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341.
Kamiya M Kobayashi H Hama Y Koyama Y Bernardo M Nagano T Choyke PL Urano Y 《Journal of the American Chemical Society》2007,129(13):3918-3929
Beta-galactosidase is a widely used reporter enzyme, but although several substrates are available for in vitro detection, its application for in vivo optical imaging remains a challenge. To obtain a probe suitable for in vivo use, we modified our previously developed activatable fluorescence probe, TG-betaGal (J. Am. Chem. Soc. 2005, 127, 4888-4894), on the basis of photochemical and photophysical experiments. The new probe, AM-TG-betaGal, provides a dramatic fluorescence enhancement upon reaction with beta-galactosidase, and further hydrolysis of the ester moiety by ubiquitous intracellular esterases affords a hydrophilic product that is well retained within the cells without loss of fluorescence. We used a mouse tumor model to assess the practical utility of AM-TG-betaGal, after confirming that tumors in the model could be labeled with an avidin-beta-galactosidase conjugate. This conjugate was administered to the mice in vivo, followed by AM-TG-betaGal, and subsequent ex vivo fluorescence imaging clearly visualized intraperitoneal tumors as small as 200 microm. This strategy has potential clinical application, for example, in video-assisted laparoscopic tumor resection. 相似文献
342.
A new fluorescent ionophore for alkaline earth metal ions, 4'-(9-fluorenecarboxamido)benzo-15-crown-5 (3), was synthesized; its photochemical behavior was investigated using UV, fluorescence, (1)H NMR, and (13)C NMR spectrometry. In the absence of a metal ion, the fluorene moiety showed weak fluorescence emission (fluorescence "Off" state). However, complexation with metal ions greatly enhanced the fluorescence intensity (fluorescence "On" state). 相似文献
343.
[structure: see text] A convergent total synthesis of khafrefungin was accomplished on the basis of (1) the highly stereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using vinylketene silyl N,O-acetal and (2) syn-selective aldol reaction of enal 5a and ethyl ketone 6 followed by anti-dehydration under Mitsunobu conditions. 相似文献
344.
A first total synthesis of broussonetine F from diethyl L-tartrate was achieved. The cornerstone of our synthesis was an orthoamide Overman rearrangement, which provided an allylic amino alcohol with complete diastereoselectivity. 相似文献
345.
Nakata S Matsushita M Sato T Suematsu NJ Kitahata H Amemiya T Mori Y 《The journal of physical chemistry. A》2011,115(26):7406-7412
The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation. 相似文献
346.
Zhao M Bai L Toki A Hasegawa R Sakai J Hasegawa T Ogura H Kataoka T Bai Y Ando M Hirose K Ando M 《Chemical & pharmaceutical bulletin》2011,59(3):371-377
A new cardenolide diglycoside (1) was isolated from Nerium oleander together with ten known cardenolide diglycosides 2-11. The structure of compound 1 was established on the basis of their spectroscopic data. The in vitro anti-inflammatory activity of compounds 1-11 was examined on the basis of inhibitory activity against the induction of the intercellular adhesion molecule-1 (ICAM-1). Compounds 2-5 were active at an IC(50) value of less than 0.8 μM. The cytotoxicity of compounds 1-11 was evaluated against three human cell lines normal human fibroblast cells (WI-38), malignant tumor cells induced from WI-38 (VA-13), and human liver tumor cells (HepG2). Compound 3 was active toward VA-13 cells, and compounds 2-5 were active toward HepG2 cells at IC(50) values of less than 1.3 μM. The multidrug resistance (MDR)-reversal activity of compounds 1-11 was evaluated on the basis of the amount of calcein in MDR human ovarian cancer 2780AD cells in the presence of each compound. Compounds 1 and 8 showed moderate effects on calcein accumulation. 相似文献
347.
