Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

Quantum Nernst effect

It is theoretically predicted that the Nernst coefficient is strongly suppressed and the thermal conductance is quantized in the quantum Hall regime of the two-dimensional electron gas. The Nernst effect is the induction of a thermomagnetic electromotive force in the y-direction under a temperature bias in the x-direction and a magnetic field in the z-direction. The quantum nature of the Nernst effect is analyzed with the use of a circulating edge current and is demonstrated numerically. The present system is a physical realization of the non-equilibrium steady state.     

A note on the angular distribution of the characteristic surface loss intensity of electrons with non-normal incidence to the foils

By using a quantized theory of non-radiative surface plasmon in a semi-infinite electron gas, where retardation is taken into account, the differential surface loss intensity of electrons in a metal foil is calculated for the case of non-normal incidence of electron to the metal surface. The result shows that the differential surface loss intensity neither has a zero at θ = 0 for the case of normal incidence nor has a zero at a forward direction (θ ≠ 0, φ = 0) for the case of non-normal incidence, whose existences were predicted by electrostatic theories, but diverges as 1/θ at θ = 0 for both cases. It is also shown that, when the angle of incidence is greater than a certain critical value, there is a region of direction to which incident electrons can be scattered by exciting any one of surface plasmons with three different wave vectors.     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Photoinduced intramolecular electron-transfer reactions in carbazole-fullerene and phenothiazine-fullerene linked compounds in benzene and benzonitrile as studied by fluorescence, transient absorption, time-resolved EPR, and magnetic field effects

Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C₆₀) (Cz(8)C₆₀) and phenothiazine (Ph)-C₆₀ (Ph(n)C₆₀ (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C₆₀ (¹C₆₀ ^*) occurred in Cz(8)C₆₀, but not to the triplet excited state (³C₆₀ ^*), while the intramolecular electron-transfer to both¹C₆₀ ^* and³C₆₀ ^* occurred in Ph(n)C₆₀ (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both¹C₆₀ ^* and³C₆₀ ^* took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents.     

Echolocation range of captive and free-ranging baiji (Lipotes vexillifer), finless porpoise (Neophocaena phocaenoides), and bottlenose dolphin (Tursiops truncatus).

The interclick intervals of captive dolphins are known to be longer than the two-way transit time between the dolphin and a target. In the present study, the interclick intervals of free-ranging baiji, finless porpoises, and bottlenose dolphins in the wild and in captivity were compared. The click intervals in open waters ranged up to 100-200 ms, whereas the click intervals in captivity were in the order of 4-28 ms. Echolocation of free-ranging dolphins appears to adapt to various distance in navigation or ranging, sometimes up to 140 m. Additionally, the difference of waveform characteristics of clicks between species was recognized in the frequency of maximum energy and the click duration.     

Complex impedance spectra of chip inductor using Li–Zn–Cu–Mn ferrite

A multi-layer chip inductor (MCI) was fabricated using polycrystalline Li–Zn–Cu–Mn ferrite and the green-sheet technique, and its complex impedance spectrum was evaluated with the help of numerical calculations. The complex impedance spectra of the MCI component using Ni–Zn–Cu ferrite, which have been widely used for this application, were very sensitive to the residual stress and deviated much from the calculated values; however, it was found that the complex impedance spectrum of the MCI component using Li–Zn–Cu–Mn ferrite is quite well reproduced by calculation, where the complex permittivity and permeability of the polycrystalline ferrite as well as the MCI dimensions, were used. It implied that the magneto-striction effect was negligible in case of MCI using Li–Zn–Cu–Mn ferrite, and that the difference was related to magneto-strictive coefficient of the polycrystalline ferrite. Consequently, utilization of Li–Zn–Cu–Mn ferrite enabled us to easily design the complex impedance of MCI component.     

Low-lying states of 6He studied via the 6Li(t,3He)6He reaction

We present the recent experimental results on the ⁶He structure studied by the ⁶Li(t, ³He)⁶He reaction at 336 MeV. Above the conspicuous peaks for ground and first excited states for ⁶He, we have observed a broad structures at E _x∼ 5 MeV, and E _x∼ 15 MeV. The angular distribution of this structure exhibits the dominance of a ΔL = 1 transition, indicating the existence of intruder dipole states at low excitation energies in ⁶He. A slight admixture of positive-parity states in this structure has been indicated as well. Received: 1 May 2001 / Accepted: 4 December 2001     

Phase rotation scheme of laser-produced ions for reduction of the energy spread

In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented.