Multiple Scenario Generation of Subsurface Models:Consistent Integration of Information from Geophysical and Geological Data throuh Combination of Probabilistic Inverse Problem Theory and Geostatistics

Neutrinos with energies above 1017 eV are detectable with the Surface Detector Array of the Pierre Auger Observatory. The identification is efficiently performed for neutrinos of all flavors interacting in the atmosphere at large zenith angles, as well as for Earth-skimming \u3c4 neutrinos with nearly tangential trajectories relative to the Earth. No neutrino candidates were found in 3c 14.7 years of data taken up to 31 August 2018. This leads to restrictive upper bounds on their flux. The 90% C.L. single-flavor limit to the diffuse flux of ultra-high-energy neutrinos with an E\u3bd-2 spectrum in the energy range 1.0 7 1017 eV -2.5 7 1019 eV is E2 dN\u3bd/dE\u3bd < 4.4 7 10-9 GeV cm-2 s-1 sr-1, placing strong constraints on several models of neutrino production at EeV energies and on the properties of the sources of ultra-high-energy cosmic rays

On the physical origins of interaction-induced vibrational (hyper)polarizabilities

This paper presents the results of a pioneering exploration of the physical origins of vibrational contributions to the interaction-induced electric properties of molecular complexes. In order to analyze the excess nuclear relaxation (hyper)polarizabilities, a new scheme was proposed which relies on the computationally efficient Bishop-Hasan-Kirtman method for determining the nuclear relaxation contributions to electric properties. The extension presented herein is general and can be used with any interaction-energy partitioning method. As an example, in this study we employed the variational-perturbational interaction-energy decomposition scheme (at the MP2/aug-cc-pVQZ level) and the extended transition state method by employing three exchange-correlation functionals (BLYP, LC-BLYP, and LC-BLYP-dDsC) to study the excess properties of the HCN dimer. It was observed that the first-order electrostatic contribution to the excess nuclear relaxation polarizability cancels with the negative exchange repulsion term out to a large extent, resulting in a positive value of Δαnr due to the contributions from the delocalization and the dispersion terms. In the case of the excess nuclear relaxation first hyperpolarizability, the pattern of interaction contributions is very similar to that for Δαnr, both in terms of their sign as well as relative magnitude. Finally, our results show that the LC-BLYP and LC-BLYP-dDsC functionals, which yield smaller values of the orbital relaxation term than BLYP, are more successful in predicting excess propertiesR. Z. gratefully acknowledges support from the National Science Centre, Poland (Grant No. 2015/19/B/ST4/01881). M. G.-B. and J. M. L. thank the Spanish Ministerio de Economía y competividad (MINECO, CTQ2014-52525-P) and the Generalitat de Catalunya project number 2014SGR931). M. M. acknowledges the financial support of the Slovak Research and Development Agency (project No. APVV-15-0105

Mechanochemical assisted chemoselective and stereoselective hydrogen-bonding catalyzed addition of dithiomalonates to enones

Dithiomalonates proved to be active nucleophiles in the stereoselective additions to chalcones, dienones, and en-ynones affording the desired Michael adducts with good to high yields and enantioselectivities. In contrast, the analogous dibenzyl malonate remained inactive. Bifunctional Cinchona-based squaramides secured the effective chirality transfer and the selectivity towards Michael adducts of various bisthiomalonates following the soft enolization approach. The thioester’s nature impacted the reactivity and stability of the reactants or products. While the reactions performed in solution led to the products, the required time along with byproducts formation such as thio-Michael adducts, limiting the applicability of reactive dithioesters. On the contrary, reactions performed under solvent-free, ball milling conditions furnished adducts up to six times faster, with subtly or no byproduct generation. Therefore, the mechanochemical approach revealed to be an effective tool for supporting the hardly effective reactions under standard solution conditions. Detailed KS-DFT studies supported the experimental observations shedding more light on the intricate active nucleophile formation, and different chemical reaction pathways, as well as indicating the crucial transitions state governing the observed stereoselectivitie

Light-Induced Modulation of Chiral Functions in G-Quadruplex-Photochrome Systems

The design of artificially engineered chiral structures has received much attention, but the implementation of dynamic functions to modulate the chiroptical response of the systems is less explored. Here, we present a light-responsive G-quadruplex (G4)-based assembly in which chirality enrichment is induced, tuned, and fueled by molecular switches. In particular, the mirror-image dependence on photoactivated azo molecules, undergoing trans-to-cis isomerization, shows chiral recognition effects on the inherent flexibility and conformational diversity of DNA G4s having distinct handedness (right- and left-handed). Through a detailed experimental and computational analysis, we bring compelling evidence on the binding mode of the photochromes on G4s, and we rationalize the origin of the chirality effect that is associated with the complexation event

Files from: The Ethidium-UA/AU Intercalation Site: Effect of Model Fragmentation and Backbone Charge State

<p>Atomic coordinates for the molecular systems studied in <a href="http://dx.doi.org/10.1021/ct200121f">The ethidium-UA/AU intercalation site: effect of model fragmentation and backbone charge state, <em>J. Chem. Theory Comp.</em>, <strong>2011</strong>, 7, pp 2600-2609</a>.</p