全文获取类型
收费全文 | 698篇 |
免费 | 67篇 |
国内免费 | 2篇 |
专业分类
化学 | 626篇 |
力学 | 14篇 |
数学 | 59篇 |
物理学 | 68篇 |
出版年
2023年 | 13篇 |
2022年 | 15篇 |
2021年 | 29篇 |
2020年 | 34篇 |
2019年 | 17篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 56篇 |
2015年 | 30篇 |
2014年 | 38篇 |
2013年 | 28篇 |
2012年 | 53篇 |
2011年 | 74篇 |
2010年 | 21篇 |
2009年 | 12篇 |
2008年 | 51篇 |
2007年 | 44篇 |
2006年 | 43篇 |
2005年 | 28篇 |
2004年 | 33篇 |
2003年 | 18篇 |
2002年 | 24篇 |
2001年 | 7篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1985年 | 5篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1961年 | 1篇 |
1960年 | 1篇 |
1957年 | 3篇 |
1956年 | 3篇 |
1944年 | 2篇 |
1943年 | 1篇 |
1936年 | 1篇 |
1935年 | 1篇 |
1931年 | 1篇 |
1930年 | 1篇 |
1921年 | 1篇 |
1899年 | 2篇 |
排序方式: 共有767条查询结果,搜索用时 15 毫秒
41.
Facchetti A Yoon MH Stern CL Hutchison GR Ratner MA Marks TJ 《Journal of the American Chemical Society》2004,126(41):13480-13501
The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) alpha,omega-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) beta,beta'-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) alpha,omega-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) beta,beta'-dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (alphanTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties. 相似文献
42.
Brown AM Ovchinnikov MV Stern CL Mirkin CA 《Journal of the American Chemical Society》2004,126(44):14316-14317
A novel reaction involving the halide-induced rearrangement of ligands within supramolecular Rh(I) complexes containing hemilabile ligands is presented. Three analogous bis- and trishemilabile ligands have been synthesized to construct bi- and trimetallic Rh(I) macrocyclic complexes. An intentionally added halide source results in the formal rotation of only one hemilabile ligand along the axis that is perpendicular to the plane defined by the aryl backbone of the hemilabile ligands. X-ray structures, as determined by X-ray crystallography, of key intermediates and products are presented. 相似文献
43.
44.
We report here several synthesis routes and their respective drawbacks/advantages for the preparation of pure LiFePO4. We demonstrate the possibility of using LiFePO4 for electrochemical applications, with respect that an effective carbon coating was realized onto the smallest particles. Actually, to bypass the weak ionic conductivity of lithium iron phosphate, the thinnest would be the particles; the highest would be the performance under severe electrochemical conditions. 相似文献
45.
Annica Tevell Åberg Charlotte Olsson Ulf Bondesson Mikael Hedeland 《Journal of mass spectrometry : JMS》2009,44(7):1026-1037
This paper describes a study where the metabolism of the non‐steroidal anti‐inflammatory drug meloxicam was investigated in six horses and in the filamentous fungus Cunninghamella elegans. The metabolites identified were compared between the species, and then the fungus was used to produce larger amounts of the metabolites for future use as reference material. C. elegans proved to be a good model of phase I meloxicam metabolism in horses since all four metabolites found were the same in both species. Apart from the two main metabolites, 5′‐hydroxymethylmeloxicam and 5′‐carboxymeloxicam, a second isomer of hydroxymeloxicam and dihydroxylated meloxicam were detected for the first time in horse urine and the microbial incubations. Phase II metabolites were not discovered in the C. elegans samples but hydroxymeloxicam glucuronide was detected intact in horse urine for the first time in this study. Urine from six horses was further analyzed in a semi‐quantitative sense and 5′‐hydroxymethylmeloxicam gave peaks with much higher intensity compared to the parent drug and the other metabolites, and was detected for at least 14 days after the last given dose in some of the horses. From the results presented in this article, we suggest that analytical methods developed for the detection of meloxicam in horse urine after prohibited use should focus on the 5′‐hydroxymethyl metabolite and that C. elegans can be used to produce large amounts of this metabolite for potential future use as a reference compound. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
46.
