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51.
[formula: see text] The conformation of the retinal chromophore in rhodopsin is central for understanding the visual transduction process. The absolute twist around the 12-s bond of the chromophore in rhodopsin has been determined by studies with 11-cis-locked 11,12-cyclopropylretinal analogues (11S,12R)-2 and (11R,12S)-3, enantioselectively synthesized with the aid of an enzyme. The finding that enantiomer 2 binds to opsin while the other 3 does not defines the absolute sense of twist around the 12-s bond. 相似文献
52.
Two novel nucleosides, mycalisines A and B, have been isolated from a marine sponge and their structures elucidated as 4-amino-5-cyano-7-(3--methyl-5-deoxy-β-D--pent-4-enofuranosyl)-pyrrolo[2,3-]pyrimidine and 5-cyano-7-(3--methyl-5-deoxy-β-D--pent-4-enofuranosyl)-pyrrolo[2,3-]pyrimidine-4-one, respectively. Both compounds inhibit cell division of fertilized starfish eggs. 相似文献
53.
Seiichi Nakamura Jun Inagaki Tomohiro Sugimoto Yasuyuki Ura Shunichi Hashimoto 《Tetrahedron》2002,58(52):10375-10386
An efficient, highly stereoselective synthesis of the C10–C31 (BCDEF ring) portion of pinnatoxin A has been achieved utilizing tandem double hemiketal formation/intramolecular hetero-Michael addition to construct the 6,5,6-dispiroketal (BCD ring) system and subsequent intramolecular ketalization to form the 5,6-bicycloketal (EF ring) system as key steps. 相似文献
54.
The present work describes the synthesis of the beta-isomer of 1-alpha-D-(5-deoxy-5-iodoarabinofuranosyl)-2-nitroimidazole (IAZA). Radioiodinated IAZA ((123)I-IAZA) has been extensively studied as a radiopharmaceutical for the diagnosis of regional and/or focal tissue hypoxia in a variety of clinical pathologies. The beta-anomer of IAZA, 1-beta-D-(5-deoxy-5-iodoarabinofuranosyl)-2-nitroimidazole (beta-IAZA, 1), was synthesized via an unconventional route starting from 1-beta-D-(ribofuranosyl)-2-nitroimidazole (AZR), with a change of configuration at the C-2'-position to afford 1-beta-D-(arabinofuranosyl)-2-nitroimidazole (beta-AZA, 7). Nucleophilic iodination of the 5'-O-toluenesulfonyl-2',3'-di-O-acetyl precursor of beta-AZA, 9, followed by deprotection, afforded 1 in satisfactory yield. beta-IAZA (1) was also synthesized from 7 using molecular iodine and triphenylphosphine. 相似文献
55.
Enami S Yamanaka T Hashimoto S Kawasaki M Tonokura K 《The journal of physical chemistry. A》2005,109(27):6066-6070
The reactions of Cl atoms with RI (R = n-C3H7, n-C4H9, cyclo-C6H11, C6H5, C6F5, and p-CH3C6H4) have been studied using cavity ring-down spectroscopy at a temperature range of 233-313 K and at 100 Torr total pressure of N2 diluent. Visible absorption spectra of the RI-Cl adducts were recorded at 440-520 nm at 263 K. The yields of the adducts were temperature-dependent. There was no discernible reaction of the adducts in the presence of 100 Torr of O2 at 263 K. Theoretical calculations were performed for C4H9I-Cl and C6H5I-Cl for quantitative explanation of the absorption spectra and the strength of the I-Cl bonds in the charge-transfer complexes. Evidence for the adduct formation following the reaction of Cl with C6H5Br was sought but not found at 440 and 520 nm. 相似文献
56.
5-Aminolaevulinic acid-mediated photodynamic therapy in multidrug resistant leukemia cells 总被引:5,自引:0,他引:5
Li W Zhang WJ Ohnishi K Yamada I Ohno R Hashimoto K 《Journal of photochemistry and photobiology. B, Biology》2001,60(2-3):79-86
To verify if photodynamic therapy (PDT) could overcome multidrug resistance (MDR) when it it applied to eradicate minimal residual disease in patients with leukemia, we investigated the fluorescence kinetics of 5-aminolaevulinic acid (ALA)-induced protoporphyrin IX (PpIX) and the effect of subsequent photodynamic therapy on MDR leukemia cells, which express P-glycoprotein (P-gp), as well as on their parent cells. Evaluation of PpIX accumulation by flow cytometry showed that PpIX accumulated at higher levels in mdr-1 gene-transduced MDR cells (NB4/MDR) and at lower levels in doxorubicin-induced MDR cells (NOMO-1/ADR) than in their parent cells. A P-gp inhibitor could not increase PpIX accumulation. Measurement of extracellular PpIX concentration by fluorescence spectrometry showed that P-gp did not mediate the fluorescence kinetics of ALA-induced PpIX production. Assessment of ferrochelatase activity using high-performance liquid chromatography indicated that PpIX accumulation in drug-induced MDR cells was probably regulated by this enzyme. Assessment of phototoxicity of PDT using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay showed that PDT was effective in NB4, NB4/MDR, NOMO-1 and NOMO-1/ADR cells, which accumulated high levels of PpIX, but not effective in K562 and K562/ADR cell lines, which accumulated relatively low levels of PpIX. These findings demonstrate that P-gp does not mediate the ALA-fluorescence kinetics, and multidrug resistant leukemia cells do not have cross-resistance to ALA-PDT. 相似文献
57.
