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181.
Alkylamides (such as N,N'-dimethylformamide, N,N'-diethylformamide, and N,N'-dimethylacetamide) are aprotic solvents that are widely used in organic synthesis. These polar molecules have no electron affinity, and it is believed that irradiated liquid and solid amides stabilize excess electrons as cavity-type species analogous to hydrated and ammoniated electrons. In this study, we use isotope substitution and EPR spectroscopy to demonstrate that, in frozen amides, the suspected "cavity electron" is, in fact, a solvent-stabilized monomer anion. Our observations call into question other attributions of such features in the literature, both in low temperature solids and room temperature liquids. We also provide a general scheme describing amide radiolysis, as the related amides are used as metal ion extracting agents in nuclear separations. 相似文献
182.
Ilya Shvartsman 《Journal of Optimization Theory and Applications》2012,153(3):578-586
In this paper, we provide a simple proof of the maximum principle for a nonsmooth discrete-time optimal control problem. The
methodology is general and encompasses all generalized derivatives for which the Lagrange multiplier rule and the chain rule
hold. This includes, but is not limited to, limiting (Mordukhovich) and Michel–Penot subdifferentials. 相似文献
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Udovydchenkov IA Brown MG Duda TF Mercer JA Andrew RK Worcester PF Dzieciuch MA Howe BM Colosi JA 《The Journal of the Acoustical Society of America》2012,131(6):4409-4427
The results of mode-processing measurements of broadband acoustic wavefields made in the fall of 2004 as part of the Long-Range Ocean Acoustic Propagation Experiment (LOAPEX) in the eastern North Pacific Ocean are reported here. Transient wavefields in the 50-90 Hz band that were recorded on a 1400-m long 40 element vertical array centered near the sound channel axis are analyzed. This array was designed to resolve low-order modes. The wavefields were excited by a ship-suspended source at seven ranges, between approximately 50 and 3200 km, from the receiving array. The range evolution of broadband modal arrival patterns corresponding to fixed mode numbers ("modal group arrivals") is analyzed with an emphasis on the second (variance) and third (skewness) moments. A theory of modal group time spreads is described, emphasizing complexities associated with energy scattering among low-order modes. The temporal structure of measured modal group arrivals is compared to theoretical predictions and numerical simulations. Theory, simulations, and observations generally agree. In cases where disagreement is observed, the reasons for the disagreement are discussed in terms of the underlying physical processes and data limitations. 相似文献
185.
Irina L. Odinets Oleg I. Artyushin Evgenii I. Goryunov Konstantin A. Lyssenko Ekaterina Yu. Rybalkina Ilya V. Kosilkin Tatiana V. Timofeeva Mikhail Yu. Antipin 《Heteroatom Chemistry》2005,16(6):497-502
In a search for cytotoxic fluorescent materials, a series of N‐phosphorylated compounds 2a–c were prepared by phosphorylation of 3,5‐bis(4‐N,N‐dimethylbenzylidene)‐4‐piperidone 1 . According to X‐ray investigations, molecule 2a is E,E‐isomer with axial position of the P(O)(OCH2CF3)2 substituent. Fluorescence of compounds 2a–c was found to be similar to fluorescence of nonphosphorylated compound 1 . The cytotoxicity of the compounds 2a–c was estimated on several human tumor cell lines (H9, K562, and MCF7). © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:497–502, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20147 相似文献
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187.
A Computational Study of Vicinal Fluorination in 2,3‐Difluorobutane: Implications for Conformational Control in Alkane Chains 下载免费PDF全文
Dr. Stephen J. Fox Dr. Stephanie Gourdain Anton Coulthurst Clare Fox Dr. Ilya Kuprov Prof. Jonathan W. Essex Dr. Chris‐Kriton Skylaris Dr. Bruno Linclau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1682-1691
A comprehensive conformational analysis of both 2,3‐difluorobutane diastereomers is presented based on density functional theory calculations in vacuum and in solution, as well as NMR experiments in solution. While for 1,2‐difluoroethane the fluorine gauche effect is clearly the dominant effect determining its conformation, it was found that for 2,3‐difluorobutane there is a complex interplay of several effects, which are of similar magnitude but often of opposite sign. As a result, unexpected deviations in dihedral angles, relative conformational energies and populations are observed which cannot be rationalised only by chemical intuition. Furthermore, it was found that it is important to consider the free energies of the various conformers, as these lead to qualitatively different results both in vacuum and in solvent, when compared to calculations based only on the electronic energies. In contrast to expectations, it was found that vicinal syn‐difluoride introduction in the butane and by extension, longer hydrocarbon chains, is not expected to lead to an effective stabilisation of the linear conformation. Our findings have implications for the use of the vicinal difluoride motif for conformational control. 相似文献
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Aleksandr I. Chumakov Ilya Sergeev Jean‐Philippe Celse Rudolf Rüffer Marc Lesourd Lin Zhang Manuel Sánchez del Río 《Journal of synchrotron radiation》2014,21(2):315-324
The performance of a cryogenically cooled double‐crystal silicon monochromator was studied under high‐heat‐load conditions with total absorbed powers and power densities ranging from 8 to 780 W and from 8 to 240 W mm?2, respectively. When the temperature of the first crystal is maintained close to the temperature of zero thermal expansion of silicon, the monochromator shows nearly ideal performance with a thermal slope error of 0.6 µrad. By tuning the size of the first slit, the regime of the ideal performance can be maintained over a wide range of heat loads, i.e. from power densities of 110 W mm?2 (at total absorbed power of 510 W) to 240 W mm?2 (at total absorbed power of 240 W). 相似文献