Characterization of C4H in the A2Π and X2Σ+ states by double resonance four-wave mixing

The B(2)Π-X(2)Σ(+) electronic spectrum of C(4)H has been studied by degenerate and double resonance four-wave mixing. The technique identifies vibrational levels in the X(2)Σ(+) ground state. Its sensitivity and unique characteristics permit detection of new levels. The A(2)Π state lying 222 cm(-1) above the X(2)Σ ground state is also observed, confirming the analysis from anion photoelectron spectroscopy but with improved accuracy. Vibrational level determination in the A(2)Π electronic manifold up to 700 cm(-1) above v = 0 is made. A Renner-Teller analysis is carried out for the two lowest bending modes v(6) and v(7) in the A(2)Π state by diagonalization of the effective Hamiltonian matrix. The Renner-Teller parameters ∈(6), ∈(7), and ∈(67), the vibrations ω(6) and ω(7) and the spin-orbit coupling constant A(so) are determined.     

Symmetric bifurcated halogen bonds: substituent and cooperative effects

ABSTRACT

The aim of this study is to investigate the geometries, interaction energies and bonding properties of the symmetrical bifurcated halogen bond interactions (BXBs) by means of ab initio calculations. For this purpose, the NCX (X = Cl, Br) molecule is paired with a series of N-formyl formamide (NFF) derivatives (NFF-Z, Z = H, CN, CCH, OH, CH₃ and Li), and the properties of the resulting complexes are studied by molecular electrostatic potential, quantum theory of atoms in molecules, noncovalent interaction index and natural bond orbital analyses. For a fixed NCX molecule, interaction energies increase in the order of Z = Li > CH₃ > H > OH > CCH > CN. We found a strong correlation between the interaction energies of NCX:NFF-Z complexes and molecular electrostatic potential minimum values associated with NFF-Z monomers. Moreover, cooperative effects between BXB and X???N halogen bond interactions are studied in the ternary NCX:NCX:NFF-Z systems. Our results indicate that the strength of BXB interactions in the ternary complexes is enhanced by the presence of X???N bonds. Besides, cooperativity effects tend to increase the covalency of BXBs in these systems.     

Design,synthesis and characterization of tin‐based cancer chemotherapy drug entity: In vitro DNA binding,cleavage, induction of cancer cell apoptosis by triggering DNA damage‐mediated p53 phosphorylation and molecular docking

A new organotin complex derived from propyl gallate and 1,10‐phenanthroline was designed, synthesized and characterized using spectroscopic and elemental analytical methods. The underlying mechanisms of the anticancer action of the tin complex were further elucidated by evaluating its in vitro DNA interaction and the regulating signaling pathways. Our results showed that the tin complex could effectively activate DNA strand breaks in MCF‐7 cells in a dose‐dependent manner after cellular internalization. Phosphorylation of a DNA damage marker, histone H2A.X (Ser139), was thus upregulated in treated cells. Additionally, our results indicate that p53 is phosphorylated in response to DNA damage, and that this phosphorylation may be involved in the subsequent induction and activation of p53. In vitro DNA binding of the complex in Tris–HCl buffer was studied using various biophysical methods, revealing that the tin complex binds to DNA non‐covalently via electrostatic interaction. The higher K_b value of the complex suggested greater DNA binding propensity. Further, to evaluate the mode of action at the molecular level, interaction studies of the tin complex with nucleotide (5′‐GMP) were carried out. The complex exhibits DNA cleavage activity with supercoiled pBR322 in the presence of different activators. The complex cleaves DNA efficiently via oxidative cleavage pathway. Molecular docking studies were performed to understand the binding mode of the tin complex with DNA (PDB ID: 1BNA).     

Optimization volumetric heating in condensing steam flow by a novel method

Journal of Thermal Analysis and Calorimetry - In the last stages of steam turbines, the formation of liquid droplets causes losses and reduces turbine efficiency. One of the major problems of wet...     

