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71.
Ueda A Kato D Kurita R Kamata T Inokuchi H Umemura S Hirono S Niwa O 《Journal of the American Chemical Society》2011,133(13):4840-4846
We have developed a new carbon film electrode material with thornlike surface nanostructures to realize efficient direct electron transfer (DET) with enzymes, which is very important for various enzyme biosensors and for anodes or cathodes used in biofuel cells. The nanostructures were fabricated using UV/ozone treatment without a mask, and the obtained nanostructures were typically 2-3.5 nm high as confirmed by atomic force microscopy measurements. X-ray photoelectron spectroscopy and transmission electron microscopy revealed that these nanostructures could be formed by employing significantly different etching rates depending on nanometer-order differences in the local sp(3) content of the nanocarbon film, which we fabricated with the electron cyclotron resonance sputtering method. These structures could not be realized using other carbon films such as boron-doped diamond, glassy carbon, pyrolyzed polymers based on spin-coated polyimide or vacuum-deposited phthalocyanine films, or diamond-like carbon films because those carbon films have relatively homogeneous structures or micrometer-order crystalline structures. With physically adsorbed bilirubin oxidase on the nanostructured carbon surface, the DET catalytic current amplification was 30 times greater than that obtained with the original carbon film with a flat surface. This efficient DET of an enzyme could not be achieved by changing the hydrophilicity of the flat carbon surface, suggesting that DET was accelerated by the formation of nanostructures with a hydrophilic surface. Efficient DET was also observed using cytochrome c. 相似文献
72.
Yuki Nagao Yuzuru Imai Jun Matsui Tomoyuki Ogawa Tokuji Miyashita 《The Journal of chemical thermodynamics》2011,43(4):613-616
We synthesized seven partially protonated poly(aspartic acids)/sodium polyaspartates (P-Asp) with different average molecular weights to study their proton transport properties. The number-average degree of polymerization (DP) for each P-Asp was 30 (P-Asp30), 115 (P-Asp115), 140 (P-Asp140), 160 (P-Asp160), 185 (P-Asp185), 205 (P-Asp205), and 250 (P-Asp250). The proton conductivity depended on the number-average DP. The maximum and minimum proton conductivities under a relative humidity of 70% and 298 K were 1.7 · 10?3 S cm?1 (P-Asp140) and 4.6 · 10?4 S cm?1 (P-Asp250), respectively. Differential thermogravimetric analysis (TG-DTA) was carried out for each P-Asp. The results were classified into two categories. One exhibited two endothermic peaks between t = (270 and 300) °C, the other exhibited only one peak. The P-Asp group with two endothermic peaks exhibited high proton conductivity. The high proton conductivity is related to the stability of the polymer. The number-average molecular weight also contributed to the stability of the polymer. 相似文献
73.
Wada Y Harayama Y Kamimura D Yoshida M Shibata T Fujiwara K Morimoto K Fujioka H Kita Y 《Organic & biomolecular chemistry》2011,9(13):4959-4976
Various analogues of the marine alkaloids, discorhabdins, have been synthesized. The strategy contains spirocyclization with phenyliodine(III) bis(trifluoroacetate) (PIFA), oxidative fragmentation of the β-amino alcohols with the hypervalent iodine reagent C(6)F(5)I(OCOCF(3))(2), the detosylation and dehydrogenation reaction of the pyrroloiminoquinone unit in the presence of a catalytic amount of NaN(3) and the bridged ether synthesis with HBr-AcOH as the key reactions. All the synthesized compounds were evaluated by in vitro MTT assay for cytotoxic activity against the human colon cancer cell line HCT-116. Furthermore, the discorhabdin A oxa analogues were also evaluated against four kinds of tumor model cells, a human colon cancer cell line (WiDr), a human prostate cancer cell line (DU-145) and murine leukemia cell lines (P388 and L1210). For the identification of the target, discorhabdin A and the discorhabdin A oxa analogue were evaluated by an HCC panel assay. In the test, discorhabdins could have a novel mode of action with the tumor cells. 相似文献
74.
Yokoe H Mitsuhashi C Matsuoka Y Yoshimura T Yoshida M Shishido K 《Journal of the American Chemical Society》2011,133(23):8854-8857
Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an α-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization. 相似文献
75.
