Spirometallodendrimers: terpyridine-based intramacromolecular cyclization upon complexation

The first examples of metallodendritic spiranes have been obtained via incorporation of single terpyridine units within each dendritic quadrant.     

Synthesis of (+)-polyoxamic acid and D-sorbitol from simple achiral allylic halides employing (S,S)-hydrobenzoin as a chiral source

Coupling of cis-1-bromo-2-pentene and (S,S)-hydrobenzoin stannylene acetal followed by regio- and stereoselective transformations of the resulting allylic ether gave (+)-polyoxamic acid and a similar procedure was applied to the synthesis of D-sorbitol from trans-1-iodo-2-hexene.     

Dispersion-based short-time Fourier transform applied to dispersive wave analysis

Although time-frequency analysis is effective for characterizing dispersive wave signals, the time-frequency tilings of most conventional analysis methods do not take into account dispersion phenomena. An adaptive time-frequency analysis method is introduced whose time-frequency tiling is determined with respect to the wave dispersion characteristics. In the dispersion-based time-frequency tiling, each time-frequency atom is adaptively rotated in the time-frequency plane, depending on the local wave dispersion. Although this idea can be useful in various problems, its application to the analysis of dispersive wave signals has not been made. In this work, the adaptive time-frequency method was applied to the analysis of dispersive elastic waves measured in waveguide experiments and a theoretical investigation on its time-frequency resolution was presented. The time-frequency resolution of the proposed transform was then compared with that of the standard short-time Fourier transform to show its effectiveness in dealing with dispersive wave signals. In addition, to facilitate the adaptive time-frequency analysis of experimentally measured signals whose dispersion relations are not known, an iterative scheme for determining the relationships was developed. The validity of the present approach in dealing with dispersive waves was verified experimentally.     

Entropy production of Brownian macromolecules with inertia

We investigate the nonequilibrium steady-state thermodynamics of single Brownian macromolecules with inertia under feedback control in an isothermal ambient fluid. With the control being represented by a velocity-dependent external force, we find such an open system can have a negative entropy production rate, and we develop a mesoscopic theory consistent with the second law. We propose an equilibrium condition and define a class of external force, which includes the transverse Lorentz force, leading to equilibrium.     

Marked increase in the binding strength between the substrate and the covalently attached monolayers of zeolite microcrystals by lateral molecular cross-linking between the neighboring microcrystals

Monolayers of cubic zeolite microcrystals (1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3) were assembled on glass plates through imine- or urethane-linkages between the zeolite-tethered 3-aminopropyl (AP) groups and the glass-bound benzaldehyde or isocyanate groups, which were prepared by treating AP-tethering glass plates with a large excess of terephthaldicarboxaldehyde (TPDA) or 1,4-diisocyanatobutane (DICB), respectively, in toluene. The additional treatment of the monolayers of zeolite microcrystals with TPDA or DICB led to lateral molecular cross-linking between the neighboring, closely packed zeolite microcrystals in the monolayers through AP-TPDA-AP imine or AP-DICB-AP urethane linkages between the zeolite-tethered AP groups and the newly introduced TPDA or DICB, respectively. The comparison of the binding strengths between the glass substrates and the monolayers revealed that the molecular cross-linking leads to as much as 7- and 38-fold (by average) increase in the binding strength in the cases of 1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3 crystals, respectively. We predict that the effect of lateral cross-linking on the binding strength will further increase with further decreasing the size of the building blocks to nanoparticles and to molecules.     

Loss-coupled distributed-feedback lasers with amplified optical feedback for optical microwave generation

Multisection semiconductor lasers for optical microwave generation have been fabricated that consist of a loss-coupled distributed feedback (LC-DFB), a phase control, and an amplifier section. High-frequency self-pulsations are generated according to the concept of a single-mode laser with short optical feedback. The effect of the optical feedback via the phase control and the amplifier section on the self-pulsation is apparently shown as a result of the superior single-mode characteristic of the LC-DFB section. Continuous frequency tuning is achieved in the range of 17-35 GHz.     

