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101.
Gold‐Catalyzed Enantioselective Synthesis,Crystal Structure,and Photophysical/Chiroptical Properties of Aza[10]helicenes
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Maya Tanaka Dr. Yu Shibata Kyosuke Nakamura Kota Teraoka Prof. Dr. Hidehiro Uekusa Dr. Kazuko Nakazono Prof. Dr. Toshikazu Takata Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9537-9541
The enantioselective synthesis of an aza[10]helicene, possessing two pyridone units, has been achieved by the gold‐catalyzed intramolecular quadruple hydroarylation of a tetrayne. This aza[10]helicene was successfully converted into a fully aromatic aza[10]helicene, possessing two pyridine units. Structure–photophysical and chiroptical properties relationship in a series of azahelicene isomers has also been disclosed. 相似文献
102.
Satoshi Futakawa Ritsuko Oka Kazuko Ogawa Yoshiaki Hagiwara Kazuya Miyashita 《Analytica chimica acta》2009,631(1):116-120
Previous reports, including our work, have shown that plasma β-galactoside α2,6-sialyltransferase (ST6Gal I) activity is significantly increased in particular hepatopathological situations, suggesting that it may represent a sensitive biomarker for diagnosing hepatic diseases. So far, activity of ST6Gal I have been measured by using radioactive tracer method in place of measuring amount of ST6Gal I. However, this method is tangled and cannot exclude other sialyltransferase activities. Thus, simple and specific methods for measuring plasma ST6Gal I had been unavailable. Here, we developed two kinds of sandwich enzyme-linked immunosorbent assay (ELISA) systems that specifically detect the soluble cleaved form of ST6Gal I in plasma. In one sandwich ELISA, we detected rat specific sequence, EFQMPK, which is N-terminus of soluble ST6Gal I. In the other sandwich ELISA, we detected internal common sequence among rat, mouse and human ST6Gal I in plasma (M2 ELISA). Using the M2 ELISA, we observed that elevation of plasma ST6Gal I was much faster than elevation of plasma aspartate aminotransferase (AST) and alanine aminotransferase (ALT) in a carbon tetrachloride (CCl4)-induced mouse liver injury model. Our data suggest that these ELISA systems are very useful tools for measuring plasma ST6Gal I, which represents a potential biomarker for diagnosing hepatic diseases. 相似文献
103.
A fifteen-year riddle has been settled: neutralization, the most popular chemical event, of a crown ether/sec-ammonium salt-type rotaxane has been achieved and a completely nonionic crown ether/sec-amine-type rotaxane isolated. A [2]rotaxane was prepared as a typical substrate from a mixture of dibenzo[24]crown-8 ether (DB24C8) and sec-ammonium hexafluorophosphate (PF(6)) with a terminal hydroxy group through end-capping with 3,5-dimethylbenzoic anhydride in the presence of tributylphosphane as a catalyst in 90% yield. A couple of approaches to the neutralization of the ammonium rotaxane were investigated to isolate the free sec-amine-type rotaxane by decreasing the degree of thermodynamic and kinetic stabilities. One approach was the counteranion-exchange method in which the soft counterion PF(6)(-) was replaced with the fluoride anion by mixing with tetrabutylammonium fluoride, thus decreasing the cationic character of the ammonium moiety. Subsequent simple washing with a base allowed us to isolate the free sec-amine-type rotaxane in a quantitative yield. The other approach was a synthesis based on a protection/deprotection protocol. The acylation of the sec-ammonium moiety with 2,2,2-trichloroethyl chloroformate gave an N-carbamated rotaxane that could be deprotected by treating with zinc in acetic acid to afford the corresponding free sec-amine-type rotaxane in a quantitative yield. The structure of the free sec-amine-type rotaxane was fully confirmed by spectral and analytical data. The generality of the counteranion-exchange method was also confirmed through the neutralization of a bisammonium-type [3]rotaxane. The mechanism was studied from the proposed potential-energy diagram of the rotaxanes with special emphasis on the role of the PF(6)(-) counterion. 相似文献
104.
