Differentially Selective Chemosensor with Fluorescence Off-On Responses on Cu2+ and Zn2+ Ions in Aqueous Media and Applications in Pyrophosphate Sensing, Live Cell Imaging, and Cytotoxicity

A new benzoyl hydrazone based chemosensor R is synthesized by Schiff base condensation of 2,6-diformyl-4-methylphenol and phenyl carbohydrazide and acts as a highly selective fluorescence sensor for Cu2+ and Zn2+ ions in aqueous media. The reaction of R with CuCl2 or ZnCl2 forms the corresponding dimeric dicopper(II) Cu-2(R)(CH3O)-(NO3)](2)(CH3O)(2) (R-Cu2+) and dizinc(1) Zn-2(R)(2)](NO3)(2) (R-Zn2+) complexes, which are characterized, as R, by conventional techniques including single-crystal X-ray analysis. Electronic absorption and fluorescence titration studies of R with different metal cations in a CH3CN/0.02 M HEPES buffer medium (pH = 7.3) show a highly selective binding affinity only toward Cu(2+)and Zn2+ ions even in the presence of other commonly coexisting ions such as Ne+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cd2+, and Hg2+. Quantification of the fluorescence titration analysis shows that the chemosensor R can indicate the presence of Cu2+ and Zn2+ even at very low concentrations of 17.3 and 16.5 ppb, respectively. R-Zn2+ acts as a selective metal-based fluorescent sensor for inorganic pyrophosphate ion (PPi) even in the presence of other common anions such as F-, Cl-, Br-, I-, CH3COO-, CO32-, HCO3-, N-3(-), SO42-, PPi, AMP, ADP, and ATP in an aqueous medium. The propensity of R as a bioimaging fluorescent probe to detect Cu2+ and Zn2+ ions in human cervical HeLa cancer cell lines and their cytotoxicity against human cervical (HeLa), breast cancer (MCF7), and noncancer breast epithelial (MCF10a) cells have also been investigated. R-Cu2+ shows better cytotoxicity and sensitivity toward cancer cells over noncancer cells than R and R-Zn2+ under identical conditions, with the appearance of apoptotic bodies.

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.

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.

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.

Interaction between a strategic mass media firm and a government

Resumen: Este artículo intenta teorizar acerca de la dinámica entre los medios masivos de comunicación y los gobiernos de los países latinoamericanos. Si bien en la última década los gobiernos atacaron públicamente a los medios de comunicación, se afirma que no se dio por las razones que dicen, sino más bien por asuntos económicos. Por lo tanto, se ha diseñado un modelo utilizando el método de “principal” vs “incumbente”, donde se alcanzará un equilibrio de Nash perfecto en subjuegos. Además de esto, se realiza un repaso por la literatura conocida, y concluye señalando las fortalezas y debilidades del modelo propuesto.

A geometry model for tortuosity of flow path in porous media

A simple geometry model for tortuosity of flow path in porous media is proposed based on the assumption that some particles in a porous medium are unrestrictedly overlapped and the others are not. The proposed model is expressed as a function of porosity and there is no empirical constant in this model. The model predictions are compared with those from available correlations obtained numerically and experimentally, both of which are in agreement with each other. The present model can also give the tortuosity with a good approximation near the percolation threshold. The validity of the present tortuosity model is thus verified.

Finding space to mental health : promoting mental health in adolescents (12 to 14 year olds): preliminary results of the intervention's effectiveness

Resumen: La salud mental y el bienestar son fundamentales para nuestra capacidad colectiva y individual como seres humanos de pensar, de exteriorizar los sentimientos, de establecer y mantener relaciones, para estudiar, para perseguir las actividades de ocio, para tomar decisiones diarias y para disfrutar de una vida plena. Una adolescencia saludable es un prerrequisito para una vida adulta saludable. Sin embargo, la realidad actual presenta un panorama preocupante. La formación del capital mental individual y colectivo - especialmente en las primeras etapas de la vida - está siendo retenida por una serie de riesgos evitables para la salud mental (World Health Organization [WHO], 2013). Los adolescentes del sur de Europa (región que ha sido más severamente afectada por la crisis financiera; e.g., Portugal) son señalados como un grupo extremadamente vulnerable, ya que su salud mental fácilmente podría ser influenciada por las dificultades económicas de sus padres y la escasez de solidaridad social (European Parliament, 2012). La promoción de la salud mental de los adolescentes es considerada como una preocupación fundamental (WHO, 2005a, 2013). En este ámbito, las intervenciones centradas en la promoción de la literacía de la salud mental han revelado importantes ventajas en la prevención, reconocimiento, intervención precoz y la reducción del estigma (Pinfold, Stuart, Thornicroft & Arboleda-Florez, 2005; Pinfold, Toulmin, Thornicroft, Huxley, Farmer & Graham, 2003; Schulze, Richter-Werling, Matschinger & Angermeyer, 2003; Stuart, 2006). En consonancia con los marcos de promoción de la salud mentales propuestos por la Organización Mundial de la Salud (2005a), tenemos que involucrar a jóvenes en los ambientes donde interactúan (Burns, 2011). Las escuelas son implícitamente uno de los locales más importantes para la promoción de la salud mental de los adolescentes (Barry, Clarke, Jenkins & Patel, 2013; WHO, 2001). El proyecto “Abrir Espacio para la Salud Mental – Promoción de la salud mental en adolescentes (12-14 años)” tiene como objetivo incrementar literacía de la salud mental en los jóvenes. En el primer año se ha desarrollado un instrumento de evaluación - Mental Health Literacy questionnaire (MHLq) - y la intervención para la promoción de la salud mental. La intervención consiste en 2 sesiones, 90 minutos cada una, implementadas con intervalo de una semana. Siguen una metodología interactiva, utilizando dinámicas de grupo, videos, música y discusión. El estudio de la eficacia de la intervención se lleva a cabo mediante un análisis pre y pos-test con el MHLq, utilizando un grupo experimental y un grupo de control. Este artículo presenta los resultados preliminares de la eficacia de la intervención de promoción de la salud mental en una muestra de 100 adolescentes portugueses (12-14 años). El pos-test mostró un incremento de los niveles de conocimientos de salud mental y estrategias de autoayuda. Los resultados sugieren que la intervención desarrollada parece ser adecuada al objetivo propuesto y refuerzan la creencia de que intervenciones escolares, sistemáticas y sostenibles, para la promoción de la salud mental con jóvenes, es un enfoque prometedor para la promoción de la literacía de la salud mental (Schulze et al., 2003; Rickwood et al., 2005; Corrigan et al., 2007; WHO, 2010).

