DFT Study of a 5‐endo‐trig‐Type Cyclization of 3‐Alkenoic Acids by Using Pd–Spiro‐bis(isoxazoline) as Catalyst: Importance of the Rigid Spiro Framework for Both Selectivity and Reactivity

The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst.     

The Euler multiplicity and addition-deletion theorems for multiarrangements

The addition–deletion theorems for hyperplane arrangements,which were originally shown by Terao [J. Fac. Sci. Univ. TokyoSect. IA Math. 27 (1980) 293–320.], provide useful waysto construct examples of free arrangements. In this article,we prove addition–deletion theorems for multiarrangements.A key to the generalization is the definition of a new multiplicity,called the Euler multiplicity, of a restricted multiarrangement.We compute the Euler multiplicities in many cases. Then we applythe addition–deletion theorems to various arrangements,including supersolvable arrangements and the Coxeter arrangementof type A₃, to construct free and non-free multiarrangements.     

Far infrared optical properties of high Tc superconductors LnBa2Cu3Ox (Ln=Y, Ho, Er, Sm, GD, Dy, Eu, Pr)

Systematic measurements of the far infrared reflection spectra of high T_c superconductors LnBa₂Cu₃O_x for various Ln as shown in the title were performed. Infrared reflection spectra of tetragonal LnBa₂Cu₃O_x exhibit Reststrahlen vibration near 640, 590, 530, 355 and 250 cm^–1, common to these materials, and the spectra of the orthorhombic LnBa₂Cu₃O_x exhibit the characteristics of free carriers except PrBa₂Cu₃O_x with weak phonon structures near 617, 570, 317 and 285 cm^–1. PrBa₂Cu₃O_x is not a superconductor, and it has no characteristic broad band due to free carriers for all x in the range of 6 to 7. Lattice dynamical calculation was performed by the use of the shell model and the calculated results express quite well the characteristic features of infrared experiments.     

Optimal consumption models in economic growth

We study the optimal consumption problem in the one-sector model of economic growth under uncertainty. We show the existence of a classical solution of the Hamilton-Jacobi-Bellman equation associated with the stochastic optimization problem, and then give an optimal consumption policy in terms of its solution.     

Synthesis and structural revision of marine eicosanoid agardhilactone

Synthesis of the marine eicosanoid agardhilactone has been achieved. The relative and absolute configuration of agardhilactone was successfully determined.     

Surface cleaning of germanium nanodot ionization substrate for surface‐assisted laser desorption/ionization mass spectrometry

In surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS), a chemical background signal, arising from organic contaminants such as plasticizers, is frequently observed mainly under m/z ca. 600, which impairs the advantages of the matrix‐free approach. Silver salts, which are used for the cationization of aromatic compounds, are also difficult to remove completely after the measurements. In this study, surface cleaning techniques used in semiconductor processing were used to clean our developed silicon‐based SALDI substrate on which self‐assembled germanium nanodots (GeNDs) had been deposited (termed a GeND chip). An immersion cleaning method using acetone with sonication, and a sulfuric‐peroxide mixture (SPM) cleaning method using a mixture of H₂SO₄/H₂O₂/deionized water, were examined for their effectiveness in removing organic compounds and residual silver salts. Removal of both types of contaminants was successfully performed by SPM cleaning. The limit of detection for glutathione was improved from ca. 5 pmol without cleaning to ca. 50 fmol after the SPM cleaning. Since GeND chips can tolerate acidic cleaning and sonication due to their chemical inertness and rigid nanodot structures, they appear to be an ideal reusable SALDI substrate. Copyright © 2009 John Wiley & Sons, Ltd.     

Optically transparent superhydrophobic TEOS-derived silica films by surface silylation method

Optically transparent silica films were prepared at room temperature (~27°C) by keeping the molar ratio of TEOS:MeOH:H₂O (0.001 M NH₄F) constant at 1:19.29:6.20, respectively. A surface chemical modification of the films was done with alkylchlorosilanes at different concentrations from 0 to 1 vol. % and aging times varied from half to 2 h. The DMCS and TMCS surface modified silica films showed the static water contact angle of 146° and 162°, respectively. When the DMCS and TMCS modified films were cured at temperatures higher than 240 and 275°C, respectively, the films became superhydrophilic. Further, the humidity study was carried out at a relative humidity of 90% at 30°C temperature over 60 days. We characterized the water repellent silica films by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, % of optical transmission, humidity tests and contact angle measurements.