A Directly Fused Subporphyrin Dimer with a Wavelike Structure

[Ni(cod)₂]‐mediated intramolecular reductive coupling of β–β′ linked meso,meso′‐dibromosubporphyrin dimer gave the anti‐isomer of meso–meso′, β–β′ doubly linked subporphyrin dimer as the first example of a fused subporphyrin dimer. The fused dimer 3 _anti displays an wavelike coplanar structure, a perturbed and red‐shifted absorption spectrum, reversible redox behaviors with a decreased electrochemical HOMO–LUMO band gap, and a short S₁‐state lifetime owing to the delocalized π‐electronic network.     

Artificial DNA made exclusively of nonnatural C-nucleosides with four types of nonnatural bases

We describe a new class of DNA-like oligomers made exclusively of nonnatural, stable C-nucleosides. The nucleosides comprise four types of nonnatural bases attached to a deoxyribose through an acetylene bond with the beta-configuration. The artificial DNA forms right-handed duplexes and triplexes with the complementary artificial DNA. The hybridization occurs spontaneously and sequence-selectively, and the resulting duplexes have thermal stabilities very close to those of natural duplexes. The artificial DNA might be applied to a future extracellular genetic system with information storage and amplifiable abilities.     

Parallel two-step phase-shifting digital holography using polarization

We propose an optical implementation of a parallel two-step phase-shifting digital holography that utilizes a polarization technique. The implementation uses a phase-shifting array device consisting of a retarder array attached to an image sensor, and does not require the optical system to image the phase-shifting array device onto the image sensor required for the previously reported optical implementation of the parallel two-step phase-shifting digital holography. Then, the proposed implementation is essentially simple to align and compose. A preliminary experiment showed that the parallel two-step phase-shifting digital holography based on the proposed implementation can remove the conjugate image clinging to the image reconstructed by Fresnel transform alone with DC term suppression. Also, when the reconstruction distance was changed, the qualities of the reconstructed images were quantitatively evaluated by using normalized root-mean-square error. It was clarified that the proposed implementation was superior to other parallel phase-shifting digital holographies and Fresnel transform alone. Thus, the validity of the proposed implementation was confirmed.     

Simultaneous observation of oxygen uptake curves and electronic states during room-temperature oxidation on Si(0 0 1) surfaces by real-time ultraviolet photoelectron spectroscopy

Ultraviolet photoelectron spectroscopy was used to measure the oxygen uptake, changes in work function due to the surface dipole layer of adsorbed-oxygen atoms, Δ?_SDL, and changes in band bending due to the defect-related midgap state, ΔBB, simultaneously during oxidation on Si(0 0 1) surface at room-temperature, RT, under an O₂ pressure of 1.3 × 10⁻⁵ Pa. The oxygen dosage dependence of Δ?_SDL revealed that dissociatively adsorbed-oxygen atoms occupy preferentially dimer backbond sites at the initial stage of Langmuir-type adsorption, which is associated with a rapid increase of ΔBB. When raising temperature to ∼600 °C, such preferential occupation of the dimer backbond sites by oxygen atoms is less significant and ΔBB becomes smaller in magnitude. The observed relation between Δ?_SDL and ΔBB indicates that point defects (emitted Si atoms + vacancies) are more frequently generated by oxygen atoms diffusing to the dimer backbond sites at lower temperature in RT −600 °C.     

Linewidth and relative intensity noise measurements of longitudinal modes in ultrahigh-speed mode-locked laser diodes

The longitudinal linewidth and corresponding relative intensity noise (RIN) of 10- and 40-GHz mode-locked laser diodes are measured for the first time to our knowledge. It is shown that the cavity Q value is a dominant parameter of the linewidth. It is also shown that the linewidth of the individual modes is almost constant. This means that the phase noise of each mode is almost the same in the mode-locked condition. The RIN value is larger for modes that are distant from the center longitudinal mode. This mode dependence is a consequence of the mode partition noise.     

Ultrasound enhances liposome-mediated gene transfection

Previous studies have shown that some series of liposomes, usually containing cationic lipids, are useful tools for gene introduction into cells. To investigate the effect of ultrasound (US) on liposome-mediated transfection, three types of liposomes (designated L1, L2 and L3, in the order of increasing transfection efficiency) containing O,O′-ditetradecanoyl-N-(-trimethylammonioacetyl) diethanolamine chloride, dioleoylphosphatidylethanolamine, and/or cholesterol at varying ratios, were used in this study. HeLa cells were treated with liposome–DNA complexes containing luciferase genes for 2 h before sonication. Optimal US condition for the enhancement was determined to be 0.5 W/cm², 1 MHz continuous wave for 1 min and was above threshold for inertial cavitation based on EPR detection of free radicals. Luciferase expressions 24 h after the treatments were significantly increased by sonication to 2.4 fold with L1, and 1.7 fold with L2. However, with L3, which showed the highest level of expression among the liposomes, significant but minimal enhancement was observed when sonication was done 15 min after the DNA-L3 treatment, suggesting that efficiency of the liposome also determines the proper timing for sonication. The 2 h pre-sonication incubation with liposome–DNA complexes for L1 and L2 (30 min for L3) required to attain enhancement, suggests that US works to enhance transfection only after cells had enough DNA uptake.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

The PMe3-catalyzed addition of enantiomerically pure (−)-MenthylO(Ph)P(O)H to electron-deficient alkenes: an efficient way for the preparation of P-stereogenic compounds

A variety of P-stereogenic organophosphorus compounds can be readily prepared by stereoretentive addition. The PMe₃-catalyzed addition of optically active (?)MenthylO(Ph)P(O)H compounds to electron deficient alkenes occur stereospecifically, to produce the corresponding P-stereogenic adducts in high yields. By simply removing the volatiles under vacuum, spectroscopically pure products can be obtained. The present method provides a salt-free clean process for the preparation of P-chiral organophosphorus compounds.     

Excess Entropy Production in Quantum System: Quantum Master Equation Approach

For open systems described by the quantum master equation (QME), we investigate the excess entropy production under quasistatic operations between nonequilibrium steady states. The average entropy production is composed of the time integral of the instantaneous steady entropy production rate and the excess entropy production. We propose to define average entropy production rate using the average energy and particle currents, which are calculated by using the full counting statistics with QME. The excess entropy production is given by a line integral in the control parameter space and its integrand is called the Berry–Sinitsyn–Nemenman (BSN) vector. In the weakly nonequilibrium regime, we show that BSN vector is described by \(\ln \breve{\rho }_0\) and \(\rho _0\) where \(\rho _0\) is the instantaneous steady state of the QME and \(\breve{\rho }_0\) is that of the QME which is given by reversing the sign of the Lamb shift term. If the system Hamiltonian is non-degenerate or the Lamb shift term is negligible, the excess entropy production approximately reduces to the difference between the von Neumann entropies of the system. Additionally, we point out that the expression of the entropy production obtained in the classical Markov jump process is different from our result and show that these are approximately equivalent only in the weakly nonequilibrium regime.