Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (T_g's) and refractive‐indices (n_D's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T_g's and n_D's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007     

Modification of the physical properties of chemical vapor-deposited nanostructure diamond by argon-hydrogen plasma surface treatment

Nanostructure diamond (NSD) film with a hardness as high as 70 GPa and an average surface roughness of 10 nm has been synthesized by the two-step negative substrate bias method combined with post-growth Ar-H₂ plasma irradiation. The Ar-H₂ plasma irradiation has been confirmed to improve the uniformity of grain size and shape and increase the hardness of the NSD film.     

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.     

Photoluminescence properties of trace amounts of Pr and Tb in yttria-stabilized zirconia

We have investigated the photoluminescence (PL) properties of trace amounts of Pr and Tb in single-crystal samples of yttria-stabilized zironia (YSZ), and found that Pr of the order of 10⁻⁶ mass% and Tb of the order of 10⁻⁵ mass% in YSZ can be detected by the PL spectroscopy. The PL spectra of the YSZ samples for the 280 nm excitation were comprised of several peaks and a broad emission. The peaks were attributed to transitions of Pr³⁺ and Tb³⁺ in the YSZ samples, whereas the broad emission seemed to be attributed to the yttria-associated oxygen vacancies. The peak intensities corresponded to the amounts of Pr and Tb in the YSZ samples, the amounts of which were analyzed by glow discharge mass spectrometry. In the PL excitation spectra, but not in the photoabsorption spectra, small peaks at 376 and 381 nm were observed, and were attributed to the transitions of Tb³⁺ in the YSZ samples. The results of the PL excitation spectra corresponding to the Pr³⁺ line emissions suggest that the charge transfer occurs between the YSZ and Pr ion in it. The trace amounts of these lanthanoids in YSZ would disturb the decay process of the photoinduced electrons to the yttria-associated oxygen vacancies.     

Construction of self-assembled monolayer terminated with N-heterocyclic carbene-rhodium(I) complex moiety

Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface.     

Ring‐opening grafting polymerization of cyclic monomers onto human hair

Natural human hair was successfully modified by the graft polymerization of trimethylene carbonate, β‐propiolactone, ε‐caprolactone, glycidol, ε‐caprolactam, and 5,5‐dimethyl‐1,3‐dioxane‐2‐thione. In contrast, we could not modify natural human hair by the graft polymerization of oxetane under similar conditions. The model reaction suggested that the main initiating species in these polymerizations were the amino, thiol, and hydroxyl groups in hair, which could induce ring‐opening polymerization. Among the tested monomers, β‐propiolactone was most effective for hair modification with its graft polymer, whose concentration was as high as 0.5 g/g of hair though polymerization under mild conditions. The effects of the hair pretreatment and polymerization temperature on the weight ratio of the grafted polymers were also investigated. Hair modified by grafted polymers was characterized with scanning electron microscopy and Fourier transform infrared measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 736–744, 2007