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Total Synthesis of the 7,10‐Epimer of the Proposed Structure of Amphidinolide N,Part II: Synthesis of C17–C29 Subunit and Completion of the Synthesis 下载免费PDF全文
Dr. Koji Ochiai Dr. Sankar Kuppusamy Yusuke Yasui Kenji Harada Dr. Nishant R. Gupta Dr. Yohei Takahashi Prof. Dr. Takaaki Kubota Prof. Dr. Jun'ichi Kobayashi Prof. Dr. Yujiro Hayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3287-3291
The total synthesis of 7,10‐epimer of the proposed structure of amphidinolide N was accomplished. The requisite chiral C17–C29 subunit was assembled stereoselectively via Keck allylation, Shi epoxidation, diastereoselective 1,3‐reduction, and a later oxidative synthesis of the THF framework. The C1–C13 and C17–C29 subunits were successfully coupled using a Enders RAMP “linchpin” as the C14–C16 three carbon unit, thereby controlling the chirality at C14 and C16. The labile allyl epoxy moiety was successfully constructed by Grieco–Nishizawa olefination at a final stage of the synthesis. 相似文献
104.
Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion‐Channel‐Forming 48‐mer Peptides with Potent Cytotoxicity 下载免费PDF全文
Atsushi Hayata Dr. Hiroaki Itoh Shoko Matsutaka Prof.Dr. Masayuki Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3370-3377
Polytheonamide B ( 1 ) is a natural peptide that displays potent cytotoxicity against P388 mouse leukemia cells (IC50=0.098 nm ). Linear 48‐mer 1 is known to form monovalent cation channels on binding to lipid bilayers. We previously developed a fully synthetic route to 1 , and then achieved the design and synthesis of a structurally simplified analogue of 1 , namely, dansylated polytheonamide mimic 2 . Although the synthetically more accessible 2 was found to emulate the channel function of 1 , its cytotoxicity was decreased 120‐fold. Herein, the chemical preparation and biological evaluation of seven analogues 3 – 9 of 2 are reported. Compounds 3 – 9 were modified at their N terminus and/or the side chain of residue 44 of 2 to alter their physicochemical properties. The total synthesis of 3 – 9 was accomplished in a unified fashion by a combination of solid‐phase and solution‐phase chemistry. Systematic evaluation of the hydrophobicities, single‐channel currents, ion‐exchange activities, and cytotoxicities of 3 – 9 revealed that their hydrophobicities are correlated with the total magnitude of ion exchange and determine their cytotoxic potency. Consequently, the most hydrophobic analogue 9 exhibited the lowest IC50 value, which is comparable to that of 1 . Therefore, these results clarified that the bioactivity of the polytheonamide‐based peptides can be rationally controlled by changing their hydrophobicity at the N and C termini of the 48‐amino‐acid sequence. 相似文献
105.
Warô Nakanishi Satoko Hayashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1833-1837
The lone pair-lone pair repulsion plays an important role in the nonbonded P;;;P interaction in naphthalene 1,8-positions. The conformations around P and Se in 8-(PhSe)-1-(Ph 2 P=O)C 10 H 6 are determined by the attractive O;;;Se--C 3c-4e type interaction. The P;;;Se interaction in the 1,8-positions is also discussed. 相似文献
106.
Abstract Postpolymerization of vinyl monomers initiated by pendant peroxycarbonate groups of grafted polymer chains on carbon black (CB) was investigated. The grafting of polymers having pendant peroxycarbonate groups onto CB was achieved by the trapping of polymer radicals formed by the thermal decomposition of copolymers of t-butylperoxy-2-methacryloyloxyethyl-carbonate (HEPO) with vinyl monomers such as vinyl acetate (VAc), styrene (St) and methyl methacrylate (MMA). The copolymers having pendant peroxycarbonate groups were prepared by copolym-erization of HEPO with vinyl monomers using azo initiator under irradiation of UV light at room temperature. The amount of remaining pendant peroxycarbonate groups of the poly(VAc-co-HEPO)-grafted CB obtained from the reaction at 90°C was maximum and decreased above the temperature. Furthermore, the postpolymerization of vinyl monomers, such as St, MMA, and VAc was initiated in the presence of poly(VAc-co-HEPO)-grafted and poly(St-co-HEPO)-grafted CB and the corresponding polymers were postgrafted onto CB to give branched polymer-grafted CB. The percentage of poly(St)-postgrafting (proportion of post-grafted poly(St) to poly(MMA-co-HEPO)-grafted CB used) increased with increasing polymerization time, but became constant at 20% after 4 hours. 相似文献
107.
