全文获取类型
收费全文 | 611篇 |
免费 | 40篇 |
国内免费 | 1篇 |
专业分类
化学 | 501篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 55篇 |
物理学 | 80篇 |
出版年
2023年 | 12篇 |
2022年 | 8篇 |
2021年 | 14篇 |
2020年 | 35篇 |
2019年 | 29篇 |
2018年 | 15篇 |
2017年 | 10篇 |
2016年 | 27篇 |
2015年 | 28篇 |
2014年 | 29篇 |
2013年 | 31篇 |
2012年 | 59篇 |
2011年 | 65篇 |
2010年 | 29篇 |
2009年 | 21篇 |
2008年 | 34篇 |
2007年 | 29篇 |
2006年 | 33篇 |
2005年 | 36篇 |
2004年 | 26篇 |
2003年 | 17篇 |
2002年 | 12篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有652条查询结果,搜索用时 15 毫秒
71.
Raphael Bigler Kyle A. Mack Jeff Shen Paolo Tosatti Chong Han Stephan Bachmann Haiming Zhang Michelangelo Scalone Andreas Pfaltz Scott E. Denmark Stefan Hildbrand Francis Gosselin 《Angewandte Chemie (International ed. in English)》2020,59(7):2844-2849
Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio‐ and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio‐ and diastereoselectivity. 相似文献
72.
73.
We consider the minimum permanents and minimising matrices on the faces of the polytope of doubly stochastic matrices whose nonzero entries coincide with those of, respectively,
74.
Lawrence C. Thompson Kyle S. Knight William T. Pennington 《Journal of chemical crystallography》2003,33(5-6):403-407
A triphenyl analog of taddol, 4-R,5-R-[5-(hydroxy-diphenyl-methyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-phenyl-methanone, has been synthesized and structurally characterized. This molecule could act as a chiral ligand building block in the creation of tuned taddol analogs. Structural analysis of the title compound reveals that the hydroxyl group is involved in an intramolecular hydrogen bond and does not take part in any intermolecular interaction. Crystal packing is influenced by C–H O hydrogen bonding and phenyl phenyl interactions. Crystal data: Triclinic, P1 (No. 1), a = 5.9343(4) Å, b = 8.2367(17) Å, c = 10.987(2) Å, = 88.290(6), = 75.442(4), = 80.655(6), V = 512.86(15) Å3, Z = 1, D
calc = 1.258 mg/m3. Final residual values were R
1 = 0.0407 for 3022 observed data (I > 2s(I) ) and wR
2 = 0.0941 for all 3524 unique data. 相似文献
75.
76.
The influence of water column variability on low-frequency, shallow water geoacoustic inversion results is considered. The data are estimates of modal eigenvalues obtained from measurements of a point source acoustic field using a horizontal aperture array in the water column. The inversion algorithm is based on perturbations to a background waveguide model with seabed properties consistent with the measured eigenvalues. Water column properties in the background model are assumed to be known, as would be obtained from conductivity, temperature, and depth measurements. The scope of this work in addressing the impact of water column variability on inversion is twofold. Range-dependent propagation effects as they pertain to eigenvalue estimation are first considered. It is shown that mode coupling is important even for weak internal waves and can enhance modal eigenvalue estimates. Second, the effect of the choice of background sound speed profile in the water column is considered for its impact on the estimated bottom acoustic properties. It is shown that a range-averaged sound velocity profile yields the best geoacoustic parameter estimates. 相似文献
77.
