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71.
Sando S Abe K Sato N Shibata T Mizusawa K Aoyama Y 《Journal of the American Chemical Society》2007,129(19):6180-6186
There have been recent advances in the ribosomal synthesis of various molecules composed of nonnatural ribosomal substrates. However, the ribosome has strict limitations on substrates with elongated backbones. Here, we show an unexpected loophole in the E. coli translation system, based on a remarkable disparity in its selectivity for beta-amino/hydroxy acids. We challenged beta-hydroxypropionic acid (beta-HPA), which is less nucleophilic than beta-amino acids but free from protonation, to produce a new repertoire of ribosome-compatible but main-chain-elongated substrates. PAGE analysis and mass-coupled S-tag assays of amber suppression experiments using yeast suppressor tRNAPheCUA confirmed the actual incorporation of beta-HPA into proteins/oligopeptides. We investigated the side-chain effects of beta-HPA and found that the side chain at position alpha and R stereochemistry of the beta-substrate is preferred and even notably enhances the efficiency of incorporation as compared to the parent substrate. These results indicate that the E. coli translation machinery can utilize main-chain-elongated substrates if the pKa of the substrate is appropriately chosen. 相似文献
72.
Gold nanoclusters covered with 4-aminothiophenol (4-ATP) self-assembled monolayers (SAMs) were electrochemically assembled on an Au or ITO electrode. The assembly mechanism is discussed on the basis of results of electrochemical, FT-IR, and XPS measurements. The intensity of plasmon absorption of the gold nanocluster assembly was shown to be dependent on applied potential as a result of electrochemical doping/undoping of a counteranion in the polyaniline film. 相似文献
73.
Noncatalytic reaction pathways and rates of dimethyl ether (DME) in supercritical water are determined in a tube reactor made of quartz according to liquid- and gas-phase 1H and 13C NMR observations. The reaction is studied at two concentrations (0.1 and 0.5 M) in supercritical water at 400 degrees C and over a water-density range of 0.1-0.6 g/cm3. The supercritical water reaction is compared with the neat one (in the absence of solvent) at 0.1 M and 400 degrees C. DME is found to decompose through (i) the proton-transferred fragmentation to methane and formaldehyde and (ii) the hydrolysis to methanol. Formaldehyde from reaction (i) is consecutively subjected to four types of redox reactions. Two of them proceed even without solvent: (iii) the unimolecular proton-transferred decarbonylation forming hydrogen and carbon monoxide and (iv) the bimolecular self-disproportionation generating methanol and carbon monoxide. When the solvent water is present, two additional paths are open: (v) the bimolecular self-disproportionation of formaldehyde with reactant water, producing methanol and formic acid, and (vi) the bimolecular cross-disproportionation between formaldehyde and formic acid, yielding methanol and carbonic acid. Methanol is produced through the three types of disproportionations (iv)-(vi) as well as the hydrolysis (ii). The presence of solvent water decelerates the proton-transferred fragmentation of DME; the rate constant is reduced by 40% at 0.5 g/cm3. This is caused by the suppression of low-frequency concerted motion corresponding to the reaction coordinate for the simultaneous C-O bond scission and proton transfer from one methyl carbon to the other. In contrast to the proton-transferred fragmentation, the hydrolysis of DME is markedly accelerated by increasing the water density. The latter becomes more important than the former in supercritical water at densities greater than 0.5 g/cm3. 相似文献
74.
Ray K Nakahara H Sakamoto A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):103-107
The fluorescence lifetimes decays and picosecond time-resolved fluorescence spectra were measured to investigate the dynamics of the excited state of sulforhodamine B (SRB) molecules adsorbed in the mono- and multilayered Langmuir-Blodgett (LB) films of octadecylamine. Steady-state and time-resolved fluorescence spectroscopy reveals that the fluorescence lifetimes and contents of the monomer and dimers in the molecular organizates depend upon the concentration of the dye in the solution and the adsorption process. SRB dye molecules adsorbed in LB films have been imaged with scanning near-field optical microscopy (SNOM). This information is exploited to map the distribution with molecular spatial resolution. SNOM provide the visual evidence of the monomers and dimers of SRB in cationic LB films. 相似文献
75.
