全文获取类型
收费全文 | 392篇 |
免费 | 7篇 |
国内免费 | 4篇 |
专业分类
化学 | 250篇 |
晶体学 | 2篇 |
力学 | 26篇 |
数学 | 65篇 |
物理学 | 60篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 4篇 |
2020年 | 2篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 4篇 |
2015年 | 4篇 |
2014年 | 6篇 |
2013年 | 15篇 |
2012年 | 30篇 |
2011年 | 23篇 |
2010年 | 23篇 |
2009年 | 24篇 |
2008年 | 22篇 |
2007年 | 37篇 |
2006年 | 21篇 |
2005年 | 9篇 |
2004年 | 23篇 |
2003年 | 17篇 |
2002年 | 5篇 |
2001年 | 8篇 |
2000年 | 9篇 |
1999年 | 14篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 11篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有403条查询结果,搜索用时 15 毫秒
71.
PEG‐400[poly(ethylene glycol‐400)] is used as a “green” recyclable solvent in the one‐pot synthesis of quinoxalines by reaction with aryl ketones, hypervalent Iodine(III) Sulfonate, and o‐phenylenediamines. Significant rate enhancements and improved yields have been observed. 相似文献
72.
Sheu SY 《The Journal of chemical physics》2006,124(15):154711
We proposed a selectivity principle for the ligand escape process from two fluctuating bottlenecks in a cavity with a multigate inside a myoglobin pocket. Our previous analytical theory proposed a fluctuating bottleneck model for a Brownian particle passing through two gates on a cavity surface of an enzyme protein and has determined the escape rate in terms of the time-dependent gate function and the competition effect. It illustrated that with two (or more than two) gates on a cavity surface the gate modulation, which is controlled by protein fluctuation, dominates the ligand escape pathway. We have performed a molecular dynamics simulation to investigate the selectivity principle of the ligand escape process from two-gate tunnel in myoglobin. The simulation results confirm our theoretical conjecture. It indicates that the escape process is actually entropy driven, and the ligand escape pathway is chosen via the gate modulation. This suggests an interesting intrinsic property, that is, the oxymyoglobin tertiary structure is favorable to the departure of the ligand from one direction rather than through a biased random walk. 相似文献
73.
In this work, the effects of preparation conditions used in roughening silver substrates by electrochemical triangular-wave oxidation-reduction cycles (ORC) on surface-enhanced Raman scattering (SERS) were first investigated. The optimum roughening conditions for obtaining strongest SERS of Rhodamine 6G (R6G) are as follows. Ag electrodes were cycled in deoxygenated aqueous solutions containing 0.1 M NaCl from −0.3 to +0.2 V versus Ag/AgCl at 25 mV s−1 for five scans. The SERS of R6G adsorbed on this optimum procedure-prepared roughened Ag substrate exhibits a higher intensity by one order of magnitude, as compared with that of R6G adsorbed on a normally roughened Ag substrate. 相似文献
74.
The organic extract of the soft coral Sinularia gibberosa, collected from the northern Taiwan, has been investigated and resulted in the isolation of five new xeniaphyllane-type diterpenoids with a rare cyclic peroxyhemiketal (3,6-dihydro-1,2-dioxin-3-ol) moiety, sinugibberosides A-E (1-5). The structures of the new terpenoids, including their stereochemistries, were established on the basis of extensive spectroscopic analysis, including 1D and 2D NMR (1H-1H COSY, HMQC, HMBC, and NOESY), and by comparison of their NMR data with those of related compounds. Metabolites 1-5 represent the first example of marine terpenoids possessing a cyclic peroxyhemiketal moiety. 相似文献
75.
CW Yeh WT Chen RS Liu SF Hu HS Sheu JM Chen HT Hintzen 《Journal of the American Chemical Society》2012,134(34):14108-14117
The orange-red emitting phosphors based on M(2)Si(5)N(8):Eu (M = Sr, Ba) are widely utilized in white light-emitting diodes (WLEDs) because of their improvement of the color rendering index (CRI), which is brilliant for warm white light emission. Nitride-based phosphors are adopted in high-performance applications because of their excellent thermal and chemical stabilities. A series of nitridosilicate phosphor compounds, M(2-x)Si(5)N(8):Eu(x) (M = Sr, Ba), were prepared by solid-state reaction. The thermal degradation in air was only observed in Sr(2-x)Si(5)N(8):Eu(x) with x = 0.10, but it did not appear in Sr(2-x)Si(5)N(8):Eu(x) with x = 0.02 and Ba analogue with x = 0.10. This is an unprecedented investigation to study this phenomenon in the stable nitrides. The crystal structural variation upon heating treatment of these compounds was carried out using the in situ XRD measurements. The valence of Eu ions in these compounds was determined by electron spectroscopy for chemical analysis (ESCA) and X-ray absorption near-edge structure (XANES) spectroscopy. The morphology of these materials was examined by transmission electron microscopy (TEM). Combining all results, it is concluded that the origin of the thermal degradation in Sr(2-x)Si(5)N(8):Eu(x) with x = 0.10 is due to the formation of an amorphous layer on the surface of the nitride phosphor grain during oxidative heating treatment, which results in the oxidation of Eu ions from divalent to trivalent. This study provides a new perspective for the impact of the degradation problem as a consequence of heating processes in luminescent materials. 相似文献
76.
