Nickel-catalyzed indium(I)-mediated double addition of aldehydes to 1,3-dienes

In the presence of InI, Ni(acac)2 and PPh3, several 1,3-dienes were reacted with two molecules of aldehyde to give the corresponding 1,4- and 1,6-diols. The regioselectivity of the 1,4-/1,6-diol was efficiently regulated by the addition of water; the 1,6-diol was obtained selectively in dry THF, whereas the 1,4-diol was obtained predominantly in DMI containing a small amount of water.     

Nickel-catalysed bis-allylation of internal alkynes with triallylindium

The Ni-catalysed reaction of triallylindium with internal alkynes underwent bis-allylation to afford octa-1,4,7-trienes in high yield.     

Symmetry properties of three-dimensional magnetization distributions induced by focused circularly polarized lights

We analyze symmetry properties of the three-dimensional magnetization distribution in the optic-magneto film induced by focused circularly polarized lights. The magnetization distributions are derived and evaluated based on the vector diffraction theory and the inverse Faraday effect of the isotropic and nonmagnetically ordered material. It is shown that for any radial symmetrical amplitude, phase, or hybrid amplitude-phase pupil filter, the magnetization distribution of the axial component is circular symmetric but those of the radial and azimuthal components are annular symmetric with regard to the optical axis. All of the three components have a symmetric distribution with regard to the focal plane. The direction of both axial and radial components can be inversed with the helicity of incident circularly polarized light but the direction of azimuthal component is independent of helicity. The axial component has a decisive effect to all-optical magnetic recording, and within the effective axial range, the size of its magnetization domain hardly expands in the transverse direction.     

Ferromagnetic Intermolecular Interaction of N-Protonated Pyridylphenylcarbene

Abstract

The HCl and DCl salts of pheny1-4-pyridyldiazomethane were prepared and irradiated at 6 K to generate the carbenes. Their ESR spectra indicated presence of plural triplet carbenes with slightly-different zero-field splitting constants. Besides the triplet species, we found a quintet species whose signal intensity decreases with increasing temperature. The quintet spin state was concluded to be a ground state which was produced by an intermolecular ferromagnetic interaction of the triplet carbenes. The ferromagnetic interaction would be explained by the McConnell mechanism, judging from the crystal structure of the HCl salt of phenyl-4-pyridylketone.     

Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

New opportunities offered by compact sub‐nanosecond supercontinuum sources in ultra‐broadband multiplex CARS microspectroscopy

We report, to the best of our knowledge, the first turn‐key and compact dual‐output sub‐nanosecond supercontinuum source applicable to ultrabroadband multiplex coherent anti‐Stokes Raman scattering microspectroscopy of biological samples. The light source design and the microspectroscopy setup are described in details. Easy multicolour imaging of Caenorhabditis elegans nematode is operated successfully and discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Force-field parametrization based on radial and energy distribution functions

We propose a novel force-field-parametrization procedure that fits the parameters of potential functions in a manner that the pair distribution function (DF) of molecules derived from candidate parameters can reproduce the given target DF. Conventionally, approaches to minimize the difference between the candidate and target DFs employ radial DFs (RDF). RDF itself has been reported to be insufficient for uniquely identifying the parameters of a molecule. To overcome the weakness, we introduce energy DF (EDF) as a target DF, which describes the distribution of the pairwise energy of molecules. We found that the EDF responds more sensitively to a small perturbation in the pairwise potential parameters and provides better fitting accuracy compared to that of RDF. These findings provide valuable insights into a wide range of coarse graining methods, which determine parameters using information obtained from a higher-level calculation than that of the developed force field. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Extension of the LP-Newton method to conic programming problems via semi-infinite representation

Numerical Algorithms - The LP-Newton method solves linear programming (LP) problems by repeatedly projecting a current point onto a certain relevant polytope. In this paper, we extend the...     

Exhaustive search of the configurational space of heat-shock protein 90 with its inhibitor by multicanonical molecular dynamics based dynamic docking

Multicanonical molecular dynamics based dynamic docking was used to exhaustively search the configurational space of an inhibitor binding to the N-terminal domain of heat-shock protein 90 (Hsp90). The obtained structures at 300 K cover a wide structural ensemble, with the top two clusters ranked by their free energy coinciding with the native binding site. The representative structure of the most stable cluster reproduced the experimental binding configuration, but an interesting conformational change in Hsp90 could be observed. The combined effects of solvation and ligand binding shift the equilibrium from a preferred loop-in conformation in the unbound state to an α-helical one in the bound state for the flexible lid region of Hsp90. Thus, our dynamic docking method is effective at predicting the native binding site while exhaustively sampling a wide configurational space, modulating the protein structure upon binding.     

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility**

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives ( 1 and 2 ) as subunits of 8-AGNR , with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR . The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm² V⁻¹ s⁻¹ for the 8-AGNR .