Chemical exchange reaction of glycinatocopper(II) complex in water: a theoretical study

The axial water exchange on glycinatocopper(II) complexes was theoretically investigated by using density functional theory (DFT) calculations. Glycinatocopper(II) complexes are well-known by the diffusion controlled exchange of axial ligands. Calculations using explicitly coordinating water molecules and solvent models showed that bis-glycinatocopper(II) complexes have a four-coordinate planar structure, in which waters are excluded from the axial positions of Cu(II) due to the Jahn-Teller effect. This may be because coordinating axial waters induce the discrepancy in the most stable ligand field splittings of inner 3d and outer 4d orbitals of the Cu(II) cation. To estimate the reactivity of the axial water exchange, we calculated the rate constant by calculating Gibbs free energies for the activation. As a result, we obtained the rate constant as k = 3.61 x 10(10) s(-1) in aqueous solution at T = 298.15 K. This rate constant is slightly larger than that of the diffusion controlled exchange of axial waters, which is experimentally observed in the order of 10(9) s(-1). Finally, we determined the structures of tris-glycinatocopper(II) complexes. It was consequently found that the third glycine is coordinated to Cu with the amino groups as experimentally observed.     

Allosteric function facilitates template assisted olefin metathesis

Template assisted olefin metathesis of an allosteric host to give the corresponding bicyclic compound was achieved and can allosterically bind the template guest diamines, and with different affinity and cooperativity.     

New anthraquinone and iridoid from the fruits of Morinda citrifolia

From the fruits of Morinda citrifolia L., one new anthraquinone, 5,15-O-dimethylmorindol, together with five known anthraquinones and one new iridoid, morindacin, together with two known iridoids, were isolated. Their structures were elucidated by analysis of spectroscopic data.     

Restricted hydration structures of Rb and Br ions confined in slit-shaped carbon nanospace

Hydration structures of "nanosolutions" around both cation and anion for rubidium bromide confined in nanospaces (pore width = 1.1 nm) of activated carbon fiber were determined with EXAFS measurements and related analysis. The analytical results indicate that the ionic solutions confined in hydrophobic nanospaces tend to form an incomplete dehydration structure, because of the spatial restriction by the nanospace and capturing water molecules in the ordered structure.     

First determination of the absolute stereochemistry of a naturally occurring 1,1'-biphenanthrene, (--)-blestriarene C,and its unexpected photoracemization

A naturally occurring 1,1'-biphenanthrene, blestriarene C, was prepared and its absolute stereochemistry was determined to be Sa-(-) by an empirical method, during which the compound was found to undergo rapid photoracemization even under ambient light exposure.     

Measurement of Wavefront Aberration of Human Eye Using Talbot Image of Two-Dimensional Grating

The measurement of human ocular aberration is now frequently performed because of the increase in refractive surgery on the human cornea. The Hartmann-Shack (H-S) wavefront sensor is considered to be the most useful wavefront sensor, and a calculation method for wavefront aberration has been established. New methods of measuring wavefront aberrations of human eyes, using the Talbot image of a two-dimensional grating as a wavefront sensor and local shift of the Talbot image to calculate tilt of the wavefront are shown. The shift of the Talbot image was determined by comparing the phases of fundamental spatial frequency between the grating and the local patch of the Talbot image by Fourier transformation. The actual experiment was performed using a modified commercially available wavefront analyzer. Using these methods, Talbot images were obtained from model eyes and a human eye, and wavefront shapes were successfully reconstructed. Wavefront aberrations can be measured even when the obtained image is degraded by defocusing or scattering.     

BINAP/1,4-diamine-ruthenium(II) complexes for efficient asymmetric hydrogenation of 1-tetralones and analogues

A combined system of a RuCl(2)(binap)(1,4-diamine) complex and t-C(4)H(9)OK in i-C(3)H(7)OH catalyzes enantioselective hydrogenation of various 1-tetralone derivatives and some methylated 2-cyclohexenones. Hydrogenation of 2-methyl-1-tetralone under dynamic kinetic resolution gives the cis alcohol with high ee. [reaction: see text]