A generalized operational formula based on total electronic densities to obtain 3D pictures of the dual descriptor to reveal nucleophilic and electrophilic sites accurately on closed-shell molecules

Indexación: Wiley Online Library. Online Version of Record published before inclusion in an issue http://onlinelibrary.wiley.com/doi/10.1002/jcc.24453/fullBy means of the conceptual density functional theory, the so-called dual descriptor (DD) has been adapted to be used in any closed-shell molecule that presents degeneracy in its frontier molecular orbitals. The latter is of paramount importance because a correct description of local reactivity will allow to predict the most favorable sites on a molecule to undergo nucleophilic or electrophilic attacks; on the contrary, an incomplete description of local reactivity might have serio us consequences, particularly for those experimental chemists that have the need of getting an insight about reactivity of chemical reagents before using them in synthesis to obtain a new compound. In the present work, the old approach based only on electronic densities of frontier molecular orbitals is replaced by the most accurate procedure that implies the use of total electronic densities thus keeping consistency with the essential principle of the DFT in which the electronic density is the fundamental variable and not the molecular orbitals. As a result of the present work, the DD will be able to properly describe local reactivities only in terms of total electronic densities. To test the proposed operational formula, 12 very common molecules were selected as the original definition of the DD was not able to describe their local reactivities properly. The ethylene molecule was additionally used to test the capability of the proposed operational formula to reveal a correct local reactivity even in absence of degeneracy in frontier molecular orbitals.http://onlinelibrary.wiley.com/doi/10.1002/jcc.24453/ful

Evaluación Bidimensional y Tridimensional de la Vía Aérea Superior

Indexación: Scopus; Scielo.The aim of this study was to validate and correlate the two-dimensional (2D) with the three-dimensional (3D) measures of the upper airway assessment. Lateral cephalograms and cone beam CT of 100 adult subjects were used to perform a 2D and 3D assessment of the upper airway. Spearman correlation coefficient was used to determine whether there was correlation between variables. Additionally, specificity, sensitivity, negative predictive value and positive predictive value was calculated for the 2D assessment of the upper airway. Correlation between all two and three dimensional variables was found. In the nasopharynx and oropharynx, a weak correlation (r <0.51) was found; in the oropharynx a moderate one (0.50 <r <0.76). The validity tests of the 2D assessment resulted in a 73% sensitivity, 45% specificity, 93% negative predictive value and 14% positive predictive value for the nasopharynx; 100% sensitivity, 51% specificity, 100% negative predictive value and 6% positive predictive value in the oropharynx and 100% sensitivity, 71% specificity, 100% negative predictive value and 13% positive predictive value in the hypopharynx. There is a weak correlation between the 2D and 3D assessment of the upper airway. However, the lateral cephalogram has a high sensitivity and high negative predictive value, therefore, an additional complementary examination would not be necessary if the 2D assessment of the upper airway throws a normal result.http://ref.scielo.org/mpkrn

The wind of rotating B supergiants, I : domains of slow and fast solution regimes

In the scenario of rotating radiation-driven wind theory for massive stars, three types of stationary hydrodynamic solutions are currently known: the classical ( fast) m-CAK solution, the Ω-slow solution that arises for fast rotators, and the so-called δ-slow solution if high values of the δ line-force parameter are allowed independently of the rotation speed. Compared to the fast solution, both ?slow solutions? have lower terminal velocities. As the study ofthe parameter domain for the slow solution is still incomplete, we perform a comprehensive analysis of the distinctive flow regimes for B supergiants that emerge from a fine grid of rotation values, Ω, and various ionizationconditions in the wind (δ) parameter. The wind ionization defines two domains: one for fast outflowing winds and the other for slow expanding flows. Both domains are clear-cut by a gap, where a kink/plateau structure of thevelocity law could exist for a finite interval of δ. The location and width of the gap depend on Teff and Ω. There is a smooth and continuous transition between the Ω-slow and δ-slow regimes, a single Ω δ-slow regime. We discussdifferent situations where the slow solutions can be found and the possibility of a switch between fast and slow solutions in B supergiant winds. We compare the theoretical terminal velocity with observations of B and Asupergiants and find that the fast regime prevails mostly for early B supergiants while the slow wind regime matches better for A and B mid- and late-type supergiants.Fil: Venero, Roberto Oscar José. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; ArgentinaFil: Curé, M.. Universidad de Valparaíso; ChileFil: Cidale, Lydia Sonia. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; ArgentinaFil: Araya, I.. Universidad de Valparaíso; Chil