A sensitive homogeneous time-resolved fluoroimmunoassay method for 3,5,3'-triiodo-l-thyronine (T3) based on the fluorescence resonance energy transfer (FRET) from a fluorescent Eu(3+) complex, {[(4,6-dichloro-1,3,5-triazin-2-yl)amino-biphenyl-4'-yl]-2,2':6',2'-terpyridine-6,6'-diyl}bis(methylenenitrilo) tetrakis(acetate)-Eu(3+) (DTBTA-Eu(3+)) (lambda(ex,max)=335nm, lambda(em,max)=615nm), to an organic fluorescence dye Cy5 has been developed. The new assay system combined the use of DTBTA-Eu(3+)-labeled T3-bovine serum albumin (BSA) conjugate and Cy5-labeled anti-T3 monoclonal antibody for a competitive-type immunoassay. After the competitive reactions of DTBTA-Eu(3+)-labeled T3-BSA and T3 sample with Cy5-labeled anti-T3 antibody, the T3 concentration was measured with a time-resolved mode by monitoring the sensitized emission of Cy5 derived from FRET in a homogeneous format. The method gives the detection limit of 0.26ng/ml. The coefficient variations of the method are less than 2.0% and the recoveries are in the range of 80-111% for serum sample measurement. The concentrations of T3 in 30 human serum samples were determined, and the results were compared with those of the independently determined by a radio-immunoassay method. A good correlation was obtained with a correlation coefficient of 0.989. 相似文献
105.
Nishioka T Yuan J Yamamoto Y Sumitomo K Wang Z Hashino K Hosoya C Ikawa K Wang G Matsumoto K 《Inorganic chemistry》2006,45(10):4088-4096
The new europium(III) chelate [2,2',2',2'-[[4'-(aminobiphenyl-4-yl)-2,2':6',2'-terpyridine- 6,6'-diyl]bis(methylenenitrilo)]tetrakis(acetato)] europium(III) (ATBTA-Eu3+) and its 4,6-dichloro-1,3,5-triazinyl and succinimidyl derivatives (DTBTA and NHS-ATBTA, respectively) were synthesized and characterized. Both labeling complexes DTBTA-Eu3+ and NHS-ATBTA-Eu3+ are luminescent. Especially DTBTA-Eu3+ is strongly luminescent, with a luminescence quantum yield of 9.1%, molar extinction coefficient of 3.1 x 10(4) cm(-1) M(-1) (335 nm), and luminescence lifetime of 1.02 ms. The excitation and emission maximum wavelengths of DTBTA-Eu3+ are 335 and 616 nm, respectively. The complex is very stable in aqueous buffers, with a conditional formation constant log K(DTBTA-Eu) of 25.0 at pH 8, and can be conjugated to DNA and proteins. The chelates are also highly resistant to thermal decomposition, photodegradation, and ozone oxidation. These properties prove that DTBTA-Eu3+ is suitable as a luminescence label in DNA assays. 相似文献
106.
Iyota H Tomimitsu T Shimada K Ikeda N Motomura K Aratono M 《Journal of colloid and interface science》2006,299(1):428-434
Adsorption and micelle formation of a surfactant in the presence of inorganic salts with different charge numbers of cations were investigated from the viewpoint of mixed adsorption and micelle formation of salt and surfactant. Surface tension of aqueous solutions of the mixtures of octyl methyl sulfoxide (OMS) with calcium chloride and lanthanum chloride was measured as a function of the total molality of the mixture and the mole fraction of OMS in the mixture at 298.15 K under atmospheric pressure. Composition of the adsorbed film and micelle was numerically evaluated from the dependence of the total molality at a given surface tension and the mixture CMC on the bulk composition to draw phase diagrams of adsorption and micelle formation. Judging from the phase diagrams together with the ones of the sodium chloride system, miscibility of inorganic salt and OMS in the adsorbed film and micelle increases with an increase in the charge number of inorganic cation, which is attributable to the attractive interaction between inorganic cation and the polar head group of OMS molecule in the adsorbed film and micelle. 相似文献
107.
