USEFUL EXTENSIONS OF THE HENRY REACTION: EXPEDITIOUS ROUTES TO NITROALKANES AND NITROALKENES IN AQUEOUS MEDIA

The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu)(3)SnH in water under microwave irradiation (80 degrees C/10 min), or dehydrated to the corresponding nitroalkenes with K2CO3 in water (generally 0-5 degrees C/20 min). Both ``one-pot'' reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.

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.

Selective and Sensitive Turn-on Chemosensor for Arsenite Ion at the ppb Level in Aqueous Media Applicable in Cell Staining

A newly designed and structurally characterized cell permeable diformyl-p-cresol based receptor (HL) selectively senses the AsO33- ion up to ca. 4.1 ppb in aqueous media over the other competitive ions at biological pH through an intermolecular H-bonding induced CHEF (chelationenhanced fluorescence) process, established by detailed experimental and theoretical studies. This biofriendly probe is highly competent in recognizing the existence of AsO33- ions in a living organism by developing an image under a fluorescence microscope and useful to estimate the amount of arsenite ions in various water samples.

Exploring sand and bentonite - enhanced sand as filter media for nitrate removal

Increasing nitrate concentrations in ground water is deleterious to human health as ingestion of such water can cause methemoglobinemia in infants and even cancer in adults (desirable limit for nitrate as NO3 - 45 mg/L, IS code 10500-1991). Excess nitrate concentrations in ground water is contributed by reason being disposal of sewage and excessive use of fertilizers. Though numerous technologies such as reverse osmosis, ion exchange, electro-dialysis, permeable reactive barriers using zerovalent iron etc exists, nitrate removal continues to be one of challenging issue as nitrate ion is highly mobile within the soil strata. The tapping the denitrification potential of soil denitrifiers which are inherently available in the soil matrix is the most sustainable approach to mitigate accumulation of nitrate in ground water. The insitu denitrification of sand and bentonite enhanced sand (bentonite content = 5%) in presence of easily assimilable organic carbon such as ethanol was studied. Batch studies showed that nitrate reduction by sand follows first order kinetics with a rate constant 5.3x10(-2) hr(-1) and rate constant 4.3 x 10(-2) hr(-1) was obtained for bentonite-enhanced sand (BS) at 25 degrees C. Filter columns (height = 5 cm and diameter = 8.2 cm) were constructed using sand and bentonite-enhanced sand as filter media. The filtration rate through both the filter columns was maintained at average value of 2.60 cm/h. The nitrate removal rates through both the filter media was assessed for solution containing 22.6 mg NO3-N/L concentrations while keeping C/N mass ratio as 3. For sand filter column, the nitrate removal efficiency reached the average value of 97.6% after passing 50 pore volumes of the nitrate solution. For bentonite-enhanced sand filter column, the average nitrate removal efficiency was 83.5%. The time required for effective operation for sand filter bed was 100 hours, while bentonite-enhanced sand filter bed did not require any maturation period as that of sand filter bed for effective performance because the presence of micropores in bentonite increases the hydraulic retention time of the solution inside the filter bed.

Long-Term Sustained Release of Salicylic Acid from Cross-Linked Biodegradable Polyester Induces a Reduced Foreign Body Response in Mice

There has been a continuous surge toward developing new biopolymers that exhibit better in vivo biocompatibility properties in terms of demonstrating a reduced foreign body response (FBR). One approach to mitigate the undesired FBR is to develop an implant capable of releasing anti-inflammatory molecules in a sustained manner over a long time period. Implants causing inflammation are also more susceptible to infection. In this article, the in vivo biocompatibility of a novel, biodegradable salicylic acid releasing polyester (SAP) has been investigated by subcutaneous implantation in a mouse model. The tissue response to SAP was compared with that of a widely used biodegradable polymer, poly(lactic acid-co-glycolic acid) (PLGA), as a control over three time points: 2, 4, and 16 weeks postimplantation. A long-term in vitro study illustrates a continuous, linear (zero order) release of salicylic acid with a cumulative mass percent release rate of 7.34 x 10(-4) h(-1) over similar to 1.5-17 months. On the basis of physicochemical analysis, surface erosion for SAP and bulk erosion for PLGA have been confirmed as their dominant degradation modes in vivo. On the basis of the histomorphometrical analysis of inflammatory cell densities and collagen distribution as well as quantification of proinflammatory cytokine levels (TNF-alpha and IL-1 beta), a reduced foreign body response toward SAP with respect to that generated by PLGA has been unambiguously established. The favorable in vivo tissue response to SAP, as manifest from the uniform and well-vascularized encapsulation around the implant, is consistent with the decrease in inflammatory cell density and increase in angiogenesis with time. The above observations, together with the demonstration of long-term and sustained release of salicylic acid, establish the potential use of SAP for applications in improved matrices for tissue engineering and chronic wound healing.

