Group 3 Metal Initiators with an [OSSO]‐Type Bis(phenolate) Ligand for the Stereoselective Polymerization of Lactide Monomers

A series of 1,ω‐dithiaalkanediyl‐bridged bis(phenols) of the general type [OSSO]H₂ with variable steric properties and various bridges were prepared. The stoichiometric reaction of the bis(phenols) 1,3‐dithiapropanediyl‐2,2′‐bis(4,6‐di‐tert‐butylphenol), 1,3‐dithiapropanediyl‐2,2′‐bis[4,6‐di(2‐phenyl‐2‐propyl)phenol], rac‐2,3‐trans‐propanediyl‐1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐di(2‐phenyl‐2‐propyl)phenol], rac‐2,3‐trans‐butanediyl‐1,4‐dithiabutane diyl‐2,2′‐bis[4,6‐di(2‐phenyl‐2‐propyl)phenol], rac‐2,3‐trans‐hexanediyl‐1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐di(2‐phenyl‐2‐propyl)phenol], 1,3‐dithiapropanediyl‐2,2′‐bis[6‐(1‐methylcyclohexyl)‐4‐methylphenol] (C₁, R=1‐methylcyclohexyl), and 1,4‐dithiabutanediyl‐2,2′‐bis[6‐(1‐methylcyclohexyl)‐4‐methylphenol] with rare‐earth metal silylamido precursors [Ln{N(SiHMe₂)₂}₃(thf)_x] (Ln=Sc, x=1 or Ln=Y, x=2; thf=tetrahydrofuran) afforded the corresponding scandium and yttrium bis(phenolate) silylamido complexes [Ln(OSSO){N(SiHMe₂)₂}(thf)] in moderate to good yields. The monomeric nature of these complexes was shown by an X‐ray diffraction study of one of the yttrium complexes. The complexes efficiently initiated the ring‐opening polymerization of rac‐ and meso‐lactide to give heterotactic‐biased poly(rac‐lactides) and highly syndiotactic poly(meso‐lactides). Variation of the ligand backbone and the steric properties of the ortho substituents affected the level of tacticity in the polylactides.     

Isotope-selective ionization utilizing molecular alignment and non-resonant multiphoton ionization

We demonstrate laser nitrogen isotope separation, which is based on field-free alignment and angular-dependent ionization of ¹⁴N₂ and ¹⁵N₂ isotopologues. A linearly polarized short laser pulse (???~?795?nm, ?????~?60?fs) creates rotational wave packets in the isotopologues, which periodically revive with different revival times as a result of different moments of inertia. Another linearly polarized short laser pulse (???~?795?nm, ?????~?60?fs) ionizes one of the isotopologues selectively as a result of their different angular distributions. In the present experiments, the ion yield ratio R [=I(¹⁵N₂ ⁺)/I(¹⁴N₂ ⁺)] can be changed in the range from 0.85 to 1.22, depending on the time delay between the two laser pulses.     

Pressure-sensitive paint measurement on co-rotating disks in a hard disk drive

There is much demand for improvement in the performance of a hard disk drive (HDD) along with recent rapid developments of information technology. While high-speed disk rotation of a HDD is necessary to accommodate such needs, it causes disk flutter induced by pressure fluctuation on disks and degrades reliability of a HDD. In order to understand the mechanism of the fluttering phenomenon, it is important to know pressure field on the rotating disk. However, it is impossible to measure the pressure by ordinary methods such as pressure taps. Pressure-sensitive paint (PSP) is a pressure measurement technique based on the oxygen quenching of luminescence and enables us to measure the pressure non-invasively. In general, however, the temperature sensitivity of PSP makes it difficult to measure the precise pressure on the surface with temperature distribution. We measured the time-averaged pressure on the disk rotating at 10 000-20 000 rpm for the first time by adopting a temperature-insensitive PSP composed of pyrene sulfonic acid (PySO₃H) as a luminophore. It was found that the pressure forms a concentric circular distribution and decreases toward the center of the disk. Additionally, we elucidate how disk rotational speed and spacing between co-rotating disks influence on the pressure field.     

Cyclic q-MZSV sum

We present a family of identities ‘cyclic sum formula’ and ‘sum formula’ for a version of multiple q-zeta star values. We also discuss a problem of q-generalization of shuffle products.     

Selective colorimetric sensing of Co(II) in aqueous media with a spiropyran-amide-dipicolylamine linkage under UV irradiation

A spiropyran-amide-dipicolylamine linkage behaves as a colorimetric receptor for selective Co(2+) sensing in aqueous media under UV irradiation. This is promoted by strong coordination of Co(2+) with amide oxygens of the receptors and efficient photoisomerization of the spiropyran moieties.     

Dimerization of the allylzinc cation: selective coupling of allyl anions in a metallo-ene reaction

Metal assistance: Dimerization of the allylzinc monocation gives the dimetalated coupling product in quantitative yield. Kinetic and thermodynamic parameters of this reversible metallo-ene reaction have been determined. This reaction serves as a model system for the alkali-metal catalyzed production of 4-methylpentene.     

The evolution of fairness under an assortative matching rule in the ultimatum game

This paper studies how a matching rule affects the evolution of fairness in the ultimatum game. Gale et al. (Games Econ Behav 8: 56–90, 1995) show that under the random matching rule, a partially fair imperfect Nash equilibrium in which all proposers are fair but some responders are selfish is asymptotically stable in the limit as noise in learning vanishes if responders are noisier than proposers. This paper shows that, under an assortative matching rule, a mutually fair imperfect Nash equilibrium in which all proposers are fair and all responders are reciprocal is limit asymptotically stable as noise due to committed agents vanishes.     

Orientation of hyperfine magnetic fields of α-iron films produced by laser deposition

Iron films were produced by pulsed laser deposition (PLD) of iron in Ar gas and M?ssbauer spectra of these films were obtained at room temperature. The orientation of the hyperfine magnetic field was found to vary depending on the pressure of the Ar gas. Iron films produced at low Ar pressures exhibited magnetic fields parallel to the substrate surface. The magnetic field became increasingly perpendicular to the substrate with increasing Ar pressure. Collisions with Ar gas molecules reduced the translational energies of laser-evaporated iron atoms and thus the orientation of crystals formed on the substrate varied depending on the Ar pressure.     

A volume‐exclusion normalization procedure for quantitative Raman confocal microspectroscopy of immersed samples applied to human embryonic stem cells

Raman microspectroscopy is a quantitative instrumental method with considerable promise for the nondestructive analysis of living biological samples. Amongst samples of particular interest are human embryonic stem cells because of their therapeutic potential and because examination using Raman microspectroscopy does not appear to adversely affect this potential. However, it can be difficult to compare different spectra obtained with this technique and to quantify the native cellular constituents of such samples because their characteristic dimensions are difficult to establish or may vary from point to point. We present here a method to normalize spectra and estimate sample thicknesses based on a reference component present in the basal cell culture medium when we perform spectroscopy on colonies of living cells. Because more basal medium is displaced from the sampling volume as the cell layer increases in thickness, and because this component is present in the medium but excluded from cells, a concomitant decline therefore occurs in the intensity of the Raman scattering from the reference component. This permits comparisons between samples because their spectra can be scaled in inverse relation to their excluded volumes. Furthermore, estimations of sample thicknesses can also be obtained based on the same concept. Thus, the absolute quantification of cellular components becomes possible because cell sample volumes can be determined. Although applied to human embryonic stem cells, the approach is sufficiently general to be adapted for use with other samples. Copyright © 2011 John Wiley & Sons, Ltd.