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71.
72.
Matsuda H Hamao M Nakamura S Kon'i H Murata M Yoshikawa M 《Chemical & pharmaceutical bulletin》2012,60(5):674-680
Effects of principal saponins, chakasaponins I-III, from the flower buds of Camellia sinensis cultivated in Fujian province, China on plasma triglyceride (TG) and glucose levels in olive oil or sucrose-loaded mice were examined. Chakasaponins I-III at 50 and 100 mg/kg significantly inhibited increases in plasma TG and glucose levels. Furthermore, they prevented gastric emptying, suggesting that the former inhibitory effect is partly dependent on the inhibition of gastric emptying. In addition, the chemical structure of a new acylated oleanane-type triterpene oligoglycoside, chakasaponin IV, was elucidated on the basis of chemical and physicochemical evidence. 相似文献
73.
Shibata N Yoshimura M Yamada H Arakawa R Sakaguchi S 《The Journal of organic chemistry》2012,77(8):4079-4086
A series of hydroxy-amide functionalized azolium salts have been designed and synthesized for Cu-catalyzed asymmetric conjugate addition reaction. The (CH(2))(2)-bridged hydroxy-amide functionalized azolium ligand precursors 2, in addition to the previously reported CH(2)-bridged azolium salts 1, have been prepared from readily available enantiopure β-amino alcohols. The combination of a Cu species with 1 or 2 efficiently promoted the 1,4-addition reaction of cyclic enones with dialkylzincs. For example, the reaction of 2-cyclohepten-1-one (17) with Bu(2)Zn in the presence of catalytic amounts of Cu(OTf)(2) and 1 gave (S)-3-butylcycloheptanone (20) in 99% yield and 96% ee. On the other hand, when the reaction was carried out under the influence of Cu(OTf)(2) combined with 2, (R)-20 in preference to (S)-20 was obtained in 98% yield and 80% ee. In this manner, the enantioselecvity was switched by controlling the structure of chiral ligand. Additionally, the reversal of enantioselectivity was also achieved by changing the Cu precatalyst from Cu(OTf)(2) to Cu(acac)(2) with the same ligand. The combination of Cu(acac)(2) with CH(2)-bridged azolium salt 1 in the reaction of 17 with Bu(2)Zn led to formation of (R)-20 as a major product in 55% yield and 80% ee. This result was in contrast to the Cu(OTf)(2)/1 catalytic system, where the 1,4-adduct with opposite configuration was obtained. Moreover, use of the Cu(acac)(2)/2 catalytic system produced (S)-20, while (R)-20 was formed by the Cu(OTf)(2)/2 catalytic system. Thus, it was found that either varying the linker of the chiral ligands or changing the counterion of Cu species between a OTf and acac ligand initially on the metal led to dual enantioselective control in the 1,4-addition reaction. 相似文献
74.
Combined experimental and theoretical studies on the photophysical properties of cycloparaphenylenes
Segawa Y Fukazawa A Matsuura S Omachi H Yamaguchi S Irle S Itami K 《Organic & biomolecular chemistry》2012,10(30):5979-5984
We studied the UV-vis absorption and fluorescence in solution/solid states of [n]cycloparaphenylene ([n]CPP: n = 9, 12, 14, 15, and 16), and conducted theoretical studies to better understand the experimental results. The representative experimental findings include (i) the most intense absorption maxima (λ(abs1)) display remarkably close values (338-339 nm), (ii) the longest-wavelength absorption maxima (λ(abs2)) are blue-shifted with increasing the ring size (395 → 365 nm), (iii) the emission maxima (λ(em)) are blue-shifted with increasing the ring size (494 → 438 nm for longest-wavelength maxima), (iv) the fluorescent quantum yields (Φ(F)) in solution are high (0.73-0.90), (v) the fluorescence lifetimes (τ(s)) of [9]- and [12]CPP are 10.6 and 2.2 ns, respectively, and (vi) the Φ(F) values slightly increase in polymer matrix but significantly decrease in the crystalline state. According to TD-DFT calculations, the longest-wavelength absorption (λ(abs2)) corresponds to a forbidden HOMO → LUMO transition and the most intense absorption (λ(abs1)) corresponds to degenerate HOMO - 1 → LUMO and HOMO → LUMO + 1 transitions with high oscillator strength. The interesting and counterintuitive optical properties of CPPs (constant λ(abs1) and blue shift of λ(abs2)) could be ascribed mainly to the ring-size effect in frontier molecular orbitals (in particular the increase of the HOMO-LUMO gap as the number of benzene rings increases). On the basis of comparative calculations using hypothetical model geometries, we conclude that the unique behavior of HOMO and LUMO of CPPs is due mainly to their lack of a conjugation length dependence in combination with a significant bending effect (particularly to HOMO) and a torsion effect (particularly to LUMO). 相似文献
75.