Over the past two decades, the spatiotemporal analysis of fluorescently labeled single RNA species has provided a broad insight into the synthesis, localization, degradation, and transport of RNA. To elucidate the dynamic behavior of functional RNAs in living cells, researchers throughout the world have proposed numerous fluorometric strategies for intracellular RNA imaging. Because, like most other biological molecules, RNA is intrinsically nonfluorescent, the development of methods for the labeling of RNAs of interest with fluorescent molecules is essential. Several artificial tag sequences have been attached onto the 3′ end of target RNAs and used as scaffolds for interacting with their fluorescent counterparts. In this Personal Account, we focus on the methods that have been developed to show how RNAs expressed in cells can be labeled and visualized by fluorescent proteins, small molecules, or nucleic acids. Each of these methods is designed to increase the sensitivity and specificity for imaging or to decrease the background fluorescence. 相似文献
108.
Hideaki Iizuka Shoko Watanabe Mayuko Koshikawa Yurie Matsumoto Yuki Aoyama Hideaki Ichiba Toshitaka Nabeshima Takeshi Fukushima 《Analytical and bioanalytical chemistry》2013,405(25):8137-8141
It has been reported that repeated phencyclidine (PCP) treatment induces schizophrenia-like behavior in mice. l-Tryptophan (Trp) concentrations in brain tissues of control (n?=?8) and PCP-treated mice (10 mg/kg/day, s.c., 14 days, n?=?10) were determined using high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC method involved pre-column fluorescence derivatization with (R)-(?)-4-(N,N-dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole (DBD-PyNCS). Eight different parts of the brain, namely, the frontal cortex, nucleus accumbens, striatum, hippocampus, amygdala, thalamus, hypothalamus, and cerebellum, of both groups were investigated. A significant decrease in the l-Trp concentration in the nucleus accumbens (p?=?0.024) and hippocampus (p?=?0.027) was observed in PCP-treated mice, suggesting that alteration of the l-Trp metabolism might occur in these brain parts. 相似文献
109.
Invited for this month''s cover picture is the group of Dr. Satoko Hayashi at Faculty of Systems Engineering and Chemistry at Wakayama University. The cover picture shows the linear Se16 σ(16c–30e) interactions, illustrated by the molecular graph type on the optimized structure of the dicationic octamer of 1,5‐(diselena)cane. HOMO‐1 of ψ462 is drawn on the structure, which is located predominantly on the Se atoms. The optimized structure is stable, due to the nice engagement between the (CH2)3 moieties. The contour maps of ρ(r) are also drawn on the molecular C s planes of the dicationic dimer and trimer to demonstrate clearly the existence of the interactions between Se atoms. Read the full text of their Full Paper at 10.1002/open.202100017.“… To improve the causality of experimental results, we have proposed a new concept, called “Keisan‐sendo…” Find out more about the story behind the front cover research at 10.1002/open.202100017. 相似文献
110.
Tetsuo Sakamoto Kenji Ohishi Shun‐ichi Hayashi Masaaki Fujii 《Surface and interface analysis : SIA》2013,45(8):1309-1312
Aiming for the highly sensitive analysis of aromatic hydrocarbons in organic mixtures, selective ionization using an ultraviolet laser ionization technique was examined for the determination of sputtered neutral species on organic surfaces. The mass spectrum of a model mixture containing pyrene and n‐alkane showed that only pyrene was ionized and detected, whereas a mass spectrum without laser irradiation, i.e. in the case of secondary ion mass spectrometry, was dominated by many n‐alkane fragment peaks. This technique was applied for the detection of polyaromatic hydrocarbons adsorbed on diesel exhaust particles. Two kinds of polyaromatic hydrocarbons were clearly detected because many aliphatic fragment signals were suppressed by means of ultraviolet laser ionization. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献