Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

On a certain move generating link-homology

Dedicated to Professor Kunio Murasugi on his sixtieth birthday     

Self-assembled DNA-conjugated polymer for novel DNA chip.

We developed DNA-conjugated polymer for DNA chip fabrication. A 30 mer probe DNA and disulfide bridges were covalently attached to the polymer side chain. The DNA-conjugated polymer can be specifically adsorbed on a gold substrate surface by a self-assembly technique. The interaction between fully matched DNA and DNA-conjugated polymer was investigated by surface plasmon resonance (SPR) technique. The DNA-conjugated polymer-modified gold surface highly recognized fully matched DNA, rather than unmatched DNA. Therefore, DNA-conjugated polymer can be used for novel DNA chip fabrication.     

Dual Si-H effects in platinum-catalyzed silane reduction of carboxamides leading to a practical synthetic process of tertiary-amines involving self-encapsulation of the catalyst species into the insoluble silicone resin formed

Combination of commercially available platinum catalysts with siloxanes containing more than two Si-H groups is found to be an efficient catalyst system for the reduction of carboxamides to amines. In particular, facile removal of silicon and platinum residues from the product can be achieved by the use of polymethylhydrosiloxanes as reducing reagents.     

Optical waveguide fabrication and integration with a micro-mirror inside photosensitive glass by femtosecond laser direct writing

Photosensitive glass is a potentially important material for micro-fluidic devices that can be integrated with micro-optical components for biochemical analysis. Here, we demonstrate the fabrication of optical waveguides inside glass by femtosecond laser direct writing. The influence of the laser parameters on the waveguide properties is investigated, and it is revealed that the waveguide mode can be well controlled. The single mode is achieved at a low writing energy, while the multimode is achieved with increasing energy. In spite of a longitudinally elongated elliptical shape of the cross-sectional profile, the far-field pattern of the single-mode waveguide shows an almost symmetric profile. The measured propagation loss and the coupling loss are evaluated to be ∼0.6 dB/cm and ∼1.6 dB at a wavelength of 632.8 nm, respectively, under the conditions of 1.0–2.0 μJ pulse energy and 200–500 μm/s scan speed. The increased optical loss is associated with a higher waveguide mode at higher writing energy. Furthermore, the integration of waveguides and a micromirror made of a hollow microplate inside the glass is demonstrated to bend the laser beam at an angle of 90° in a small chip. The bending loss is estimated to be smaller than 0.3 dB. PACS 42.62.-b; 42.82.Cr; 82.50.Pt; 42.79.Gn; 42.81.Qb     

Methanol synthesis from CO2-H2 and from CO-H2 under atmospheric pressure over Pd and Cu catalysts

Under atmospheric pressure, methanol was produced from CO₂–H₂ over Pd/ZnO and from CO–H₂ over Pd/MgO catalyst. Similar support effects were observed over Cu catalysts.     

Structural studies of the carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F: suggestion for the initial activation site for dihydrogen

The carbon monoxide complex of [NiFe]hydrogenase from Desulfovibrio vulgaris Miyazaki F has been characterized by X-ray crystallography and absorption and resonance Raman spectroscopy. Nine crystal structures of the [NiFe]hydrogenase in the CO-bound and CO-liberated forms were determined at 1.2-1.4 A resolution. The exogenously added CO was assigned to be bound to the Ni atom at the Ni-Fe active site. The CO was not replaced with H(2) in the dark at 100 K, but was liberated by illumination with a strong white light. The Ni-C distances and Ni-C-O angles were about 1.77 A and 160 degrees, respectively, except for one case (1.72 A and 135 degrees ), in which an additional electron density peak between the CO and Sgamma(Cys546) was recognized. Distinct changes were observed in the electron density distribution of the Ni and Sgamma(Cys546) atoms between the CO-bound and CO-liberated structures for all the crystals tested. The novel structural features found near the Ni and Sgamma(Cys546) atoms suggest that these two atoms at the Ni-Fe active site play a role during the initial H(2)-binding process. Anaerobic addition of CO to dithionite-reduced [NiFe]hydrogenase led to a new absorption band at about 470 nm ( approximately 3000 M(-1)cm(-1)). Resonance Raman spectra (excitation at 476.5 nm) of the CO complex revealed CO-isotope-sensitive bands at 375/393 and 430 cm(-1) (368 and 413 cm(-1) for (13)C(18)O). The frequencies and relative intensities of the CO-related Raman bands indicated that the exogenous CO is bound to the Ni atom with a bent Ni-C-O structure in solution, in agreement with the refined structure determined by X-ray crystallography.     

Iron-metal multilayers studied by Mössbauer spectroscopy,RBS and X-ray diffraction

Fe/M (M = Ag, Zn and Sn) multilayers prepared by a vacuum evaporation method are studied by Mössbauer spectroscopy (MS), Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). For the case of an M = Ag multilayer, MS reveals that Fe in the multilayer remains as an-phase down to the layer thickness of 10 nm. This result is in agreement with the RBS result that Fe and Ag form a completely discrete layer structure without any mutual mixing. For the case of M = Zn and Sn, RBS reveals that a considerable mixing has taken place between Fe and Sn during the specimen preparation. MS on Fe/Sn specimens with different layer thickness shows that an alloy phase of about 5 nm thickness is formed at the interface. Structural as well as magnetic properties of the alloy phase are discussed based on MS at different temperatures and on reported results of the intermetallic compound FeSn.