Ogawa A Miyamae Y Honma A Koyama T Yazawa K Shigemori H 《Chemical & pharmaceutical bulletin》2011,59(5):672-675
A new compound, pycnalin (1), together with four known compounds, ginnalins A (2), B (3), C (4), and 3,6-di-O-galloyl-1,5-anhydro-D-glucitol (3,6-di-GAG) (5), were isolated from Acer pycnanthum. The structure of 1 was determined on the basis of 2D-NMR spectral data and synthesis of 1. Pycnalin (1) is the first 1,5-anhydro-D-mannitol linked to a gallic acid, while compounds 2-5 were 1,5-anhydro-D-glucitol linked to gallic acids. All compounds were tested in vitro for α-glucosidase inhibitory and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activities. Pycnalin (1) exhibited moderate α-glucosidase inhibitory activity as well as free radical scavenging activity. Ginnalin A (2) and 3,6-di-GAG (5), which have two galloyl groups, exhibited potent α-glucosidase inhibition, compared to those of other compounds 1, 3, and 4 containing a galloyl group. These results suggest that α-glucosidase inhibition is influenced by the number of galloyl groups. 相似文献
76.
Tsunashima R Long DL Endo T Noro S Akutagawa T Nakamura T Cabrera RQ McMillan PF Kögerler P Cronin L 《Physical chemistry chemical physics : PCCP》2011,13(16):7295-7297
The Dawson-type polyanion [α-Mo(18)O(54)(SO(3))(2)](4-), with two SO(3)(2-) templates embedded inside a polyoxomolybdate(vi) cage, exhibits thermochromism over an exceptionally wide temperature range (~500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO-LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion. 相似文献
77.
Tomoyuki Suzuki 《Algebra Universalis》2011,66(3):243-276
In this paper, we discuss the canonical extension of poset expansions. To obtain canonicity results on poset expansions, we
study Ghilardi and Meloni’s canonicity methodology for Heyting algebras with unary modalities, raise the problem of extending
the technique to poset expansions, and give a possible solution for the problem. Finally, we obtain a syntactic account of
canonical inequalities on poset expansions consisting of constants, e^{\epsilon_{\bot}} -additive operations, eT{\epsilon^{\top}} -multiplicative operations, diamond, box, and strict adjoint pairs, and bounded poset expansions consisting of constants,
e{\epsilon} -join preserving operations, e{\epsilon} -meet preserving operations, e{\epsilon} -additive operations, e{\epsilon} -multiplicative operations and adjoint pairs, which are more restricted than the case of lattice expansions, but can still
account for Sahlqvist-like canonicity results. 相似文献
78.
Kentaro Noda Nguyen Binh-Khiem Yusuke Takei Tomoyuki Takahata Kiyoshi Matsumoto Isao Shimoyama 《Applied physics. B, Lasers and optics》2014,115(1):69-76
This paper reports on a detailed deformation model of varifocal liquid lenses fabricated by Parylene-on-liquid-deposition (POLD), which can be applied to measure and adjust the focal length of such lenses without using extra sensors or sensing mechanisms. The lens was fabricated by encapsulating a liquid between a transparent electrode and a polymer film that was covered with a metal electrode. When voltage is applied to the two electrodes, the lens deforms due to the electrostatic force, and its focal length and the capacitance between the two electrodes change simultaneously. This characteristic enables the focal length of the lens to be adjusted and detected by measuring the capacitance change. The focal length of the fabricated varifocal liquid lens changed from 153.6 to 82.6 mm by applying 150-V. The focal length change of the liquid lens was calculated from the change in its capacitance. Finally, to confirm the efficiency of this varifocal liquid lens, we fabricated a confocal distance sensor using the lens for laser scanning and demonstrated that this system can be used to measure distances of 94–140 mm with an average error of 0.83 mm and a standard deviation of 0.77 mm. 相似文献
79.
Tomoyuki Manaka Shin‐Ichiro Nagayama Wannaporn Desadee Naoki Yajima Takuya Kumamoto Toshiko Watanabe Tsutomu Ishikawa Masatoshi Kawahata Kentaro Yamaguchi 《Helvetica chimica acta》2007,90(1):128-142
Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, SN2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6). 相似文献
80.