Sakamoto M Moriyasu T Minowa K Kishimoto K Kadoi H Hamano T Fukaya H 《Journal of AOAC International》2012,95(4):1048-1052
A sildenafil-related compound was detected in a dietary supplement marketed as an aphrodisiac. The compound was detected during analysis of the dietary supplement using LC-UV and LC/electrospray ionization-MS. The structure of the compound was established using high resolution MS, NMR spectrometry, and X-ray crystal structure analysis. The compound was identified as 5-(5-((3,5-dimethylpiperazin-1-yl)sulfonyl)-2-ethoxyphenyl)-l-methyl-7-((1-methyl-4-nitro-1H-imidazol-5-yl)thio)-3-propyl-1H-pyrazolo[4,3-d] pyrimidine. Based on this structure, the compound was named nitroprodenafil. The dietary supplement was found to contain 90 mg nitroprodenafil/capsule. This article describes the structural characterization of a new sildenafil-related compound. The compound was detected during analysis of a dietary supplement using LC-UV and LC/electrospray ionization (ESI)-MS. The structure was established using high resolution MS (HRMS), NMR spectrometry, and X-ray crystal structure analysis. The structures of methisosildenafil, thiomethisosildenafil, and this new analog, named nitroprodenafil (21), are shown in Figure 1. In the Demizu et al. report, the compound is named mutaprodenafil instead ofnitroprodenafil. Considering the naming right, the authors of this paper think the use of mutaprodenafil is appropriate as the compound name, although nitroprodenafil is used. 相似文献
76.
Yoshimura K Muramatsu J Davis P Harayama T Okumura H Morikatsu S Aida H Uchida A 《Physical review letters》2012,108(7):070602
We propose a secure key distribution scheme based on correlated physical randomness in remote optical scramblers driven by common random light. The security of the scheme depends on the practical difficulty of completely observing random optical phenomena. We describe a particular realization using the synchronization of semiconductor lasers injected with common light of randomly varying phase. We experimentally demonstrate the feasibility of the scheme over a distance of 120 km. 相似文献
77.
Kazunori Nozaki Masanori Nakamura Haruka Takimoto Shigeo Wada 《Journal of computational science》2012,3(5):298-305
Sibilant /s/, which is an unvoiced sound, is believed to be produced by a jet of air through a sibilant groove toward the sharp edges of the teeth. We investigated what effects the expiratory flow rate had on the acoustic characteristics of sibilant /s/ in the present study. A large eddy simulation was implemented to investigate the flow in an oral cavity model that simplified the important anatomical features of the oral cavity when sibilant /s/ was pronounced. The results illustrated that an increase in the expiratory flow rate caused turbulence to develop in the separated flow from the edge of the obstacle wall which mimics a tooth. The increase in turbulent intensity induced a dramatic elevation in Lamb-vector divergence in the flow-separation region, which was regarded as a sound source of sibilant /s/. The total power of the sound source which was located near the obstacle edge of the obstacle wall at smaller flow rates, extended downstream in the flow separation as the expiratory flow rate increased through which turbulence developed. These results demonstrated that the expiratory flow rate had a significant influence on the acoustic characteristics of sibilant /s/ particularly when the flow rate increased to cause turbulence. 相似文献
78.
Tanabe K Iida H Haruna K Kamei T Okamoto A Nishimoto S 《Journal of the American Chemical Society》2006,128(3):692-693
Amperometry was employed to characterize the anthraquinone (AQ)-photoinjected hole transport through a 20-mer oligodeoxynucleotide (ODN) duplex, as immobilized on the surface of a gold electrode, and its triplex forms converted by association with several third oligopyrimidine (OPD) short strands. While the cathodic photocurrent was observed upon irradiation at 365 nm of the AQ photosensitizer linked to the end of DNA duplex, a marked lowering of the current density was identified to occur by the triplex formation of a duplex with a given third OPD short strand. The photocurrent through the DNA duplex showed a reversible fall-rise response concomitant with alternating association-dissociation cycle of the OPD short-strand, as regulated by temperature change around the corresponding melting temperature of the DNA triplex. Both the switched photoirradiation and the thermally alternating duplex-triplex conversion could provide tools of regulating the DNA hole transport. 相似文献
79.
A stereocontrolled route via allyl 1,2-diols to vicinal diamines based on the [3.3] sigmatropic rearrangement of allyl cyanate has been developed. Our approach consists of two consecutive steps: stereoselective construction of allyl anti- and syn-1,2-diols followed by [1,3]-chirality transfer by sigmatropic rearrangement, which allow an access to anti-(2R,3R)- and syn-(2R,3S)-2,3-diaminobutanoic acids. [reaction: see text] 相似文献
80.
Takashi Mino Shingo Komatsu Kazuya Wakui Haruka Yamada Hiroaki Saotome Masami Sakamoto Tsutomu Fujita 《Tetrahedron: Asymmetry》2010,21(6):711-718
N-Aryl indole-derived C–N bond axially chiral phosphine ligands 2a–c were obtained by DDQ oxidation of N-aryl indoline-derived phosphine oxide followed by silane reduction. Resolution of C–N bond atropisomers was achieved by chiral HPLC. The investigation of the rotation barrier for the C–N bond axial stability of phosphines and the determination of the absolute configuration of 2c are described. Finally, the ability of the chiral ligand 2c was demonstrated in a palladium-catalyzed asymmetric allylic alkylation (up to 99% ee). 相似文献