Theoretical Study of Kinetics and Thermodynamics of Hetero Diels-Alder Reaction of Thiazole and Isothiazol with Thiophene-2,5-dione

DFT methods have been used to study the hetero Diels-Alder reaction of thiazole and isothiazole with thiophen-2,5-dione.The thermodynamic and kinetic parameters were calculated.The relative stabilities of the transition structures corresponding to the endo/exo stereoisomers have been rationalized on the basis of the secondary molecular orbital interactions.NBO analysis was carried out to calculate the synchronicity index.It was shown that all reactions are synchronous.A HOMO-LUMO energy gap shows both reactions are normal electron demand.     

A new kinetic spectrophotometric method for the determination of major metabolite of heroin in biological samples

This study describes a simple,rapid and selective catalytic kinetic spectrophotometric method for the determination of 6- monoacetylmorphine（6-MAM） as major metabolite of heroin in biological samples.The method is based upon the catalytic effect of 6-MAM on the oxidation of Janus Green by bromate in acid media.The reaction was followed spectrophotometrically by measuring the decrease in absorbance of Janus Green at 618 nm.The dependence of sensitivity on the reaction variables was studied.Under optimum conditions,two linear calibration curves over the range 0.1-1.0μg mL^-1 and 1.0-34.0μg mL^-1 of 6- MAM were obtained.The detection limit was 1.2×10²μg mL^-1 of 6-MAM.The relative standard deviations for six replicate determinations of 0.8 and 5.0μg mL^-1 of 6-MAM were 1.4 and 1.1%respectively.The effect of various species commonly associated with heroin in real samples was also investigated.The proposed method was successfully applied in human urine and serum samples with satisfactory results.     

4E analysis and tri-objective optimization of a triple-pressure combined cycle power plant with combustion chamber steam injection to control NOx emission

This article presents a novel triple-pressure combined cycle power plant (CCPP) with a heat recovery steam generator (HRSG) configured with heat exchangers of multiple pressure levels, same as the real case. In addition, combustion chamber steam injection is added to the top cycle in order to reduce hazardous emissions. The research investigates energy, exergy, economic, and environmental aspects of the system to initiate sustainable development in said areas. A thorough parametric study is carried out to evaluate the effects of steam injection and other decision variable on emissions and system performance. Then, the total cost rate and the CO₂ index are minimized while maximizing the second law efficiency via a tri-objective optimization using the genetic algorithm. The outcome of the economic analysis is that the HRSG has the maximum total cost rate among all the components, namely 0.1673 $/s. The environmental impact  assessments indicate that the CO₂ and NO emission has considerable molar fractions of 0.035 and 6.88?×?10^?4, respectively. As a result of the tri-objective optimization, a 3D Pareto Frontier is presented, which pointed out the maximum attainable exergy efficiency is 50.32%, as well as the minimum total cost rates of 8.04 $/s and CO₂ index of 0.34 kg/kWh. Finally, the scatter distribution of major decision variables revealed the optimum range of decision variables in which the optimum points of the Pareto Frontier are obtained. Accordingly, the scatter distribution showed that 46 kg s^?1 is the optimum value for steam injection flow rate in terms of efficiency, cost and emission optimization.

     

Effects of Various Amounts of New Hepta-Ether as the Internal Donor on the Polymerization of Propylene with and without the External Donor

The new hepta-ether compound as the internal donor was synthesized using the Williamson reaction of dipentaerythritol with sodium hydride as the strong base and iodomethane as the alkyl halide. The hepta-ether compound was characterized by NMR, FTIR, and GC techniques. The MgCl₂-supported catalysts incorporated with different amounts of hepta-ether compound as the internal donor and without the internal donor were synthesized and characterized. The propylene polymerization was carried out using these catalysts in the presence of triethylaluminum as a co-catalyst and hydrogen as a chain transfer agent, with and without the external donor. The effect of a new internal donor on propylene polymerization using prepared MgCl₂-supported Ziegler-Natta catalysts was investigated.     

Exploration of the binding properties of the human serum albumin sites with neurology drugs by docking and molecular dynamics simulation

In this study, the binding properties of a set of neurology drugs to human serum albumin (HSA) were studied by docking and molecular dynamic (MD) methods. Based on the RMSD values for the MD simulation processes, the drug–protein complexes are stable. Site II of the HSA shows the best affinity for the studied drugs. Different kinds of interactions, including hydrogen bonding, π-cation interactions, and π–π interactions, are observable between ligand and protein during the MD simulation process. The MMGBSA calculations were done to evaluate the binding energy of the ligands and protein. The calculated energies are in good agreement with the previously reported experimental results. In some cases, there is a direct relation between the calculated binding energy with the half-life of the drugs, as it was expected.     