Stress-distribution around a rigid line in dissimilar media

The elastic plane problem of a rigid line inclusion between two dissimilar media was considered. By solving the Riemann-Hilbert problem, the closed-form solution was obtained and the stress distribution around the rigid line was investigated. It was found that the modulus of the singular behavior of the stress remains proportional to the inverse square root of the distance from the rigid line end, but the stresses possess a pronounced oscillatory character as in the case of an interfacial crack tip.

Comparisons of static, quasi-static and dynamic 3D porous media scale network models for two-phase immiscible flow in porous media

A dynamic 3D pore-scale network model is formulated for investigating the effect of interfacial tension and oil-water viscosity during chemical flooding. The model takes into account both viscous and capillary forces in analyzing the impact of chemical properties on flow behavior or displacement configuration, while the static model with conventional invasion percolation algorithm incorporates the capillary pressure only. From comparisons of simulation results from these models. it indicates that the static pore scale network model can be used successfully when the capillary number is low. With the capillary increases due to the enhancement of water viscosity or decrease of interfacial tension, only the quasi-static and dynamic model can give insight into the displacement mechanisms.

A CE/SE Scheme for Flows in Porous Media and Its Applications

In this paper, a new computational scheme for solving flows in porous media was proposed. The scheme was based on an improved CE/SE method (the space-time Conservation Element and Solution Element method). We described porous flows by adopting DFB (Brinkman-Forchheimer extended Darcy) equation. The comparison between our computational results and Ghia's confirmed the high accuracy, resolution, and efficiency of our CE/SE scheme. The proposed first-order CE/SE scheme is a new reliable way for numerical simulations of flows in porous media. After investigation of effects of Darcy number on porous flow, it shows that Darcy number has dominant influence on porous flow for the Reynolds number and porosity considered.

Studies of Organic Molecule Recognition by Synthetic Cyclophane Receptors in Aqueous Media

The behaviors of six new cyclophane receptors for organic guest molecules in aqueous media are reported. These new hosts are modifications of more basic parent structures, and the main goal of their examination has been to determine how the modifications affect host selectivity for cationic guests. In particular, we have been interested in determining how additional non-covalent binding interactions can complement the cation-π interactions active in the parent systems. Three types of modifications were made to these systems. Firstly, neutral methoxy and bromine substituents were added to produce four of the six new macrocycles. Secondly, two additional aromatic rings (relative to the parent host) capable of making cation-π interactions with charged guest species were appended. Thirdly, a negatively charged carboxyl group was attached to produce a cavity in which electrostatic interactions should enhance cationic guest binding. ^1H-NMR and circular dichroic techniques were employed to determine the binding affinities of a wide variety of organic guests for the parent and modified structures in aqueous media.

Bromination of the parent host greatly enhances its binding in a general fashion, primarily as the result of hydrophobic interactions. The addition of methoxy groups does not enhance binding, apparently as a result of a collapse of the hosts into a conformation that is not suitable for binding. The appendage of extra aromatic rings enhances the binding of positively charged guests, most likely in response to more complete encapsulation of guest species. The addition of a negatively charged carboxylate enhances the binding to only selective groups of cationic guests. AM1 calculations of the electrostatic potentials of several guests molecules suggests that the enhancements seen with the modified receptor compared to the parent are most likely the result of close contact between regions of highest potential on the guest and the appended carboxylate.

Incoherent subharmonic light scattering in isotropic media

Incoherent subharmonic light scattering in isotropic media is a new kind of nonlinear light scattering, which involves single input photon and multiple output photons of equal frequency. We investigate theoretically the dependence of the subharmonic scattering intensity on the hyperpolarizability of molecules and the incident intensity using nonlinear optics theory similar to that used for Hyper-Rayleigh scattering and degenerate optical parametric oscillators. It is derived that the subharmonic scattering intensities grow exponentially or superexponentially with the hyperpolarizability of molecules and the incident intensity. (C) 2004 Elsevier B.V. All rights reserved.