全文获取类型
收费全文 | 2009篇 |
免费 | 71篇 |
国内免费 | 24篇 |
专业分类
化学 | 1244篇 |
晶体学 | 9篇 |
力学 | 61篇 |
数学 | 391篇 |
物理学 | 399篇 |
出版年
2022年 | 13篇 |
2021年 | 19篇 |
2020年 | 23篇 |
2019年 | 25篇 |
2018年 | 18篇 |
2017年 | 21篇 |
2016年 | 56篇 |
2015年 | 48篇 |
2014年 | 47篇 |
2013年 | 83篇 |
2012年 | 108篇 |
2011年 | 144篇 |
2010年 | 64篇 |
2009年 | 63篇 |
2008年 | 97篇 |
2007年 | 114篇 |
2006年 | 137篇 |
2005年 | 124篇 |
2004年 | 80篇 |
2003年 | 84篇 |
2002年 | 91篇 |
2001年 | 37篇 |
2000年 | 24篇 |
1999年 | 18篇 |
1998年 | 26篇 |
1997年 | 28篇 |
1996年 | 20篇 |
1995年 | 12篇 |
1994年 | 23篇 |
1993年 | 30篇 |
1992年 | 30篇 |
1991年 | 27篇 |
1990年 | 10篇 |
1989年 | 16篇 |
1988年 | 12篇 |
1987年 | 24篇 |
1986年 | 14篇 |
1985年 | 20篇 |
1984年 | 25篇 |
1983年 | 23篇 |
1982年 | 20篇 |
1981年 | 22篇 |
1980年 | 18篇 |
1979年 | 11篇 |
1978年 | 25篇 |
1977年 | 17篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1973年 | 13篇 |
1972年 | 9篇 |
排序方式: 共有2104条查询结果,搜索用时 15 毫秒
91.
92.
This paper presents a 3D topology optimization approach for designing shell structures with a porous or void interior. It is shown that the resulting structures are significantly more robust towards load perturbations than completely solid structures optimized under the same condi-tions. The study indicates that the potential benefit of using porous structures is higher for lower total volume fractions. Compared to earlier work dealing with 2D topology opti-mization, we found several new effects in 3D problems. Most notably, the opportunity for designing closed shells signifi-cantly improves the performance of porous structures due to the sandwich effect. Furthermore, the paper introduces improved filter boundary conditions to ensure a completely uniform coating thickness at the design domain boundary. 相似文献
93.
Ahmad Arouri Anders Højgaard Hansen Thomas Elmelund Rasmussen Ole G. Mouritsen 《Current Opinion in Colloid & Interface Science》2013,18(5):419-431
Colloidal and interfacial phenomena lie at the core of drug formulation, drug delivery, as well as drug binding and action at diseased sites, e.g., in cancer therapy. We review a class of liposome-based drug-delivery systems whose design and functional properties are intimately controlled by the stability of sub-micron structures, lipid-bilayer interfaces, and interfacially activated enzymes that can be exploited to target and deliver drugs. Moreover these drugs can themselves be special lipid molecules in the form of lipid prodrugs that both form the liposomal carrier as well as the substrate for endogenously upregulated lipases that turn the prodrugs into potent drugs precisely at the diseased site. 相似文献
94.
A one-step synthesis of the stable [4]helicenium dye, 1,13-dimethoxy-chromeno[2,3,4-kl]xanthenium hexafluorophosphate (DMCX+) from the readily available tris(2,6-dimethoxyphenyl)carbenium ion is reported. The crystal structure, the chemical stability, and dye properties of the DMCX+ helicenium system are described. 相似文献
95.
96.
Abstract A general deformation of a smectic C liquid crystal is composed of five different distortions, each of which can be made independently. Here we show that to each of these distortions we can assign a simple vector operator. Use of these five basis operators enables us to write down the elastic free energy density as a quadratic form consisting of nine terms. We also discuss how the nine elastic constants defined by the elastic energy expansion must fulfil certain restrictions in terms of inequalities and a specific tilt angle dependence. Assuming the smectic layers to be incompressible, we examine how certain arrangements of the smectic layers can be stable due to an interplay between the incompressibility condition and the boundary conditions which we impose on the director. One such stable configuration is the wedge, where the smectic layers form parts of concentric cylinders with the common axis coinciding with the centre of the wedge. For such a system we discuss the different director configurations which can be achieved and their stability. We also discuss the possibility of inducing Frederiks transitions for some of these configurations and calculate the corresponding thresholds, thereby demonstrating the design of an experiment which would make it possible to measure those elastic constants which are related to the deformations of the smectic layers, constants which are normally difficult to determine experimentally. 相似文献
97.
