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91.
Kikura-Hanajiri R Kawamura M Miyajima A Sunouchi M Goda Y 《Analytical and bioanalytical chemistry》2011,400(1):165-174
In order to develop an analytical method for the discrimination of dextromethorphan (an antitussive medicine) from its enantiomer,
levomethorphan (a narcotic) in biological samples, chiral analyses of these drugs and their O-demethyl and/or N-demethyl metabolites in rat plasma, urine, and hair were carried out using LC-MS/MS. After the i.p. administration of dextromethorphan
or levomethorphan to pigmented hairy male DA rats (5 mg/kg/day, 10 days), the parent compounds and their three metabolites
in plasma, urine and hair were determined using LC-MS/MS. Complete chiral separation was achieved in 12 min on a Chiral CD-Ph
column in 0.1% formic acid–acetonitrile by a linear gradient program. Most of the metabolites were detected as being the corresponding
O-demethyl and N, O-didemethyl metabolites in the rat plasma and urine after the hydrolysis of O-glucuronides, although obvious differences in the amounts of these metabolites were found between the dextro and levo forms.
No racemation was observed through O- and/or N-demethylation. In the rat hair samples collected 4 weeks after the first administration, those differences were more clearly
detected and the concentrations of the parent compounds, their O-demethyl, N-demethyl, and N, O-didemethyl metabolites were 63.4, 2.7, 25.1, and 0.7 ng/mg for the dextro forms and 24.5, 24.6, 2.6, and 0.5 ng/mg for the
levo forms, respectively. In order to fully investigate the differences of their metabolic properties between dextromethorphan
and levomethorphan, DA rat and human liver microsomes were studied. The results suggested that there might be an enantioselective
metabolism of levomethorphan, especially with regard to the O-demethylation, not only in DA rat but human liver microsomes as well. The proposed chiral analyses might be applied to human
samples and could be useful for discriminating dextromethorphan use from levomethorphan use in the field of forensic toxicology,
although further studies should be carried out using authentic human samples. 相似文献
92.
Tanaka S Kubo Y Yokoyama Y Toda A Taguchi K Kajioka H 《The Journal of chemical physics》2011,135(23):234503
We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C(12)E(5)) solutions focusing on the growth law of separated domains. The solutions confined between two glass plates were found to exhibit the phase inversion, characteristic of the viscoelastic phase separation; the majority phase (water-rich phase) nucleated as droplets and the minority phase (micelle-rich phase) formed a network temporarily, then they collapsed into an usual sea-island pattern where minority phase formed islands. We found from the real-space microscopic imaging that the dynamic scaling hypothesis did not hold throughout the coarsening process. The power law growth of the domains with the exponent close to 1/3 was observed even though the coarsening was induced mainly by hydrodynamic flow, which was explained by Darcy's law of laminar flow. 相似文献
93.
Amaya T Hifumi M Okada M Shimizu Y Moriuchi T Segawa K Ando Y Hirao T 《The Journal of organic chemistry》2011,76(19):8049-8052
Oxosumanenes were synthesized through benzylic oxidation. The electronic and redox properties were revealed to exhibit the expanded π-conjugation compared to sumanene. Single-crystal X-ray analysis of monooxosumanene showed columnar π-stacking in a concave-convex fashion. Stereoselective trimethylation of the trioxo derivative was performed via 1,2-addition to the carbonyl groups. 相似文献
94.
Fukui H Shigeta Y Nakano M Kubo T Kamada K Ohta K Champagne B Botek E 《The journal of physical chemistry. A》2011,115(6):1117-1124
Using the spin-unrestricted hybrid density functional theory method, we have investigated the intermolecular interaction effects on the longitudinal static second hyperpolarizability (γ) of open-shell singlet slipped-stack dimers composed of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands, Ni(o-C(6)H(4)X(2))(2) (where X = O, NH, S, Se, PH). For comparison, we have also examined the γ values of a closed-shell singlet slipped-stack dimer composed of closed-shell monomers Ni[o-C(6)H(4)S(NH(2))](2). It is found that for interplanar distance ranging between 3.0 and 5.0 ? the slipped-stack dimers with intermediate monomer diradical characters exhibit larger γ values per monomer (γ(dimer)/2) than those with large monomer diradical characters or than the closed-shell dimer. These results extend the domain of validity of the relationship found between γ and the diradical character for individual molecules. It also turns out that the ratio R = (γ(dimer)/2)/γ(monomer) increases upon decreasing the interplanar distance and that this increase is larger for intermediate diradical character than for the other cases. These phenomena have been analyzed by considering the γ density distributions of the dimers, demonstrating a significant field-induced third-order charge transfer between the monomers in the case of intermediate diradical character. The present results indicate that open-shell singlet slipped-stack aggregates composed of monomers with intermediate diradical characters constitute another mean for achieving highly efficient and tunable third-order nonlinear optical materials. 相似文献
95.
