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71.
Sakurai J Oguchi T Watanabe K Abe H Kanno S Ishikawa M Katoh T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(3):829-837
Biologically important and structurally unique marine natural products avarone (1), avarol (2), neoavarone (3), neoavarol (4) and aureol (5), were efficiently synthesized in a unified manner starting from (+)-5-methyl-Wieland-Miescher ketone 10. The synthesis involved the following crucial steps: i) Sequential BF(3)Et(2)O-induced rearrangement/cyclization reaction of 2 and 4 to produce 5 with complete stereoselectivity in high yield (2 --> 5 and 4 --> 5); ii) strategic salcomine oxidation of the phenolic compounds 6 and 8 to derive the corresponding quinones 1 and 3 (6 --> 1 and 8 --> 3); and iii) Birch reductive alkylation of 10 with bromide 11 to construct the requisite carbon framework 12 (10 + 11 --> 12). An in vitro cytotoxicity assay of compounds 1-5 against human histiocytic lymphoma cells U937 determined the order of cytotoxic potency (3 > 1 > 5 > 2 > 4) and some novel aspects of structure-activity relationships. 相似文献
72.
A reduction-triggered delivery by a liposomal carrier possessing membrane-permeable ligands and a detachable coating 总被引:5,自引:0,他引:5
To control the cellular uptake of drugs and genes, we synthesized a liposomal carrier possessing membrane-permeable ligands and a detachable poly(ethylene glycol) (PEG) coating. For the detachable coating, a lipid having a thiolytic cleavable spacer (PEG-S-S-DOPE) was synthesized by the reaction of dioleoylphosphatidylethanolamine (DOPE) with a PEG chain via a disulfide linkage. The liposomes were prepared from a mixture of dipalmitoylphosphatidylcholine (DPPC), DOPE, PEG-S-S-DOPE, and cholesteryl hemisuccinate (CHEMS). The octamer (R8 peptide) of arginine was chosen as the membrane-permeable ligand and covalently immobilized onto the CHEMS portion of the liposome surface (PEG-S-S-R8-liposome). The disulfide bond of the PEG chain was cleaved to display the R8 peptides on the liposome surface by adding a reducing agent such as L-cysteine, and thereby internalization of the liposomes was significantly facilitated. When L-cysteine was added to the mixture of cells and the liposome that incorporated plasmids encoding the enhanced green fluorescence protein (pEGFP), the expression of EGFP was low but could be observed in almost 100% of the cells. 相似文献
73.
Mahesh Datt Bhatt Akihisa Baba Takeaki Sakurai Katsuhiro Akimoto 《Journal of Solid State Electrochemistry》2012,16(3):1141-1149
We have performed ultraviolet photoelectron spectroscopy measurements and density functional theory calculations to study
the electronic structure at the interface between organic semiconductor (3-(4-biphenylyl)-4-phenyl-5-(4-tert-butyl phenyl)-1,2,4-triazole
(TAZ)) and metals (Ca, Mg, Ag, and Au). The basic mechanism of interface states at organic–metal interfaces can be understood
by controlling the injection of charge carriers at these interfaces. The position of highest occupied molecular orbital relative
to the Fermi level and the magnitude of the interface dipole are measured for each organic–metal interface. For TAZ on Ca,
Mg, and Ag, interface states are observed near the Fermi level. However, no interface state is observed for TAZ on Au. It
is analyzed qualitatively that the interface state is formed due to interaction of TAZ lowest unoccupied molecular orbital
composed of C2p and metal s levels. It is suggested that the interface state plays an important role in charge transport at
the interface. The mechanism of formation of interface states and electrical properties are discussed. 相似文献
74.
The title compound shows dual fluorescence depending on polarity of the solvent used. The fluorescence in the nonpolar solvent, cyclohexane, has a maximuni at 370 nm, while the fluorescence in the polar solvent, methanol, has a maximum at 400nm. The short and long wavelength fluorescences were assigned to the syn and anti conformers, respectively. From these observations one is allowed to conclude that a novel solvent dipole-induced rotational isomerism takes place in the excited singlet state. 相似文献
75.