Generalized Partial Response Equalization and Data-Dependent Noise Predictive Signal Detection Over Media Models for TDMR

Two-dimensional magnetic recording (2-D TDMR) is an emerging technology that aims to achieve areal densities as high as 10 Tb/in(2) using sophisticated 2-D signal-processing algorithms. High areal densities are achieved by reducing the size of a bit to the order of the size of magnetic grains, resulting in severe 2-D intersymbol interference (ISI). Jitter noise due to irregular grain positions on the magnetic medium is more pronounced at these areal densities. Therefore, a viable read-channel architecture for TDMR requires 2-D signal-detection algorithms that can mitigate 2-D ISI and combat noise comprising jitter and electronic components. Partial response maximum likelihood (PRML) detection scheme allows controlled ISI as seen by the detector. With the controlled and reduced span of 2-D ISI, the PRML scheme overcomes practical difficulties such as Nyquist rate signaling required for full response 2-D equalization. As in the case of 1-D magnetic recording, jitter noise can be handled using a data-dependent noise-prediction (DDNP) filter bank within a 2-D signal-detection engine. The contributions of this paper are threefold: 1) we empirically study the jitter noise characteristics in TDMR as a function of grain density using a Voronoi-based granular media model; 2) we develop a 2-D DDNP algorithm to handle the media noise seen in TDMR; and 3) we also develop techniques to design 2-D separable and nonseparable targets for generalized partial response equalization for TDMR. This can be used along with a 2-D signal-detection algorithm. The DDNP algorithm is observed to give a 2.5 dB gain in SNR over uncoded data compared with the noise predictive maximum likelihood detection for the same choice of channel model parameters to achieve a channel bit density of 1.3 Tb/in(2) with media grain center-to-center distance of 10 nm. The DDNP algorithm is observed to give similar to 10% gain in areal density near 5 grains/bit. The proposed signal-processing framework can broadly scale to various TDMR realizations and areal density points.

Modeling the co-transport of viruses and colloids in unsaturated porous media

A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations,are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Cluysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWL A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AIM, virus interaction with mobile and immobile colloids, virus attachment to solid-water interface (SWI), and colloid interaction with SWI and AWL The virus BTC is relatively insensitive to parameters describing the maximum adsorption capacity of the AWI for colloids, inlet colloid concentration, virus detachment rate coefficient from the SW!, maximum adsorption capacity of the AWI for viruses and inlet virus concentration. (C) 2015 Elsevier B.V. All rights reserved.

Bearing capacity of a circular foundation on layered sand-clay media

The bearing capacity of a circular footing lying over fully cohesive strata, with an overlaying sand layer, is computed using the axisymmetric lower bound limit analysis with finite elements and linear optimization. The effects of the thickness and the internal friction angle of the sand are examined for different combinations of c(u)/(gamma b) and q, where c(u)=the undrained shear strength of the cohesive strata, gamma=the unit weight of either layer, b=the footing radius, and q=the surcharge pressure. The results are given in the form of a ratio (eta) of the bearing capacity with an overlaying sand layer to that for a footing lying directly over clayey strata. An overlaying medium dense to dense sand layer considerably improves the bearing capacity. The improvement continuously increases with decreases in c(u)/(gamma b) and increases in phi and q/(gamma b). A certain optimum thickness of the sand layer exists beyond which no further improvement occurs. This optimum thickness increases with an increase in 0 and q and with a decrease in c(u)/(gamma b). Failure patterns are also drawn to examine the inclusion of the sand layer. (C) 2015 The Japanese Geotechnical Society. Production and hosting by Elsevier B.V. All rights reserved.

Parameters Inversion of Fluid-Saturated Porous Media Based on Neural Networks

The multi-layers feedforward neural network is used for inversion of material constants of fluid-saturated porous media. The direct analysis of fluid-saturated porous media is carried out with the boundary element method. The dynamic displacement responses obtained from direct analysis for prescribed material parameters constitute the sample sets training neural network. By virtue of the effective L-M training algorithm and the Tikhonov regularization method as well as the GCV method for an appropriate selection of regularization parameter, the inverse mapping from dynamic displacement responses to material constants is performed. Numerical examples demonstrate the validity of the neural network method.

