全文获取类型
收费全文 | 107篇 |
免费 | 1篇 |
专业分类
化学 | 87篇 |
数学 | 8篇 |
物理学 | 13篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2019年 | 1篇 |
2018年 | 1篇 |
2016年 | 2篇 |
2015年 | 1篇 |
2014年 | 2篇 |
2013年 | 7篇 |
2012年 | 5篇 |
2011年 | 8篇 |
2010年 | 1篇 |
2009年 | 1篇 |
2008年 | 5篇 |
2007年 | 7篇 |
2006年 | 7篇 |
2005年 | 10篇 |
2004年 | 7篇 |
2003年 | 8篇 |
2002年 | 6篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 6篇 |
1997年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1990年 | 1篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有108条查询结果,搜索用时 15 毫秒
91.
Matsuda H Nakamura S Iwami J Li X Pongpiriyadacha Y Nakai M Kubo M Fukuyama Y Yoshikawa M 《Chemical & pharmaceutical bulletin》2011,59(3):365-370
The methanolic extract and its EtOAc-soluble fraction from the rhizomes of Zingiber cassumunar inhibited invasion of human fibrosarcoma HT 1080 cells. From the EtOAc-soluble fraction, eight new phenylbutanoids, cassumunols A-H, were isolated together with 30 known constituents. The structures of new phenylbutanoids were elucidated on the basis of chemical and physicochemical evidence. Principal constituents were examined the inhibitory effects on the invasion of HT 1080 cells. Among them, phlain I and III, (E)-1-(3,4-dimethoxyphenyl)buta-1,3-diene, (E)-1-(2,4,5-trimethoxyphenyl)buta-1,3-diene, and (-)-β-sesquiphellandrene showed anti-invasion effects. Interestingly, (E)-1-(2,4,5-trimethoxyphenyl)buta-1,3-diene [inhibition (%) 46.8 ± 7.2 (p<0.05) at 30 μM] significantly inhibited the invasion, and only a weak cytotoxic effect was observed. 相似文献
92.
Behavior of dynamical process of complex systems is investigated. Specifically we analyse two types of ideal complex systems. For analysing the ideal complex systems, we define the response functions describing the internal states to an external force. The internal states are obtained as a relaxation process showing a “power law” distribution, such as scale free behaviors observed in actual measurements. By introducing a hybrid system, the logarithmic time, and double logarithmic time, we show how the “slow relaxation” (SR) process and “super slow relaxation” (SSR) process occur. Regarding the irregular variations of the internal states as an activation process, we calculate the response function to the external force. The behaviors are classified into “power”, “exponential”, and “stretched exponential” type. Finally we construct a fractional differential equation (FDE) describing the time evolution of these complex systems. In our theory, the exponent of the FDE or that of the power law distribution is expressed in terms of the parameters characterizing the structure of the system. 相似文献
93.
Yamaguchi D Matsumoto T Watanabe K Takagi N Matsumoto Y 《Physical chemistry chemical physics : PCCP》2006,8(1):179-185
The photochemistry of cyclohexane on Cu(111) and its excitation mechanism have been studied by temperature-programmed desorption, ultraviolet and X-ray photoelectron spectroscopy. Cyclohexane weakly adsorbed on Cu(111) has been known to show a broadened and redshifted CH stretching band, i.e., CH vibrational mode softening. Although no dehydrogenation takes place thermally on this surface and by the irradiation of photons at 5.0 eV, adsorbed cyclohexane is dissociated to cyclohexyl and hydrogen by the irradiation of photons at 6.4 eV. This is a marked contrast to cyclohexane in the gas phase where the onset of absorption is located at 7 eV. When the surface irradiated by 6.4-eV photons is further annealed, cyclohexyl is dehydrogenated to form cylcohexene that desorbs at 230 K. The systematic measurements of photochemical cross sections at 6.4 eV with linearly polarized light as a function of incident angle indicate that the electronic transition from the highest occupied band of cyclohexane to a partially occupied hybridized band near the Fermi level is responsible for the photochemistry. The hybridized band is formed by the interactions between the electronic states of cyclohexane and the metal substrate. The role of the hybridized band in the photochemistry and the CH vibrational mode softening is discussed. 相似文献
94.
