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111.
Ruthenium‐Immobilized Periodic Mesoporous Organosilica: Synthesis,Characterization, and Catalytic Application for Selective Oxidation of Alkanes
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Nobuhiro Ishito Dr. Hirokazu Kobayashi Dr. Kiyotaka Nakajima Yoshifumi Maegawa Dr. Shinji Inagaki Dr. Kenji Hara Prof. Dr. Atsushi Fukuoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15564-15569
Periodic mesoporous organosilica (PMO) is a unique material that has a crystal‐like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2(CO)3]2, is successfully immobilized onto 2,2’‐bipyridine (BPy) units of PMO to form a single‐site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru‐immobilized PMO oxidizes the tertiary C?H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C?H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis‐decalin to cis‐9‐decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions. 相似文献
112.
Tsukamoto D Ikeda M Shiraishi Y Hara T Ichikuni N Tanaka S Hirai T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9816-9824
Semiconductor TiO2 particles loaded with WO3 (WO3/TiO2), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO3/TiO2 catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO2. In particular, a catalyst loading 7.6 wt % WO3 led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO2 surface of the catalyst, which is active for oxidation, is partially coated by the WO3 layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO2 surface. This suppresses subsequent decomposition of the aldehyde on the TiO2 surface and results in high aldehyde selectivity. The WO3/TiO2 catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity. 相似文献
113.
Nakajima K Baba Y Noma R Kitano M Kondo JN Hayashi S Hara M 《Journal of the American Chemical Society》2011,133(12):4224-4227
Niobic acid, Nb(2)O(5)·nH(2)O, has been studied as a heterogeneous Lewis acid catalyst. NbO(4) tetrahedra, Lewis acid sites, on Nb(2)O(5)·nH(2)O surface immediately form NbO(4)-H(2)O adducts in the presence of water. However, a part of the adducts can still function as effective Lewis acid sites, catalyzing the allylation of benzaldehyde with tetraallyl tin and the conversion of glucose into 5-(hydroxymethyl)furfural in water. 相似文献
114.
We examined two-dimensional (2D) optical feedback control of phototaxis flagellate Euglena cells confined in closed-type microfluidic channels (microaquariums), and demonstrated that the 2D optical feedback enables the control of the density and position of Euglena cells in microaquariums externally, flexibly, and dynamically. Using three types of feedback algorithms, the density of Euglena cells in a specified area can be controlled arbitrarily and dynamically, and more than 70% of the cells can be concentrated into a specified area. Separation of photo-sensitive/insensitive Euglena cells was also demonstrated. Moreover, Euglena-based neuro-computing has been achieved, where 16 imaginary neurons were defined as Euglena-activity levels in 16 individual areas in microaquariums. The study proves that 2D optical feedback control of photoreactive flagellate microbes is promising for microbial biology studies as well as applications such as microbe-based particle transportation in microfluidic channels or separation of photo-sensitive/insensitive microbes. 相似文献
115.
Hara H Kobayashi A Noro S Chang HC Kato M 《Dalton transactions (Cambridge, England : 2003)》2011,40(31):8012-8018
Four new bimetallic coordination polymers (CPs), {M[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n) (M = Mg(2+), Ca(2+), Sr(2+), Ba(2+); 5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) were synthesized using four alkaline-earth metal ions and a Pt(II)-diimine metalloligand [Pt(CN)(2)(5,5'-H(2)dcbpy)]. All four CPs are isomorphous with the Zn complex, {Zn[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n), which exhibits effective metallophilic interactions between Pt(II) ions. These CPs exhibited colourful thermochromic behaviour and solid-state solvatochromic-like behaviours when suspended in various solvents. Thermogravimetric analysis and vapour-adsorption measurements revealed that the CPs can reversibly adsorb water and MeOH vapours. The emission energy of the triplet metal-metal-to-ligand charge-transfer ((3)MMLCT) state varied markedly upon guest adsorption/desorption. The chromic and vapour-adsorption properties of these CPs depend strongly on the cross-linking M(2+) ions. 相似文献
116.
