Solvent-induced changes on the polarity of the triplet excited state of 2-chlorothioxanthone: From time-resolved absorption and resonance Raman spectroscopies

Solvent polarity has been known to influence the triplet state structure and reactivity. Here, we present our experimental and theoretical study on the effect of solvent on the lowest triplet excited state structure of 2-chlorothioxanthone (CTX). Time-resolved absorption (TA) spectroscopy has been employed to understand the triplet state electronic structure; whereas solvent-induced structural changes have been studied using time-resolved resonance Raman (TR3) spectroscopy. Both the DFT and TD-DFT calculations have been performed in the solution phase employing self-consistent reaction field implicit solvation model to support the experimental data. It has been observed that CO stretching frequencies of the excited triplet state are sensitive to the solvent polarity and increase with the increase in the solvent polarity. Both TA and TR3 studies reveal that specific solvent effect (H-bonding) is more pronounced in comparison to the nonspecific solvent effect. (C) 2013 Elsevier B.V. All rights reserved.

Evaluation of the accuracy of an impact load cell using lumped parameter modeling and analysis

The objective of the current study is to evaluate the fidelity of load cell reading during impact testing in a drop-weight impactor using lumped parameter modeling. For the most common configuration of a moving impactor-load cell system in which dynamic load is transferred from the impactor head to the load cell, a quantitative assessment is made of the possible discrepancy that can result in load cell response. A 3-DOF (degrees-of-freedom) LPM (lumped parameter model) is considered to represent a given impact testing set-up. In this model, a test specimen in the form of a steel hat section similar to front rails of cars is represented by a nonlinear spring while the load cell is assumed to behave in a linear manner due to its high stiffness. Assuming a given load-displacement response obtained in an actual test as the true behavior of the specimen, the numerical solution of the governing differential equations following an implicit time integration scheme is shown to yield an excellent reproduction of the mechanical behavior of the specimen thereby confirming the accuracy of the numerical approach. The spring representing the load cell, however,predicts a response that qualitatively matches the assumed load-displacement response of the test specimen with a perceptibly lower magnitude of load.

An enthalpy method for modeling eutectic solidification

This paper presents a new micro-scale model for solidification of eutectic alloys. The model is based on the enthalpy method and simulates the growth of adjacent alpha and beta phases from a melt of eutectic composition in a two-dimensional Eulerian framework. The evolution of the two phases is obtained from the solution of volume averaged energy and species transport equations which are formulated using the nodal enthalpy and concentration potential values. The three phases are tracked using the beta-phase fraction and the liquid fraction values in all the computational nodes. Solutal convection flow field in the domain is obtained from the solution of volume-averaged momentum and continuity equations. The governing equations are solved using a coupled explicit-implicit scheme. The model is qualitatively validated with Jackson-Hunt theory. Results show expected eutectic growth pattern and proper species transfer and diffusion field ahead of the interface. Capabilities of the model such as lamella width selection, division of lamella into thinner lamellae and the presence of solutal convection are successfully demonstrated. The present model can potentially be incorporated into the existing framework of enthalpy based micro-scale dendritic solidification models thus leading to an efficient generalized microstructure evolution model. (C) 2014 Elsevier Inc. All rights reserved.

Large deformation dynamic finite element analysis of delaminated composite plates using contact-impact conditions

A new C-0 composite plate finite element based on Reddy's third order theory is used for large deformation dynamic analysis of delaminated composite plates. The inter-laminar contact is modeled with an augmented Lagrangian approach. Numerical results show that the widely used ``unconditionally stable'' beta-Newmark method presents instability problems in the transient simulation of delaminated composite plate structures with large deformation. To overcome this instability issue, an energy and momentum conserving composite implicit time integration scheme presented by Bathe and Baig is used. It is found that a proper selection of the penalty parameter is very crucial in the contact simulation. (C) 2014 Elsevier Ltd. All rights reserved.

A media access and feedback protocol for reliable multicast over wireless channel

A link level reliable multicast requires a channel access protocol to resolve the collision of feedback messages sent by multicast data receivers. Several deterministic media access control protocols have been proposed to attain high reliability, but with large delay. Besides, there are also protocols which can only give probabilistic guarantee about reliability, but have the least delay. In this paper, we propose a virtual token-based channel access and feedback protocol (VTCAF) for link level reliable multicasting. The VTCAF protocol introduces a virtual (implicit) token passing mechanism based on carrier sensing to avoid the collision between feedback messages. The delay performance is improved in VTCAF protocol by reducing the number of feedback messages. Besides, the VTCAF protocol is parametric in nature and can easily trade off reliability with the delay as per the requirement of the underlying application. Such a cross layer design approach would be useful for a variety of multicast applications which require reliable communication with different levels of reliability and delay performance. We have analyzed our protocol to evaluate various performance parameters at different packet loss rate and compared its performance with those of others. Our protocol has also been simulated using Castalia network simulator to evaluate the same performance parameters. Simulation and analytical results together show that the VTCAF protocol is able to considerably reduce average access delay while ensuring very high reliability at the same time.

