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81.
The formation of carbon-carbon bond by sulfur extrusion such as pyrolysis of cyclic sulfones is well known as an important synthetic method, especially for the synthesis of cyclophane framework.1) Little is known about selenium extrusion as the counterpart, though organoseleniums have been properly appreciated as a useful tool for manipulating a functional group.2) Lardon reported that the thermal decomposition of dibenzyl diselenide led to a mixture of dibenzyl selenide and polyselenides.3) In contrast, recent reports showed that at 210°C, heating bis(diphenylmethyl) diselenide resulted in ready selenium extrusion to 1,1,2,2-tetraphenylethane4), and dianthrylmethyl mono- and diselenides to 1,2-dianthrylethane.5) Therefore,- it is worthwhile to study the thermal behavior of dibenzyl selenide itself. 相似文献
82.
Masashi Daido Yukio Kawashima Masanori Tachikawa 《Journal of computational chemistry》2013,34(28):2403-2411
The structure of Watson–Crick‐type adenine‐thymine and guanine‐cytosine pairs has been studied by hybrid Monte Carlo (HMC) and path integral hybrid Monte Carlo (PIHMC) simulations with the use of semiempirical PM6‐DH+ method in the gas phase. We elucidated the nuclear quantum effect and temperature dependency on the hydrogen‐bonded moiety of base pairs. It was shown that the contribution of nuclear quantum effect on the hydrogen‐bonded structure is significant not only at low temperature 150 K but also at temperature as high as 450 K. The relative position of hydrogen‐bonded proton between two heavy atoms and the nuclear quantum nature of the proton are also shown. Furthermore, we have applied principal component analysis to HMC and PIHMC simulations to analyze the nuclear quantum effect on intermolecular motions. We found that the ratio of Buckle mode (lowest vibrational mode from normal mode analysis) decreases due to the nuclear quantum effect, whereas that of Propeller mode (second lowest vibrational mode) increases. In addition, nonplanar structures of base pairs were found to become stable due to the nuclear quantum effect from two‐dimensional free energy landscape along Buckle and Propeller modes. © 2013 Wiley Periodicals, Inc. 相似文献
83.
A novel oligonucleotide delivery system that is based on oligonucleotide–nanoparticle conjugates has been described. Installed oligonucleotides were modified with the carbohydrate at the 3′ terminus, accordingly, constructed nanoparticles display clustered carbohydrates on their outer layer for the targeted delivery of oligonucleotides. The method for the construction of ligand-functionalized nanoparticle was simple and reproducible. The stability of the nanoparticles displaying clustered carbohydrates greatly increased in serum compared to nanoparticles without carbohydrates. In order to investigate the targetability of oligonucleotide–nanoparticle conjugates into primary hepatic parenchymal cells, freshly isolated rat hepatocytes were incubated with nanoparticles and the amount of internalized gold nanoparticles was evaluated by an inductively coupled plasma mass spectroscopy analysis. Nanoparticles displaying clustered carbohydrates internalized more efficiently than nanoparticles without carbohydrate modifications. In particular, the cellular uptakes of oligonucleotide-conjugated gold nanoparticle increased 1.7 ~2.0-fold by galactose modification. Competition assay revealed that clustered galactose enhanced the internalization of the nanoparticle into primary hepatic parenchymal cells by a receptor-mediated process. Figure
A novel oligonucleotide delivery system that is based on oligonucleotide-nanoparticle conjugates has been described. Constructed nanoparticles display clustered carbohydrates on their outer layer. The stability of the nanoparticles displaying clustered carbohydrates increased in serum, and clustered galactose enhanced the internalization of the nanoparticle to hepatic parenchymal cells by a receptor-mediated process 相似文献
84.
In this paper, as a first step to study the global structure of solution, we treat a class of reaction–diffusion systems with competitive interaction, and discuss a uniqueness theorem of radially symmetric solutions for the system. To do this, the comparison principle and the shooting method are employed, and the spatial profile is investigated. 相似文献
85.
Yutaka Aoyagi Kei Ozawa Tatsuya Kobayashi Tomoyo Hasuda Ming-Yu Gui Yong-Ri Jin Xu-Wen Li Haruhiko Fukaya Reiko Yano Yukio Hitotsuyanagi Koichi Takeya 《Tetrahedron》2014
Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed. 相似文献
86.
