An enthalpic approach to delineate the interactions of cations of imidazolium-based ionic liquids with molecular solvents

We present a systematic investigation on the enthalpic assessment of the interactions operating between the cation and anion of four imidazolium ionic liquids with aqueous and various nonaqueous solvents. Accurate experimental information gathered with the help of an isothermal titration calorimeter at 298.15 K has been analyzed for excess partial molar enthalpy of the ionic liquid, H(IL)(E), in terms of hydrophobic and solvation effects. The variations in the limiting excess partial molar enthalpy of the ionic liquid, H(IL)(E, ∞), have been correlated with solvent properties. We have quantified the enthalpic effects due to dissociation of ionic liquids in very dilute solutions and to clathrate formation with the increasing concentration of ionic liquid. A change in enthalpic behavior from endothermic to exothermic is observed on increasing the carbon chain length attached to the imidazolium ring. The solvent reorganization around the cationic species has been unraveled by employing the ionic liquid interaction parameters called as H(IL-IL)(E) deduced from the H(IL)(E) data. The apparent relative molar enthalpy, φ(L), derived from H(IL)(E) data has been examined in the light of the specific ion interaction theory as advanced by Pitzer with accurate results.     

Diode‐Like I–V Characteristics of a Nonplanar Polyaromatic Compound: a Spectroscopic Study of Isolated and Stacked Dibenzo[g,p]chrysene

In this scanning‐tunneling‐microscopy/spectroscopy study (STM/STS), samples of isolated and close‐packed dibenzo[g,p]chrysene (DBC), a nonplanar polyaromatic compound, are used as model systems to demonstrate the effect of intermolecular interactions on the electronic structures. For dropcast films, DBC molecules adopt an edge‐on orientation in a close‐packed structure on graphite. Isolated DBC molecules are prepared on graphite from a DBC‐coated STM tip by a ca. 7 V/10 μs pulse. STS spectra for both isolated‐ and close‐packed DBC molecules exhibit diode‐like I–V curves in which the latter shows a turn‐on voltage (0.47 V) smaller than that of the former (0.91 V). The diode‐like behaviors are attributed to the more‐facile tunneling of electrons through the HOMO of DBC than through the LUMO. The reduced turn‐on voltage for the films is ascribed to the diminished HOMO–LUMO gap based on the results of DFT (density functional theory) simulations for the energy‐level couplings of π‐stacked DBC molecules.     

Shale-Gas Permeability and Diffusivity Inferred by Improved Formulation of Relevant Retention and Transport Mechanisms

A theoretically improved model incorporating the relevant mechanisms of gas retention and transport in gas-bearing shale formations is presented for determination of intrinsic gas permeability and diffusivity. This is accomplished by considering the various flow regimes according to a unified Hagen–Poiseuille-type equation, fully compressible treatment of gas and shale properties, and numerical solution of the non-linear pressure equation. The present model can accommodate a wide range of fundamental flow mechanisms, such as continuum, slip, transition, and free molecular flow, depending on the prevailing flow conditions characterized by the Knudsen number. The model indicates that rigorous determination of shale-gas permeability and diffusivity requires the characterization of various important parameters included in the present phenomenological modeling approach, many of which are not considered in previous studies. It is demonstrated that the improved model matches a set of experimental data better than a previous attempt. It is concluded that the improved model provides a more accurate means of analysis and interpretation of the pressure-pulse decay tests than the previous models which inherently consider a Darcian flow and neglect the variation of parameters with pressure.     

Impacts of TV and radio advertisements on the dynamics of an infectious disease: A modeling study

TV and radio advertisements are widely acknowledged as important interventions in raising issues of public health care and play promising role to control the infection through propagating awareness among the individuals. In this paper, a nonlinear susceptible‐infected‐susceptible (SIS) model is proposed and analyzed to see the impacts of TV and radio advertisements on the spread of influenza epidemic. In the model formulation, it is assumed that the susceptible individuals contract infection through the direct contact with infected individuals. The information regarding the protection against the disease is propagated via TV and radio advertisements, and their growth rates are assumed to be proportional to the fraction of infected individuals. However, the growth rate of TV advertisements decreases with the increase in number of aware individuals. The information broadcasted through TV and radio advertisements induces behavioral changes among the susceptible individuals, and they form an isolated aware class. The epidemiological feasible equilibria, their stability properties, and direction of bifurcation are discussed. The expression for modified basic reproduction number is obtained. The model analysis shows that the dissemination rate of awareness among susceptible individuals due to TV and radio advertisements and baseline number of TV and radio advertisements have potential to reduce the epidemic peak and, thus, control the spread of infection. Further, the analytical findings are well supported through numerical simulation.     

Molecular orbital study of excited state geometry of substituted benzenes

The liquid-like structure of a polystyrene latex solution of particle size 109 nm and its dependence on the ionic strength of added sodium chloride is investigated via the static light scattering structure factor S(Q). The experimental S(Q)s are compared with structure factors derived in the rescaled mean spherical approximation (RMSA) of Hansen and Hayter. After adjustment of the macromolecular charge Z _M such that the neat (salt free) latex solution is best represented by the RMSA, the experimental structure factors obtained after addition of salt can adequately be accounted for in terms of the RMSA by merely readjusting the ionic strength in the calculations. Our investigation indicates that the RMSA and the underlying screened Coulomb potential are suited for a detailed simulation of the structure and structural changes due to a variation of the ionic strength of liquid-like ordered solutions.     