Jonas Örtegren Philippe Busson Ulf W. Gedde Anders Hult Anders Eriksson Mikael Lindgren 《Liquid crystals》2013,40(6):861-868
We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d 23-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles. 相似文献
98.
David Wensbo Posaric Anders Andersson Karl-Erik Bergquist Anders Isaksson 《Analytical and bioanalytical chemistry》2014,406(19):4735-4744
Various phosphatidylethanol (PEth) derivatives, the corresponding reversed positional isomers (RPI-PEths), lyso-PEth-16:0, and penta-deuterium-labeled PEth analogs (d5-PEths), were synthesized by enzyme-independent synthetic routes. A general solvent system consisting of a mixture of acetone-d6 and methanol-d4 (97:3; v/v) was found to provide a good solubilizing capacity and excellent hydrogen-1 NMR (1H-NMR) peak resolution of various PEth homologues. Analytical differentiation of PEth from the corresponding RPI-PEth by carbon-13 NMR (13C-NMR) was demonstrated by comparison of the 13C-NMR signals of the carbonyl groups, the allylic positions, and of the β-carbons. An exemplary stable long-term room temperature, DMSO-d6-based, and proton-sensitive quantitative nuclear magnetic resonance (1H-qNMR) independently quantified calibrator comprising PEth-16:0/18:1 for liquid chromatography (tandem) mass spectrometry (LC-MS/MS) analytical applications were prepared by employment of sodium dodecyl sulfate (SDS) as a solubilizing additive. In summary, novel hypothetically occurring PEth derivatives, e.g., RPI-PEths, have been independently synthesized with regio- and stereochemical control. Use of polar organic solvents, e.g., mixtures of acetone-d6 and methanol-d4 or DMSO-d6, improves spectral line shapes as compared to traditional hydrophobic solvents and allow for analytical differentiation between closely related PEth derivatives, as well as LC-MS/MS-independent concentration determination of dissolved single species by employment of 1H-qNMR. Figure
? 相似文献
99.
Malte Behrends Charlotta Wallinder Anna Wieckowska Marie-Odile Guimond Anders Hallberg Nicole Gallo-Payet Mats Larhed 《ChemistryOpen》2014,3(2):65-75
A novel series of ligands for the recombinant human AT2 receptor has been synthesized utilizing a fast and efficient palladium-catalyzed procedure for aminocarbonylation as the key reaction. Molybdenum hexacarbonyl [Mo(CO)6] was employed as the carbon monoxide source, and controlled microwave heating was applied. The prepared N-aryl isoleucine derivatives, encompassing a variety of amide groups attached to the aromatic system, exhibit binding affinities at best with Ki values in the low micromolar range versus the recombinant human AT2 receptor. Some of the new nonpeptidic isoleucine derivatives may serve as starting points for further structural optimization. The presented data emphasize the importance of using human receptors in drug discovery programs. 相似文献
100.
Kristina Westerlund Anders Myrhammar Hanna Tano Maxime Gestin Amelie Eriksson Karlstrm 《Molecules (Basel, Switzerland)》2021,26(10)
Natural backbone-cyclized proteins have an increased thermostability and resistance towards proteases, characteristics that have sparked interest in head-to-tail cyclization as a method to stability-enhance proteins used in diagnostics and therapeutic applications, for example. In this proof-of principle study, we have produced and investigated a head-to-tail cyclized and HER2-specific ZHER2:342 Affibody dimer. The sortase A-mediated cyclization reaction is highly efficient (>95%) under optimized conditions, and renders a cyclic ZHER3:342-dimer with an apparent melting temperature, Tm, of 68 °C, which is 3 °C higher than that of its linear counterpart. Circular dichroism spectra of the linear and cyclic dimers looked very similar in the far-UV range, both before and after thermal unfolding to 90 °C, which suggests that cyclization does not negatively impact the helicity or folding of the cyclic protein. The cyclic dimer had an apparent sub-nanomolar affinity (Kd ~750 pM) to the HER2-receptor, which is a ~150-fold reduction in affinity relative to the linear dimer (Kd ~5 pM), but the anti-HER2 Affibody dimer remained a high-affinity binder even after cyclization. No apparent difference in proteolytic stability was detected in an endopeptidase degradation assay for the cyclic and linear dimers. In contrast, in an exopeptidase degradation assay, the linear dimer was shown to be completely degraded after 5 min, while the cyclic dimer showed no detectable degradation even after 60 min. We further demonstrate that a site-specifically DyLight 594-labeled cyclic dimer shows specific binding to HER2-overexpressing cells. Taken together, the results presented here demonstrate that head-to-tail cyclization can be an effective strategy to increase the stability of an Affibody dimer. 相似文献