全文获取类型
收费全文 | 1024篇 |
免费 | 43篇 |
国内免费 | 8篇 |
专业分类
化学 | 811篇 |
晶体学 | 16篇 |
力学 | 13篇 |
数学 | 94篇 |
物理学 | 141篇 |
出版年
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 22篇 |
2019年 | 24篇 |
2018年 | 12篇 |
2017年 | 13篇 |
2016年 | 20篇 |
2015年 | 20篇 |
2014年 | 25篇 |
2013年 | 60篇 |
2012年 | 70篇 |
2011年 | 73篇 |
2010年 | 47篇 |
2009年 | 33篇 |
2008年 | 63篇 |
2007年 | 58篇 |
2006年 | 52篇 |
2005年 | 64篇 |
2004年 | 44篇 |
2003年 | 39篇 |
2002年 | 40篇 |
2001年 | 15篇 |
2000年 | 17篇 |
1999年 | 15篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 15篇 |
1995年 | 5篇 |
1994年 | 12篇 |
1993年 | 13篇 |
1992年 | 3篇 |
1989年 | 7篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1985年 | 3篇 |
1984年 | 12篇 |
1983年 | 3篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 14篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 21篇 |
1972年 | 7篇 |
1971年 | 3篇 |
1957年 | 3篇 |
排序方式: 共有1075条查询结果,搜索用时 62 毫秒
991.
Heat may be a mutagenic agent which could be more important to evolution than are the ordinary errors in DNA replication. Therefore, it is necessary to know the stability of heredity determinants to thermal energy. Consequently, a thermal analysis, via differential scanning calorimetry (DSC), has been undertaken, using model compounds (crystalline 2'-deoxyribonucleosides and their 5-halo derivatives) to provide information regarding: 1. bond free energies maintaining the fibrous structure in nucleic acids e.g. H-bonding,π-complexing and dipole induced dipole interaction. 2. susceptibility to thermal degradation e.g. thermolytic cleavage of the glycosidic bond and deamination of the bases. Interpretation of the thermal curves has been facilitated and enhanced by utilization of a DSC-TLC analytical technique. Based on these data, a mechanism for the thermolysis of the glycosidic bond in the melt has been considered. 相似文献
992.
Protonic conduction across the membrane of a polymer electrolyte fuel cell is intimately related to the dynamic behavior of water present within the membrane. To further the understanding of water dynamics in these materials, quasielastic neutron scattering (QENS) has been used to investigate the picosecond dynamic behavior of water within a perfluorosulfonated ionomer (PFSI) membrane under increasing hydration levels from dry to saturation. Evaluation of the elastic incoherent structure factor (EISF) reveals an increase in the characteristic length-scale of confinement as the number of water molecules in the membrane increases, tending to an asymptotic value at saturation. The fraction of elastic incoherent scattering observed at high Q over all hydration levels is well fit by a simple model that assumes a single, nondiffusing hydronium ion per membrane sulfonic acid site. The quasielastic component of the fitted data indicates confined dynamic behavior for scattering vectors less than 0.7 A(-1). As such, the dynamic behavior was interpreted using continuous diffusion confined within a sphere at Q < 0.7 A(-1) and random unconstrained jump diffusion at Q > 0.7 A(-1). As the number of water molecules in the membrane increases, the characteristic residence times obtained from both models is reduced. The increased dynamical frequency is further reflected in the diffusion coefficients predicted by both models. Between low hydration (2 H2O/SO3H) and saturation (16 H2O/SO3H), the continuous spherical diffusion coefficient changes from 0.46 +/- 0.12 to 1.04 +/- 0.12 (10(-5) cm2/s) and jump diffusion indicates an increase from 1.21 +/- 0.03 to 2.14 +/- 0.08 (10(-5) cm2/s). Overall, the dynamic behavior of water has been quantified over different length scale regimes, the results of which may be rationalized on the basis of the formation of water clusters in the hydrophilic domain that expand toward an asymptotic upper limit with increased hydration. 相似文献
993.
Ilker MF Nüsslein K Tew GN Coughlin EB 《Journal of the American Chemical Society》2004,126(48):15870-15875
Amphiphilic cationic polynorbornene derivatives, soluble in water, were prepared from modular norbornene monomers, with a wide range of molecular weights (M(n) = 1600-137 500 g/mol) and narrow polydispersities (PDI = 1.1-1.3). The antibacterial activity determined by growth inhibition assays and the hemolytic activity against human red blood cells were measured and compared to determine the selectivity of the polymers for bacterial over mammalian cells. The effects of monomer repeat unit hydrophobicity and polymer molecular weight on antibacterial and hemolytic activities were determined. The hydrophobicity of the repeat unit was observed to have dramatic effects on antibacterial and hemolytic activities. Lipid membrane disruption activities of the polymers was confirmed by measuring polymer-induced dye leakage from large unilamellar vesicles. By tuning the overall hydrophobicity of the polymer through random copolymerizations of modular norbornene derivatives, highly selective, nonhemolytic antibacterial activities were obtained. For appropriate monomer composition, selectivity against bacteria versus human red blood cells was determined to be over 100. 相似文献
994.
