全文获取类型
收费全文 | 1661篇 |
免费 | 54篇 |
国内免费 | 12篇 |
专业分类
化学 | 1333篇 |
晶体学 | 9篇 |
力学 | 23篇 |
数学 | 126篇 |
物理学 | 236篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 25篇 |
2020年 | 32篇 |
2019年 | 22篇 |
2018年 | 15篇 |
2017年 | 13篇 |
2016年 | 32篇 |
2015年 | 44篇 |
2014年 | 55篇 |
2013年 | 88篇 |
2012年 | 129篇 |
2011年 | 143篇 |
2010年 | 79篇 |
2009年 | 51篇 |
2008年 | 107篇 |
2007年 | 109篇 |
2006年 | 97篇 |
2005年 | 111篇 |
2004年 | 87篇 |
2003年 | 71篇 |
2002年 | 69篇 |
2001年 | 29篇 |
2000年 | 25篇 |
1999年 | 14篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 19篇 |
1995年 | 15篇 |
1994年 | 16篇 |
1993年 | 15篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 19篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1973年 | 10篇 |
1969年 | 7篇 |
1968年 | 4篇 |
1943年 | 3篇 |
排序方式: 共有1727条查询结果,搜索用时 15 毫秒
11.
12.
Jacques Kagan Chris P. Kolyvas Jeffery A. Jaworski Edgard D. Kagan Isabelle A. Kagan Li-Hsin Zang 《Photochemistry and photobiology》1984,40(4):479-483
Abstract 2,5-Diphenyloxazole (POP) is widely used for the determination of radioactivity by scintillation counting. It has been found to be phototoxic to the yeasts Saccharomyces cerevisiae and Candida utilis , to the first instar larvae of the mosquito Aedes aegypti , to the crustaceans Daphnia magna and Artemia salida , as well as to the eggs of Drosophila melanogaster . The related molecule 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP) is also phototoxic, but to a lesser degree. Both POP and POPOP can sensitize the formation of singlet oxygen. 相似文献
13.
Rogelio P. Frutos Isabelle Gallou Diana Reeves Yibo Xu Dhileepkumar Krishnamurthy Chris H. Senanayake 《Tetrahedron letters》2005,46(48):8369-8372
Expedient and practical new methodology for the synthesis of substituted imidazoles was developed to provide a rapid access to a variety of 2-substituted, 1,2-disubstituted and 1,2,4-trisubstituted imidazoles by the direct CuCl-mediated reaction of nitriles with α-amino acetals in an intermolecular as well as intramolecular fashion. 相似文献
14.
Christophe Biot Jean Dessolin Isabelle Ricard 《Journal of organometallic chemistry》2004,689(25):4678-4682
Starting from triazacyclononane, easily accessible ferrocenic quinoline derivatives were synthesized. Their antiplasmodial properties were investigated against chloroquine sensitive (HB3) and chloroquine-resistant (Dd2) Plasmodium falciparum. One of them, 7-chloro-4-[4-(7-chloro-4-quinolyl)-7-ferrocenylmethyl-1,4,7- triazacyclononan-1-yl]quinoline (4) showed potent antimalarial activity in vitro against the chloroquine-resistant strain Dd2 and therefore revealed to be the most promising lead from the present work for new organometallic antimalarial agents. 相似文献
15.
[structure: see text] An improved, third-generation, total synthesis of (+)-discodermolide, a potent microtubule-stabilizing anticancer agent of marine sponge origin, is achieved in 11.1% yield over 21 steps. Key steps include a Still-Gennari HWE olefination, performed using NaH as the base, between C1-C8 beta-ketophosphonate 7 and C9-C24 aldehyde 8, introducing the (8Z)-alkene with 10:1 selectivity, and K-Selectride reduction of the derived enone 16, installing the (7S)-configuration. 相似文献
16.