YoungSook Yun Mariko Shioura Yukio Hitotsuyanagi Satoshi Yotsumoto Yuji Takahashi Yutaka Aoyagi Takeshi Kinoshita Koichi Takeya Hideshi Inoue 《Molecules (Basel, Switzerland)》2021,26(9)
Cytotoxicity and apoptosis-inducing properties of compounds isolated from Garcinia subelliptica leaves were investigated. The hexane-soluble portion of MeOH extracts of G. subelliptica leaves that showed cytotoxic activity was separated to yield seven compounds 1–7. Chemical structure analysis using NMR spectroscopy and mass spectrometry confirmed that compound 1 was canophyllol, and compounds 2–7 were garcinielliptones N, O, J, G, F, and garcinielliptin oxide, respectively. Among them, garcinielliptone G (5) showed growth inhibition by causing apoptosis in THP-1 and Jurkat cells derived from human acute monocytic leukemia and T lymphocyte cells, respectively. Apoptosis induced by garcinielliptone G (5) was demonstrated by the detection of early apoptotic cells with fluorescein-labeled Annexin V and increases in cleaved caspase-3 and cleaved PARP protein levels. However, the addition of caspase inhibitor Z-VAD-FMK did not affect growth arrest or apoptosis induction. These results suggest that garcinielliptone G (5) can induce both caspase-3 activation and caspase-independent apoptosis. Therefore, garcinielliptone G (5) may be a potential candidate for acute leukemia treatment. 相似文献
87.
Total Synthesis of the Antibiotic Kendomycin: A Macrocyclization Using the Tsuji–Trost Etherification 下载免费PDF全文
Dr. Tetsuya Sengoku Dr. Shu Xu Kenji Ogura Yoshinori Emori Kenji Kitada Prof. Dr. Daisuke Uemura Prof. Dr. Hirokazu Arimoto 《Angewandte Chemie (International ed. in English)》2014,53(16):4213-4216
A highly stereocontrolled, convergent total synthesis of kendomycin [(?)‐TAN2162], an ansa‐macrocyclic antibiotic, is reported. The key of the strategy is an unprecedented Tsuji–Trost macrocyclic etherification, followed by a transannular Claisen rearrangement to construct the 18‐membered carbocyclic framework. The oxa‐six‐ and five‐membered rings were also stereoselectively constructed respectively by a cascade oxidative cyclization at an unfunctionalized benzylic position and using a one‐pot epoxidation/5‐exo‐tet epoxide opening. 相似文献
88.
Jie Zhu Dr. Ryota Osuga Prof. Ryo Ishikawa Prof. Naoya Shibata Prof. Yuichi Ikuhara Prof. Junko N. Kondo Prof. Masaru Ogura Prof. Jihong Yu Prof. Toru Wakihara Prof. Zhendong Liu Prof. Tatsuya Okubo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19837-19842
Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity. 相似文献
89.
Raku Watanabe Dr. Nobuki Kato Kengo Hayashi Sho Tozawa Dr. Yusuke Ogura Prof. Shigefumi Kuwahara Prof. Minoru Ueda 《ChemistryOpen》2020,9(10):1008-1017
An efficient and stereoselective syntheses of all the possible stereoisomers of coronafacic acid (CFA) has been developed. The stereochemistries of C3a and C7a were controlled in a diastereoselective Diels-Alder type cycloaddition using a chiral auxiliary. CFA and 6-epi-CFA were synthesized by hydrogenation of a common intermediate. During the synthesis of 6-epi-CFA, we established that its cis-fused configuration is important for the introduction of C4-C5 double bond by dehydration. This report is the first practical synthesis of both 6-epi-CFA, and its enantiomer. 相似文献
90.
Zircon-type compounds LnCrO4 (Ln=Nd, Sm, and Dy) were prepared. Their precise crystal structures at room temperature were determined from X-ray diffraction measurements. These compounds have a tetragonal system with space group I41/amd. Magnetic susceptibility and specific heat measurements have been performed for all the compounds in the temperature range between 1.8 and 300 K. For NdCrO4, an antiferromagnetic transition was found at 25.2 K. SmCrO4 and DyCrO4 show magnetic transitions at 15.0 and 22.8 K, respectively. In addition, structural phase transitions were observed at 58.5 and 31.2 K, respectively. For DyCrO4, the crystal structure below the transition temperature was determined by low-temperature powder X-ray diffraction measurements to be orthorhombic with space group Imma. 相似文献