Synthesis of Novel and Thermally Stable Water Insoluble Coumarin‐based Azo Dyes via a Mild and Green Procedure

A series of novel azo coumarin dyes were synthesized by the diazotization of 7‐amino coumarins in the presence of catalytic amounts of tungstate sulfuric acid (TSA) followed by coupling with phenol derivatives. Tungstate sulfuric acid catalyzes this reaction at room temperature and short reaction time with high yields.     

On Some Properties of Convolutions in Variable Exponent Lebesgue Spaces

A convolution in the variable exponent Lebesgue spaces \(L_{2\pi }^{p\left( \cdot \right) }\) is defined and its basic properties are investigated. It is also proved that this convolution can be approximated in \(L_{2\pi }^{p\left( \cdot \right) }\) by the finite linear combinations of Steklov means of the original function.     

Prediction of the penetrated rust into the microcracks of concrete caused by reinforcement corrosion

Consider a steel-rust-concrete composite consisting of a circular cylindrical concrete cover and a coaxial uniformly corroding steel reinforcement. Prediction of the amount of rust penetrated into the microcracks of concrete cover from a set of data measured at the surface of the concrete is of particular interest. The steel is assumed to be linear isotropic and rust follows a power law stress–strain relation. For the concrete, anisotropic behavior and post-cracking softening model is employed. The formulations lead to a nonlinear boundary value problem which is solved analytically. A key parameter β, defined as the ratio of the volume of corrosion products inside the cracks to the volume of the cracks, is calculated. With some efforts, this parameter is also extracted from the available theoretical and experimental studies for the purpose of comparison. The effects of the mechanical properties of rust and concrete on β is addressed.     

Tuning of carbon bonds by substituent effects: an ab initio study

ABSTRACT

An ab initio study, at the MP2/aug-cc-pVTZ level of theory, is performed to study σ-hole bond in binary XH₃C···CNY complexes, where X = CN, F, NO₂, CCH and Y = H, OH, NH₂, CH₃, C₂H₅, Li. This type of interaction is labelled as ‘carbon bond’, since a covalently bonded carbon atom acts as the Lewis acid in these systems. The geometrical and energetic parameters of the resulting complexes are analysed in details. The interaction energies of these complexes are between ?4.97 kJ/mol in (HCC)H₃C···CNH and ?23.07 kJ/mol in (O₂N)H₃C···CNLi. It is found that the electrostatic interaction plays a key role in the overall stabilisation of these carbon-bonded complexes. To deepen the understanding of the nature of the carbon-bonding, the molecular electrostatic potential, natural bond orbital, quantum theory of atoms in molecules and non-covalent interaction index analyses are also used. Our results indicate that the carbon bond is favoured over the C-H···C hydrogen bond in the all complexes considered and may suggest the possible important roles of the C···C interactions in the crystal growth and design.     

Cluster increments for macropolyhedral boranes

Cluster increments derived for individual cluster fragments reproduce the DFT computed relative stabilities of macropolyhedral boranes usually within +/-6 kcal mol(-1). A simple summation procedure helps to select the best partner for a given cluster fragment in order to construct the thermodynamically most stable macropolyhedral borane. Cluster increments are considerably smaller for nido-cluster fragments with an even number of vertexes than for odd nido-cluster fragments pointing towards high thermodynamic stability of macropolyhedral boranes with even numbered nido-units.     

Application of elastically supported single-walled carbon nanotubes for sensing arbitrarily attached nano-objects

The potential application of SWCNTs as mass nanosensors is examined for a wide range of boundary conditions. The SWCNT is modeled via nonlocal Rayleigh, Timoshenko, and higher-order beam theories. The added nano-objects are considered as rigid solids, which are attached to the SWCNT. The mass weight and rotary inertial effects of such nanoparticles are appropriately incorporated into the nonlocal equations of motion of each model. The discrete governing equation pertinent to each model is obtained using an effective meshless technique. The key factor in design of a mass nanosensor is to determine the amount of frequency shift due to the added nanoparticles. Through an inclusive parametric study, the roles of slenderness ratio of the SWCNT, small-scale parameter, mass weight, number of the attached nanoparticles, and the boundary conditions of the SWCNT on the frequency shift ratio of the first flexural vibration mode of the SWCNT as a mass sensor are also discussed.     

Microvascular blood flow with heat transfer in a wavy channel having electroosmotic effects

The present paper addresses microvascular blood flow with heat and mass transfer in complex wavy microchannel modulated by electroosmosis. Investigation is carried out with joule heating and chemical reaction effects. Further, viscous dissipation is also considered. Using Debye–Huckel, lubrication theory, and long wavelength approximations, analytical solutions of dimensionless boundary value problems are obtained. The impacts of different parameters are examined for temperature and concentration profile. Furthermore, nature of pressure rise is also investigated to analyze the pumping characteristics. Important results of flow phenomena are explored by means of graphs.     

Investigation of Solution p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> and Thermodynamic Values of Lamivudine and Pefloxacin Drugs by Ab initio and DFT Methods

In this work we investigate the thermodynamic properties and pK_a value of lamivudine and pefloxacin drugs, in aqueous solutions, by ab initio and density functional theory (DFT) methods at different temperatures. Molecular structures and solute–solvent effects of the anions, cations, and neutral molecules of lamivudine and pefloxacin were studied by the polarizable continuum model (PCM). The calculation was done at the DFT-B3LYP/6-31+G(d) level of theory using Tomasi’s method to analyze the formation of intermolecular hydrogen bonds (IHB) in aqueous solution. The pK_a1 values of lamivudine and pK_a2 values of pefloxacin increase with temperature increase. In contrast, the pK_a1 values of pefloxacin decrease when the temperature increases. Further, the thermodynamic properties of the ionization processes (?H, ?S and ?G) of the drugs in aqueous solution were determined and discussed. The results of this work are in good agreement with the literature data at 298.15 K.     

Scanning electrochemical microscopy. 59. Effect of defects and structure on electron transfer through self-assembled monolayers

Electron transfer (ET) rate kinetics through n-alkanethiol self-assembled monolayers (SAMs) of alkanethiols of different chain lengths [Me(CH2)nSH; n=8, 10, 11, 15] on Au and Hg surfaces and ferrocene (Fc)-terminated SAMs (poly-norbornylogous and HS(CH2)12CONHCH2Fc) on Au were studied using cyclic voltammetry and scanning electrochemical microscopy (SECM). The SECM results allow determination of the ET kinetics of solution-phase Ru(NH3)63+/2+ through the alkanethiol SAMs on Au and Hg. A model using the potential dependence of the measured rate constants is proposed to compensate for the pinhole contribution. Extrapolated values of koML for Ru(NH3)63+/2+ using the model follow the expected exponential decay (beta is 0.9) for different chain lengths. For a Fc-terminated poly-norbornyl SAM, the standard rate constant of direct tunneling (ko is 189+/-31 s(-1)) is in the same order as the ko value of HS(CH2)12CONHCH2Fc. In blocking and Fc SAMs, the rates of ET are demonstrated to follow Butler-Volmer kinetics with transfer coefficients alpha of 0.5. Lower values of alpha are treated as a result of the pinhole contribution. The normalized rates of ET are 3 orders of magnitude higher for Fc-terminated than for blocking monolayers. Scanning electron microscopy imaging of Pd nanoparticles electrochemically deposited in pinholes of blocking SAMs was used to confirm the presence of pinholes.