Efficient catalysis of Nazarov cyclization using a cationic iridium complex possessing adjacent labile coordination sites

The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BARF)2 having adjacent labile sites has been found to be a very effective catalyst for promoting the Nazarov cyclization of aryl vinyl and divinyl ketones. Spectroscopic evidence for a substate-catalyst complex before cyclization is presented. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via chelation.     

Freon (CHF<Subscript>3</Subscript>)-assisted atomization for the determination of titanium using ultrasonic slurry sampling–graphite furnace atomic absorption spectrometry (USS–GFAAS): a simple and advantageous method for solid samples

A simple and advantageous method for the determination of titanium using graphite furnace atomic absorption spectrometry with slurry sampling has been developed. Titanium is one of the refractory elements that form thermally stable carbides in the graphite tube, which leads to severe memory effects. Trifluoromethane (Freon-23) was applied in the purge gas during the atomization step or alternatively just prior to the atomization to successfully eliminate the problems of carbide formation and increase the lifetime of the furnace tube which could be used for more than 600 heating cycles. A flow rate of 40 mL min^–1 (5% of Freon in argon) was used to obtain symmetrical peaks with no tailing. However, when the gas flow rate was too high (250 mL min^–1) the peak-tailing and memory effects reappeared. Ti was determined in various materials covering a wide range of concentrations, from 2.8 g g^–1 to 12% (m/m) Ti. The accuracy of the method was confirmed by analyzing certified reference materials (CRMs) or by comparing the results with those obtained using inductively coupled plasma–atomic emission spectrometry (ICP–AES) after decomposition of the samples. The materials analyzed were soil, plant, human hair, coal, urban particulate matters, toothpaste, and powdered paint.     

Tandem Nazarov cyclization-michael addition sequence catalyzed by an Ir(III) complex

The first examples of a tandem Nazarov cyclization/Michael addition process are described. The sequence is efficiently catalyzed by Ir[Me(CO)(dppe)(DIB)]2+ and occurs with high diastereoselectivity, creating three contiguous stereocenters. The mechanistic factors controlling the reactivity and diastereoselectivity are discussed.     

Template-induced enhanced ordering under confinement

We report a surprisingly strong ordering of Si-(CH(3))(2) groups upon confinement between two surfaces, an oxidized poly(dimethyl siloxane) (PDMS(ox)) elastomer and a methyl-terminated self-assembled monolayer (octadecyltrichlorosilane (OTS)) on sapphire substrates. This enhanced ordering is induced by the template of ordered methyl groups of OTS and is not observed for other surfaces (fluorinated monolayers and sapphire substrates). This strong ordering is reminiscent of layering observed for confined symmetric molecules between two mica surfaces but was expected to vanish between rough macroscopic surfaces. These results provide new insights on confined structure at the interface between two solids and are important in the understanding of surface-controlled processes of practical importance.     

Effect of chain stiffness on the morphology of diblock copolymer melts

The authors have studied the microphase separation of symmetric diblock copolymers with variable block stiffness and different block chain lengths using coarse-grained molecular dynamics simulations. The simulation results show that for symmetric diblock copolymers, a combination of chain length and relative stiffness between the blocks may play the major role in determining the equilibrium morphology of the system. When the variation in stiffness between blocks is small, the equilibrium morphology of the diblock system is found to be lamellar; this is also the case for systems with small chain lengths, regardless of the difference in block stiffness. However, in systems with longer chains with modest variation in stiffness between the blocks, an ordered cylindrical phase is formed in which the stiffer blocks form cylinders completely surrounded by the flexible components. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2556–2565, 2009     

Effect of thermal inhomogeneity on the performance of a Brownian heat engine

We explore the effect of thermal inhomogeneity on the performance of a Brownian heat engine by considering exactly solvable models. We first consider a Brownian heat engine which is modeled as a Brownian particle in a ratchet potential moving through a highly viscous medium driven by the thermal kick it receives from a linearly decreasing background temperature. We show that even though the energy transfer due to kinetic energy is neglected, Carnot efficiency cannot be achieved at quasistatic limit. At quasistatic limit, the efficiency for such a Brownian heat engine approaches the efficiency of endoreversible engine η = 1 ? √T _c /T _h [F.L. Curzon, B. Ahlborn, Am. J. Phys. 43, 22 (1975)]. Moreover, the dependence of the current, the efficiency and the coefficient of performance of the refrigerator on the model parameters is also explored via Brownian dynamic simulations and analytically. We show that such a Brownian heat engine has a higher performance when acting as a refrigerator than when operating as a device subjected to a piecewise constant temperature [M. Asfaw, M. Bekele, Eur. Phys. J. B 38, 457 (2004), M. Asfaw, M. Bekele, Physica A 384, 346 (2007)]. Furthermore, for a Brownian heat engine driven by a piecewise constant temperature, we show that systematic removal of the inhomogeneous medium leads to a homogeneous medium with a uniform temperature where the effect of temperature inhomogeneity is replaced by an effective load.     

Effects of annealing on the structure and photoluminescence of ZnO-sputtered coaxial nanowires

We reported the preparation and annealing effects of Zinc oxide ZnO/SiO_x core-shell nanowires, in which ZnO shell layers were deposited by sputtering. Based on scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and photoluminescence (PL) investigations, we monitored structural and optical changes with respect to the post-annealing process. The samples were mostly amorphous with some crystalline ZnO structure, whereas annealing at 900-1000 °C reduced the amount of Zn elements. Thermal annealing induced change in the shape of the PL emission spectra.