Chiara Saggese Charlotte M. Thomas Scott W. Wagnon Goutham Kukkadapu Song Cheng Dongil Kang S. Scott Goldsborough William J. Pitz 《Proceedings of the Combustion Institute》2021,38(1):415-423
Propanol and butanol isomers have received significant research attention as promising fuel additives or neat biofuels. Robust chemical kinetic models are needed that can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions. This study seeks to improve the understanding of ignition and combustion behavior of pure C3-C4 linear and iso-alcohols, and their blends with gasoline at engine-relevant conditions. In this work, a kinetic model with improved thermochemistry and reaction kinetics was developed based on recent theoretical calculations of H-atom abstraction and peroxy radical reaction rates. Kinetic model validations are reported, and the current model reproduces the ignition delay times of the C3 and C4 alcohols well. Variations in reactivity over a wide range of temperatures and other operating conditions are also well predicted by the current model. Recent ignition delay time measurements from a rapid compression machine of neat iso-propanol and iso-butanol [Cheng et al., Proc. Combust Inst. (2020)] and blends with a research grade gasoline [Goldsborough et al., Proc. Combust Inst. (2020)] at elevated pressure (20–40 bar) and intermediate temperatures (780–950 K) were used to demonstrate the accuracy of the current kinetic model at conditions relevant to boosted spark-ignition engines. The effects of alcohol blending with gasoline on the autoignition behavior are discussed. The current model captures the suppression of reactivity in the low-temperature and negative-temperature-coefficient (NTC) region when either isopropanol and isobutanol are added to a research grade gasoline. Sensitivity and reaction flux analysis were performed to provide insights into the relevant fuel chemistry of the C3-C4 alcohols. 相似文献
47.
Mulet X Kaasgaard T Conn CE Waddington LJ Kennedy DF Weerawardena A Drummond CJ 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):18415-18423
Three nucleoside lipids have been synthesized: 3'-oleoylthymidine, 3',5'-dioleoylthymidine, and 3'-phytanoylthymidine. Differential scanning calorimetry and X-ray diffraction have been employed to characterize the physical properties of these neat lipids. Polarizing optical microscopy, small-angle X-ray scattering, and cryo-transmission electron microscopy techniques have been used to investigate the phase behavior in aqueous systems. Both oleoyl-based nucleoside lipids adopted a lamellar crystalline phase in the neat form at room temperature, and the phytanoyl derivative exhibited a fluid isotropic phase. Under excess water conditions, the presence of one branched (phytanoyl) or one unsaturated (oleoyl) chain promoted the formation of a liquid-crystalline lamellar phase at physiological temperatures. In contrast, the 3',5'-dioleoylthymidine derivative is nonswelling and does not exhibit lyotropic liquid-crystalline phase behavior. The nucleolipids' propensity for DNA-type binding and recognition has been evaluated by using a monolayer system to measure surface pressure-area isotherms in a Langmuir trough and indicates that the nucleoside base is available for nonspecific hydrogen bonding in the monolayer liquid expanded state for the single-chain nucleolipids but not for the dual-chain amphiphile. 相似文献
48.
Martineau C Engelke F Taulelle F 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,212(2):311-319
The effects of multiple-resonance heteronuclear decoupling under magic angle spinning (MAS) on the resolution of one-dimensional 19F and 31P and various two-dimensional MAS NMR spectra and on the residual non-refocusable coherence lifetimes in fluorinated aluminophosphate AlPO4-CJ2, i.e. a compound that contains numerous highly abundant nuclei but no homonuclear spin bath, has been investigated. The design of the four-channel (1H, 19F, 27Al, 31P) MAS probe used for this study is first described. 1H and 1H–27Al double-resonance decouplings allows lengthening the optimized transverse relaxation and increasing the resolution in the 19F and 31P dimensions. Under the application of multi-nuclear decoupling, a two-dimensional 19F–31P CP-HETCOR correlation spectrum for AlPO4-CJ2 is recorded with unprecedented high-resolution in the two dimensions. Moreover, because 1H-decoupling increases the 19F , it has been applied during the entire duration of the 2D NMR experiments, allowing the direct use of residual small interactions to generate 19F–19F and 19F–27Al 2D NMR correlation spectra in AlPO4-CJ2. 相似文献
49.
Regina Schmitt Patrick Mayer Benjamin Kirsch Jan Aurich Charlotte Kuhn Ralf Müller Kaushik Bhattacharya 《PAMM》2014,14(1):383-384
This work is motivated by cryogenic turning which allows end shape machining and simultaneously attaining a hardened surface due to deformation induced martensitic transformations. To study the process on the microscale, a multivariant phase field model for martensitic transformations in conjunction with a crystal plastic material model is introduced. The evolution of microstructure is assumed to follow a time-dependent Ginzburg-Landau equation. To solve the field equations the finite element method is used. Time integration is performed with Euler backward schemes, on the global level for the evolution equation of the phase field, and on the element level for the crystal plastic material law. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
50.
Charlotte Kestner 《Archive for Mathematical Logic》2014,53(5-6):593-620
In this paper we prove that in modules, MS-measurability (in the sense of Macpherson–Steinhorn) depends on being able to define a measure function on the p.p. definable subgroups. We give a classification of abelian groups in terms of measurability. Finally we discuss the relation with \({\mathbb{Q}[t]}\) -valued measures. 相似文献