Isomeric pyridylcarbenes and their Si and Ge heavier analogues at DFT: stabilization through π–p or n–p interaction

To realize the effects of the pyridyl group on the stability, multiplicity, and geometry of isomeric pyridylcarbenes and their heavier Si and Ge analogues, a theoretical study was performed at B3LYP/6-311++G(d,p)//B3LYP/6-31G(d). The behavior of nitrogen atom was totally different in each multiplicity (singlet and triplet), structural isomer (ortho-, meta-, and para-), and divalent center (C, Si, and Ge). All pyridylcarbenes have triplet ground states, while the stable silylene and germylene analogues are singlet. The pyridyl group stabilizes both singlet and triplet states divalent centers with more pronounced effects on the singlet states in the order: carbene>germylene>silylene. While all planar species benefit from common π–p conjugative interaction of the pyridyl ring, in the ortho-isomers of 2-pyridylsilylene and 2-pyridylgermylene there is another interaction, n–p, that leads to two stable non-planar conformers. This finding is confirmed by NBO charges, calculated UV–vis spectra, philicity indices (N and ω), and isodesmic reactions.     

Increasing the cisplatin cytotoxicity and cisplatin-induced DNA damage by conferone in 5637 cells

Despite widespread application of cisplatin in treatment of transitional cell carcinomas, its efficiency is far from satisfactory due to acquired drug resistance. The present study was carried out to estimate the effects of conferone, a sesquiterpene-coumarin isolated from Ferula badrakema, on increasing cisplatin cytotoxicity in 5637 cells. In order to determine conferone effects, 5637 cells were cultured in the presence of different concentrations of conferone and cisplatin in combination. The cytotoxicity and DNA damaging effects were then studied using MTT and comet assays, respectively. The results revealed that 24?h after the combination of 1?μg?mL?1 cisplatin with 32?μg?mL?1 conferone, the cytotoxicity of cisplatin was increased by 36.76%, and comet assay analyses showed that conferone could enhance the DNA damaging effects of cisplatin by 41%.     

Four techniques based on the B‐spline expansion and the collocation approach for the numerical solution of the Lane–Emden equation

Four numerical techniques based on the linear B‐spline functions are presented for the numerical solution of the Lane–Emden equation. Some properties of the B‐spline functions are presented and are utilized to reduce the solution of the Lane–Emden equation to the solution of algebraic equations. Illustrative examples are included to demonstrate the validity and applicability of the new techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

Calculation of critical properties for the anisotropic two-layer Ising model on the Kagome lattice: Cellular automata approach

The critical point (K_c) of the two-layer Ising model on the Kagome lattice has been calculated with a high precision, using the probabilistic cellular automata with the Glauber algorithm. The critical point is calculated for different values of the inter- and intra-layer couplings (K₁≠K₂≠K₃≠K_z), where K₁, K₂ and K₃ are the nearest-neighbor interactions within each layer in the 1, 2 and 3 directions, respectively, and K_z is the intralayer coupling. A general ansatz equation for the critical point is given as a function of the inter- and intra-layer interactions, ξ=K₃/K₁,σ=K₂/K₁ and ω=K_z/K₁ for the one- and two-layer Ising models on the Kagome lattice.     

Propagation of infinitesimal thermo-mechanical waves during the finite-deformation loading of a viscoelastic material: general theory

We study the theory of propagation of infinitesimal thermo-mechanical waves in a special class of nonlinear viscoelastic materials under homogeneous and inhomogeneous finite static and time-varying deformations. These results are based on a thermodynamically consistent finite-deformation nonlinear viscoelastic model that reduces to a general linear viscoelastic model of integral form. On a thermo-mechanically deforming body, we impose a thermo-mechanical perturbation history and obtain the equations to solve for the perturbation parameters from the constitutive model and the balance laws. We use these equations to study the characteristics of different perturbations. We develop the special equations for both time-harmonic and time-damping plane waves for homogeneous pre-loads.     

The effect of NaCl and Na2SO4 concentration in aqueous phase on the phase inversion temperature O/W nanoemulsions

The effect of NaCl and Na₂SO₄ concentrations in aqueous phase on the phase inversion temperature (PIT) in nanoemulsions of water/Brij30/n-hexadecane system has been studied separately, and then compared. The variation of conductivity with temperature was measured by Cyber Scan PC510 conductivity meter for emulsions with 20 wt% hexadecane and 8 wt% Brij30 concentration and different concentrations of NaCl and Na₂SO₄ in aqueous phase. The results showed that with increasing concentrations of NaCl and Na₂SO₄ in aqueous phase, the PIT of nanoemulsions decreases. The effect of the elevation of concentration on the decrease of PIT was more for Na₂SO₄ in aqueous phase than NaCl with equal concentrations.     

