The unstable behavior of cellular premixed flames induced by intrinsic instability

The unstable behavior of cellular premixed flames induced by intrinsic instability is studied by two-dimensional unsteady calculations of reactive flows. In the present numerical simulation, the compressible Navier–Stokes equation including a one-step irreversible chemical reaction is employed. We consider two basic types of phenomena to account for the intrinsic instability of premixed flames, i.e., hydrodynamic and diffusive-thermal effects. The hydrodynamic effect is caused by the thermal expansion through the flame front; the diffusive-thermal effect is caused by the preferential diffusion of mass versus heat. A disturbance with several wavelength components is superimposed on a planar flame, and the formation of a cellular flame induced by hydrodynamic and diffusive-thermal effects is numerically simulated. After the cellular-flame formation, the combination and division of cells are observed. The behavior of cellular-flame fronts becomes more unstable when the Lewis number is lower than unity, since the diffusive-thermal effect has a great influence on the unstable behavior. The cell size changes with time, and its average is greater than the critical wavelength and becomes smaller by decreasing the Lewis number. The flame velocity of cellular flames depends strongly on the length of computational domain in the direction tangential to the flame front. As the length of computational domain increases, the flame velocity becomes larger. This is because the long-wavelength components of disturbances play an important role in the shape of cellular flames, i.e., in the flame-surface area.     

Stability analysis of cyclic switched nonlinear systems via event-triggered method

In this paper, the exponential stability problem is addressed for a class of cyclic switched nonlinear systems with unstable modes. A novel event-triggered cyclic switching scheme (ETCSS) is proposed to generate a cyclic switching signal that exponentially stabilizes the considered system for any given initial configuration. Some easily verifiable stability criteria for switched nonlinear and linear systems are established, and the effects of event parameters on the convergence rate are also analyzed. Different from the existing studies, here the developed switching scheme is not only cyclic but also event-triggered and thereby the switching frequency is relatively low. Finally, a numerical example is given to verify the efficiency of the method.     

Optical Absorption and Magnetic Field Effect Based Imaging of Transient Radicals

Short‐lived radicals generated in the photoexcitation of flavin adenine dinucleotide (FAD) in aqueous solution at low pH are detected with high sensitivity and spatial resolution using a newly developed transient optical absorption detection (TOAD) imaging microscope. Radicals can be studied under both flash photolysis and continuous irradiation conditions, providing a means of directly probing potential biological magnetoreception within sub‐cellular structures. Direct spatial imaging of magnetic field effects (MFEs) by magnetic intensity modulation (MIM) imaging is demonstrated along with transfer and inversion of the magnetic field sensitivity of the flavin semiquinone radical concentration to that of the ground state of the flavin under strongly pumped reaction cycling conditions. A low field effect (LFE) on the flavin semiquinone–adenine radical pair is resolved for the first time, with important implications for biological magnetoreception through the radical pair mechanism.     

Integrated One‐Flow Synthesis of Heterocyclic Thioquinazolinones through Serial Microreactions with Two Organolithium Intermediates

The synthesis of pharmaceutical compounds via short‐lived intermediates in a microreactor is attractive, because of the fast flow and high throughput. Additionally, intermediates can be utilized sequentially to efficiently build up a library in a short time. Here we present an integrated microfluidic synthesis of biologically active thioquinazolinone libraries. Generation of o‐lithiophenyl isothiocyanate and subsequent reaction with aryl isocyanate is optimized by controlling the residence time in the microreactor to 16 ms at room temperature. Various S‐benzylic thioquinazolinone derivatives are synthesized within 10 s in high yields (75–98 %) at room temperature. These three‐step reactions involve two organolithium intermediates, an isothiocyanate‐functionalized aryllithium intermediate, and a subsequent lithium thiolate intermediate. We also demonstrate the gram‐scale synthesis of a multifunctionalized thioquinazolinone in the microfluidic device with a high yield (91 %) and productivity (1.25 g in 5 min).     

Tuning the Redox Properties of a Nonheme Iron(III)–Peroxo Complex Binding Redox‐Inactive Zinc Ions by Water Molecules

Redox‐inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox‐inactive metal ions. The coordination of two water molecules to a Zn²⁺ ion in (TMC)Fe^III‐(O₂)‐Zn(CF₃SO₃)₂ ( 1 ‐Zn²⁺) decreases the Lewis acidity of the Zn²⁺ ion, resulting in the decrease of the one‐electron oxidation and reduction potentials of 1 ‐Zn²⁺. This further changes the reactivities of 1 ‐Zn²⁺ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1 ‐Zn²⁺, whereas 1 ‐Zn²⁺ coordinating two water molecules, (TMC)Fe^III‐(O₂)‐Zn(CF₃SO₃)₂‐(OH₂)₂ [ 1 ‐Zn²⁺‐(OH₂)₂], releases the O₂ unit in the oxidation reaction. In the reduction reactions, 1 ‐Zn²⁺ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1 ‐Zn²⁺‐(OH₂)₂. The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.     

Effect of Lateral Linear Stiffness on Nonlinear Characteristics of Hunting Motion of a Railway Wheelset

Railway wheelset experiences the problem of hunting above a critical speed, which is a kind of self-excited oscillation. At the critical speed, it is known that the system undergoes a subcritical Hopf bifurcation. Therefore, for clarifying the nonlinear characteristics of hunting it is very important to detect, for example, the nonlinear forces in the wheelset due to the creep forces acting between the wheels and rails, and the nonlinear component of the resorting forces by the suspensions. However, it is impossible to determine each force quantitatively. In the present paper, it is first shown, by using the center manifold theory and the method of normal form, that the nonlinear characteristics of the bifurcation in a wheelset model with two degrees of freedom are governed by a single parameter, hence each nonlinear force need not be detected when examining the nonlinear characteristics. Also, a method of determining the governing parameter from experimentally observed radiuses of the unstable limit cycle is proposed. Next, we experimentally investigate the variation of the parameter due to the presence of linear spring suspensions in the lateral direction and discuss the variation of the nonlinear characteristics of the hunting motion, which depends on the lateral stiffness. As a result, the improvement of the stability of the wheelset against the disturbance by the linear spring suspensions is clarified.