Electrical characterization of PVA-based nanocomposite electrolyte nanofibre mats doped with a multiwalled carbon nanotube

An attempt has been made to prepare and characterise ammonium thiocyanate (NH₄SCN) salt and a multiwall carbon nanotube (MWNT)-doped polyvinyl alcohol-based nanofibre mats using an electrospinning process. The X-ray diffraction result shows an improvement in the amorphous nature of composite electrolyte fibre mats with increasing concentrations of the MWNT filler. The DSC behaviour of these nanofibre mat exhibits better thermal response upon dispersal of the filler. Composite electrolyte nanofibre mat doped with 6 wt% MWNT shows optimum conductivity, viz., 5.8?×?10^?4 Scm^?1. The temperature dependence of the bulk electrical conductivity displays a combination of Arrhenius and Vogel–Tammam–Fulcher nature. Dielectric loss studies have also been used to understand the conduction process in the system. Jonscher power law seems to be obeyed during ac conductivity measurements of the fibre mats.     

Methyl hydrogen peroxide dimer: A structural study

Methyl hydrogen peroxide (MHP) exhibits a tendency to form a stable dimer by hydrogen-bonding. Ab initio theoretical investigations on methyl hydrogen peroxide dimer (MHPD) carried out herein lead to several energetically stable structures that have a direct bearing on the reactivity of the monomer in terms of its molecular electrostatic potential (MESP). To gauge the role played by the electron-correlation in lending stability to MHP and its dimer, we employ the density functional theory (DFT) (as implemented by B3LYP-functional), and subsequently second order Møller-Plesset (MP2) perturbation theory, using the basis sets 6-31G(d, p) and 6-311++G(2d, 2p). Simulated infra-red vibrational spectra lead to spectral intensity redistribution upon dimerization. Energetically the lowest MHPD is endowed with inversion symmetry and has two hydrogen bonds, while three other structures emerge: one energetically very close with two H-bonds, and the two others, with three H-bonds each, yet higher by about 2 kcal mol⁻¹.     

Heteroaryl substituted ansa‐titanocene anti‐cancer drugs derived from fulvenes and titanium dichloride

Starting from 2‐furylfulvene (1a) , 2‐thiophenylfulvene (1b) , and 1‐methyl‐2‐pyrrolylfulvene (1c), [1,2‐di(cyclopentadienyl)‐1,2‐di‐(2‐furyl)ethanediyl] titanium dichloride (2a) , [1,2‐di(cyclopentadienyl)‐1,2‐di‐(2‐thiophenyl)ethanediyl] titanium dichloride (2b) , and [1,2‐di(cyclopentadienyl)‐1,2‐bis‐(1‐methyl‐2‐pyrrolyl)ethanediyl] titanium dichloride (2c) were synthesized. When titanocenes (2a–c) were tested against pig kidney carcinoma cells (LLC‐PK), inhibitory concentrations (50%) of 4.5 × 10^?4 M , 2.9 × 10^?4 M and 2.0 × 10^?4 M respectively were observed. Copyright © 2005 John Wiley & Sons, Ltd.     

Characterizing the coating and size-resolved oxidative stability of carbon-coated aluminum nanoparticles by single-particle mass-spectrometry

Aluminum nanoparticles are of significant interest in enhancing the rate of energy release from propellants. One of the major impediments to their use is that bare aluminum is highly reactive, while oxide coated aluminum significantly decreases overall performance. We investigate creating aluminum nanoparticles with a thin carbon coating using either a laser induced plasma or a DC plasma-arc. The carbon coating was created by injecting ethylene (C₂H₄) directly downstream of the plasma. The elemental composition of the coated aluminum nanoparticles was measured in real time with a recently developed quantitative single particle mass spectrometer (SPMS). We found that the aluminum nanoparticles were coated with a carbon layer of thickness around 1–3 nm.The thermal and oxidative stability of these particles was determined by passing the aerosols through a heated flow reactor in a carrier flow of either air or argon, and measuring the aluminum, carbon and oxygen content in the particles with the single particle mass spectrometer. We found that below 700°C the coating was stable, but that the coating oxidized above ∼ ∼800°C. In contrast the carbon coating was thermally stable above ∼ ∼900°C. These results indicate that a carbon coating may be a suitable passivating agent.     

Environmentally benign synthesis of sydnone containing 1,3,4-thiadiazines under microwave and solvent-free conditions

Novel, convenient and benign synthesis of 2-arylamino-5-(3′-arylsydnone-4-yl)-1,3,4-thiadiazines 3a-l by the interaction of 3-substituted-4-bromoacetyl sydnones 1 with substituted thiosemicarbazides 2 under MW irradiation and solvent-free condition is described.