Sensitization in 5XXX aluminum alloys is an insidious problem characterized by the gradual formation and growth of beta phase (Mg2Al3) at grain boundaries, which increases the susceptibility of alloys to intergranular corrosion (IGC) and intergranular stress-corrosion cracking (IGSCC). The degree of sensitization (DoS) is currently quantified by the ASTM G67 Nitric Acid Mass Loss Test, which is destructive and time consuming. A fast, reliable, and non-destructive method for rapid detection and the assessment of the condition of DoS in AA5XXX aluminum alloys in the field is highly desirable. In this paper, we describe a non-destructive method for measurements of DoS in aluminum alloys with an electromagnetic acoustic transducer (EMAT). AA5083 aluminum alloy samples were sensitized at 100 °C with processing times varying from 7 days to 30 days. The DoS of sensitized samples was first quantified with the ASTM 67 test in the laboratory. Both ultrasonic velocity and attenuation in sensitized specimens were then measured using EMAT and the results were correlated with the DoS data. We found that the longitudinal wave velocity was almost a constant, independent of the sensitization, which suggests that the longitudinal wave can be used to determine the sample thickness. The shear wave velocity and especially the shear wave attenuation are sensitive to DoS. Relationships between DoS and the shear velocity, as well as the shear attenuation have been established. Finally, we performed the data mining to evaluate and improve the accuracy in the measurements of DoS in aluminum alloys with EMAT. 相似文献
78.
79.
Apeng Chen Kyle B. Lynch Xiaochun Wang Joann J. Lu Congying Gu Shaorong Liu 《Analytica chimica acta》2014
We integrate a high-pressure electroosmotic pump (EOP), a nanoflow gradient generator, and a capillary column into a miniaturized liquid chromatographic system that can be directly coupled with a mass spectrometer for proteomic analysis. We have recently developed a low-cost high-pressure EOP capable of generating pressure of tens of thousands psi, ideal for uses in miniaturized HPLC. The pump worked smoothly when it was used for isocratic elutions. When it was used for gradient elutions, generating reproducible gradient profiles was challenging; because the pump rate fluctuated when the pump was used to pump high-content organic solvents. This presents an issue for separating proteins/peptides since high-content organic solvents are often utilized. In this work, we solve this problem by incorporating our high-pressure EOP with a nano-flow gradient generator so that the EOP needs only to pump an aqueous solution. With this combination, we develop a capillary-based nano-HPLC system capable of performing nano-flow gradient elution; the pump rate is stable, and the gradient profiles are reproducible and can be conveniently tuned. To demonstrate its utility, we couple it with either a UV absorbance detector or a mass spectrometer for peptide separations. 相似文献
80.
Lipids and block copolymers can be individually assembled into unsupported, spherical membranes (liposomes or polymersomes), each having their own particular benefits and limitations. Here we demonstrate the preparation of microscale, hybrid "lipopolymersomes" composed of the common lipid POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine) and the commercially available copolymer PBd-b-PEO (polybutadiene-b-poly(ethylene oxide)) with the goal of incorporating the advantageous qualities of the unitary systems into mixed-membrane capsules. We investigate the lipopolymersomes using confocal fluorescence microscopy and demonstrate that these hybrid membranes are well mixed on nanoscopic length scales within the permittable compositional windows for hybrid vesicle formation. We measure the intramembrane dynamics and mechanical properties of these hybrid membranes by fluorescence recovery after photobleaching (FRAP) and micropipet aspiration, respectively. For the first time, we demonstrate the demixing of lipid-rich and polymer-rich membrane domains within the same vesicle membrane. This is achieved by the biotinylation of one of the constituent species and cross linking with the protein NeutrAvidin. The resultant domain patterning is dependent upon which component carries the biotin functionality: cross linking of the copolymer species results in domains that ripen into a single, large, copolymer-rich island, and cross linking of the lipids yields many small, "spot-like", lipid-rich domains within a copolymer-rich matrix. We discuss these morphological differences in terms of the fluidity and mechanical properties of the membrane phases and the possible resultant interdomain interactions within the membrane. These heterogeneous hybrid lipopolymersomes could find applications in fields such as targeted delivery, controlled release, and environmental detection assays where these capsules possess the characteristics of biocompatible lipid membranes combined with enhanced mechanical strength and stability from the copolymer matrix. 相似文献