Kramers Escape Rate in Nonlinear Diffusive Media

In this paper, we study nonlinear Kramers problem by investigating overdamped systems ruled by the one-dimensional nonlinear Fokker-Planck equation. We obtain an analytic expression for the Kramers escape rate under quasistationary conditions by employing

State Vector: A New Approach to Prediction of the Failure of Brittle Heterogeneous Media and Large Earthquakes

The concept of state vector stems from statistical physics, where it is usually used to describe activity patterns of a physical field in its manner of coarsegrain. In this paper, we propose an approach by which the state vector was applied to describe quantitatively the damage evolution of the brittle heterogeneous systems, and some interesting results are presented, i.e., prior to the macro-fracture of rock specimens and occurrence of a strong earthquake, evolutions of the four relevant scalars time series derived from the state vectors changed anomalously. As retrospective studies, some prominent large earthquakes occurred in the Chinese Mainland (e.g., the M 7.4 Haicheng earthquake on February 4, 1975, and the M 7.8 Tangshan earthquake on July 28, 1976, etc) were investigated. Results show considerable promise that the time-dependent state vectors could serve as a kind of precursor to predict earthquakes.

Influencia de diferentes períodos de destete sobre la ganancia media en conejos de engorde procedentes de conejas primiparas

El presente trabajo se realizó con el objetivo de estudiar el efecto del destete a los 15, 30 y 45 días, sobre la ganancia media en conejos con alimento concentrado comercial tipo único, y ad-libitum, hasta los 75 días de vida, procedentes de hembras primiparas. Para la evaluación estadística se empleó un diseño completamente aleatorio (DCA) con cuatro repeticiones por periodos de destete. Cada unidad experimental o repetición correspondió a una camada, en las que se registraron loe pesos vivos cada 15 días y el número de crías vivas por camada. Esta última característica con el objetivo de corregir las ganancias a un tamaño de camada uniforme de existir regresión lineal significativa. Cada camada se alojó en una jaula de 0.49 m2. En el análisis de varianza (ANDEVA) dé la ganancia media por gazapo al cabo de 30 días, se observaron diferencias significativas entre periodos de destete resultando un promedio de 0,344 kg y 0.510 kg para destetes de 15 días y 30 días respectivamente. En el Análisis de varianza de la ganancia media por gazapo al cabo de 45, 60 y 75 días, se observaron diferencias no significativas al 10%. Resultado que se corroboró con el procedimiento de comparación de medias de Duncan. Las ganancias medias por gazapo obtenido en las camadas a los 75 días de vida resultó de 1.676 kg, 1. 939 kg y 1.846 kg para los destete de 15, 30 y 45 días respectivamente. Durante. El ensayo fue evidente el estrés post destete, acentuándose más en las camadas destetadas a los 15 días. Analizando el efecto de los períodos de destete sobre la ganancia media en conejos a los 45, 60 y 75 días de vida. Se determinó que dicho efecto no es significativo debido al rango de ganancia media mostrado por las variables en estudio y que estas no fueron afectadas por la covariable número de conejos por camada.

Catastrophic Rupture Induced Damage Coalescence in Heterogeneous Brittle Media

In heterogeneous brittle media, the evolution of damage is strongly influenced by the multiscale coupling effect. To better understand this effect, we perform a detailed investigation of the damage evolution, with particular attention focused on the catastrophe transition. We use an adaptive multiscale finite-element model (MFEM) to simulate the damage evolution and the catastrophic failure of heterogeneous brittle media. Both plane stress and plane strain cases are investigated for a heterogeneous medium whose initial shear strength follows the Weibull distribution. Damage is induced through the application of the Coulomb failure criterion to each element, and the element mesh is refined where the failure criterion is met. We found that as damage accumulates, there is a stronger and stronger nonlinear increase in stress and the stress redistribution distance. The coupling of the dynamic stress redistribution and the heterogeneity at different scales result in an inverse cascade of damage cluster size, which represents rapid coalescence of damage at the catastrophe transition.

Long-Range Stress Redistribution Resulting From Damage in Heterogeneous Media

It has been shown in CA simulations and data analysis of earthquakes that declustered or characteristic large earthquakes may occur with long-range stress redistribution. In order to understand long-range stress redistribution, we propose a linear-elastic but heterogeneous-brittle model. The stress redistribution in the heterogeneous-brittle medium implies a longer-range interaction than that in an elastic medium. Therefore, it is surmised that the longer-range stress redistribution resulting from damage in heterogeneous media may be a plausible mechanism governing main shocks.