High iso Aldehyde Selectivity in the Hydroformylation of Short‐Chain Alkenes

The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed.     

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.     

Exploring the operation of a tiny heat engine

We model a tiny heat engine as a Brownian particle that moves in a viscous medium in a sawtooth potential (with or without load) assisted by alternately placed hot and cold heat baths along its path. We find closed form expression for the steady-state current as a function of the model parameters. This enables us to deal with the energetics of the model and evaluate either its efficiency or its coefficient of performance depending upon whether the model functions either as a heat engine or as a refrigerator, respectively. We also study the way current changes with changes in parameters of interest. When we plot the phase diagrams showing the way the model operates, we not only find regions where it functions as a heat engine and as a refrigerator but we also identify a region where the model functions as neither of the two.     

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     

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 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.     

Sedimentation rate of erythrocyte from physics prospective

The European Physical Journal E - A two-dimensional multiphase cellular automaton (CA) model is proposed for the prediction of growth kinetics and microstructural evolution during peritectic...     

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.