Long-term Variability of H2_2CO Masers in Star-forming Regions

We present results of a multi-epoch monitoring program on variability of 6$\,$cm formaldehyde (H$_2$CO) masers in the massive star forming region NGC$\,$7538$\,$IRS$\,$1 from 2008 to 2015 conducted with the GBT, WSRT, and VLA. We found that the similar variability behaviors of the two formaldehyde maser velocity components in NGC$\,$7538$\,$IRS$\,$1 (which was pointed out by Araya and collaborators in 2007) have continued. The possibility that the variability is caused by changes in the maser amplification path in regions with similar morphology and kinematics is discussed. We also observed 12.2$\,$GHz methanol and 22.2$\,$GHz water masers toward NGC$\,$7538$\,$IRS$\,$1. The brightest maser components of CH$_3$OH and H$_2$O species show a decrease in flux density as a function of time. The brightest H$_2$CO maser component also shows a decrease in flux density and has a similar LSR velocity to the brightest H$_2$O and 12.2$\,$GHz CH$_3$OH masers. The line parameters of radio recombination lines and the 20.17 and 20.97$\,$GHz CH$_3$OH transitions in NGC$\,$7538$\,$IRS$\,$1 are also reported. In addition, we observed five other 6$\,$cm formaldehyde maser regions. We found no evidence of significant variability of the 6$\,$cm masers in these regions with respect to previous observations, the only possible exception being the maser in G29.96$-$0.02. All six sources were also observed in the H$_2^{13}$CO isotopologue transition of the 6$\,$cm H$_2$CO line; H$_2^{13}$CO absorption was detected in five of the sources. Estimated column density ratios [H$_2^{12}$CO]/[H$_2^{13}$CO] are reported.Comment: 29 pages, 9 figure

Self-Assembly Behavior of Amphiphilic Janus Dendrimers in Water: A Combined Experimental and Coarse-Grained Molecular Dynamics Simulation Approach

Indexación: Scopus.Acknowledgments: M.E.E.G. thank the Ph. D. scholarship (251115) from CONACyT. The authors would like to thank: Luis Elizalde-Herrera (CIQA) for his help running the NMR spectra; Gloria Macedo-Raygoza and Miguel J. Beltrán-García (UAG), for their help in the measuring of MALDI-TOF mass spectra; and Maricela Rodríguez-Nieto and Jorge Luis Menchaca (UANL), for their help with the AFM measurements. FDGN thanks to the USA Air Force Office of Scientific Research Awards.Amphiphilic Janus dendrimers (JDs) are repetitively branched molecules with hydrophilic and hydrophobic components that self-assemble in water to form a variety of morphologies, including vesicles analogous to liposomes with potential pharmaceutical and medical application. To date, the self-assembly of JDs has not been fully investigated thus it is important to gain insight into its mechanism and dependence on JDs’ molecular structure. In this study, the aggregation behavior in water of a second-generation bis-MPA JD was evaluated using experimental and computational methods. Dispersions of JDs in water were carried out using the thin-film hydration and ethanol injection methods. Resulting assemblies were characterized by dynamic light scattering, confocal microscopy, and atomic force microscopy. Furthermore, a coarse-grained molecular dynamics (CG-MD) simulation was performed to study the mechanism of JDs aggregation. The obtaining of assemblies in water with no interdigitated bilayers was confirmed by the experimental characterization and CG-MD simulation. Assemblies with dendrimersome characteristics were obtained using the ethanol injection method. The results of this study establish a relationship between the molecular structure of the JD and the properties of its aggregates in water. Thus, our findings could be relevant for the design of novel JDs with tailored assemblies suitable for drug delivery systems. © 2018 by the authors.https://www.mdpi.com/1420-3049/23/4/96

Diagnosis of educational needs for the implementation of blended courses based on the blended learning model. The case of the Social Sciences Faculty of the National University of Costa Rica

This study is accomplished from the educational needs assessment in the framework of educational research. The objective is to identify, analyse and assess human resources and materials. In this sense, didactic principles will also form part of the analysis. In particular, those applied in studies offered by the Social Sciences Faculty of the National University of Costa Rica (SSF) to implement blended courses based on the blended learning model. Quantitative and qualitative research techniques were used to gather information from a complementary approach, in order to describe and interpret the different sources. That process included three phases: document review; surveys done to students and teachers; structured interviews to school principals and deanship. The results show there are appropriate curricular elements to venture into innovation proposals regarding academic offer in terms of flexibility and ICT incorporation in training programs. Likewise, the blended learning is an option which contributes to the quality of education, access opportunities and the educational processes improvement

Subjects in the blended learning model design. Theoretical-methodological elements

Curriculum design at different levels explains the intentions of an educational project in its particular context. The subjects design is specified in micro planning, and orients didactics around the questions of the teaching and learning process in the classroom. This research was conducted in order to determine theoretical-methodological elements for the design of courses following the blended learning model. As point of departure, two questions were considered: How others do it? And what do we count on to be able to perform subjects based on this model? The method used was based on the case study, from a hermeneutic-phenomenological approach. Quantitative and qualitative techniques were also used such as surveys, interviews, and documentary analysis. Results are specified in a proposal that integrates three dimensions: intentions and principles, scope and development, and assessment

Analytical solutions for radiation-driven winds in massive stars, I: the fast regime

Accurate mass-loss rate estimates are crucial keys in the study of wind properties of massive stars and for testing different evolutionary scenarios. From a theoretical point of view, this implies solving a complex set of differential equations in which the radiation field and the hydrodynamics are strongly coupled. The use of an analytical expression to represent the radiation force and the solution of the equation of motion has many advantages over numerical integrations. Therefore, in this work, we present an analytical expression as a solution of the equation of motion for radiation-driven winds in terms of the force multiplier parameters. This analytical expression is obtained by employing the line acceleration expression given by Villata and the methodology proposed by Müller & Vink. On the other hand, we find useful relationships to determine the parameters for the line acceleration given by Müller & Vink in terms of the force multiplier parameters.Facultad de Ciencias Astronómicas y Geofísica