A robust layer adapted difference method for singularly perturbed two-parameter parabolic problems

A finite difference method for a time-dependent singularly perturbed convection-diffusion-reaction problem involving two small parameters in one space dimension is considered. We use the classical implicit Euler method for time discretization and upwind scheme on the Shishkin-Bakhvalov mesh for spatial discretization. The method is analysed for convergence and is shown to be uniform with respect to both the perturbation parameters. The use of the Shishkin-Bakhvalov mesh gives first-order convergence unlike the Shishkin mesh where convergence is deteriorated due to the presence of a logarithmic factor. Numerical results are presented to validate the theoretical estimates obtained.

Mode coupling theory analysis of electrolyte solutions: Time dependent diffusion, intermediate scattering function, and ion solvation dynamics

A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering function, F(k, t), exhibits markedly different relaxation dynamics at different length scales. At small wave numbers, we find the emergence of a step-like relaxation, indicating the presence of both fast and slow time scales in the system. Such behavior allows an intriguing analogy with temperature dependent relaxation dynamics of supercooled liquids. We find that solvation dynamics of a tagged ion exhibits a power law decay at long times-the decay can also be fitted to a stretched exponential form. The emergence of the power law in solvation dynamics has been tested by carrying out long Brownian dynamics simulations with varying ionic concentrations. The solvation time correlation and ion-ion intermediate scattering function indeed exhibit highly interesting, non-trivial dynamical behavior at intermediate to longer times that require further experimental and theoretical studies. (c) 2015 AIP Publishing LLC.

Damage quantification under sliding and seizure condition using first-of-a-kind fretting machine

In a practical situation, it is difficult to model exact contact conditions clue to challenges involved in the estimation of contact forces, and relative displacements between the contacting bodies. Sliding and seizure conditions were simulated on first-of-a-kind displacement controlled system. Self-mated stainless steels have been investigated in detail. Categorization of contact conditions prevailing at the contact interface has been carried out based on the variation of coefficient of friction with number of cycles, and three-dimensional fretting loops. Surface and subsurface micro-cracks have been observed, and their characteristic shows strong dependence on loading conditions. Existence of shear bands in the subsurface region has been observed for high strain and low strain rate loading conditions. Studies also include the influence of initial surface roughness on the damage under two extreme contact conditions. (C) 2013 Elsevier B.V. All rights reserved.

Genome-wide analysis correlates Ayurveda Prakriti

The practice of Ayurveda, the traditional medicine of India, is based on the concept of three major constitutional types (Vata, Pitta and Kapha) defined as ``Prakriti''. To the best of our knowledge, no study has convincingly correlated genomic variations with the classification of Prakriti. In the present study, we performed genome-wide SNP (single nucleotide polymorphism) analysis (Affymetrix, 6.0) of 262 well-classified male individuals (after screening 3416 subjects) belonging to three Prakritis. We found 52 SNPs (p <= 1 x 10(-5)) were significantly different between Prakritis, without any confounding effect of stratification, after 10(6) permutations. Principal component analysis (PCA) of these SNPs classified 262 individuals into their respective groups (Vata, Pitta and Kapha) irrespective of their ancestry, which represent its power in categorization. We further validated our finding with 297 Indian population samples with known ancestry. Subsequently, we found that PGM1 correlates with phenotype of Pitta as described in the ancient text of Caraka Samhita, suggesting that the phenotypic classification of India's traditional medicine has a genetic basis; and its Prakriti-based practice in vogue for many centuries resonates with personalized medicine.

Transonic Aeroelastic Numerical Simulation in Aeronautical Engineering

A lower-upper symmetric Gauss-Seidel (LU-SGS) subiteration scheme is constructed for time-marching of the fluid equations. The Harten-Lax-van Leer-Einfeldt-Wada (HLLEW) scheme is used for the spatial discretization. The same subiteration formulation is applied directly to the structural equations of motion in generalized coordinates. Through subiteration between the fluid and structural equations, a fully implicit aeroelastic solver is obtained for the numerical simulation of fluid/structure interaction. To improve the ability for application to complex configurations, a multiblock grid is used for the flow field calculation and transfinite interpolation (TFI) is employed for the adaptive moving grid deformation. The infinite plate spline (IPS) and the principal of virtual work are utilized for the data transformation between the fluid and structure. The developed code was first validated through the comparison of experimental and computational results for the AGARD 445.6 standard aeroelastic wing. Then, the flutter character of a tail wing with control surface was analyzed. Finally, flutter boundaries of a complex aircraft configuration were predicted.

