriorates.

Surfaces of Bounded Mean Curvature In Riemannian Manifolds

Consider a sequence of closed, orientable surfaces of fixed genus g in a Riemannian manifold M with uniform upper bounds on the norm of mean curvature and area. We show that on passing to a subsequence, we can choose parametrisations of the surfaces by inclusion maps from a fixed surface of the same genus so that the distance functions corresponding to the pullback metrics converge to a pseudo-metric and the inclusion maps converge to a Lipschitz map. We show further that the limiting pseudo-metric has fractal dimension two. As a corollary, we obtain a purely geometric result. Namely, we show that bounds on the mean curvature, area and genus of a surface F subset of M, together with bounds on the geometry of M, give an upper bound on the diameter of F. Our proof is modelled on Gromov's compactness theorem for J-holomorphic curves.

Reconstructing Solid Model from 2D Scanned Images of Biological Organs for Finite Element Simulation

This work presents a methodology to reconstruct 3D biological organs from image sequences or other scan data using readily available free softwares with the final goal of using the organs (3D solids) for finite element analysis. The methodology deals with issues such as segmentation, conversion to polygonal surface meshes, and finally conversion of these meshes to 3D solids. The user is able to control the detail or the level of complexity of the solid constructed. The methodology is illustrated using 3D reconstruction of a porcine liver as an example. Finally, the reconstructed liver is imported into the commercial software ANSYS, and together with a cyst inside the liver, a nonlinear analysis performed. The results confirm that the methodology can be used for obtaining 3D geometry of biological organs. The results also demonstrate that the geometry obtained by following this methodology can be used for the nonlinear finite element analysis of organs. The methodology (or the procedure) would be of use in surgery planning and surgery simulation since both of these extensively use finite elements for numerical simulations and it is better if these simulations are carried out on patient specific organ geometries. Instead of following the present methodology, it would cost a lot to buy a commercial software which can reconstruct 3D biological organs from scanned image sequences.

On the evidence for the effect of bubble interference on cavitation noise

Cavitation-noise measurements from an axisymmetric body with ‘controlled’ generation of cavitation are reported. The control was achieved by seeding artificial nuclei in the boundary layer by electrolysis. It was possible to alter the number density of nuclei by varying the electrolysis voltage, polarity and the geometry of the electrode. From the observed trend of cavitation-noise data it is postulated that there exists an ‘interference effect’ which influences cavitation noise. When the nucleus-number density is high and cavitation numbers are low this effect is strong. Under these conditions the properties of cavitation noise are found to differ considerably from those expected based on theories concerning noise from single-spherical-bubble cavitation.

Variational Asymptotic Analysis of a Self-healing SMA Composite

A Shape Memory Alloy (SMA) wire reinforced composite shell structure is analyzed for self-healing characteristic using Variational Asymptotic Method (VAM). SMA behavior is modeled using a onedimensional constitutive model. A pre-notched specimen is loaded longitudinally to simulate crack propagation. The loading process is accompanied by martensitic phase transformation in pre-strained SMA wires, bridging the crack. To heal the composite, uniform heating is required to initiate reverse transformation in the wires and bringing the crack faces back into contact. The pre-strain in the SMA wires used for reinforcement, causes a closure force across the crack during reverse transformation of the wires under heating. The simulation can be useful in design of self-healing composite structures using SMA. Effect of various parameters, like composite and SMA material properties and the geometry of the specimen, on the cracking and self-healing can also be studied.

Topology Optimization of Micromachined Structures with the Manufacturing Constraints of KOH Etching of (110) Silicon

The focus of this paper is on designing useful compliant micro-mechanisms of high-aspect-ratio which can be microfabricated by the cost-effective wet etching of (110) orientation silicon (Si) wafers. Wet etching of (110) Si imposes constraints on the geometry of the realized mechanisms because it allows only etch-through in the form of slots parallel to the wafer's flat with a certain minimum length. In this paper, we incorporate this constraint in the topology optimization and obtain compliant designs that meet the specifications on the desired motion for given input forces. Using this design technique and wet etching, we show that we can realize high-aspect-ratio compliant micro-mechanisms. For a (110) Si wafer of 250 µm thickness, the minimum length of the etch opening to get a slot is found to be 866 µm. The minimum achievable width of the slot is limited by the resolution of the lithography process and this can be a very small value. This is studied by conducting trials with different mask layouts on a (110) Si wafer. These constraints are taken care of by using a suitable design parameterization rather than by imposing the constraints explicitly. Topology optimization, as is well known, gives designs using only the essential design specifications. In this work, we show that our technique also gives manufacturable mechanism designs along with lithography mask layouts. Some designs obtained are transferred to lithography masks and mechanisms are fabricated on (110) Si wafers.