Adsorption states and photochemistry of methane physisorbed on Pd(111) have been investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy and compared with those on Pt(111). On both of the surfaces, methane is either dissociated into a hydrogen atom and a methyl radical or molecularly desorbed by 6.4 eV photon irradiation. In the photochemistry, the direct electronic excitation of the adsorbate-substrate complex plays an important role. Different features observed for Pd(111) compared with Pt(111) are: (1) the adsorbate-substrate interaction is slightly stronger; (2) methane adsorbates show a (√3√3)R30° LEED pattern at 40 K; (3) the photochemical cross-section is larger by 60%; and (4) the photochemistry is not self-quenched at prolonged irradiation. The origins of these features are discussed in terms of the differences in the electronic structure between the two surfaces. 相似文献
95.
The absolute configuration of vibsanin F (1), one of the simplest 11-membered ring vibsane-type diterpene, was established to be 6R, 7S and 11S by asymmetric synthesis. A diastereomer (1a) with a 6S, 7S and 11S configuration was synthesized starting from myrcene by procedures featuring a Sharpless asymmetric epoxidation and a high diastereoselective eleven-membered ring formation between a π-allylpalladium complex and a β-ketoester nucleophile. Subsequent reduction of epoxide in 1a with LiAlH4 gave a diol, which was identical with that derived from vibsanin F. 相似文献
96.
We demonstrate the mode-selective excitation of coherent phonons at Pt(111) surfaces covered with submonolayer caesium atoms. A burst of 150 fs laser pulses with the repetition rate of 2.0-2.9 THz was synthesized by using a spatial-light modulator, and used for the coherent surface phonon excitation. The coherent nuclear motion was monitored by time-resolved second harmonic generation. By tuning the repetition rate, we succeeded in controlling the relative amplitude of the vibrational coherence of the Cs-Pt stretching mode (2.3-2.4 THz) to that of the Pt surface Rayleigh phonon mode (2.6 or 2.9 THz, depending on the Cs coverage). 相似文献
97.
Optically active Prelog-Djerassi Lactonic Acid was synthesized from D-glucal: the crucial point being the elaboration of the carboxylic group as shown in eq. 1 and 2 which involve the sequential process [i] asymmetric addition of methyl anion onto the hetero-olefin 2, [ii] trapping the carbanion intermediate [E=Li to SePh] and [iii] oxidative hydrolysis of sila-pummerer rearrangement into . 相似文献
98.
An efficient total synthesis of (+)-conagenin was achieved. The right fragment of conagenin, alpha-methylserine containing a quaternary stereocenter attached to nitrogen, was synthesized using allyl cyanate-to-isocyanate rearrangement. The left fragment, 2,4-dihydroxy-3-methylpentanoic acid, has three contiguous stereogenic centers, which was efficiently constructed by enantioselective monoreduction of 2-alkyl-1,3-diketones reported by Cossy, and chelation-controlled stereoselective reduction of beta-hydroxy ketone. These two fragments were coupled through intramolecular amide bond formation with high efficiency. 相似文献
99.
Minoru Isobe Yoshiyasu Ichikawa Hisanori Masaki Toshio Goto 《Tetrahedron letters》1984,25(33):3607-3610
Okadaic acid was antithesized into three segments A, B and C, and this paper deals with the synthesis of the C-segment in the form of 24, which was prepared in 16 steps from a D-glucopyranose derivative (11) via the lactone 18. The key step is the introduction of the C-29 asymmetric carbon via hetero-conjugate addition at neighbouring spiro ethers. 相似文献
100.
[formula: see text] A convenient method for the synthesis of carbamates using polymer-supported N-hydroxysuccinimide is described. Various carbamates were synthesized in highly pure form without the need for chromatographic purification. This new "catch and release"-type solid-phase synthesis should be useful for combinatorial synthesis of various carbamates. 相似文献