Wheeler EK Hara CA Frank J Deotte J Hall SB Benett W Spadaccini C Beer NR 《The Analyst》2011,136(18):3707-3712
Nucleic acid amplification is enormously useful to the biotechnology and clinical diagnostic communities; however, to date point-of-use PCR has been hindered by thermal cycling architectures and protocols that do not allow for near-instantaneous results. In this work we demonstrate PCR amplification of synthetic SARS respiratory pathogenic targets and bacterial genomic DNA in less than three minutes in a hardware configuration utilizing convenient sample loading and disposal. Instead of sample miniaturization techniques, near-instantaneous heating and cooling of 5 μL reaction volumes is enabled by convective heat transfer of a thermal fluid through porous media combined with an integrated electrical heater. This method of rapid heat transfer has enabled 30 cycles of PCR amplification to be completed in as little as two minutes and eighteen seconds. Surprisingly, multiple enzymes have been shown to work at these breakthrough speeds on our system. A tool for measuring enzyme kinetics now exists and can allow polymerase optimization through directed evolution studies. Pairing this instrument technology with modified polymerases should result in a new paradigm for high-throughput, ultra-fast PCR and will hopefully improve our ability to quickly respond to the next viral pandemic. 相似文献
117.
Image analysis applied to study on frictional-drag reduction by electrolytic microbubbles in a turbulent channel flow 总被引:1,自引:0,他引:1
We investigate frictional-drag reduction with electrolytic microbubbles based on image measurement of a turbulent flow in
a water channel at Re = 4800 (based on the half channel height). Microbubbles with a diameter ranging 30–200 μm can reduce frictional drag by as
much as 30% relative to single-phase flow even at low void fractions (α ≈ 3 × 10−4); however, drag reduction is only effective within a limited downstream distance from an electrode array. Arrangement of
the optical system allows us to measure the bubble-production rate by water electrolysis from images near the wall and to
trace the motion of bubbles. We also measure velocity fields using particle-tracking velocimetry based on a shallow depth-of-field
approach by segregating tracer particles from microbubbles. Vertically oscillating microbubbles likely represent interaction
with vortical structures near the wall, and bubbles approaching the wall appear to induce negative streamwise velocity relative
to the surrounding fluid. We relate the wall friction with the double integral of the Reynolds-stress profile and show that
its variation due to microbubbles decreases the drag on the wall. Microbubbles tend to coalesce downstream resulting in a
fewer bubbles but with greater size; accordingly, the oscillatory motion diminishes, and the frictional drag rather increases. 相似文献
118.
This paper proposes a delayed feedback control (DFC) based on the act-and-wait concept, which reduces the dynamics of DFC
systems to that of discrete-time systems. Based on this concept, a delayed feedback controller is designed for a prototype
two-dimensional oscillator using a simple systematic procedure. This control has two advantages: the feedback delay time can
be large and it can obtain deadbeat behavior. A numerical example using a double-scroll circuit model demonstrates these theoretical
results. 相似文献
119.
A highly sensitive and rapid liquid chromatographic method for the determination of methylglyoxal in mouse blood is described, based on the precolumn conversion of methylglyoxal to a highly fluorescent 3-methyl-6,7-methylenedioxyquinoxaline by reaction with 1,2-diamino- 4,5-methylenedioxybenzene. The method is applied to the determination of methylglyoxal (0.1- 104 pmol) in 5 μ1 of blood. 相似文献
120.
Kyoko TakahashiKenichiro Hashimoto Ayako FujiyamaJunko Yamada Noriko KobayashiMasuo Morisaki Sayaka NakanoNoriyuki Hara Yoshinori Fujimoto 《Tetrahedron letters》2003,44(2):341-344
Feeding of the chemically prepared [24-13C, 24-2H]desmosterol to cell-free systems derived from rat liver and silkworm gut and to cultured cells of Oryza sativa followed by deuterium-decoupled 1H, 13C shift correlation NMR analysis of the biosynthesized cholesterol revealed the stereospecific incorporation of hydrogen atoms from the re-face of the C-24 position of desmosterol. 相似文献