An air-stable P-chiral phosphine ligand for highly enantioselective transition-metal-catalyzed reactions

A new P-chiral phosphine ligand, (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline, has been prepared by the reaction of enantiomerically pure tert-butylmethylphosphine-borane with 2,3-dichloroquinoxaline. This ligand, in contrast to most of the previously reported P-chiral ligands, is an air-stable solid and exhibits excellent enantioselectivities in both Rh-catalyzed asymmetric hydrogenations and Rh- or Pd-catalyzed carbon-carbon bond-forming reactions.     

New design of a radio-frequency plasma torch

A numerical model has been developed for predicting the two-dimensional flow and temperature fields in a radio-frequency (rf) plasma torch. The method employed here is based on Boulos' model with the exception of the boundary conditions for the electric and magnetic field equations. Calculations have been made for the confirmation of a new sample injection method, which is capable of completely evaporating refractory materials at high feeding rates without interfering with the stability of the plasma. In the newly designed torch, the reagent is radially injected into the hottest part of the plasma through quartz capillary tubes set symmetrically between an inductor coil. Experimental investigations have also been performed for verifying the proper function of the design. These results provide evidence that our radial injection method developed here is more effective in practical processing than the conventional axial injection methods.     

Spin-oriented projectile fragments: The first application tog-factor measurements

Ejectile nuclei in the fragmentation of intermediate-energy heavy-ion projectiles were found to be largely spin polarized. The observed polarization as a function of the outgoing momentum was nicely explained by a simple kinematical argument based on the participant-spectator model of projectile fragmentation. The measurements extended to cover several different targets, incident energies, exit channels, and emission angles revealed that substantial polarization shows up widely in projectile fragmentation reactions. Furthermore, this polarization exhibits an interesting behavior which may be interpreted as a manifestation of a gradual change in the deflection angle from positive to negative values as the energy increases and/or the target-Z decreases. The present polarization results also suggests various applications of spin polarized radioactive beams. As the first example of such an application, we present a recent result on theg-factor measurements on neutron-rich nuclei.     

Signal quality improvement of holographic data storage using adaptive two-dimensional filter

Holographic data storage is being widely studied for the purpose of developing next-generation large optical memories. A prospective use of this type of memory is in building image archives in large-scale data centers. In particular, demand for energy conservation at data centers, and therefore for holographic data storage, is growing. In holographic data storage, interference between bits occurs owing to wave aberration in the optical system, shrinkage of the medium, and crosstalk noise from neighboring holograms during multiplex recording; as a result of the interference, the reproduced image deteriorates and the bit error rate (BER) increases. In this study, to reduce the BER in both off-axis-type recording and coaxial-type recording, a two-dimensional finite impulse response (FIR) filter is applied to a reproduced image that has been recorded by angle multiplex recording and shift multiplex recording. First, for the optimization of the FIR filter coefficients, the linear minimum mean square error (LMMSE) method is applied; this method optimizes the coefficients by reducing the BER. Furthermore, for evaluating the optimization performance of the LMMSE method, the optimization performance is compared with that of the real-coded genetic algorithm (RCGA), which has the capability to search a wide range of coefficients. The optimization by the LMMSE method has been found to be excellent for off-axis-type recording but not for coaxial-type recording. It is speculated that this is because of the brightness irregularity in the reproduced image, resulting from crosstalk. On the other hand, a marked reduction in the BER is observed using the RCGA, despite the brightness irregularity. In this study, the effectiveness of the LMMSE method for signals recorded by coaxial-type recording, in which large brightness irregularity is expected, is examined using automatic gain control (AGC). It is found that the application of AGC reduces the BER even in the case of coaxial-type recording.     

