Visible-Light-Driven One-Pot Synthesis of Benzimidazoles,Benzothiazoles, and Quinazolinones Catalyzed by Scalable and Reusable Ba-Doped CoMoO4 Nanoparticles Under Air Atmosphere

Herein we report a simple and efficient oxidative coupling of various aryl methyl amines with diverse coupling partners, such as o-phenylenediamine (benzene-1,2-diamine), 2-aminobenzenethiol and 2-aminobenzamide, to synthesize the corresponding heterocycles using scalable and reusable heterogeneous catalysts under visible light irradiation. A systematic investigation led to the synthesis of benzimidazoles, benzothiazoles and quinazolinones under air atmosphere in very good to excellent yields. The strategy is atom economical and found to be tolerance towards different functional groups, and wide range of substrate scope. Furthermore, the methodology was demonstrated for its suitability on scale up and reusability. The density functional theory (DFT) calculations and the analysis of band structures of pristine and Ba doped CoMoO₄ systems showed that the doping of Ba in place of Co improved the catalytic performance of the system.     

Structurally Simple Osmium(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy in the Near Infrared**

Five osmium(II) polypyridyl complexes of the general formula [Os(4,7-diphenyl-1,10-phenanthroline)₂ L ]²⁺ were synthesized as photosensitizers for photodynamic therapy by varying the nature of the ligand L . Thanks to the pronounced π-extended structure of the ligands and the heavy atom effect provided by the osmium center, these complexes exhibit a high absorption in the near-infrared (NIR) region (up to 740 nm), unlike related ruthenium complexes. This led to a promising phototoxicity in vitro against cancer cells cultured as 2D cell layers but also in multicellular tumor spheroids upon irradiation at 740 nm. The complex [Os(4,7-diphenyl-1,10-phenanthroline)₂(2,2′-bipyridine)]²⁺ was found to be the most efficient against various cancer cell lines, with high phototoxicity indexes. Experiments on CT26 tumor-bearing BALB/c mice also indicate that the Os^II complexes could significantly reduce tumor growth following 740 nm laser irradiation. The high phototoxicity in the biological window of this structurally simple complex makes it a promising photosensitizer for cancer treatment.     

Antioxidant and Prooxidant Nanozymes: From Cellular Redox Regulation to Next-Generation Therapeutics

Nanozymes, nanomaterials with enzyme-mimicking activity, have attracted tremendous interest in recent years owing to their ability to replace natural enzymes in various biomedical applications, such as biosensing, therapeutics, drug delivery, and bioimaging. In particular, the nanozymes capable of regulating the cellular redox status by mimicking the antioxidant enzymes in mammalian cells are of great therapeutic significance in oxidative-stress-mediated disorders. As the distinction of physiological oxidative stress (oxidative eustress) and pathological oxidative stress (oxidative distress) occurs at a fine borderline, it is a great challenge to design nanozymes that can differentially sense the two extremes in cells, tissues and organs and mediate appropriate redox chemical reactions. In this Review, we summarize the advances in the development of redox-active nanozymes and their biomedical applications. We primarily highlight the therapeutic significance of the antioxidant and prooxidant nanozymes in various disease model systems, such as cancer, neurodegeneration, and cardiovascular diseases. The future perspectives of this emerging area of research and the challenges associated with the biomedical applications of nanozymes are described.     

Stability and Hopf bifurcation analysis of novel hyperchaotic system with delayed feedback control

In this article, a novel four dimensional autonomous nonlinear systezm called hyperchaotic Rikitake system is proposed. Basic properties of the new system are investigated and the complex dynamical behaviors, such as time series, bifurcation diagram, and Lyapunov exponents are analyzed by dynamic analysis approaches. To control the new hyperchaotic system, the delayed feedback control is introduced. Regarding the time delay as a bifurcation parameter, stability and bifurcations with respect to time delay are investigated. Conditions assuring the existence of Hopf bifurcation and the distribution of roots to the associated characteristic equation are investigated by utilizing the polynomial theorem. Besides, the Hopf bifurcation is proved to occur when the bifurcation parameter (time delay) crosses through derived critical value. Finally, numerical simulations are provided to prove the consistence with the derived theoretical results. © 2015 Wiley Periodicals, Inc. Complexity 21: 180–193, 2016     