CFD Based Design Optimizations of the Diffuser of a Gas Dynamically Driver Laser Cavity

Based on the an earlier CFD analysis of the performance of the gas-dynamically controlled laser cavity [1]it was found that there is possibility of optimizing the geometry of the diffuser that can bring about reductions in both size and cost of the system by examining the critical dimensional requirements of the diffuser. Consequently,an extensive CFD analysis has been carried out for a range of diffuser configurations by simulating the supersonic flow through the arrangement including the laser cavity driven by a bank of converging – diverging nozzles and the diffuser. The numerical investigations with 3D-RANS code are carried out to capture the flow patterns through diffusers past the cavity that has multiple supersonic jet interactions with shocks leading to complex flow pattern. Varying length of the diffuser plates is made to be the basic parameter of the study. The analysis reveals that the pressure recovery pattern during the flow through the diffuser from the simulation, being critical for the performance of the laser device shows its dependence on the diffuser length is weaker beyond a critical lower limit and this evaluation of this limit would provide a design guideline for a more efficient system configuration.The observation based on the parametric study shows that the pressure recovery transients in the near vicinity of the cavity is not affected for the reduction in the length of the diffuser plates up to its 10% of the initial size, indicating the design in the first configuration that was tested experimentally has a large factor of margin. The flow stability in the laser cavity is found to be unaffected since a strong and stable shock is located at the leading edge of the diffuser plates while the downstream shock and flow patterns are changed, as one would expect. Results of the study for the different lengths of diffusers in the range of 10% to its full length are presented, keeping the experimentally tested configuration used in the earlier study [1] as the reference length. The conclusions drawn from the analysis is found to be of significance since it provides new design considerations based on the understanding of the intricacies of the flow, allowing for a hardware optimization that can lead to substantial size reduction of the device with no loss of performance.

Convergence problems in a class of model reference adaptive control systems

A class of model reference adaptive control system which make use of an augmented error signal has been introduced by Monopoli. Convergence problems in this attractive class of systems have been investigated in this paper using concepts from hyperstability theory. It is shown that the condition on the linear part of the system has to be stronger than the one given earlier. A boundedness condition on the input to the linear part of the system has been taken into account in the analysis - this condition appears to have been missed in the previous applications of hyperstability theory. Sufficient conditions for the convergence of the adaptive gain to the desired value are also given.

Parallel Computation of 2D Morse-Smale Complexes

The Morse-Smale complex is a useful topological data structure for the analysis and visualization of scalar data. This paper describes an algorithm that processes all mesh elements of the domain in parallel to compute the Morse-Smale complex of large two-dimensional data sets at interactive speeds. We employ a reformulation of the Morse-Smale complex using Forman's Discrete Morse Theory and achieve scalability by computing the discrete gradient using local accesses only. We also introduce a novel approach to merge gradient paths that ensures accurate geometry of the computed complex. We demonstrate that our algorithm performs well on both multicore environments and on massively parallel architectures such as the GPU.

A Numerical Scheme for Three-Dimensional Front Propagation and Control of Jordan Mode

As an example of a front propagation, we study the propagation of a three-dimensional nonlinear wavefront into a polytropic gas in a uniform state and at rest. The successive positions and geometry of the wavefront are obtained by solving the conservation form of equations of a weakly nonlinear ray theory. The proposed set of equations forms a weakly hyperbolic system of seven conservation laws with an additional vector constraint, each of whose components is a divergence-free condition. This constraint is an involution for the system of conservation laws, and it is termed a geometric solenoidal constraint. The analysis of a Cauchy problem for the linearized system shows that when this constraint is satisfied initially, the solution does not exhibit any Jordan mode. For the numerical simulation of the conservation laws we employ a high resolution central scheme. The second order accuracy of the scheme is achieved by using MUSCL-type reconstructions and Runge-Kutta time discretizations. A constrained transport-type technique is used to enforce the geometric solenoidal constraint. The results of several numerical experiments are presented, which confirm the efficiency and robustness of the proposed numerical method and the control of the Jordan mode.

Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-pi complexes

We have investigated quadratic nonlinearity (beta(HRS)) and linear and circular depolarization ratios (D and D', respectively) of a series of 1:1 complexes of tropyliumtetrafluoroborate as a cation and methyl-substituted benzenes as pi-donors by making polarization resolved hyper-Rayleigh scattering measurements in solution. The measured D and D' values are much lower than the values expected from a typical sandwich or a T-shaped geometry of a complex. In the cation-pi complexes studied here, the D value varies from 1.36 to 1.46 and D' from 1.62 to 1.72 depending on the number of methyl substitutions on the benzene ring. In order to probe it further, beta, D and D' were computed using the Zerner intermediate neglect of differential overlap-correction vector self-consistent reaction field technique including single and double configuration interactions in the absence and presence of BF4- anion. In the absence of the anion, the calculated value of D varies from 4.20 to 4.60 and that of D' from 2.45 to 2.72 which disagree with experimental values. However, by arranging three cation-pi BF4- complexes in a trigonal symmetry, the computed values are brought to agreement with experiments. When such an arrangement was not considered, the calculated beta values were lower than the experimental values by more than a factor of two. This unprecedented influence of the otherwise ``unimportant'' anion in solution on the beta value and depolarization ratios of these cation-pi complexes is highlighted and emphasized in this paper. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4716020]

Involvement of Src family of kinases and cAMP phosphodiesterase in the luteinizing hormone/chorionic gonadotropin receptor-mediated signaling in the corpus luteum of monkey

Background: In higher primates, during non-pregnant cycles, it is indisputable that circulating LH is essential for maintenance of corpus luteum (CL) function. On the other hand, during pregnancy, CL function gets rescued by the LH analogue, chorionic gonadotropin (CG). The molecular mechanisms involved in the control of luteal function during spontaneous luteolysis and rescue processes are not completely understood. Emerging evidence suggests that LH/CGR activation triggers proliferation and transformation of target cells by various signaling molecules as evident from studies demonstrating participation of Src family of tyrosine kinases (SFKs) and MAP kinases in hCG-mediated actions in Leydig cells. Since circulating LH concentration does not vary during luteal regression, it was hypothesized that decreased responsiveness of luteal cells to LH might occur due to changes in LH/CGR expression dynamics, modulation of SFKs or interference with steroid biosynthesis. Methods: Since, maintenance of structure and function of CL is dependent on the presence of functional LH/CGR its expression dynamics as well as mRNA and protein expressions of SFKs were determined throughout the luteal phase. Employing well characterized luteolysis and CL rescue animal models, activities of SFKs, cAMP phosphodiesterase (cAMP-PDE) and expression of SR-B1 (a membrane receptor associated with trafficking of cholesterol ester) were examined. Also, studies were carried out to investigate the mechanisms responsible for decline in progesterone biosynthesis in CL during the latter part of the non-pregnant cycle. Results and discussion: The decreased responsiveness of CL to LH during late luteal phase could not be accounted for by changes in LH/CGR mRNA levels, its transcript variants or protein. Results obtained employing model systems depicting different functional states of CL revealed increased activity of SFKs pSrc (Y-416)] and PDE as well as decreased expression of SR-B1correlating with initiation of spontaneous luteolysis. However, CG, by virtue of its heroic efforts, perhaps by inhibition of SFKs and PDE activation, prevents CL from undergoing regression during pregnancy. Conclusions: The results indicated participation of activated Src and increased activity of cAMP-PDE in the control of luteal function in vivo. That the exogenous hCG treatment caused decreased activation of Src and cAMP-PDE activity with increased circulating progesterone might explain the transient CL rescue that occurs during early pregnancy.

Changing resonator geometry to boost sound power decouples size and song frequency in a small insect

Despite their small size, some insects, such as crickets, can produce high amplitude mating songs by rubbing their wings together. By exploiting structural resonance for sound radiation, crickets broadcast species-specific songs at a sharply tuned frequency. Such songs enhance the range of signal transmission, contain information about the signaler's quality, and allow mate choice. The production of pure tones requires elaborate structural mechanisms that control and sustain resonance at the species-specific frequency. Tree crickets differ sharply from this scheme. Although they use a resonant system to produce sound, tree crickets can produce high amplitude songs at different frequencies, varying by as much as an octave. Based on an investigation of the driving mechanism and the resonant system, using laser Doppler vibrometry and finite element modeling, we show that it is the distinctive geometry of the crickets' forewings (the resonant system) that is responsible for their capacity to vary frequency. The long, enlarged wings enable the production of high amplitude songs; however, as a mechanical consequence of the high aspect ratio, the resonant structures have multiple resonant modes that are similar in frequency. The drive produced by the singing apparatus cannot, therefore, be locked to a single frequency, and different resonant modes can easily be engaged, allowing individual males to vary the carrier frequency of their songs. Such flexibility in sound production, decoupling body size and song frequency, has important implications for conventional views of mate choice, and offers inspiration for the design of miniature, multifrequency, resonant acoustic radiators.