Three new abietane diterpenes, sugikurojins D (1), E (2), and F (3), and two new abietanes which incorporate cadinane, sugikurojins G (4) and H (5) were isolated from the bark of Cryptomeria japonica. These structures were elucidated primarily by extensive NMR experiments. The structure of sugikurojin D (1) was deduced to be 6alpha-acetoxy-7beta,11-dihydroxy-12-methoxy-8,11,13-abietatriene. Sugikurojin E (2) was deduced to be 6alpha-acetoxy-7beta,12-dihydroxy-8,11,13-abietatriene. Sugikurojin F (3) was 7alpha-methoxy-8,13-abietadien-11,12-dione. Sugikurojins G (4) and H (5) had a unique skeleton incorporating an alpha-cadinol or a 1alpha-hydroxy-T-cadinol in ferruginol, respectively. Also obtained in this investigation were the known diterpenes (6-14). An antibacterial activity of ten among these against Staphylococcus aureus and Escherichia coli was inactive at the (MIC: 125 microg/ml) level. Meanwhile, in the cytotoxic activity against HL-60, compounds 4, 8, and 11 showed moderate (IC50: 4, 35.4; 8, 28.0; 11, 52.4 microM) though weak (IC50: 4, 100; 8, 80.8; 11, 100 microM) activity against HCT-15. 相似文献
108.
The C-S bond formation reactions of the transition metal sulfides with organic molecules are collected and reviewed to understand the reactivity of the sulfide ligands supported by the transition metals. As an example of the role of the sulfide, the C-H bond activation is focused and discussed. 相似文献
109.
Kenji Nomura Kazuko Hirayama Takeo Ohsaka Masahiro Nakanishi Osamu Hatozaki Noboru Oyama 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2-3):593-608
The electrochemical and electrochromic properties of polymer films containing a conductive powder (SnO2/TiO2) have been investigated. The films are complexes of polytetramethyleneviologen and poly(p-styrenesulfonic acid). It was found that the coloration (purple) and bleaching rates of the composite films increase markedly with increasing conductive powder content(x). The coloring and bleaching of the composite film with x = 95 wt% were about 7 and 44 times faster, respectively, than those for an equivalent film without conductive powder. This increase in the rate of color change by introduction of a conductive powder was found to be correlated with the apparent diffusion coefficient (D app) for the diffusionlike charge-transport process within the composite films which increases with increasing x. The D app for the reduction process of the film with x = 95 wt% was larger by about 3 orders of magnitude than that for the unfilled film. 相似文献
110.
Hyun Su Min Hyun Jin Kim Mitsuru Naito Satomi Ogura Kazuko Toh Kotaro Hayashi Beob Soo Kim Shigeto Fukushima Yasutaka Anraku Kanjiro Miyata Kazunori Kataoka 《Angewandte Chemie (International ed. in English)》2020,59(21):8173-8180
Current antisense oligonucleotide (ASO) therapies for the treatment of central nervous system (CNS) disorders are performed through invasive administration, thereby placing a major burden on patients. To alleviate this burden, we herein report systemic ASO delivery to the brain by crossing the blood–brain barrier using glycemic control as an external trigger. Glucose‐coated polymeric nanocarriers, which can be bound by glucose transporter‐1 expressed on the brain capillary endothelial cells, are designed for stable encapsulation of ASOs, with a particle size of about 45 nm and an adequate glucose‐ligand density. The optimized nanocarrier efficiently accumulates in the brain tissue 1 h after intravenous administration and exhibits significant knockdown of a target long non‐coding RNA in various brain regions, including the cerebral cortex and hippocampus. These results demonstrate that the glucose‐modified polymeric nanocarriers enable noninvasive ASO administration to the brain for the treatment of CNS disorders. 相似文献