Interaction of different types of nanocages (Al12N12, Al12P12, B12N12, Be12O12, Mg12O12, Si12C12 and C24) with HCN and ClCN: DFT,TD-DFT,QTAIM, and NBO calculations

In this work, the ability of different types of nanocages including Al₁₂N₁₂, Al₁₂P₁₂, Be₁₂O₁₂, B₁₂N₁₂, Si₁₂C₁₂, Mg₁₂O₁₂ and C₂₄ for the adsorption and detection of poisonous gases HCN and ClCN has been investigated, theoretically using the D3 dispersion corrected density functional theory (DFT-D3). The absorption spectra of HCN–nanocage and ClCN–nanocage complexes were calculated by the time-dependent density functional theory (TD-DFT) and compared with the calculated absorption spectrum of isolated nanocage to investigate the ability of nanocage for sensing of HCN and ClCN gases. It was found that the strongest interaction between HCN (ClCN) molecule and nanocage takes place when the molecule is adsorbed via its N atom on the surface of nanocage except for C₂₄. Also, it was shown that the Al₁₂N₁₂ is the best adsorbent for HCN and ClCN gases among the selected nanocages and Si₁₂C₁₂ is the best sensor for the detection of these gases using the electroconductivity and absorption spectroscopy techniques.     

Investigation of substituent effects in aerogen‐bonding interaction between ZO3 (Z=Kr,Xe) and nitrogen bases

The substituent effects in aerogen bond interactions between ZO₃ (Z = Kr, Xe) and different nitrogen bases are studied at the MP2/aug‐cc‐pVTZ level of theory. The nitrogen bases include the sp bases NCH, NCF, NCCl, NCBr, NCCN, NCOH, NCCH₃ and the sp³ bases NH₃, NH₂F, NH₂Cl, NH₂Br, NH₂CN, NH₂OH, and NH₂CH₃. The nature of aerogen bonds in these complexes is analyzed by means of molecular electrostatic potential, electron localization function, quantum theory atoms in molecules, noncovalent interaction index, and natural bond orbital analyses. The interaction energy (E_int) ranges from ?4.59 to ?9.65 kcal/mol in the O₃Z···NCX complexes and from ?5.30 to ?13.57 kcal/mol in the O₃Z···NH₂X ones. The dominant charge‐transfer interaction in these complexes occurs across the aerogen bond from the nitrogen lone‐pair (n_N) of the Lewis base to the σ*_Z‐O antibonding orbital of the ZO₃. Besides, the formation of aerogen bond tends to decrease the ⁸³Kr or ¹³¹Xe chemical shielding values in these complexes. © 2016 Wiley Periodicals, Inc.     

Cooperative interaction between π-hole and single-electron σ-hole interactions in O2S···NCX···CH3 and O2Se···NCX···CH3 complexes (X = F,Cl, Br and I)

Ab initio calculations are performed to analyse the cooperative effects between π-hole and single-electron σ-hole interactions in O₂S···NCX···CH₃ and O₂Se···NCX···CH₃ complexes, where X = F, Cl, Br and I. These effects are investigated in terms of geometric and energetic features of the complexes, which are computed by UMP2/aug-cc-pVTZ(-PP) method. Our results indicate that the shortening of the each π-hole bond distance in the complexes is dependent on the strength of the σ-hole interaction. The maximum and minimum energetic cooperativity values correspond to the most and least stable complexes studied in the present work. The cooperativity between both types of interaction is chiefly caused by the electrostatic effects. The topological analysis, based on the quantum theory of atoms in molecules, is used to characterise the interactions and analyse their enhancement with varying electron density at bond critical points.     

Nano-sized silica supported FeCl3 as an efficient heterogeneous catalyst for the synthesis of 1,2,4-triazine derivatives

The one‐pot synthesis of a series of 1,2,4‐triazines from the reactions of semicarbazide or thiosemi‐carbazide with various α,β‐dicarbonyl compounds under reflux conditions in a EtOH‐H2O (9:1) mixture ...     

A Non-myopic Utility Function for Statistical Global Optimization Algorithms

The high cost of providing worst-case solutions to global optimization problems has motivated the development of average-case algorithms that rely on a statistical model of the objective function. The critical role of the statistical model is to guide the search for the optimum. The standard approach is to define a utility function u(x) that in a certain sense reflects the benefit of evaluating the function at x. A proper utility function needs to strike a balance between the immediate benefit of evaluating the function at x – a myopic consideration; and the overall effect of this choice on the performance of the algorithm – a global criterion. The utility functions currently used in this context are heuristically modified versions of some myopic utility functions. We propose using a new utility function that is provably a globally optimal utility function in a non-adaptive context (where the model of the function values remains unchanged). In the adaptive context, this utility function is not necessarily optimal, however, given its global nature, we expect that its use will lead to the improved performance of statistical global optimization algorithms. To illustrate the approach, and to test the above assertion, we apply this utility function to an existing adaptive multi-dimensional statistical global optimization algorithm and provide experimental comparisons with the original algorithm.     

Influence of photoperiod and running wheel access on the entrainment of split circadian rhythms in hamsters

Background  

In the laboratory, behavioral and physiological states of nocturnal rodents alternate, with a period near 24 h, between those appropriate for the night (e.g., elevated wheel-running activity and high melatonin secretion) and for the day (e.g., rest and low melatonin secretion). Under appropriate 24 h light:dark:light:dark conditions, however, rodents may be readily induced to express bimodal rest/activity cycles that reflect a global temporal reorganization of the central neural pacemaker in the hypothalamus. We examine here how the relative length of the light and dark phases of the environmental cycle influences this rhythm splitting and the necessity of a running wheel for expression of this entrainment condition.     

Spin-dependent resistivity at transitions between integer quantum hall states

The longitudinal resistivity at transitions between integer quantum Hall states in two-dimensional electrons confined to AlAs quantum wells is found to depend on the spin orientation of the partially filled Landau level in which the Fermi energy resides. The resistivity can be enhanced by an order of magnitude as the spin orientation of this energy level is aligned with the majority spin. We discuss possible causes and suggest a new explanation for the spikelike features observed at the edges of quantum Hall minima near Landau level crossings.     

Synthesis of benzodiazepines catalyzed by chitosan functionalized by triacid imide as a superior catalyst

Research on Chemical Intermediates - Chitosan functionalized by triacid imide has been applied as an effective catalyst for the synthesis of benzodiazepines by one-pot reactions of...     

Focused grid‐based resampling for protein docking and mapping

The fast Fourier transform (FFT) sampling algorithm has been used with success in application to protein‐protein docking and for protein mapping, the latter docking a variety of small organic molecules for the identification of binding hot spots on the target protein. Here we explore the local rather than global usage of the FFT sampling approach in docking applications. If the global FFT based search yields a near‐native cluster of docked structures for a protein complex, then focused resampling of the cluster generally leads to a substantial increase in the number of conformations close to the native structure. In protein mapping, focused resampling of the selected hot spot regions generally reveals further hot spots that, while not as strong as the primary hot spots, also contribute to ligand binding. The detection of additional ligand binding regions is shown by the improved overlap between hot spots and bound ligands. © 2016 Wiley Periodicals, Inc.