Electric-pulse-induced local conducting area and joule heating effect in VO2/Al2O3 films

We investigated the effect of an electric-pulse on the insulator–metal phase transition of VO₂/Al₂O₃ films using synchrotron-based infrared microspectroscopy. By monitoring the time-resolved optical response, we could demonstrate that local conducting areas are formed under the influence of the electric-pulse, and the Joule heat generated from the local current flow drives a consecutive thermal phase transition in the adjacent sample area.     

Bacterial formation of extracellular U(VI) nanowires

Shewanella oneidensis MR-1 rapidly accumulates long, extracellular, U(VI) nanowires composed of polycrystalline chains of discrete meta-schoepite (UO(3)·2H(2)O) nanocrystallites. The production of uranium(VI) nanowires could provide a novel strategy for remediation of uranium contamination in sediments and aquifers, as well as the recovery of uranium in manufacturing processes.     

Phosphorus ligands for iron(III)‐mediated ATRP of styrene via generation of activators by monomer addition

Styrene polymerization via generation of activators by monomer addition (GAMA) for atom transfer radical polymerization (ATRP) has been examined extensively with bulk FeX₃ and FeX₂ at 110 °C in conjunction with various phosphorus‐bearing ligands. It was found that GAMA possesses advantages over normal ATRP. Most importantly, narrower polydispersity index (PDI) values were observed from the styrene polymerizations with Fe(III) over those with Fe(II). Every instance of 2‐(diphenylphosphino)‐N,N′‐dimethyl‐[1,1′‐biphenyl]‐2‐amine and 2‐(diphenylphosphino) pyridine with the Fe(III) system were controlled excellently without addition of any radical initiator or reducing agent additives. Initiator type was found to exert a significant factor to influence on the controllability of polymerization. The initiation of 1‐phenylethyl chloride and methyl‐2‐chloropropionate gave rise to formation of polymers with narrow PDI (1.05–1.20), whereas those from 1‐phenylethyl bromide increased to 1.35. The GAMA of bulk styrene exhibited the best performance in terms of both rate and controllability compared with toluene and anisole. Both formation of block copolymer from the macroinitiator and efficient perturbation of polymerization with 2,2,6,6‐tetramethylpiperidine 1‐oxyl provided firm evidence to support the living and radical characteristics for the GAMA of styrene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 144–151, 2010     

Hydrophilic functionalization of syndiotactic polystyrene via a combination of electrophilic bromination and Suzuki–Miyaura reaction

Postfunctionalization of high‐molecular‐weight syndiotactic polystyrene (sPS) was achieved via combination of electrophilic bromination at the para‐position of the polymer aromatic ring and subsequent Suzuki–Miyaura cross‐coupling reactions with functionalized phenylboronic acids. The concentration of brominated styrene repeating unit in sPS was conveniently controlled by changing the ratio of added bromine relative to the polymer repeating unit. Brominated sPS (8.5 mol %) was converted quantitatively to other polar functional groups via Suzuki–Miyaura cross‐coupling reactions with various functional group‐substituted phenylboronic acids. The surface properties of functionalized sPS were studied by measuring water contact angles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4335–4343, 2010     

Addition reactions to chiral aziridine-2-carboxaldimine toward various enantiopure nitrogen-containing heterocycles

Chiral (2R,1′R)-(1′-phenylethyl)aziridine-2-carboxaldimine was utilized as a nitrogen-containing starting substrate for the preparation of various enantiopure nitrogen-containing heterocycles. The additions of nucleophiles including organomagnesium reagents, cyanotrimethylsilane and ketene acetal to the chiral (2R,1′R)-(1′-phenylethyl)aziridine-2-carboxaldimine proceeded in highly stereoselective manner via chelation controlled transition states. Subsequent treatment of adducts with triphosgene and NaH yielded 5-substituted-4-chloromethylimidazolidin-2-ones. This imine was also served as either aza-diene or aza-dienophile with olefin or diene to provide hetero-Diels-Alder adducts 2-aziridinylpiperidines or 1,2,3,4-tetrahydroquinolines.     

Newtonian versus relativistic nonlinear cosmology

Both for the background world model and its linear perturbations Newtonian cosmology coincides with the zero-pressure limits of relativistic cosmology. However, such successes in Newtonian cosmology are not purely based on Newton's gravity, but are rather guided ones by previously known results in Einstein's theory. The action-at-a-distance nature of Newton's gravity requires further verification from Einstein's theory for its use in the large-scale nonlinear regimes. We study the domain of validity of the Newtonian cosmology by investigating weakly nonlinear regimes in relativistic cosmology assuming a zero-pressure and irrotational fluid. We show that, first, if we ignore the coupling with gravitational waves the Newtonian cosmology is exactly valid even to the second order in perturbation. Second, the pure relativistic correction terms start appearing from the third order. Third, the correction terms are independent of the horizon scale and are quite small in the large-scale near the horizon. These conclusions are based on our special (and proper) choice of variables and gauge conditions. In a complementary situation where the system is weakly relativistic but fully nonlinear (thus, far inside the horizon) we can employ the post-Newtonian approximation. We also show that in the large-scale structures the post-Newtonian effects are quite small. As a consequence, now we can rely on the Newtonian gravity in analyzing the evolution of nonlinear large-scale structures even near the horizon volume.     

Bandwidth-tunable band-rejection filter based on helicoidal fiber grating pair of opposite helicities

We have developed a new type of all-fiber band-rejection filter consisting of a helicoidal long-period fiber grating pair of opposite helicities, which provides highly flexible spectral control over the rejection bandwidth. The detailed fabrication method and operation principles of the proposed bandwidth-tunable band-rejection filter are described. The proposed device enables unique rejection bandwidth tuning over more than 14 nm at the rejection level of 15 dB, with low insertion loss and polarization-dependent loss achieved by adjusting torsion stress.     

Catalytic conversion of lactic acid into propylene glycol over various metals supported on silica

Catalytic hydrogenation of lactic acid to propylene glycol was performed over various metals (Ag, Co, Cu, Ni, Pt, and Ru) supported on silica prepared by an incipient wetness impregnation method. The loading amount of each metal was 5 wt%. Crystallinity of the synthesized catalysts was investigated by X-ray diffraction (XRD), and the BET method was utilized to examine the surface area. Pore volume and pore size of catalysts were determined using BJH analysis of the N₂ adsorption isotherm. Particle sizes of various metals were determined from transmission electron microscopy (TEM) images. The catalytic activity was found to be strongly dependent on the supported metal. Among catalysts tested, Ru/SiO₂ showed the highest propylene glycol yield. The yield of propylene glycol increased with pressure, and the highest yield was achieved at 130 °C.