A measurement technique similar to optical absorption spectroscopy but based on evanescent acoustic waves is described in this paper. This format employs a planar spiral coil to vibrate a single crystal of quartz from 6 to 400 MHz, in order to measure multifrequency acoustic spectra. Consistency with the defined Sauerbrey and Kanazawa terms K1 and K2 when applied to multiple frequencies was found for these specific operating conditions in terms of a significant fit between the measured and calculated values: For an IgG surface density of 13.5 ng mm(-2) the measured value of K1 is 22.5 x 10(-6) and the calculated value is 20.4 x 10(-6), whilst for glycerol viscous loadings of 5.131 cP the measured value of K2 is 0.47 and the calculated value is 0.54. Thus for these specific surface loadings the multifrequency data fits to the predictions of the Sauerbrey model to within 10% and to Kanazawa model within 13%. However collective frequency shifts for 5.131 cP solutions of sucrose, dextran and glucose were found to exhibit an unanticipated additional variability (R2 < 0.4) with frequency, but retained a square root of frequency dependency within a factor 2 of the interpolated K2 values. The response to the 5.131 cP dextran solution was found to be significantly below the other isoviscous solutions, with a substantially reduced frequency shift and K2 value than would be expected from its bulk viscosity. In comparison with these viscous solutions, IgG protein films consistently produced linear frequency shifts with little scatter (R2 > 0.96) that were proportional to the operating frequency, and fully consistent with the Sauerbrey model under these specific conditions. A t-test value of 14.52 was calculated from the variance and mean of the two groups, and demonstrates that the acoustic spectrophonometer can be used to distinguish between the acoustic impedance characteristics of two chemical systems that are not clearly differentiable at a single operating frequency. 相似文献
17.
Lisiecki I 《The journal of physical chemistry. B》2005,109(25):12231-12244
In this review, we show that chemical reduction in colloidal assemblies favors the formation of size- and shape-controlled metallic nanoparticles. The key parameters that make possible the size control of spherical nanoparticles produced in spherical reverse micelles are the degree of hydration of the reactants, the dynamic character of the micelles, the capping with the surfactant, and the reducing agent concentration. The particle shape can be controlled by combining the strategy of the surfactant-based template and the capping of salts or molecules. Proof of the quality of the samples is given by the observation of two- and three-dimensional spontaneous self-organizations. 相似文献
18.
Complexation of AlIIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H2O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools. 相似文献
19.
A planar spiral coil has been used to induce hypersonic evanescent waves in a quartz substrate with the unique ability to focus the acoustic wave down onto the chemical recognition layer. These special sensing conditions were achieved by investigating the application of a radio frequency current to a coaxial waveguide and spiral coil, so that wideband repeating electrical resonance conditions could be established over the MHz to GHz frequency range. At a selected operating frequency of 1.09 GHz, the evanescent wave depth of a quartz crystal hypersonic resonance is reduced to 17 nm, minimising unwanted coupling to the bulk fluid. Verification of the validity of the hypersonic resonance was carried out by characterising the system electrically and acoustically: Impedance calculations of the combined coil and coaxial waveguide demonstrated an excellent fit to the measured data, although above 400 MHz a transition zone was identified where unwanted impedance is parasitic of the coil influence efficiency, so the signal-to-noise ratio is reduced from 3000 to 300. Acoustic quartz crystal resonances at intervals of precisely 13.2138 MHz spacing, from the 6.6 MHz ultrasonic range and onto the desired hypersonic range above 1 GHz, were incrementally detected. Q factor measurements demonstrated that reductions in energy lost from the resonator to the fluid interface were consistent with the anticipated shrinkage of the evanescent wave with increasing operating frequency. Amplitude and frequency reduction in contact with a glucose solution was demonstrated at 1.09 GHz. The complex physical conditions arising at the solid-liquid interface under hypersonic entrainment are discussed with respect to acceleration induced slippage, rupture, longitudinal and shear radiation and multiphase relaxation affects. 相似文献
20.
Jockusch RA Kroemer RT Talbot FO Snoek LC Carçabal P Simons JP Havenith M Bakker JM Compagnon I Meijer G von Helden G 《Journal of the American Chemical Society》2004,126(18):5709-5714
The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it. 相似文献