96.
97.
Osamu Ohtaka Naoyuki Ohnishi Katsuyuki Kubo Hiroshi Arima Hiroshi Fukui Takamitsu Yamanaka 《高压研究》2013,33(1):11-15
Using a hot isostatic pressing (HIP) technique, we synthesized diamond/SiC composites from diamond and Si powders. At an HIP condition of 1450 °C and 100 MPa, a pressure much lower than that of the diamond stability field, diamond powders react with molten Si to form well-sintered diamond/SiC composites. Cubes of the composites with 15 mm edge length were thereby fabricated, and an application to the second stage anvils in a Kawai-type high-pressure apparatus was attempted. A hybrid anvils system using four cubes of the composites and four of the conventional WC was introduced and heating experiments up to 1600 °C became possible. Because the diamond/SiC composites are transparent to X-rays, the present system is applicable not only to diffraction studies but also to radiographic studies that need a larger window for an X-ray image. 相似文献
98.
Five types of non-symmetric calamitic dimers were synthesized to investigate the effect of the core structure and length of the spacer on mesomorphic properties. Two non-symmetric dimers containing a troponoid and benzenoid unit showed smectic A and C phases whereas the corresponding benzenoid dimers showed no mesophase. Non-symmetric dimers with a three-ring system showed smectic A and C phases with higher transition temperatures than the two-ring system. We propose packing models for these non-symmetric dimers by considering the direction of the dipole moments of the ring structures and microsegregation between the polar units and the non-polar chains. 相似文献
99.
Takahito Itoh Motoka Ikeda Nobuyuki Hirata Yuji Moriya Zhaoyin Wen Yoshiaki Ichikawa Masataka Kubo Osamu Yamamoto 《Ionics》2002,8(1-2):44-52
Terminal-acetylated hyperbranched poly(ethylene glycol) derivatives containing diethylene, triethylene, and hexaethylene and
3,5-dioxybenzoate branching units (poly-Ac1a, poly-Ac1b, and poly-Ac1c) were synthesized. Electrochemical and thermal properties of the hyperbranched polymer electrolytes with lithium salts such
as LiCF3SO3 and LiN(CF3SO2)2, the composite hyperbranched polymer electrolytes with LiN(CF3SO2)2 containing α-LiAlO2 and γ-LiAlO2 fillers, and the hyperbranched polymer blended poly(ethylene oxide) electrolytes with LiN(CF3SO2)2 were investigated and discussed.
Paper presented at the 8th EuroConference on Ionics, Carvoeire, Algarve, Portugal, Sept. 16–22, 2001. 相似文献
100.
T. Araki J. Kubo E. A. Paschos 《The European Physical Journal C - Particles and Fields》2006,45(2):465-475
We consider leptogenesis in a minimal S3 extension of the standard model with an additional Z2 symmetry in the leptonic sector. It is found that the CP phase appearing in the mass matrix of the left-handed neutrinos is the same as that for the CP asymmetries responsible for leptogenesis. Because of the discrete S3 x Z2 flavor symmetries, the CP asymmetries are strongly suppressed. To obtain a realistic size of the baryon number asymmetry in the universe, we therefore
have to assume that resonant enhancement of the CP asymmetries takes place, and that three degenerate right-handed neutrino masses of O(10) TeV are present.
Arrival of the final proofs: 22 November 2005
PACS:
11.30.Hv, 12.15.Ff, 14.60.Pq 相似文献