Local mode frequencies, omega, and anharmonicities, omegax, are obtained from the delta upsilon(CH) = 2-7 spectral regions of 1,3,5,7-cyclooctatetraene (COT) and 1,1,1-trichloroethane. In 1,1,1-trichloroethane omega and omega x are used in conjunction with ab initio potential energy surfaces to calculate local mode anharmonicity-torsion coupling terms, delta(omega x), and frequency-torsion coupling terms, delta(omega). Blue-shifting of sterically hindered CH oscillators in 1,1,1-trichloroethane indicates nonbonded, through-space intramolecular interactions with Cl. Multiple, complex Fermi resonances are observed in 1,1,1-trichloroethane and in COT between local mode states and local mode/normal mode combination states. Intensities of vibrational overtone transitions are calculated in the range delta upsilon(CH) = 3-9 using ab initio dipole moment functions and the harmonically coupled anharmonic oscillator (HCAO) model. HCAO intensities are compared to experimental intensities at delta upsilon(CH) = 3. 相似文献
995.
Dudley ME Morshed MM Brennan CL Islam MS Ahmad MS Atuu MR Branstetter B Hossain MM 《The Journal of organic chemistry》2004,69(22):7599-7608
Several commercial Lewis acids, including those of the Bronsted type, specifically HBF(4).OEt(2), are able to catalyze the reaction between aromatic aldehydes and ethyl diazoacetate to produce 3-hydroxy-2-arylacrylic acid ethyl esters and 3-oxo-3-arylpropanoic acid ethyl esters. Reactions catalyzed by the iron Lewis acid [(eta(5)-C(5)H(5))Fe(+)(CO)(2)(THF)]BF(4)(-) (i.e., 1) have the best yields and greatest ratio of 3-hydroxy-2-arylacrylic acid ethyl ester. The product distribution of 1 is not affected in the presence of Proton Sponge, but is dependent on temperature and the nature of the substrate aldehyde, whereas the activity of HBF(4).OEt(2) is affected by the presence of Proton Sponge and is reactive at temperatures as low as -78 degrees C. Consequently, both 1 and HBF(4).OEt(2) are valuable catalysts in producing important 3-hydroxy-2-arylacrylic acid ethyl esters as precursors to biologically active compounds. 相似文献
996.
Munro TA Goetchius GW Roth BL Vortherms TA Rizzacasa MA 《The Journal of organic chemistry》2005,70(24):10057-10061
[reaction: see text] Treatment of salvinorin A (1a) with KOH in MeOH gave the enedione 3, for which the dienone structure 7 was recently proposed. Also isolated, after methylation, were the secotriesters 4a-c. A mechanism for this unusual series of autoxidations is proposed. Surprisingly, 4a showed weak affinity at the kappa-opioid receptor. Divinatorins A-C (2a-c) showed no affinity at opioid receptors. Attempted reduction of 3 to a novel salvinorin diol (9d) was unsuccessful, but careful deacetylation of salvinorin C (9a) provided a viable route to this compound. A general method for identifying salvinorin 8-epimers by TLC is also presented. 相似文献
997.
A method for determining crude fat in animal feed, cereal grain, and forage (plant tissue) was collaboratively studied. Crude fat was extracted from the animal feed, cereal grain, or forage material with hexanes by the Randall method, also called the Soxtec method or the submersion method. The use of hexanes provides for an alternative to diethyl ether for fat extractions. The proposed submersion method considerably decreases the extraction time required to complete a batch of samples compared to Soxhlet. The increase in throughput is very desirable in the quest for faster turnaround times and the greater efficiency in the use of labor. In addition, this method provides for reclamation of the solvent as a step of the method. The submersion method for fat extraction was previously studied for meat and meat products and was accepted as AOAC Official Method 991.36. Fourteen blind samples were sent to 14 collaborators in the United States, Sweden, Canada, and Germany. The within-laboratory relative standard deviation (repeatability) ranged from 1.23 to 5.80% for crude fat. Among-laboratory (including within) relative standard deviation (reproducibility) ranged from 1.88 to 14.1%. The method is recommended for Official First Action. 相似文献
998.
999.
Melville JL Lovelock KR Wilson C Allbutt B Burke EK Lygo B Hirst JD 《Journal of chemical information and modeling》2005,45(4):971-981
Quantitative Structure-Selectivity Relationships (QSSR) are developed for a library of 40 phase-transfer asymmetric catalysts, based around quaternary ammonium salts, using Comparative Molecular Field Analysis (CoMFA) and closely related variants. Due to the flexibility of these catalysts, we use molecular dynamics (MD) with an implicit Generalized Born solvent model to explore their conformational space. Comparison with crystal data indicates that relevant conformations are obtained and that, furthermore, the correct biphenyl twist conformation is predicted, as illustrated by the superiority of the resulting model (leave-one-out q(2) = 0.78) compared to a random choice of low-energy conformations for each catalyst (average q(2) = 0.22). We extend this model by incorporating the MD trajectory directly into a 4D QSSR and by Boltzmann-weighting the contribution of selected minimized conformations, which we refer to as '3.5D' QSSR. The latter method improves on the predictive ability of the 3D QSSR (leave-one-out q(2) = 0.83), as confirmed by repeated training/test splits. 相似文献
1000.
Bryan MC Fazio F Lee HK Huang CY Chang A Best MD Calarese DA Blixt O Paulson JC Burton D Wilson IA Wong CH 《Journal of the American Chemical Society》2004,126(28):8640-8641
A covalent array for the display of complex oligosaccharides in microtiter plates has been developed. This strategy is conducive to the display of carbohydrates to proteins of interest such as lectins and antibodies, including the broadly neutralizing antibody 2G12 against HIV envelope oligomannose and can be cleaved from the surface for further characterization by mass spectrometry. The system was used to probe the multivalent interaction of 2G12 with an optimal epitope (Kd 0.1 muM). 相似文献