Ox-LDL suppresses PMA-induced MMP-9 expression and activity through CD36-mediated activation of PPAR-g

During chronic inflammatory response, mono- cytes/macrophages produce 92-kDa matrix metalloproteinase-9 (MMP-9), which may contribute to their extravasation, migration and tissue remodeling. Activation of peroxisome proliferator- activated factor receptor-g (PPAR-g) has been shown to inhibit MMP-9 activity. To evaluate whether ox-LDL, a PPAR-g activator, inhibits PMA-induced MMP-9 expression and activity, and if so, whether CD36 and PPAR-g are involved in this process, we investigated the effect of ox-LDL on MMP-9 expression and activity in PMA-activated human monocytic cell line U937. PMA-induced MMP-9 expression and activity were suppressed by the treatment with ox-LDL (50 mg/ml) or PPAR-g activators such as troglitazone (5 mM), ciglitazone (5 mM), and 15d- PGJ2 (1 mM) for 24 h. This ox-LDL or PPAR-g activator-mediated inhibition of MMP-9 activity was diminished by the pre-treatment of cells with a blocking antibody to CD36, or PGF2a (0.3 mM), which is a PPAR-g inhibitor, as well as overexpression of a dominant-negative form of CD36. Taken together, these results suggest that ox-LDL suppresses PMA-induced MMP-9 expression and activity through CD36-mediated activation of PPAR-g.     

Polymeric enzyme mimics: catalytic activity of ribose-containing polymers for a phosphate substrate

The polymers containing ribose rings: poly(5'-acrylamido-5'-deoxy-1',2'-O-isopropylidene-alpha-D-ribose) (11), poly(5'-acrylamido-5'-deoxy-alpha-D-ribose) (12) and poly(5'-acrylamido-5'-deoxy-1'-O-methyl-D-ribose) (13) were prepared as enzyme mimics. Polymers 12 and 13 with free vic-cis-diol groups catalyzed the hydrolysis of phosphodiester (ethyl p-nitrophenyl phosphate and N-methylpyridinium 4-tert-butylcatechol cyclic phosphate) and phosphomonoester substrates with a rate acceleration of 10 approximately equal to 10(3) compared with the uncatalyzed reaction. They also catalyzed the reverse reactions, i.e., the esterification of phosphomonoester to phosphodiester and the phosphorylation of alcohols with phosphate ions. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles. The catalytic activity was negligible for polymer 11 where vic-cis-diol groups were blocked with isopropylidene groups. The catalytic activity was attributable to the vic-cis-diols of riboses on polymer chains, which formed hydrogen bonds with two phosphoryl oxygen atoms of phosphates so as to activate the phosphorus atoms to be attacked by nucleophiles.     

Effects of co-substitution on the electrical properties of BiFeO3 thin films prepared by chemical solution deposition

Ferroelectric BiFeO₃ thin films with Nd-Cr (or Sm-Cr) co-substitution (denoted by BNdFCr and BSmFCr, respectively) were deposited on the Pt(2 0 0)/TiO₂/SiO₂/Si(1 0 0) substrates by a chemical solution deposition method. X-ray diffraction patterns revealed the formation of BNdFCr and BSmFCr thin films without any secondary phases. The co-substituted BNdFCr (or BSmFCr) thin films, which were annealed at 550 °C for 30 min in N₂ atmosphere, exhibited enhanced electrical properties compared to BFO thin films with the remanent polarization (2P_r) and coercive electric field (2E_c) of 196, 188 μC/cm² and 600, 570 kV/cm with the electric field of 800 kV/cm, respectively. The leakage current densities of BNdFCr and BSmFCr thin films measured at room temperature were approximately three orders of magnitude lower than that of BFO thin film, and the leakage current at room temperature of the thin films exhibited three distinctive conduction behaviors. Furthermore, the values of pulse polarizations [i.e., +(P*-P^{^}) or −(P*-P^{^})] of BNdFCr and BSmFCr thin films were reasonably unchanged up to 1.4 × 10¹⁰ switching cycles.     

Mechanically formed loss-tunable long-period fiber gratings realized on the periodic arrayed metal wires

A new method to tune the peak loss of mechanically formed long-period fiber gratings (MLPFGs) is proposed. Periodic arrayed metal wires are used to obtain the gratings along a single mode fiber (SMF). Self-maintaining gratings are achieved by the bonding force of an UV-adhesive between two glass plates. The initial index modulation formed at room temperature creates a maximum attenuation of −9 dB and −12 dB for coated and uncoated SMF, respectively. By changing the temperature, the peak loss is tuned due to the large thermal expansion of the UV-adhesive. Thermally tunable characteristics caused by the coating layer of the SMF are also described and compared with the results of the device with an uncoated SMF.