Normal shock boundary layer control with various vortex generator geometries

Various vortex generators which include ramp, split-ramp and a new hybrid concept "ramped-vane" are investigated under normal shock conditions with a diffuser at Mach number of 1.3. The dimensions of the computational domain were designed using Reynolds Average Navier-Stokes studies to be representative of the flow in an external-compression supersonic inlet. Using this flow geometry, various vortex generator concepts were studied with Implicit Large Eddy Simulation. In general, the ramped-vane provided increased vorticity compared to the other devices and reduced the separation length downstream of the device centerline. In addition, the size, edge gap and streamwise position respect to the shock were studied for the ramped-vane and it was found that a height of about half the boundary thickness and a large trailing edge gap yielded a fully attached flow downstream of the device. This ramped-vane also provided the largest reduction in the turbulent kinetic energy and pressure fluctuations. Additional benefits include negligible drag while the reductions in boundary layer displacement thickness and shape factor were seen compared to other devices. © 2010 by Sang Lee.

Normal shock boundary layer control with various vortex generator geometries

Various vortex generators which include ramp, split-ramp and a new hybrid concept "ramped-vane" are investigated under normal shock conditions with a diffuser at Mach number of 1.3. The dimensions of the computational domain were designed using Reynolds Average Navier-Stokes studies to be representative of the flow in an external-compression supersonic inlet. Using this flow geometry, various vortex generator concepts were studied with Implicit Large Eddy Simulation. In general, the ramped-vane provided increased vorticity compared to the other devices and reduced the separation length downstream of the device centerline. In addition, the size, edge gap and streamwise position respect to the shock were studied for the ramped-vane and it was found that a height of about half the boundary thickness and a large trailing edge gap yielded a fully attached flow downstream of the device. This ramped-vane also provided the largest reduction in the turbulent kinetic energy and pressure fluctuations. Additional benefits include negligible drag while the reductions in boundary layer displacement thickness and shape factor were seen compared to other devices. © 2011 Elsevier Ltd.

Iberoamérica de reojo en la visión de Tocqueville

Resumen: La democracia en América de Alexis de Tocqueville contiene una teoría de las causas de la república democrática anglosajona en el norte del continente que se entremezcla con la explicación de los factores de la prosperidad norteamericana. A lo largo del libro el autor francés formula una serie de observaciones dispersas sobre los países del Nuevo Mundo colonizados por España y Portugal. El artículo analiza sistemáticamente estas observaciones, de manera de reconstruir la teoría comparativa del desarrollo económico de ambas regiones culturales, en parte esbozada y en parte implícita en este libro de Tocqueville. La revisión del peso relativo de a) las leyes, b) las costumbres y c) lo que Tocqueville llama circunstancias o causas accidentales en el desarrollo de la república democrática y su prosperidad, descubre inconsistencias de interés para quienes desean comprender las causas del atraso material de Iberoamérica respecto de Angloamérica.

Neighborhoods attributes as determinants of children's academic achievement

Resumen: Los estudios sobre los efectos del vecindario sobre los logros educativos han confirmado la existencia de estos efectos particularmente en la adolescencia. Una deficiencia común de la investigación empírica hasta la fecha, la falta de información en múltiples contextos, se aborda en este trabajo mediante el uso de encuestas escolares de datos para obtener una mayor comprensión sobre el efecto de la pobreza en los niños que cursan el nivel primario de enseñanza en los EE.UU. Este trabajo propone la utilización de un modelo jerárquico lineal de clasificación cruzada para tomar en cuenta en forma apropiada la estructura anidada de la información ya que los niños pertenecen simultáneamente a los dos grupos, el barrio y la escuela. Los resultados que se presentan, basados en la encuesta ECLS-K, una muestra de más de 20000 niños en aproximadamente 1.000 vecindarios y 1200 escuelas 1200, pone de manifiesto la asociación entre la composición socioeconómica del vecindario y los resultados académicos de los estudiantes. Este estudio proporciona evidencia a favor de las teorías de la socialización y epidémica. La presencia de adultos con buen nivel educativo en el vecindario así como la mediana de ingresos tienen impacto positivo en el logro del estudiante. De la misma forma, elevados niveles de pobreza tienen una influencia significativa, pero negativa en los resultados académicos. Sin embargo, el impacto se produce cuando se supera el umbral de 30% de hogares pobres en el vecindario. Los resultados agregados son invariantes a distintas especificaciones en términos de variables, esto no sucede cuando se analizan subgrupos clasificados según su origen étnico, género y estatus socio-económico.

Medición y realidad : reflexiones para una economía realista

Resumen: El trabajo constituye una presentación general del análisis de la circulación económica elaborado por B. Lonergan quien, desde presupuestos filosóficos diferentes de los implícitos en la teoría económica dominante, desarrolló una aproximación sistémica a la problemática económica que revela ciertas insuficiencias en las mediciones vigentes. En efecto, las variables de interés se ven modificadas cuando cambian las categorías fundamentales de análisis. En la primera sección se exponen los supuestos gnoseológicos y epistemológicos realistas desarrollados por este autor. Estos fundamentos permiten reconocer con mayor claridad las bases endebles de los abordajes actuales. Tras una breve enumeración de algunas críticas al paradigma vigente de parte de diversos autores, se exponen las líneas generales del esquema propuesto por Lonergan.