FT-IR study of the interlamellar water confined in glycolipid nanotube walls

The local hydrogen-bonding environment of water confined in glycolipid nanotubes (LNTs) was investigated by Fourier transform infrared (FT-IR) spectroscopy. Using X-ray diffraction (XRD), we estimated the thickness of an interlamellar water layer, which was confined between the bilayer membranes constructing the walls of the LNTs, to be 1.3 +/- 0.3 nm. FT-IR spectroscopic measurement of the confined water showed an obvious reduction in IR absorption in both the low-energy (around 3000 cm(-1)) and high-energy regions (around 3600 cm(-1)) of the OH stretching band as compared to bulk water. The reduction around 3000 cm(-1) indicated a decrease in the relative proportion of the water molecules with a long-range network structure due to a geometrical restriction. This agrees with the results obtained for other multilamellar systems. On the other hand, the remarkable reduction around 3600 cm(-1), which was not observed in the other systems, indicated the absence of weakly hydrogen-bonded water aggregates due to the effect of sugar headgroups.     

A design of fluorescent probes for superoxide based on a nonredox mechanism

Fluorometric detection of O2-* is performed based on desulfonylation of 3 to the corresponding fluoresceins 4 through nucleophilic substitution, and this fluorescing process is quite specific toward O2-* over H2O2, t-BuOOH, NaOCl, 1O2, HO*, NO*, and ONOO-. Furthermore, effects of glutathione, cytochrome P450 reductase/NADPH, and diaphorase/NADH are relatively small on the fluorescing process of probe 3 with X = Y = F, which is useful to detect O2-* released from neutrophils stimulated by phorbol myristate acetate with satisfactory sensitivity.     

C high-resolution NMR study of the effect of the deuterium isotope on liquid crystal CBOOA-d17

High-resolution ¹³C NMR experiments were performed in isotropic liquid and liquid crystalline phases of 4-octyloxy-N-(4-cyanobenzylidene)aniline (CBOOA) and its chain-deuterated analogue (CBOOA-d₁₇). The spin-lattice relaxation times (T₁) for each carbon atom in the molecules were measured to elucidate the differences between molecular interactions in CBOOA and CBOOA-d₁₇.     

Redox-assisted ring closing reaction of the photogenerated cyclophanediene form of bis(ferrocenyl)dimethyldihydropyrene with interferrocene electronic communication switching

We synthesized ferrocene-attached dimethyldihydropyrene (DHP) derivatives and investigated their photochemical and redox behaviors. For bis(ferrocenylethynyl)dimethyldihydropyrene (1), reversible photoisomerization between the closed DHP form (1c) and the open CPD form (1o) occurred in high yields upon alternate irradiation of visible (578 nm) light and UV (303 nm) light, whereas no photoisomerization proceeded for bis(pentamethylferrocenylethynyl)dimethyldihydropyrene (2). 1 exhibited reversible switching of electronic communication between the ferrocene (Fc) moieties by photoisomerization of the DHP moiety and demonstrated a novel ring closing reaction induced by oxidation of the Fc moieties. The magnitude of electronic communication, deltaE0' (the difference between the redox potentials of two Fc's), was 63 mV in 1c and 16 mV in 1o, indicating that the electronic communication through the spacer is enhanced in the more developed pi-conjugation of the DHP moiety. The rate constants of the ring closing reaction from 1o+ to 1c+ and from 1o2+ to 1c2+ were estimated at 3.7 and 0.50 s(-1), respectively, by the simulation of cyclic voltammograms.     

Realization of SOMO-HOMO level conversion for a TEMPO-dithiolate ligand by coordination to platinum(II)

We developed a TEMPO-bound dithiolate ligand (= tempodt) and its Pt(diimine)(dithiolate) complex to realize a unique electronic structure with the potential for unprecedented functionalities. The physical properties and electronic structures of tempodt, (tempodt)Pt, and their related compounds were investigated by cyclic voltammetry, UV-visible spectroscopy, electron spin resonance (ESR) spectroscopy, and other techniques. It was revealed that (tempodt)Pt showed an unusual electronic structure in which the HOMO level (= pi-conjugated dithiolate-based orbital) was located above the SOMO level attributed to the TEMPO moiety, and that this situation was achieved via a drastic electronic structure change of SOMO-HOMO level conversion through complex formation. These findings were further supported by an investigation into a one-electron oxidized (tempodt)Pt and related complexes.     

Revised structures of gambiriins A1, A2, B1, and B2, chalcane-flavan dimers from gambir (Uncaria gambir extract)

Gambir, the aqueous extract from Uncaria gambir (Rubiaceae), has been used as an astringent medicine in Asian countries. Investigation of the constituents in the extract led to the isolation of four chalcane-flavan dimers, gambiriin A1 (6), A2 (7), B1 (8), and B2 (9), in addition to (+)-catechin (1), (+)-epicatechin (2), and dimeric proanthocyanidins, procyanidin B1 (3), procyanidin B3 (4), and gambiriin C (5). The spectroscopic and chemical data obtained in the present study indicated that their previously proposed structures 6a, 7a, 8a, and 9a should be revised to 6, 7, 8, and 9, respectively.     

Micromachining and surface processing of the super-hard nano-polycrystalline diamond by three types of pulsed lasers

Laser beam micromachining was applied to super-hard nano-polycrystalline diamond (NPD) synthesized by the direct conversion of graphite at high pressure and high temperature. Three types of pulsed lasers were tested: nanosecond near-infrared, nanosecond near-ultraviolet, and femtosecond near-infrared lasers. The latter two were also applied for synthetic single crystal of diamond to compare the results with those of the NPD. It was demonstrated that the nanosecond near-infrared laser was the most efficient device for rough shaping of the NPD, while the ultraviolet and femtosecond lasers give satisfactory results for precise surface finishing of it. The properties of the laser-processed surfaces were analyzed by scanning and transmission electron microscopy, laser scanning microscopy, and micro Raman spectroscopy. These analyses demonstrated that the three types of lasers play different and complementary roles, and that their combination is the best suitable solution for micromachining of the hardest diamond into any desired shapes.     

Tripartite single-photon entangled states in noisy quantum channels

A tripartite single-photon state shared through noisy quantum channels is considered for three different system configurations. The quantum teleportation of a single-photon state between two parties is investigated in cases with and without the assistance of a third party. The condition that the quantum teleportation is superior to the classical one is provided in terms of the damping rate and detector efficiency.     

Superior Electron‐Transport Ability of π‐Conjugated Redox Molecular Wires Prepared by the Stepwise Coordination Method on a Surface

Electronic conductivity of molecular wires is a critical fundamental issue in molecular electronics. π‐Conjugated redox molecular wires with the superior long‐range electron‐transport ability could be constructed on a gold surface through the stepwise ligand–metal coordination method. The β^d value, indicating the degree of decrease in the electron‐transfer rate constant with distance along the molecular wire between the electrode and the redox active species at the terminal of the wire, were 0.008–0.07 Å^?1 and 0.002–0.004 Å^?1 for molecular wires of bis(terpyridine)iron and bis(terpyridine)cobalt complex oligomers, respectively. The influences on β^d by the chemical structure of molecular wires and the terminal redox units, temperature, electric field, and electrolyte concentration were clarified. The results indicate that facile sequential electron hopping between neighboring metal–complex units within the wire is responsible for the high electron‐transport ability.