The mechanism of the gold nanocluster‐catalyzed aerobic homocoupling of arylboronic acids has been elucidated by means of DFT calculations with Au20? as a model cluster for the Au:[poly(N‐vinylpyrrolidin‐2‐one)] catalyst. We found that oxygen affects the adsorption of phenylboronic acid and, by lowering the energy barrier, a water molecule enhances dissociation of the C?B bond, which is probably the rate‐determining step. The key role of oxygen is in activating the surface of the gold cluster by generating Lewis acidic sites for adsorption and activation of the phenylboronic acid, leading to the formation of biphenyl through a superoxo‐like species. Moreover, the oxygen adsorbed on the Au nanocluster can act as an oxidant for phenylboronic acid, giving phenol as a byproduct. As shown by NBO analysis, the basic aqueous reaction medium facilitates the reductive elimination process by weakening the Au?C bond, thereby enhancing the formation of biphenyl. The coupling of phenyl and reductive elimination of biphenyl occur at the top or facet site with low‐energy‐barrier through spillover of phenyl group on Au NC. The present findings are useful for the interpretation or design of other coupling reactions with Au NC. 相似文献
76.
Jin Q Ikeda T Fujishima M Tada H 《Chemical communications (Cambridge, England)》2011,47(31):8814-8816
The electronic modification of TiO(2) with highly dispersed NiO particles smaller than ca. 2 nm by the chemisorption-calcination-cycle technique has given rise to a high level of visible-light-activity exceeding that of iron oxide-surface modified TiO(2) simultaneously with the UV-light-activity being significantly increased. 相似文献
77.
Kajitani T Onouchi H Sakurai S Nagai K Okoshi K Onitsuka K Yashima E 《Journal of the American Chemical Society》2011,133(24):9156-9159
We report a unique macromolecule consisting of a rodlike helical polyisocyanide backbone with a narrow molecular weight distribution and rigid mesogenic chiral pendants linked via a flexible spacer that exhibits lyotropic nematic and latticelike new smectic (lat-Sm) liquid crystal phases at different concentrations. The unprecedented lat-Sm phase is associated with the smectic ordering of both the stiff polymer backbone and the rigid-rod side groups. A detailed investigation of the films using X-ray scattering and atomic force microscopy revealed a novel tilted smectic layer structure of the polymer backbone aligned perpendicular to the smectic layer of the mesogenic pendants, which arrange in an antiparallel overlapping interdigitated manner. 相似文献
78.
Yamashita S Fukushima H Niidome Y Mori T Katayama Y Niidome T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(23):14621-14626
Controlled-release systems that respond to external stimuli have received great interest for use in medical treatments such as for drug delivery to specific sites. Gold nanorods have an absorption band at the near-infrared region and convert the absorbed light energy into heat, which is known as a "photothermal effect". Therefore, gold nanorods are expected to act not only as an on-demand thermal converter for photothermal therapy but also as a controller of a drug-release system capable of responding to the near-infrared light irradiation. In this study, to construct a controlled-release system that responds to near-infrared light irradiation, we modified gold nanorods with polyethylene glycol (PEG) through Diels-Alder cycloadducts. When the modified gold nanorods were irradiated by near-infrared light, the PEG chains were released from the gold nanorods because of the retro Diels-Alder reaction induced by the photothermal effect. As a result of the PEG release, the gold nanorods formed aggregates. This type of controlled-release system coupled with the aggregate formation of the gold nanorods triggered by near-infrared light could be expanded to applications of gold nanorods in medical fields such as drug and photothermal therapy. 相似文献
79.
Bromomagnesium ureide-carbon dioxide adducts, models of the carboxylated biotin complex, undergo caboxylation of a variety of carbonyl compounds in good yield. 相似文献
80.
Mark Kristan Espejo Cabello Dr. Yuta Uetake Dr. Yu Yao Prof. Dr. Susumu Kuwabata Prof. Dr. Hidehiro Sakurai 《化学:亚洲杂志》2021,16(16):2280-2285
An aqueous colloidal dispersion of Pt nanoparticles (NPs) stabilized by fullerenol C60(OH)12 (Pt:C60(OH)12) was successfully synthesized via liquid-phase chemical reduction. The subsequent pyrolysis of Pt:C60(OH)12 at different temperatures was conducted to afford Pt-doped carbon with different chemical compositions (Pt:C60n). X-ray absorption spectroscopy (XAS) and Infrared (IR) absorption spectroscopy and thermogravimetric measurements revealed that the thus-prepared nanocomposite consists of Pt NPs and high valent Pt-C60(OH)12 complex. One distinct feature of C60(OH)12 matrix as catalyst support is the suppression of size growth of Pt NPs during the pyrolysis up to 300 °C. Electrochemical experiments using cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were performed to find that Pt:C60300 (pyrolyzed at 300 °C) exhibited higher activity than others, that was attributed to the π-extended feature of the as-obtained carbon. 相似文献