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41.
Kunihiko Takabe Takashi Yamada Takenori Miyamoto Nobuyuki Mase 《Tetrahedron letters》2008,49(41):6016-6018
Acid promoted cyclization of the geranylamine N-oxide (E)-4 followed by base-catalyzed intramolecular aldol condensation afforded 1-acetyl-4,4-dimethyl-1-cyclohexene (7) in one-pot operation. Reduction of 7, which possess strong fruity odor, followed by lipase-catalyzed kinetic resolution furnished the acetate (R)-26 (>49.9% yield, >99% ee) and the recovered alcohol (S)-25 (>49.9% yield, >99% ee, herbal odor). 相似文献
42.
Population study of sizes and components of self-reproducing giant multilamellar vesicles 总被引:1,自引:0,他引:1
Toyota T Takakura K Kageyama Y Kurihara K Maru N Ohnuma K Kaneko K Sugawara T 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3037-3044
Population analysis of a system of self-reproducing giant multilamellar vesicles (GMVs) was carried out by means of flow cytometry. The multidimensional distribution of forward light scattering (FS), side light scattering (SS), and fluorescence (FL) intensities originating from each GMV provided information about changes in a population composed of 104 vesicles. FS-FL dot plots indicated that, after the addition of the membrane precursor, the size distribution of the newly generated vesicles was nearly the same as that of the original, but the catalyst content was reduced. This result can be interpreted as evidence for the occurrence of the self-reproduction of GMVs. Moreover, the new GMVs recovered the amount of catalyst to the initial value, keeping their size distribution constant, when a solution of the catalyst was added to the new GMVs. These results are the first experimental evidence for a novel phenomenon on GMV size distribution during their self-reproducing cycle. 相似文献
43.
Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta6-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations. [reaction: see text]. 相似文献
44.
45.
Suzuko Yamazaki Hiroyuki Abe Toshifumi Tanimura Yousuke Yamasaki Kenji Kanaori Kunihiko Tajima 《Research on Chemical Intermediates》2009,35(1):91-101
The thermal treatment of TiO2 pellets prepared by the sol–gel method decreased the photocatalytic activity. The activity divided by the specific surface
area of the pellets for the complete mineralization of ethylene or chloroform was maximized at the firing temperature of 400°C.
For the photocatalytic degradation of trichloroethylene (TCE), most of them were converted to chlorinated by-products, such
as dichloroacetic acid, chloroform, and phosgene, and the stoichiometric ratio of [CO2]formed/[TCE]degraded showed a maximal value at 400°C. The electron spin resonance (ESR) spin-trapping with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO)
in the flow injection system indicated that firing at 400°C gave the highest signal intensity of DMPO–OH adducts. These findings
indicated that the OH radical was produced most effectively on the TiO2 fired at 400°C, which would be related to the content of anatase and rutile. Concerning the formation of chlorinated by-products
from TCE, more dichloroacetic acid (DCAA) were detected and less CHCl3 and COCl2 were formed at lower firing temperatures, suggesting that the branching ratio of chloroethoxy radicals to the formation of
DCAA or CHCl3 and COCl2 by C–C bond scission depended on the firing temperature. 相似文献
46.
Mori K Asakawa D Sunner J Hiraoka K 《Rapid communications in mass spectrometry : RCM》2006,20(17):2596-2602
The electrospray droplets that are sampled through an orifice into the vacuum chamber are accelerated by 10 kV and impact on the stainless steel substrate. The mass and the kinetic energy of electrospray droplets are roughly estimated to be a few 10(6) u and approximately 10(6) eV, respectively. The molecular ion M(+.) and the protonated molecule [M+H](+) are observed as secondary ions for chrysene and coronene deposited on the metal substrate (no matrix used). The ionization may take place in the shock wave generated by the high-momentum coherent collision between the droplet projectile and the solid sample. Cluster ions of H(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n), with n up to approximately 150, were observed as secondary ions formed by the electrospray droplet impact ionization (EDI) for 10(-2) M trifluoroacetic acid (TFA) aqueous solution. This indicates that the charged droplets that collide with the metal substrate with the kinetic energy of approximately 10(6) eV do not vaporize completely but are disintegrated into many tiny microdroplets. The ion signal intensity anomalies (i.e. magic numbers) were observed for the cluster ions of H(3)O(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n) for 10(-2) M TFA aqueous solution and of Cs(+)(H(2)O)(n), I(-)(H(2)O)(n), Cs(+)(CsI)(n), and I(-)(CsI)(n) for 10(-2) M CsI aqueous solution. 相似文献
47.
Bhargava S Kitadai K Masashi T Drumm DW Russo SP Yam VW Lee TK Wagler J Mirzadeh N 《Dalton transactions (Cambridge, England : 2003)》2012,41(16):4789-4798
A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(μ-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations. 相似文献
48.
Kunihiko Kaneko 《Journal of statistical physics》2012,148(4):686-704
The characterization of plasticity, robustness, and evolvability, an important issue in biology, is studied in terms of phenotypic fluctuations. By numerically evolving gene regulatory networks, the proportionality between the phenotypic variances of epigenetic and genetic origins is confirmed. The former is given by the variance of the phenotypic fluctuation due to noise in the developmental process; and the latter, by the variance of the phenotypic fluctuation due to genetic mutation. The relationship suggests a link between robustness to noise and to mutation, since robustness can be defined by the sharpness of the distribution of the phenotype. Next, the proportionality between the variances is demonstrated to also hold over expressions of different genes (phenotypic traits) when the system acquires robustness through the evolution. Then, evolution under environmental variation is numerically investigated and it is found that both the adaptability to a novel environment and the robustness are made compatible when a certain degree of phenotypic fluctuations exists due to noise. The highest adaptability is achieved at a certain noise level at which the gene expression dynamics are near the critical state to lose the robustness. Based on our results, we revisit Waddington’s canalization and genetic assimilation with regard to the two types of phenotypic fluctuations. 相似文献
49.
Kunihiko Sadakane 《Journal of Algorithms in Cognition, Informatics and Logic》2003,48(2):294-313
New text indexing functionalities of the compressed suffix arrays are proposed. The compressed suffix array proposed by Grossi and Vitter is a space-efficient data structure for text indexing. It occupies only O(n) bits for a text of length n; however it also uses the text itself that occupies
bits for the alphabet
. In this paper we modify the data structure so that pattern matching can be done without any access to the text. In addition to the original functions of the compressed suffix array, we add new operations search, decompress and inverse to the compressed suffix arrays. We show that the new index can find occ occurrences of any substring P of the text in O(|P|logn+occlogεn) time for any fixed 1ε>0 without access to the text. The index also can decompress a part of the text of length m in O(m+logεn) time. For a text of length n on an alphabet
such that
, our new index occupies only
bits where
is the order-0 entropy of the text. Especially for ε=1 the size is
bits. Therefore the index will be smaller than the text, which means we can perform fast queries from compressed texts. 相似文献
50.
Spatiotemporal chaos and noise 总被引:1,自引:0,他引:1
Low-dimensional chaotic dynamical systems can exhibit many characteristic properties of stochastic systems, such as broad Fourier spectra. They are distinguishable from stochastic processes through finite values for their dimension, Lyapunov exponents, and Kolmogorov-Sinai entropy. We discuss how these characteristic observables are modified in spatiotemporal chaotic systems like. coupled map lattices. We analyze with the help of Lyapunov concepts how the stochastic limit is approached and how these properties can be observed directly through local dimension measurements from reconstructed time series. Finally, we discuss the interaction of spatiotemporal attractors with external noise and possible connections to problems of pattern selection and stability. 相似文献