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81.
Iida T Satoh H Maeda K Yamamoto Y Asakawa K Sawada N Wada T Kadowaki C Itoh T Mase T Weissman SA Tschaen D Krska S Volante RP 《The Journal of organic chemistry》2005,70(23):9222-9229
[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1. 相似文献
82.
Junko Iida Takehiro Takeda Takumi Takasuga John Moncur Phil Ireland Barry Wright 《Journal of separation science》1991,14(2):103-109
A hybrid mass spectrometer with an EBQQ configuration was used to investigate two approaches to trace dioxin analysis: high resolution gas chromatography – high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography – mass spectrometry – mass spectrometry (HRGC-MS-MS). It is shown that selected ion monitoring (SIM) HRGC-HRMS exhibits better selectivity for dioxins separated on a cyanopropyl column than is otherwise obtained under medium resolution mass spectrometry (3,000 resolution), while optimization of conditions for HRGC-MS-MS allowed the observation of 350 femtograms of the highly toxic 2,3,7,8-TCDF at a S/N ratio of 5:1. Both methods were applied to environmental samples with good results. 相似文献
83.
Fatty acid methyl esters from various fats and oils were separated by comprehensive two-dimensional supercritical fluid chromatography with conventional packed columns and FID detection. The first dimension was a silica gel column and the second dimension was an ODS column. This combination was largely orthogonal for the separation of fatty acid methyl esters. The first dimension separations were primarily based on the number of double bonds while the second dimension separations were based on the chain length. The highly-ordered chromatograms and improved resolution allowed the easy detection and identification of minor components. Although the first dimension separations were performed under isobaric conditions where the peak width increased in proportion to the retention, the programming of the sampling duration allowed us to maintain the optimum re-injection frequency (3–4 times) per peak into the second dimension and so to minimize the total analysis time without deteriorating the resolution. 相似文献
84.
85.
Observation of bubble layer formed on hydrogen and oxygen gas-evolving electrode in a magnetic field
Hisayoshi Matsushima Takami Iida Yasuhiro Fukunaka 《Journal of Solid State Electrochemistry》2012,16(2):617-623
The evolution of hydrogen and oxygen gasses in a 0.36-M KOH electrolyte was observed in a magnetic field, and the void fraction
was calculated by a hydrodynamic model. Both gasses evolving on a platinum working electrode formed a bubble layer which increased
the ohmic resistance. In addition to natural convection, magnetohydrodynamic (MHD) convection in a magnetic field improved
the electrolytic conductivity by supplying a fresh solution (pumping effect) and removing gas bubbles. The MHD convection
reduced the void fraction of hydrogen gas more than that of oxygen, which can be explained by the poor wettability of the
oxygen evolving electrode. 相似文献
86.
Seiichi Ohta Susumu Inasawa Yukio Yamaguchi 《Journal of Polymer Science.Polymer Physics》2012,50(12):863-869
When a mixture of liquid crystal (LC) and photo reactive monomer is irradiated by UV light, polymerization occurs and LC droplets form through phase separation, producing polymer dispersed LCs (PDLCs). Although size control of LC droplets and reduced amounts of LC in PDLC films are important in applications, precise size control of LC droplets at a low LC fraction has not yet been accomplished. In this study, the phase diagrams of the LC/initial monomer and the LC/polymer during polymerization were used to control LC droplet size at various LC fractions. Both the relative position of the sample in the initial phase diagram and the shift of the phase separation line during polymerization were shown to be important in determining the size of LC droplets. Our results are expected to provide a new strategy for precise size control of LC droplets especially at a low LC fraction range, which would be a great help for PDLC applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
87.
For a spatial characteristic, there exist commonly fat-tail frequency distributions of fragment-size and -mass of glass, areas enclosed by city roads, and pore size/volume in random packings. In order to give a new analytical approach for the distributions, we consider a simple model which constructs a fractal-like hierarchical network based on random divisions of rectangles. The stochastic process makes a Markov chain and corresponds to directional random walks with splitting into four particles. We derive a combinatorial analytical form and its continuous approximation for the distribution of rectangle areas, and numerically show a good fitting with the actual distribution in the averaging behavior of the divisions. 相似文献
88.
89.
Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines 下载免费PDF全文
Wataru Makiguchi Shinzo Kobayashi Keisuke Furukawa Hiroki Iida Yoshio Furusho Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):990-999
An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999 相似文献
90.
Stereoselective analysis of flecainide enantiomers using reversed‐phase liquid chromatography for assessing CYP2D6 activity 下载免费PDF全文
Kosuke Doki Yukio Sekiguchi Keisuke Kuga Kazutaka Aonuma Yukinao Kohda Masato Homma 《Biomedical chromatography : BMC》2014,28(9):1193-1198
Stereoselective analyses of flecainide enantiomers were performed using reversed‐phase high‐performance liquid chromatography (HPLC) equipped with a polysaccharide‐based chiral column (Chiralpak AS‐RH) and fluorescence detector. Excitation and emission wavelengths were set at 300 and 370 nm, respectively. Flecainide enantiomers in serum and urine were extracted using diethyl ether. The mobile phase solution, comprising 0.1 m potassium hexafluorophosphate and acetonitrile (65:35, v/v), was pumped at a flow rate of 0.5 mL/min. The recoveries of flecainide enantiomers were greater than 94%, with the coefficients of variation (CVs) <6%. The calibration curves of flecainide enantiomers in serum and urine were linear in the concentration range 5–500 ng/mL and 0.75–15 µg/mL (r > 0.999), respectively. CVs in intra‐day and inter‐day assays were 1.8–5.8 and 3.4–7.5%, respectively. In a pharmacokinetic study, the ratios of (S)‐ to (R)‐flecainide (S/R ratio) in the area under the curve and the amount of flecainide enantiomers excreted in urine were lower in a subject carrying CYP2D6*10/*10 than in subjects carrying CYP2D6*1/*2. The S/R ratio of trough serum flecainide concentration ranged from 0.79 to 1.16 in patients receiving oral flecainide. The present HPLC method can be used to assess hepatic flecainide metabolism in a pharmacokinetic study and therapeutic drug monitoring. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献