Computation of cascade flutter by uncoupled and coupled methods

A computational method for flutter prediction of turbomachinery cascades is presented. The flow through multiple blade passages is calculated using a time-domain approach with coupled aerodynamic and structural models. The unsteady Euler/Navier-Stokes equations are solved in quasi-three-dimensions using a second-order implicit scheme with dual time-stepping and a multigrid method. A structural model for the blades with bending and torsion degrees of freedom is integrated in time together with the flow field. Information between structural and aerodynamic models is exchanged until convergence in each real-time step. Computational results for a cascade are presented and compared with those obtained by the conventional energy method and with experimental and numerical data by other authors. Significant differences are found between the coupled and uncoupled methods at low mass ratios. A transonic test case with strong nonlinear phenomena is investigated with the fluid-structure coupled method. Results for inviscid flow are compared with results of Navier-Stokes computations.     

Plunging wake analysis of an airfoil equipped with a Gurney flap

Experimental Techniques - Experimental measurements were conducted on a plunging Eppler 361 Gurney flapped airfoil to study wake structure and dynamic stall phenomenon in the wake. The heights of...     

Working group report: Neutrino and astroparticle physics

This is the report of neutrino and astroparticle physics working group at WHEPP-7. Discussions and work on CP violation in long baseline neutrino experiments, ultra high energy neutrinos, supernova neutrinos and water Cerenkov detectors are discussed.     

Nonlinear tunneling of optical soliton in 3 coupled NLS equation with symbolic computation

We investigated the soliton solution for N$N$ coupled nonlinear Schrödinger (CNLS) equations. These equations are coupled due to the cross-phase-modulation (CPM). Lax pair of this system is obtained via the Ablowitz–Kaup–Newell–Segur (AKNS) scheme and the corresponding Darboux transformation is constructed to derive the soliton solution. One and two soliton solutions are generated. Using two soliton solutions of 3 CNLS equation, nonlinear tunneling of soliton for both with and without exponential background has been discussed. Finally cascade compression of optical soliton through multi-nonlinear barrier has been discussed. The obtained results may have promising applications in all-optical devices based on optical solitons, study of soliton propagation in birefringence fiber systems and optical soliton with distributed dispersion and nonlinearity management.     

Three-stage auto-ignition of n-heptane and methyl-cyclohexane mixtures at lean conditions in a flat piston rapid compression machine

One approach to enhancing the thermal efficiency of combustion systems is to burn fuels at ultra-lean conditions (equivalence ratio below 0.5). It has been recently reported that the auto-ignition of some hydrocarbon fuels, under specific temperature, pressure, and mixture conditions, releases heat in three distinctive stages. The three auto-ignition stages can be divided as a first low-temperature auto-ignition stage with conventional low temperature, and a high-temperature stage separated into two sub-stages. This study presents ignition delay time measurements of n-heptane and methyl-cyclohexane (MCH) mixtures in a flat piston rapid compression machine (RCM) under ultra-lean conditions. It provides experimental evidence of three-stage auto-ignition. This phenomenon of delayed high-temperature heat release is seldom reported in the literature and this is the first time to be reported for these types of fuels. The experiments cover two binary n-heptane/MCH mixtures of 15/85 and 70/30 by volume, pressures of 11 bar and 16 bar, temperature range of 700 to 900 K, and equivalence ratio of 0.4. The RCM optical access was utilized for high-speed chemiluminescence imaging. Detailed chemical kinetic simulations in a homogenous batch reactor with variable volume were conducted to further interrogate the three-stage auto-ignition phenomenon. Chemiluminescence shows that three-stage auto-ignition occurs in the adiabatically compressed end-gas, which indicates that this phenomenon is chemically-driven and is not induced by a thermal stratification in the RCM experiments. The model predicts the features of three-stage auto-ignition, which were experimentally observed at temperatures approximately below 750 K. As expected, significant discrepancies are observed in the ignition delays of experiment and simulation in the negative temperature coefficient (NTC) region. The simulation of the n-heptane/MCH 70/30 mixture shows better agreement with experiments in the Positive Temperature Coefficient (PTC) region compared to the 15/85 mixture.