Reaction of cyclic imidates with α,β‐unsaturated esters: Synthesis of new pyrrolo[2,1‐b]‐1,3‐oxazine and pyrido[2,1‐b]‐1,3‐oxazine derivatives

The cycloaddition reaction of cyclic imidates, 2‐benzyl‐5,6‐dihydro‐4H‐1,3‐oxazines 1a , 1b , 1c , 1d , 1e , 1f , with dimethyl acetylenedicarboxylate 2 , trimethyl ethylenetricarboxylate 4 , or dimethyl 2‐(methoxymethylene)malonate 6 afforded new fused heterocyclic compounds, such as methyl (6‐oxo‐3,4‐dihydro‐2H‐pyrrolo[2,1‐b]‐1,3‐oxazin‐7‐ylidene)acetates 3a , 3b , 3c , 3d , 3e , 3f (71–79%), dimethyl 2‐(6‐oxo‐3,4,6,7‐tetrahydro‐2H‐pyrrolo[2,1‐b]‐1,3‐oxazin‐7‐yl)malonates 5b , 5c , 5d , 5e , 5f (43–71%), or methyl 6‐oxo‐3,4‐dihydro‐2H,6H‐pyrido[2,1‐b]‐1,3‐oxazine‐7‐carboxylates 7a , 7b , 7c , 7d , 7e , 7f (32–59%), respectively. In these reactions, 1a , 1b , 1c , 1d , 1e , 1f (cyclic imidates, iminoethers) functioned as their N,C‐tautomers (enaminoethers) 2 to α,β‐unsaturated esters 2 , 4, and 6 to give annulation products 3 , 5 , and 7 following to the elimination of methanol, respectively. J. Heterocyclic Chem., (2011).     

Effect of Nonmagnetic Substitution on the Magnetic Properties and Charge-Transfer Phase Transition of an Iron Mixed-Valence Complex, (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)] (dto = C(2)O(2)S(2))

The iron mixed-valence complex (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)] exhibits a novel type of phase transition called charge-transfer phase transition (CTPT), where the thermally induced electron transfer between Fe(II) and Fe(III) occurs reversibly at ～120 K, in addition to the ferromagnetic phase transition at T(C) = 7 K. To investigate the mechanism of the CTPT, we have synthesized a series of magnetically diluted complexes (n-C(3)H(7))(4)N[Fe(II)(1-x)Zn(II)(x)Fe(III)(dto)(3)] (dto = C(2)O(2)S(2); x = 0-1), and carried out magnetic susceptibility and dielectric constant measurements and (57)Fe M?ssbauer spectroscopy. With increasing Zn(II) concentration (x), the CTPT is gradually suppressed and disappears at x ≈ 0.13. On the other hand, the ferromagnetic transition temperature (T(C)) is initially enhanced from 7 K to 12 K between x = 0.00 and 0.05, despite the nonmagnetic nature of Zn(II) ions, and then it decreases monotonically from 12 K to 3 K with increasing Zn(II) concentration. This anomalous dependence of T(C) on Zn(II) concentration is related to a change in the spin configuration of the ferromagnetic state caused by the partial suppression of the CTPT.     

Motional narrowing and ergodic bands in excited superdeformed states of 194Hg

The E(gamma) - E(gamma) coincidence spectra from the electromagnetic decay of excited superdeformed states in (194)Hg reveal surprisingly narrow ridges, parallel to the diagonal. A total of 100-150 excited bands are found to contribute to these ridges, which account for nearly all the unresolved E2 decay strength. Comparison with theory suggests that these excited bands have many components in their wave functions, yet they display remarkable rotational coherence. This phenomenon can be explained in terms of the combination of shell effects and motional narrowing.     

Inner-valence states of N2+ and the dissociation dynamics studied by threshold photoelectron spectroscopy and configuration interaction calculation

The N2(+) states lying in the ionization region of 26-45 eV and the dissociation dynamics are investigated by high-resolution threshold photoelectron spectroscopy and threshold photoelectron-photoion coincidence spectroscopy. The threshold photoelectron spectrum exhibits several broad bands as well as sharp peaks. The band features are assigned to the N2(+) states associated with the removal of an inner-valence electron, by a comparison with a configuration interaction calculation. In contrast, most of the sharp peaks on the threshold photoelectron spectrum are allocated to ionic Rydberg states converging to N2(2+). Dissociation products formed from the inner-valence N2(+) states are determined by threshold photoelectron-photoion coincidence spectroscopy. The dissociation dynamics of the inner-valence ionic states is discussed with reference to the potential energy curves calculated.