Hui-Yu Fang Chih-Chuang Liaw Chih-Hua ChaoZhi-Hong Wen Yang-Chang WuChi-Hsin Hsu Chang-Feng DaiJyh-Horng Sheu 《Tetrahedron》2012,68(47):9694-9700
Nine new steroids, sclerosteroids A-I (1, 5, 6, 8-13), along with 18 known metabolites (2-4, 7, 14-27), were isolated from the soft coral Scleronephthya gracillimum. These structures were elucidated on the basis of detailed spectroscopic analysis. The absolute configurations of sugar moieties in steroidal glycosides 10-13 were determined by HPLC analysis of the o-tolylthiocarbamate derivatives of the liberated sugars from hydrolysis of these steroidal giycosides. Cytotoxic and anti-inflammatory activities of these compounds were measured in vitro. 相似文献
77.
Pei-Han Hong Yin-Di Su Nai-Cheng Lin Yung-Husan Chen Yueh-Hsiung Kuo Tsong-Long Hwang Wei-Hsien Wang Jih-Jung Chen Jyh-Horng Sheu Ping-Jyun Sung 《Tetrahedron letters》2012,53(14):1710-1712
A novel 2-ketobriarane diterpenoid, briarenolide E (1), was isolated from an octocoral Briareum sp. The structure of briarane 1 was elucidated by interpretations of spectral data. Compound 1 displayed modestly inhibitory effects on the generation of superoxide anions and the release of elastase by human neutrophils. 相似文献
78.
YC Kao T Huang DY Lin YS Huang KK Tiong HY Lee JM Lin HS Sheu CM Lin 《The Journal of chemical physics》2012,137(2):024509
The high pressure induced phase transition in rhenium diselenides (ReSe(2)) and gold-doped rhenium diselenides (Au-ReSe(2)) at ambient temperature have been investigated using angular-dispersive x-ray diffraction (ADXRD) under high pressure up to around 10.50 and 9.98 GPa, respectively. In situ ADXRD measurements found that the phase transition pressures of ReSe(2) and Au-ReSe(2) began at 9.98 and 8.52 GPa, respectively. Compressibilities analysis shows the relationship of along c-axis > along a-axis > along b-axis. The linear compressibility of the pressure dependence of α, β, and γ of ReSe(2) shows that a phase transition can be related to a counterclockwise rotational trend of the selenium atoms around the chain of Re(4) atoms during the decrease of the c-axis distance by a combination of stresses due to the bending effect of α and stretching effect of β. The cause of the reduction of the phase transition pressure of Au-ReSe(2) is attributed mainly to a structural distortion as evidenced by the observation of a weak clockwise rotational trend of Se atoms around the chain of Re(4) atoms in the pressure range 3.99-4.99 GPa which subsequently reversed to counterclockwise rotation under higher pressure. 相似文献
79.
2,3‐Dimethylpentacene (DMP) and 2,3‐dimethyltetracene (DMT) were synthesized, characterized and employed as the channel material in the fabrication of thin‐film transistors. The two methyl groups increase the chemical stability of the compounds versus the pristine acene analogues. The crystals maintain herringbone‐like molecular packing, whereas the weak dipole associated with the unsymmetrical molecule induces an anti‐parallel alignment among the neighbors. This structural motif favors layered film growth on SiO2/Si surface. Thin film transistors prepared on SiO2/Si and n‐nonyltrichlorosilane‐modified SiO2/Si at different substrate temperatures were compared. DMP‐based transistors prepared on rubbed n‐nonyltrichlorosilane‐modified SiO2/Si substrate gave the highest field‐effect mobility of 0.46 cm2/Vs, whereas DMT‐based transistor gave a mobility of 0.028 cm2/Vs. 相似文献
80.
Experiments of helical excitation using piezoelectric actuators on jet flows and lifted flames are performed to enhance the
understanding of the effects of vortical structures of various instability modes on the stabilization mechanism of the lifted
flame. In addition to the common ring and braid structures, five or seven azimuthal fingers (or lobes) can be identified in
the transverse image of the jet near field. Excitation with various helical modes enhances the azimuthal structures and entrainment
in the near field. When helically excited with the asymmetric m=1 mode, one of the fingers is enhanced and may evolve into a strong streamwise vortex. The streamwise vortices generated
in the braid region between the adjacent ring vortices may enhance fuel-air mixing due to additional azimuthal entrainment
upstream of a lifted flame when helically excited with the m=1 mode. Therefore, the streamwise vortex serves as an additional path of high probability of premixed flammable layer for
the upstream propagation of the lifted flame so that the flame base on one side of the lifted flame may extend farther upstream
and the flame base is inclined. In addition to the inclined flame base, multiple-legs phenomenon is also observed in the flame
base, which is strongly associated with fingers of the helical modes of the jet flow.
Received: 21 August 1997/Accepted: 24 January 1999 相似文献