The double H‐atom acceptability of the P=O group in new XP(O)(NHCH2C6H4‐2‐Cl)2 phosphoramidates [X = C6H5O– and CF3C(O)NH–]: a database analysis of compounds having a P(O)(NHR) group

In the hydrogen‐bond patterns of phenyl bis(2‐chlorobenzylamido)phosphinate, C₂₀H₁₉Cl₂N₂O₂P, (I), and N,N′‐bis(2‐chlorobenzyl)‐N′′‐(2,2,2‐trifluoroacetyl)phosphoric triamide, C₁₆H₁₅Cl₂F₃N₃O₂P, (II), the O atoms of the related phosphoryl groups act as double H‐atom acceptors, so that the P=O...(H—N)₂ hydrogen bond in (I) and the P=O...(H—N_amide)₂ and C=O...H—N_C(O)NHP(O) hydrogen bonds in (II) are responsible for the aggregation of the molecules in the crystal packing. The presence of a double H‐atom acceptor centre is a result of the involvement of a greater number of H‐atom donor sites with a smaller number of H‐atom acceptor sites in the hydrogen‐bonding interactions. This article also reviews structures having a P(O)NH group, with the aim of finding similar three‐centre hydrogen bonds in the packing of phosphoramidate compounds. This analysis shows that the factors affecting the preference of the above‐mentioned O atom to act as a double H‐atom acceptor are: (i) a higher number of H‐atom donor sites relative to H‐atom acceptor centres in molecules with P(=O)(NH)₃, (N)P(=O)(NH)₂, C(=O)NHP(=O)(NH)₂ and (NH)₂P(=O)OP(=O)(NH)₂ groups, and (ii) the remarkable H‐atom acceptability of this atom relative to the other acceptor centre(s) in molecules containing an OP(=O)(NH)₂ group, with the explanation that the N atom bound to the P atom in almost all of the structures found does not take part in hydrogen bonding as an acceptor. Moreover, the differences in the H‐atom acceptability of the phosphoryl O atom relative to the O atom of the alkoxy or phenoxy groups in amidophosphoric acid esters may be illustrated by considering the molecular packing of compounds having (O)₂P(=O)(NH) and (O)P(=O)(NH)(N)groups, in which the unique N—H unit in the above‐mentioned molecules almost always selects the phosphoryl O atom as a partner in forming hydrogen‐bond interactions. The P atoms in (I) and (II) are in tetrahedral coordination environments, and the phosphoryl and carbonyl groups in (II) are anti with respect to each other (the P and C groups are separated by one N atom). In the crystal structures of (I) and (II), adjacent molecules are linked via the above‐mentioned hydrogen bonds into a linear arrangement parallel to [100] in both cases, in (I) by forming R₂²(8) rings and in (II) through a combination of R₂²(10) and R₂¹(6) rings.     

Numerical solution of Fokker‐Planck equation using the cubic B‐spline scaling functions

In this article a numerical technique is presented for the solution of Fokker‐Planck equation. This method uses the cubic B‐spline scaling functions. The method consists of expanding the required approximate solution as the elements of cubic B‐spline scaling function. Using the operational matrix of derivative, the problem will be reduced to a set of algebraic equations. Some numerical examples are included to demonstrate the validity and applicability of the technique. The method is easy to implement and produces very accurate results. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2009     

Numerical study of electroosmotic micromixing of non-Newtonian fluids

Biofluids which exhibit non-Newtonian behavior are widely used in microfluidic devices which involve fluid mixing in microscales. In order to study the effects of shear depending viscosity of non-Newtonian fluids on characteristics of electroosmotic micromixing, a numerical investigation of flow of power-law fluid in a two-dimensional microchannel with nonuniform zeta potential distributions along the channel walls was carried out via finite volume scheme. The simulation results confirmed that the shear depending viscosity has a significant effect on the degree of mixing efficiency. It was shown as the fluid behavior index of power-law fluid, n, decreases, more homogeneous solution can be achieved at the microchannel outlet. Hence, electroosmotic micromixing was found more practical and efficient in microscale mixing of pseudoplastic fluids rather than those Newtonian and dilatant ones. Furthermore, it was found that increase in Reynolds number results in lower mixing efficiency while electroosmotic forces are kept constant.     

Horizon problem remediation via deformed phase space

We investigate the effects of a special kind of dynamical deformation between the momenta of the scalar field of the Brans–Dicke theory and the scale factor of the FRW metric. This special choice of deformation includes linearly a deformation parameter. We trace the deformation footprints in the cosmological equations of motion when the BD coupling parameter goes to infinity. One class of the solutions gives a constant scale factor in the late time that confirms the previous result obtained via another approach in the literature. This effect can be interpreted as a quantum gravity footprint in the coarse grained explanation. The another class of the solutions removes the big bang singularity, and the accelerating expansion region has an infinite temporal range which overcomes the horizon problem. After this epoch, there is a graceful exiting by which the universe enters in the radiation dominated era.