Sn(iv) phosphonates as catalysts in solvent-free Baeyer-Villiger oxidations using H(2)O(2)

We have designed a new family of layered Sn(iv)phosphonate (SnPP) materials which are very efficient catalysts in the BV oxidation of aromatic aldehydes without any solvent and using aqueous H(2)O(2) (30%) as the oxidant.     

Microwave assisted synthesis of thiazolo[3,2‐b][1,2,4]‐triazoles containing 1,8‐naphthyridine moiety

A simple and efficient protocol for the synthesis of 5‐aryl‐2‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐thiazolo[3,2‐b][1,2,4]triazoles ( 4 ) is achieved by cyclocondensation of 3‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐1,2,4‐triazoles ( 3 ) with α‐halogenoketones in anhyd. methanol under microwave irradiation. The products are obtained in good yields and in a state of high purity.     

Two‐Dimensional Molybdenum Trioxide and Dichalcogenides

In the quest to discover the properties of planar semiconductors, two‐dimensional molybdenum trioxide and dichalcogenides have recently attracted a large amount of interest. This family, which includes molybdenum trioxide (MoO₃), disulphide (MoS₂), diselenide (MoSe₂) and ditelluride (MoTe₂), possesses many unique properties that make its compounds appealing for a wide range of applications. These properties can be thickness dependent and may be manipulated via a large number of physical and chemical processes. In this Feature Article, a comprehensive review is delivered of the fundamental properties, synthesis techniques and applications of layered and planar MoO₃, MoS₂, MoSe₂, and MoTe₂ along with their future prospects.     

Explicit algebraic Reynolds stress model (EARSM) for compressible shear flows

We develop an explicit algebraic Reynolds stress model (EARSM) for high-speed compressible shear flows and validate the model with direct numerical simulation (DNS) data of homogeneous shear flow and experimental data of high-speed mixing-layers. Starting from a pressure–strain correlation model that incorporates compressibility effects, the weak-equilibrium assumption is invoked to derive the EARSM closure expression. The resulting closure is fully explicit and physically realizable and is a function of mean flow strain rate, rotation rate, turbulent kinetic energy, dissipation rate, and gradient Mach number. Homogeneous shear flow calculations show that the model captures the asymptotic behavior of DNS quite well. Linear EARSM calculations of a plane supersonic mixing-layer are performed, and comparison with experimental data shows good agreement. Salient results are agreement of streamwise velocity similarity profiles, mixing-layer spreading rates, and capturing the Langley curve trend.     

Characterizing the rotation of non symmetric objects in an optical tweezer

We present an optical tweezer based study of the rotation of microscopic objects with shape asymmetry. Thermal fluctuations and rotations are simultaneously monitored through laser back scattering. The rotation causes a modulation in intensity of the back scattered light incident on a quadrant photo detector. The resulting power spectrum is a modified Lorentzian with additional peaks located at the fundamental rotational frequency of the object and at the integer harmonics. The manifestation of these peaks reveals that the rotations are periodic but with varying angular velocity. We model our experimental results to illustrate the hydrodynamic interplay between the rotor and the surrounding medium that results in the time dependence of the angular speed of the former. Further, we demonstrate the use of video microscopy for characterization of low reflectivity rotors, such as biological cells. We propose through these studies that an analysis of these rotations can provide insights into the role of hydrodynamics at micron levels.     

Polarization of line radiation in the presence of external electric quadrupole and uniform magnetic fields

The polarization of emission lines formed in a medium immersed in external electric and magnetic fields is studied. The electric field is assumed to be quadrupolar in nature, while the magnetic field is uniform. We show that the quadrupole electric field produces line splitting which is characteristically different from the Zeeman effect. While the line components emitted along the quantization axis are circularly polarized in Zeeman effect, they are, in contrast, linearly polarized in the case of a pure quadrupole electric field. The emission perpendicular to the quantization axis produces three linearly polarized components in Zeeman effect, whereas only two linearly polarized components are observed in the case of quadrupole electric fields. Lack of azimuthal symmetry in the quadrupole electric field leads to polarized line components which appear quite differently for different azimuthal angles of the line of sight.     

Control of Switching Modes and Conductance Quantization in Oxygen Engineered HfOx based Memristive Devices

Hafnium oxide (HfO_x)‐based memristive devices have tremendous potential as nonvolatile resistive random access memory (RRAM) and in neuromorphic electronics. Despite its seemingly simple two‐terminal structure, a myriad of RRAM devices reported in the rapidly growing literature exhibit rather complex resistive switching behaviors. Using Pt/HfO_x/TiN‐based metal–insulator–metal structures as model systems, it is shown that a well‐controlled oxygen stoichiometry governs the filament formation and the occurrence of multiple switching modes. The oxygen vacancy concentration is found to be the key factor in manipulating the balance between electric field and Joule heating during formation, rupture (reset), and reformation (set) of the conductive filaments in the dielectric. In addition, the engineering of oxygen vacancies stabilizes atomic size filament constrictions exhibiting integer and half‐integer conductance quantization at room temperature during set and reset. Identifying the materials conditions of different switching modes and conductance quantization contributes to a unified switching model correlating structural and functional properties of RRAM materials. The possibility to engineer the oxygen stoichiometry in HfO_x will allow creating quantum point contacts with multiple conductance quanta as a first step toward multilevel memristive quantum devices.     

Synthesis of the A,B,C-ring system of hexacyclinic acid

[structure: see text] The synthesis of the A,B,C-ring system (2) of hexacyclinic acid (1) is achieved starting from a selective Diels-Alder reaction followed by vinyl cuprate addition. The diastereoselective reduction of the ketone carbonyl at C16 could be achieved with LiAlH(4). An intramolecular Michael addition established the ring system stereoselectively, providing access to the selective generation of 9 out of the 14 stereocenters of hexacyclinic acid.