Jun-Ichiro Makiura Takuma Higo Yutaro Kurosawa Kota Murakami Shuhei Ogo Hideaki Tsuneki Yasushi Hashimoto Yasushi Sato Yasushi Sekine 《Chemical science》2021,12(6):2108
Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. Results show that a novel Cu–In2O3 structured oxide can show a remarkably higher CO2 splitting rate than ever reported. Various analyses revealed that RWGS-CL on Cu–In2O3 is derived from redox between Cu–In2O3 and Cu–In alloy. Key factors for high CO2 splitting rate were fast migration of oxide ions in the alloy and the preferential oxidation of the interface of alloy–In2O3 in the bulk of the particles. The findings reported herein can open up new avenues to achieve effective CO2 conversion at lower temperatures.Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. 相似文献
58.
Kazue Kudo 《Entropy (Basel, Switzerland)》2022,24(8)
Detecting many-body localization (MBL) typically requires the calculation of high-energy eigenstates using numerical approaches. This study investigates methods that assume the use of a quantum device to detect disorder-induced localization. Numerical simulations for small systems demonstrate how the magnetization and twist overlap, which can be easily obtained from the measurement of qubits in a quantum device, changing from the thermal phase to the localized phase. The twist overlap evaluated using the wave function at the end of the time evolution behaves similarly to the one evaluated with eigenstates in the middle of the energy spectrum under a specific condition. The twist overlap evaluated using the wave function after time evolution for many disorder realizations is a promising probe for detecting MBL in quantum computing approaches. 相似文献
59.
Takashi Mino Kohei Watanabe Takumu Akiyama Yuki Mizutani Kazuki Miura Masatoshi Hashimoto Yasushi Yoshida Masami Sakamoto 《Tetrahedron》2018,74(28):3871-3878
We previously reported the synthesis of BICMAP (1a) via 6-diphenylphosphino-2,3-dihydrobenzofuran as a key intermediate. However, we did not successfully synthesize BICMAP analogues via a similar synthetic route. Herein we report the second-generation synthesis of BICMAP and its derivatives via diethylphosphonate as a key intermediate. 相似文献
60.
Ohkoshi S Tokoro H Hozumi T Zhang Y Hashimoto K Mathonière C Bord I Rombaut G Verelst M Cartier dit Moulin C Villain F 《Journal of the American Chemical Society》2006,128(1):270-277
This article describes the studies of a photomagnetic cyanide-bridged Cu-Mo bimetallic assembly, Cu(II)(2)[Mo(IV)(CN)(8)].8H(2)O (Cu(II), S = (1)/(2); Mo(IV), S = 0) (1), which has an intervalence transfer (IT) band from Mo(IV)-CN-Cu(II) to Mo(V)-CN-Cu(I) around 480 nm. Wide-angle X-ray scattering and X-ray spectroscopic studies provide precise information about the 3D connectivity and the local environment of the transition metal ions. Irradiating with blue light causes solid 1 to exhibit a spontaneous magnetization (Curie temperature = 25 K). The thermal reversibility is carefully studied and shows the long-time stability of the photoinduced state up to 100 K. Photoreversibility is also observed; i.e., the magnetization is induced by irradiation with light below 520 nm, while the magnetization is reduced by irradiation with light above 520 nm. The UV-vis absorption spectrum after irradiation shows a decrease of the IT band and the appearance of the reverse-IT band in the region of 600-900 nm (lambda(max) = 710 nm). This UV-vis absorption spectrum is recovered to the original spectrum by irradiation with 658-, 785-, and 840-nm light. In this photomagnetic effect, the excitation of the IT band causes an electron transfer from Mo(IV) to Cu(II), producing a ferromagnetic mixed-valence isomer of Cu(I)Cu(II)[Mo(V)(CN)(8)].8H(2)O (Cu(I), S = 0; Cu(II), S = (1)/(2); Mo(V), S = (1)/(2)) (1'). 1' returns to 1 by irradiation of the reverse-IT band, which obeys the scheme for the potential energy surface in mixed-valence class II compounds. 相似文献