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Pd-PEPPSI type complexes are widely used as precatalyst in a variety of organic reactions, including the Negishi, Kumada and Suzuki-Miyaura cross-coupling reactions. The aim of this research is to determine potential proposed reaction pathways 1, 2, or 2′ (See Schemes 1 and S1–S4 ) for Pd-PEPPSI precatalyst activation in the presence of ethylene glycol as a solvent also in the gas phase at Cam-B3LYP-D3 method nominated among eight DFT methods examined. There is also investigation into the impact of promoter bases (NaOEt, NaOⁱPr, NaO^tBu) on precatalyst activation of Pd-PEPPSI. Eventually, the most favorable proposed reaction pathway and promoter base for reducing Pd(II) to Pd(0) are predicted computationally. Notably, our findings are consistent with the organ Pd-PEPPSI type complexes that offer increased catalytic activity and provide basic information in the presence of solvents designing the monoligated Pd(0)-solvent.     

Synthesis of Novel Triazole Incorporated Thiazolone Motifs Having Promising Antityrosinase Activity through Green Nanocatalyst CuI-Fe3O4@SiO2 (TMS-EDTA)

In the present work, novel 5-((1-benzyl-1,2,3-triazol-4-yl)methoxybenzylidene)-2-(arylamino)thiazol-4-one thiazolone incorporated triazole derivatives have been designed as tyrosinase inhibitors. The compounds were synthesized through click reaction in good yield. Moreover, the antityrosinas activity of the synthesized derivatives was evaluated. In the search for establishing a click copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction under strict conditions, in terms of a novel air-stable, a recyclable and efficient magnetic catalyst was planned for new triazole derivatives as a well-organized copper iodide supported on the functionalized Fe₃O₄@SiO₂ core-shell (CuI/Fe₃O₄@SiO₂(TMS-EDTA) nanoparticles). The engineered nanocatalyst synthesized for the first time and characterized by different methods, including FT-IR spectroscopy, XRD, FESEM, EDX, TEM, TGA, and BET analysis. The excellent catalytic performance in ethanol with high surface area (351.7 m²g⁻¹) and short reaction time for diverse functional groups (120–200 min), no use of toxic solvents, reusability of the catalyst, and using eco-friendly conditions are the advantageous of this work. Moreover,the nanocatalyst can be used at least five times without any significant decrease in the yield of the reaction. The thiazolidine-triazole derivatives 9a , 9c , 9e , and 9 g showed promising tyrosinase inhibitory activity with IC₅₀ values in the range of 5.90–9.81 μM. The compounds were found to be considerably more potent tyrosinase inhibitors than the reference inhibitor kojic acid (IC₅₀ = 18.36 μM).     

Analytical solution of stochastic differential equation by multilayer perceptron neural network approximation of Fokker–Planck equation

The Fokker–Planck equation is a useful tool to analyze the transient probability density function of the states of a stochastic differential equation. In this paper, a multilayer perceptron neural network is utilized to approximate the solution of the Fokker–Planck equation. To use unconstrained optimization in neural network training, a special form of the trial solution is considered to satisfy the initial and boundary conditions. The weights of the neural network are calculated by Levenberg–Marquardt training algorithm with Bayesian regularization. Three practical examples demonstrate the efficiency of the proposed method.     

A quantum chemical study of the interactions of uracil as a constituent of ribonucleic acid (RNA) with thiazolidinedione and rhodanine bioactive molecules: an insight into energetic and structural features

In this study, the biologically active configurations composed of Thiazolidinedione–Uracil (TU) and Rhodanine–Uracil (RU) have been fully investigated from the energetic and structural points of view, employing B3LYP and M062X functionals in combination with the different basis sets. Dispersion corrections to the interaction energy using M062X–GD3 and double hybrid density functionals (B2PLYP–GD2, B2PLYP–GD3 and mPW2PLYP–GD2) are also taking into account. The basis set superposition error-corrected interaction energy for hydrogen bonded configurations ranges from ??5.27 to ??13.53 and ??5.25 to ??12.93 kcal/mol for TU and RU complexes respectively as calculated at M062X/6–311++G(df,pd) level. The charge transfer process within all of the TU and RU configurations were analyzed using Natural Bond Orbital (NBO) calculations. The nature of the interactions is analyzed with NBO and Atoms in Molecules (AIM) analysis at M062X/6–311++G(df,pd) and energy decomposition analysis at BP86–D3/TZ2P(ZORA)//M062X/6–311++G(df,pd) level of theory. The results confirm that the nature of the interactions is nearly electrostatic, with a contribution of about 51–56% of the total interaction energy. The orbital interactions (ΔE_orb) for the considered TU and RU complexes have a contribution of about 24–38% of the total interaction energy. Based on the AIM and NBO results, the interactions were defined as electrostatic H-bonds with partially covalent character. In addition, correlation between interaction energies and vibrational frequency changes was investigated.     