Upon reaction of the 3',4'-unsaturated adenosine derivative 2 with N-iodosuccinimide (NIS) and thiophenol, an unexpected electrophilic hydrophenylsulfanylation proceeded to provide 4'-phenylsulfanylcordycepin 7 in 79% yield with the ratio 7a/7b = 6.6/1. A study of the reaction mechanism revealed that hydrogen iodide (HI) generated from NIS and PhSH acted as an active species. On the basis of a deuterium experiment using PhSD, initial protonation occurred at the β face of the double bond to furnish the β-π complex III, which underwent anti addition of PhSH as a major pathway. Nucleophilic substitution of N(6)-pivaloylated 9 with various alcohols in the presence of N-bromosuccinimide (NBS) gave the respective 4'-α-alkoxycordycepins 15a-21a as the major stereoisomers. Use of DAST in place of an alcohol gave the 4'-α-fluoro analogue 23a stereoselectively. Radical-mediated carbon-carbon bond construction was also applicable to 7, giving 4'-α-allylcordycepin (24a) and 4'-α-cyanoethylcordycepin (25) derivatives. 相似文献
348.
Prof. Dr. Kenshu Fujiwara Yuki Suzuki Nao Koseki Yu‐ichi Aki Yuta Kikuchi Shun‐ichi Murata Fuyuki Yamamoto Mariko Kawamura Prof. Dr. Toshio Norikura Prof. Dr. Hajime Matsue Prof. Dr. Akio Murai Prof. Dr. Ryo Katoono Prof. Dr. Hidetoshi Kawai Prof. Dr. Takanori Suzuki 《Angewandte Chemie (International ed. in English)》2014,53(3):780-784
Pectenotoxin‐2 (PTX2) is a shellfish toxin and has a non‐anomeric spiroacetal, which is not stabilized by an anomeric effect. The selective construction of the non‐anomeric spiroacetal has been a major problem in the synthesis of PTX2. Described herein is the stereoselective total synthesis of PTX2 via the isomerization of anomeric spiroacetal pectenotoxin‐2b (PTX2b). The synthesis of PTX2b was achieved by a simple process including sulfone‐mediated assembly of spirocyclic and bicyclic acetals and subsequent macrocyclization by ring‐closing olefin metathesis. Finally, the selective construction of PTX2 was accomplished by the early termination of a dynamic transition process to equilibrium in the acid‐catalyzed isomerization of anomeric PTX2b. [6,6]‐Spiroacetal pectenotoxin‐2c (PTX2c) was also synthesized from PTX2b. The cytotoxicity assay of the synthetic compounds against HepG2 and Caco2 cancer cells showed a potency of the order: PTX2?PTX2b>PTX2c. 相似文献
349.
Yabushita A Hama T Iida D Kawanaka N Kawasaki M Watanabe N Ashfold MN Loock HP 《The Journal of chemical physics》2008,129(4):044501
The production of H(2) in highly excited vibrational and rotational states (v=0-5, J=0-17) from the 157 nm photodissociation of amorphous solid water ice films at 100 K was observed directly using resonance-enhanced multiphoton ionization. Weaker signals from H(2)(v=2,3 and 4) were obtained from 157 nm photolysis of polycrystalline ice, but H(2)(v=0 and 1) populations in this case were below the detection limit. The H(2) products show two distinct formation mechanisms. Endothermic abstraction of a hydrogen atom from H(2)O by a photolytically produced H atom yields vibrationally cold H(2) products, whereas exothermic recombination of two H-atom photoproducts yields H(2) molecules with a highly excited vibrational distribution and non-Boltzmann rotational population distributions as has been predicted previously by both quantum-mechanical and molecular dynamics calculations. 相似文献
350.
Two types of naphthalene trimers linked by 1,3,4-oxadiazole spacers were synthesized and investigated for their physical and electronic properties. 2,6- and 2,7-isomers on central naphthalene moieties were obtained in the forms of pale yellow solids and colorless crystals, respectively. The melting point of the 2,6-isomer was higher than that of the 2,7-isomer. An X-ray crystallographic analysis revealed a π-stacked column with a short intermolecular distance in the crystals of the 2,6-isomer. The absorption maximum of the 2,6-isomer was red-shifted as compared to that of the 2,7-isomer, indicating a π-conjugation between di-2-naphthyloxadiazole moieties in the 2,6-isomer. The quantum yields of the 2,6- and 2,7-isomers were measured to be 0.97 and 0.74, relative to that of 2,5-di-2-naphthyl-1,3,4-oxadiazole (0.85). Molecular orbital (MO) calculations demonstrated that the 2,6-isomer had a higher electron affinity than the 2,7-isomer. Thus, the crosslinking of building blocks is important for the design of functional materials. 相似文献