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81.
Till J. B. Zähringer Julian A. Moghtader Maria-Sophie Bertrams Dr. Bibhisan Roy Masanori Uji Prof. Dr. Nobuhiro Yanai Prof. Dr. Christoph Kerzig 《Angewandte Chemie (International ed. in English)》2023,62(8):e202215340
Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable light-to-chemical energy conversion systems. 相似文献
82.
Dr. Yusuke Imamura Kyohei Takaoka Yuma Komori Dr. Masanori Nagatomo Prof. Dr. Masayuki Inoue 《Angewandte Chemie (International ed. in English)》2023,62(10):e202219114
Taxol is a clinically used drug for the treatment of various types of cancers. Its 6/8/6/4-membered ring (ABCD-ring) system is substituted by eight oxygen functional groups and flanked by four acyl groups, including a β-amino acid side chain. Here we report a 34-step total synthesis of this unusually oxygenated and intricately fused structure. Inter- and intramolecular radical coupling reactions connected the A- and C-ring fragments and cyclized the B-ring, respectively. Functional groups of the A- and C-rings were then efficiently decorated by employing newly developed chemo-, regio-, and stereoselective reactions. Finally, construction of the D-ring and conjugation with the β-amino acid delivered taxol. The powerful coupling reactions and functional group manipulations implemented in the present synthesis provide new valuable information for designing multistep target-oriented syntheses of diverse bioactive natural products. 相似文献
83.
Ryuhei Wakita Masanori Miyakoshi Yohji Nakatsuji Mitsuo Okahara 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):127-139
A series of noncyclic neutral ionophores has been synthesized by the reaction of oligoethylene glycol dihalides with 8-quinolinol. Complexation properties for alkali metal picrates were evaluated from solvent extraction and bulk liquid membrane transport experiments. Complexation profiles of the newly synthesized ionophores with a hexyl chain were similar to those of their homologues without the hexyl chain in the extraction experiments. Among them, the pentaethylene glycol derivatives showed the highest extraction efficiency and selectivity towards potassium ion. From the1H NMR spectra (400 MHz), the change in chemical shifts of the aromatic protons upon the addition of alkali metal thiocyanates suggested the existence of a stabilization effect which is caused by intramolecular stacking conformations between the quinoline rings during complexation. Aryl stacking interactions depend on the size of the cations and on the chain length of the oligoethylene glycol. The relationship between transport ability towards alkali metal cations and lipophilicity of these ionophores is also discussed. 相似文献
84.
Liquid scintillation radioassay for multiple radionuclide mixtures by the most probable value theory
Multiple radionuclide mixtures which have similar scintillation pulse height distributions can be accurately radioassayed by the most probable value theory. This liquid scintillation technique is based on the construction of more observation equations than the number of nuclides to be analyzed. The technique has been applied to3H–14C–125I and3H–14C–51Cr mixture samples, and found to be very practicable with the aid of computerized data processing for mixture samples having a wide range (ca. 10 times) of activity ratios. 相似文献
85.
When preparing an affinity column and a biosensor, it is desirable to immobilize a unimolecular layer of pure protein on a matrix. In this work, we tried to immobilize a monoclonal antibody on a surface of a glass test-tube as a model, to confirm the stability of this ultra-thin layer by an enzyme immunoassay, and to estimate the thickness of the layer on a slide glass by Fourier transform infrared reflection spectrometry. A new test-tube was washed and dried. The tube was filled with 5% 3-aminopropyltriethoxysilane. The 3-aminopropylsilylated surface was treated with glutaraldehyde and 5.6.10(-2) mg/ml solution of a normal mouse monoclonal antibody. The Schiff base between glutaraldehyde and the antibody was further reduced with 7.9.10(-3)% NaBH4. The tube was washed with 0.05% Tween 20 to block non-specific binding. The antibody immobilized on the surface was measured by an enzyme immunoassay based on a reaction of anti-mouse immunoglobulin G labelled with alkaline phosphatase, with which p-nitrophenol was produced from p-nitrophenylphosphate as a substrate. Meanwhile, various amounts of the antibody were immobilized on slide glasses in the same manner. The antibody on each surface was measured by Fourier transform infrared reflection spectrometry. The antibody immobilized under the final conditions was detectable by the enzyme immunoassay, and stable at 4 degrees C for ten days. The antibody on the slide glass was a unimolecular layer, as judged from the Fourier transform infrared spectra referred to -CONH- band semiquantitatively. Thus, we found the optimal conditions for immobilizing an ultra-thin layer of the monoclonal antibody on the glass surface.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
86.
The formation constants of the mono-adducts of α-acylcamphorato-copper(II) chelates such as (+)-Cu(facam)2, (?)-Cu(facam)2, (+)-Cu(hfbc)2 and (?)-Cu(hfbc)2 with some chiral Lewis bases were determined spectrophotometrically in benzene. In order to compare the adduct formation constants obtained with the (+)- and (?)-forms, some pairs of chiral Lewis bases such as 1-amino-2-propanol [(R)(?), (S)(+)], 1-(α-naphthyl)ethylamine [(R)(+), (S)(?)], α-phenyl ethylamine [(R)(+), (S)(?)] and also quinine and quinidine were examined as neutral ligands. Although not very pronounced, the effects of combinations obtained for (+)- or (?)-Cu(II) chelates and (+)- or (?)-ligands indicate that formation constants obtained by the formation of adducts with the ligands having different directions of the optical rotation seems to be superior to those with the same direction. 相似文献
87.
Dr. Masanori Shigeno Takuya Okawa Masaya Imamatsu Kanako Nozawa-Kumada Yoshinori Kondo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10294-10297
We herein demonstrate that the amide base generated in situ from CsF and N(TMS)3 catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds. 相似文献
88.
Prof. Dr. Yasuchika Hasegawa Takafumi Matsui Dr. Yuichi Kitagawa Dr. Takayuki Nakanishi Dr. Tomohiro Seki Prof. Dr. Hajime Ito Prof. Dr. Yuta Nakasaka Prof. Dr. Takao Masuda Prof. Dr. Koji Fushimi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12308-12315
Oxygen-sensitive and near-infrared (NIR) luminescent YbIII coordination polymers incorporating ligands based on pyrene derivatives were synthesized: YbIII–TBAPy and YbIII–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of YbIII–TIAPy has been evaluated by measuring its N2 adsorption isotherm. The NIR luminescence properties of YbIII–TBAPy and YbIII–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. YbIII–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent YbIII coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors. 相似文献
89.
Tomihiro Nishiyama Shigeki Matsui Fukiko Yamada 《Journal of heterocyclic chemistry》1986,23(5):1427-1429
Heterocyclic compounds of four 5-methyl-3-phenyl-1,3-oxazolidin-2-ones have been synthesized by the reaction of N-2-hydroxyethyl- or N-2-hydroxypropylanilines with phosgene in the presence of pyridine. From the spectral behavior, the title compounds are found to exist in the trans and cis forms. 相似文献
90.