Equational Compactness of G-sheaves

Purity and equational compactness play a role at least in the Theories of Modules, Acts, Model, and Category. Adámek and Rosický have studied them categorically, Rothmaler model-theoretically, and some authors, including Banaschewski, Gould, and Normak have studied these notions on G-acts. We take both the group G and the set A in the definition of a G-act to be sheaves and study equationally compact G-sheaves. We get different kinds of equationally compact G-sheaves, study them and their interrelations, give some conditions for their proper behavior, and generalize some of the existing results.     

The dual reciprocity boundary elements method for the linear and nonlinear two‐dimensional time‐fractional partial differential equations

In this paper, we apply the dual reciprocity boundary elements method for the numerical solution of two‐dimensional linear and nonlinear time‐fractional modified anomalous subdiffusion equations and time‐fractional convection–diffusion equation. The fractional derivative of problems is described in the Riemann–Liouville and Caputo senses. We employ the linear radial basis function for interpolation of the nonlinear, inhomogeneous and time derivative terms. This method is improved by using a predictor–corrector scheme to overcome the nonlinearity which appears in the nonlinear problems under consideration. The accuracy and efficiency of the proposed schemes are checked by five test problems. The proposed method is employed for solving some examples in two dimensions on unit square and also in complex regions to demonstrate the efficiency of the new technique. Copyright © 2016 John Wiley & Sons, Ltd.     

A meshless method based on the dual reciprocity method for one‐dimensional stochastic partial differential equations

This article describes a new meshless method based on the dual reciprocity method (DRM) for the numerical solution of one‐dimensional stochastic heat and advection–diffusion equations. First, the time derivative is approximated by the time–stepping method to transforming the original stochastic partial differential equations (SPDEs) into elliptic SPDEs. The resulting elliptic SPDEs have been approximated with the new method, which is a combination of radial basis functions (RBFs) method and the DRM method. We have used inverse multiquadrics (IMQ) and generalized IMQ (GIMQ) RBFs, to approximate functions in the presented method. The noise term has been approximated at the source points, at each time step. The developed formulation is verified in two test problems with investigating the convergence and accuracy of numerical results. © 2015 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 32: 292–306, 2016     

B-, N-doped and BN codoped C60 heterofullerenes for environmental monitoring of NO and NO2: a DFT study

ABSTRACT

Using density functional theory calculations, we investigate the gas sensing performance of B-, N-doped and BN-codoped C₆₀ fullerenes towards NO and NO₂ molecules. The calculated adsorption energies and net charge-transfer values indicate that NO and NO₂ molecules have a stronger interaction with the BN-codoped fullerenes compared to the B- or N-doped ones. It is also found that the electronic properties of the BN-codoped C₆₀ exhibit a larger sensitivity towards NO and NO₂ molecules. An increase in the concentration of doped/co-doped B and N atoms tends to weaken the gas sensing ability of these systems.     

Prediction and characterisation of a chalcogen···π interaction with acetylene as a potential electron donor in XHS···HCCH and XHSe···HCCH (X = F,Cl, Br,CN, OH,OCH3, NH2, CH3) σ-hole complexes

It is well-known that many covalently bonded atoms of group VI have specific positive regions of electrostatic potential (σ-holes) through which they can interact with Lewis bases. This interaction is called ‘chalcogen bond’ by analogy with halogen bond and hydrogen bond. In this study, ab initio calculations are performed to predict and characterise chalcogen···π interactions in XHS···HCCH and XHSe···HCCH complexes, where X = F, Cl, Br, CN, OH, OCH₃, NH₂, CH₃. For the complexes studied here, XHS(Se) and HCCH are treated as a Lewis acid and a Lewis base, respectively. The CCSD(T)/aug-cc-pVTZ interaction energies of this type of σ-hole bonding range from ?1.18 to ?4.83 kcal/mol. The calculated interaction energies tend to increase in magnitude with increasing positive electrostatic potential on the extension of X–S(Se) bond. The stability of chalcogen···π complexes is attributed mainly to electrostatic and correlation effects. The nature of chalcogen···π interactions is unveiled by means of the atoms in molecules, natural bond orbital, and electron localisation function analyses.