Sk. A. Latif Y. Oura M. Ebihara G. W. Kallemeyn H. Nakahara C. Yonezawa T. Matsue H. Sawahata 《Journal of Radioanalytical and Nuclear Chemistry》1999,239(3):577-580
Neutron-induced prompt gamma-ray analysis (PGA) was applied to seven meteorite samples (Allende, Zagami, Acfer 209, ALH77005,
ALH84001, EET79001 and Neagari). Samples were irradiated in both the thermal neutron and the cold neutron guided beams of
JRR-3M at JAERI. Multiple samples of an Allende standard powder were analyzed for Si using two different methods: (1) the
comparison method, using a Si standard, and (2) the mono-standard method, using Fe as an internal reference element. The Si
concentrations determined by these two methods are in good agreement with literature values. The analytical sensitivity for
Si using the cold neutron guided beam is∼14.3× higher than that for the thermal neutron guided beam. Other elements determined
(B, Ca, Ti and S) also showed higher sensitivities using the cold neutron beam. The other meteorites studied showed some anomalous
B and S values likely due to the effects of terrestrial weathering/contamination. 相似文献
76.
77.
Hargovind Rathore Toshihiro Hashimoto Kikuo Igarashi Haruo Nukaya Dwight S. Fullerton 《Tetrahedron》1985,41(23):5427-5438
As part of a continuing study of cardiac g1ycos1des,1,2 stereoselective syntheses of the four possible glucosides of digitoxigenin were developed via the thermodynamically produced tetra-O-benzyl-D- and L-glucosyl α-trichloroacetaimidates 2α and 11α, and the kinetically produced β-trichloroacetaimidates 2β and 11β. A 58%:19% isolated yield ratio of α-D and β-D benzyl protected glycosides 6 and 3 could be obtained in 30 minutes reaction at ?10°. Halide ion catalysis with a 2:1 excess of tetra-O-benzyl-α-D-glucopyranosyl bromide for 14 days in methylene chloride at room temperature gave a 39%:11% ratio of 6 and 3, along with 43% of recovered digitoxigenin. Debenzylation of the D-glucosides required milder conditions (20% Pd/C, atmospheric pressure, 45 min-1 hr) than the L-glucosides (40% Pd/C, 2 hr) but yields were typically 80% for both groups. 相似文献
78.
Two novel aromatic glycosides were obtained from Puerariae Radix and their chemical structures were characterized. 相似文献
79.
Suenaga Yuma Kawano Hiroaki Takamatsu Toshihiro Matsumura Yuriko Ito Norihiko Iwasawa Atsuo Okino Akitoshi 《Plasma Chemistry and Plasma Processing》2022,42(3):575-586
Plasma Chemistry and Plasma Processing - Atmospheric low-temperature plasma has received attention for application in disinfection methods. In this study, we develop a plasma bubbling method as a... 相似文献
80.
Shinichi Kinugasa Hisae Nakahara Jun-Ichi Kawahara Yoshinori Koga Haruo Takaya 《Journal of Polymer Science.Polymer Physics》1996,34(3):583-586
Static light scattering measurements were performed on dilute solutions of monodisperse poly(ethylene oxide) (PEO) in methanol at 25°C. PEOs of five different molecular weights ranging from nominal Mw = 8.6 × 104 to 9.13 × 105 were used. Linear Zimm plots were obtained for all the PEO samples: no downturn was observed at small angles, indicating that no large aggregates of PEO molecules exist in the solution. From the plots, values of the weight-average molecular weight, Mw, the radius gyration, RG, and the second virial coefficient, A2, were successfully determined for respective PEOs. Observed relationship between RG and Mw indicates that methanol is certainly a good solvent for the polymer. © 1996 John Wiley & Sons, Inc. 相似文献