Experimental and theoretical characterization of 3-amino-1-phenyl-2-buten-1-onato ligand and its copper(II) and nickel(II) complexes: synthesis, characterization, X-ray structures, DFT and TDDFT studies

This article presents a combined experimental and computational investigation of 3-amino-1-phenyl-2-buten-1-onato, APBO ligand and its copper(II) and nickel(II) complexes. APBO is an unsymmetrical, bidentate and monoanionic ligand with different coordinating atoms (N,O). A comparison among different possible conformers of the ligand has been carried out using density functional theory (DFT) method at the B3LYP/6-31+G(d,p) level. It was demonstrated that two factors control stability of the compounds as hydrogen bonding (conventional and nonconventional) and resonance effect. The effectiveness of each of these parameters on the stability of ligands is discussed. The prepared homoleptic complexes of [Ni(APBO)₂] and [Cu(APBO)₂] were characterized with IR, NMR, UV–Vis spectroscopic techniques. The X-ray crystallography of [Ni(APBO)₂] demonstrated that the bidentate APBO binds to the metal center in trans fashion and the geometry around the nickel atom is square planar. The experimental studies on the complexes were accompanied computationally by the DFT and time-dependent DFT calculations.     

Novel Conductive PANI/Hydrophilic Thiacalix[4]areneNanocomposites: Synthesis,Characterization andInvestigation of Properties简

Nanocomposites of polyaniline(PANI) and the macrocycle thiacalix[4]arene tetra sulfonate(TCAS) were successfully synthesized in feed ratios of 1:0.25, 1:0.50 and 1:0.75 by three prevail synthetic methods, i.e. in situ polymerization, emulsion polymerization and solution casting technique. The structures of the nanocomposites were confirmed by FTIR, UV-Vis, XRD, SEM, and TEM techniques. The conductivity was measured by a four probe method. The conductivity was recorded to be as high as 105 × 10 2S cm 1for the nanocomposite with a nanometer size structure and homogeneously distributed morphology. The electroactivity of the nanocomposites was approved by cyclic voltammetry(CV) and impedance spectroscopy technique(EIS). The antioxidant ability and thermal property of the composites were further studied. Preliminary studies have evidenced the production of conductive nanocomposites with good thermal property and relatively good solubility in N-methyl 2-pyrrolidone(NMP), with the antioxidant activity reaching up to 80%.     

Finite-time synchronization control for a class of perturbed nonlinear systems with fixed convergence time and hysteresis quantizer: applied to Genesio–Tesi chaotic system

In the present article, a terminal sliding mode control strategy has been proposed in order to address the synchronization problem for a class of perturbed nonlinear systems with fixed convergence time and input quantization. The proposed protocol guarantees the fixed-time convergence of the sliding manifold to the origin, which means that the convergence time of the proposed sliding manifold does not change on the variations of initial values, different from typical control methods. Here, the hysteresis quantizer, as a specific type of quantizer with nonlinear sector-bounded, is applied in order to quantize the input signal. The proposed quantized control scheme vigorously prevents the potential adverse chattering phenomenon which is experienced in the common quantization methods. The proposed controller does not need the limiting criteria related to considered parameters of quantization compared to recent control approaches. Finally, the designed controller is implemented on the perturbed Genesio–Tesi (G–T) chaotic systems to verify effectiveness and strength of the proposed method.

     

A LBM–DEM solver for fast discrete particle simulation of particle–fluid flows

The lattice Boltzmann method (LBM) for simulating fluid phases was coupled with the discrete element method (DEM) for studying solid phases to formulate a novel solver for fast discrete particle simulation (DPS) of particle–fluid flows. The fluid hydrodynamics was obtained by solving LBM equations instead of solving the Navier–Stokes equation by the finite volume method (FVM). Interparticle and particle–wall collisions were determined by DEM. The new DPS solver was validated by simulating a three-dimensional gas–solid bubbling fluidized bed. The new solver was found to yield results faster than its FVM–DEM counterpart, with the increase in the domain-averaged gas volume fraction. Additionally, the scalability of the LBM–DEM DPS solver was superior to that of the FVM–DEM DPS solver in parallel computing. Thus, the LBM–DEM DPS solver is highly suitable for use in simulating dilute and large-scale particle–fluid flows.