Flux modelling in the finite-volume lattice Boltzmann approach

In this article, a novel approach for flux treatment is presented in conjunction with cell-centred Finite-Volume Lattice Boltzmann Method (FVLBM). The distribution functions are determined by using a pressure-based flux weighting factor on a D₂Q₉ lattice. A consistent open and solid boundary treatment is also addressed, which resulted in a wider domain of stability and faster convergence. For time discretisation, a fifth-order Runge–Kutta algorithm was applied. An in-house FORTRAN code has been written by the authors which uses the time-marching along with FVLBM. Two test cases, namely, flow over a backward-facing step and around a circular cylinder are carried out. The results are compared with the available solutions in which favourable agreement was observed.     

Developing mixed convection in vertical eccentric annuli

This paper deals with the problem of combined (forced–free) convection in vertical eccentric annuli with simultaneously developing hydrodynamic and thermal boundary layers. A bipolar model has been developed and a numerical algorithm for solving this model is outlined. Results, not available in the literature, are presented for the developing velocity profiles, axial variation of pressure, full development length, and heat transfer parameters under thermal boundary conditions of having one of the annulus boundaries at a constant temperature while the other boundary is insulated. Both aiding and opposing free convection have been considered and possibilities of flow reversal occurrence have also been checked. After a distance from the channel entrance and provided that the value of Gr/Re is sufficiently large, aiding free convection can develop to overcome the fluid friction and the eccentric annular channel eventually works as a diffuser. The value of Gr/Re for which a vertical eccentric annular channel can work as a diffuser decreases as the eccentricity increases. The axial distance from the entrance at which the channel starts to work as a diffuser decreases as Gr/Re increases.     

Application of Si‐doped graphene as a metal‐free catalyst for decomposition of formic acid: A theoretical study

Using density functional theory calculations, the adsorption and catalytic decomposition of formic acid (HCOOH) over Si‐doped graphene are investigated. For the stable adsorption geometries of HCOOH over Si‐doped graphene, the electronic structure properties are analyzed by adsorption energy, density of states, and charge density difference. A comparison of the reaction pathways reveals that both dehydration and dehydrogenation of HCOOH can occur over Si‐doped graphene. The estimated reaction energies and the activation barriers suggest that for the dehydration of HCOOH on the Si‐doped graphene, the rate‐controlling step is H + OH → H₂O reaction. For the dehydrogenation of HCOOH, the rate‐determining step is the breaking of the C? H bond of the HCOO group to form the CO₂ molecule and the atomic H. Our results reveal that the low cost Si‐doped graphene can be used as an efficient nonmetal catalyst for O? H bond cleavage of HCOOH. © 2015 Wiley Periodicals, Inc.     

Cu(II)-β-cyclodextrin-catalyzed synthesis of spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitrile derivatives

Cu(II)-β-cyclodextrin-catalyzed synthesis of spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitriles through the reaction of isatin derivatives, 4-hydroxycoumarin, and malononitrile in ethanol at room temperature.     

Electrochemical Oxidation of Desipramine Drug in the Presence of 4,6‐Dimethylpyrimidine‐2‐thiol Nucleophile in Aqueous Acidic Medium

Electrochemical oxidation of desipramine (DES) has been studied in the presence of 4,6‐dimethylpyrimidine‐2‐thiol (DMPT) as nucleophile in acidic medium by means of cyclic voltammetry, controlled‐potential electrolysis and spectroscopic data, as diagnostic techniques. Voltammetric studies of electro‐oxidation of desipramine were realized in a range of pH 1.0 to 8.0 in the absence and presence of DMPT. The results indicate the participation of the product of electrochemical oxidation of desipramine in the reaction with DMPT with ECEC electrochemical mechanism. However, the voltammetry and coulometry results imply existence of a catalytic (EC′) electrochemical mechanism in parallel with ECEC electrochemical mechanism. The product has been characterized by IR, ¹H NMR, ¹³C NMR and MS methods.     

Defining the characteristics of spherical Janus particles by investigating the behavior of their corresponding particles at the oil/water interface in a Pickering emulsion

In this study, a new analytical/experimental method is proposed in order to investigate the adsorption of different-sized spherical silica particles at the oil/water interface in a Pickering emulsion system as a well-known method to produce Janus particles. Accordingly, the characteristic of the produced silica Janus particles was defined based on their penetration depth into dispersed oil droplets. To ensure the accuracy of the method, the penetration depth of silica particles was also measured using field emission scanning electron microscopy images of solidified oil droplets covered with particles. The results revealed that the penetration depth increases with the size of the particles.