全文获取类型
收费全文 | 834篇 |
免费 | 0篇 |
国内免费 | 5篇 |
专业分类
化学 | 695篇 |
力学 | 16篇 |
数学 | 79篇 |
物理学 | 49篇 |
出版年
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 7篇 |
2016年 | 10篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 20篇 |
2012年 | 34篇 |
2011年 | 55篇 |
2010年 | 25篇 |
2009年 | 13篇 |
2008年 | 40篇 |
2007年 | 44篇 |
2006年 | 48篇 |
2005年 | 45篇 |
2004年 | 47篇 |
2003年 | 37篇 |
2002年 | 29篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 10篇 |
1998年 | 15篇 |
1997年 | 19篇 |
1996年 | 19篇 |
1995年 | 14篇 |
1994年 | 8篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 16篇 |
1990年 | 16篇 |
1989年 | 8篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 5篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 13篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1977年 | 8篇 |
1976年 | 9篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 14篇 |
1972年 | 3篇 |
1971年 | 4篇 |
1967年 | 3篇 |
排序方式: 共有839条查询结果,搜索用时 15 毫秒
121.
Preat J Jacquemin D Wathelet V André JM Perpète EA 《The journal of physical chemistry. A》2006,110(26):8144-8150
The UV absorption spectra of more than 80 substituted coumarins and chromones have been investigated with the PCM-TD-DFT theoretical scheme using three hybrid functionals (O3LYP, B3LYP, and PBE0) and taking into account methanol or ethanol solvation effects. For most of the studied derivatives, there are at least two allowed excited states presenting a strong oscillator strength in the UV region. The first allowed excitation is associated to a HOMO-LUMO transition whereas the second corresponds to a transition from the HOMO-1 to the LUMO. Both involve a charge transfer from the benzenic cycle to the pyranone moiety. Statistically treating the PBE0 results allows a prediction of the lambda(max) with small standard deviations: in methanol, 6 nm (0.07 eV) for the first excitation (lambda(max)(1)) and 5 nm (0.08 eV) for the second one (lambda(max)(2)), whereas in ethanol 6 nm (0.08 eV) for (lambda(max)(1)) and 6 nm (0.13 eV) for (lambda(max)(2)). 相似文献
122.
123.
Morin B Bourhis JM Belle V Woudstra M Carrière F Guigliarelli B Fournel A Longhi S 《The journal of physical chemistry. B》2006,110(41):20596-20608
We used site-directed spin-labeling electron paramagnetic resonance (EPR) spectroscopy to study the induced folding of the intrinsically disordered C-terminal domain of measles virus nucleoprotein (N(TAIL)). Four single-site N(TAIL) mutants (S407C, S488C, L496C, and V517C), located in three conserved regions, were prepared and labeled with a nitroxide paramagnetic probe. We could monitor the gain of rigidity that N(TAIL) undergoes in the presence of either the secondary structure stabilizer 2,2,2-trifluoroethanol (TFE) or one of its physiological partners, namely, the C-terminal domain (XD) of the viral phosphoprotein. The mobility of the spin label grafted at positions 488, 496, and 517 was significantly reduced upon addition of XD, contrary to that of the spin label bound to position 407, which was unaffected. Furthermore, the EPR spectra of spin-labeled S488C and L496C bound to XD in the presence of 30% sucrose are indicative of the formation of an alpha-helix in the proximity of the spin labels. Such an alpha-helix had been already identified by previous biochemical and structural studies. Using TFE we unveiled a previously undetected structural propensity within the N-terminal region of N(TAIL) and showed that its C-terminal region "resists" gaining structure even at high TFE concentrations. Finally, we for the first time showed the reversibility of the induced folding process that N(TAIL) undergoes in the presence of XD. These results highlight the suitability of site-directed spin-labeling EPR spectroscopy to identify protein regions involved in binding and folding events, while providing insights at the residue level. 相似文献
124.
Gabriel R. Barrenechea Gabriel N. Gatica Jean-Marie Thomas 《Numerical Functional Analysis & Optimization》2013,34(1-2):7-32
We apply the boundary integral equation method and a primal mixed finite element approach to study the weak solvability and Galerkin approximations of linear interior transmission problems arising in potential theory and elastostatics. The existence and uniqueness of solution of the resulting weak formulations and of the associated discrete schemes are derived by using the classical theory for variational problems with constraints. Suitable finite element subspaces of Lagrange type satisfying the compatibility conditions are utilized for defining the Galerkin scheme. The error analysis and corresponding rates of convergence are also provided. 相似文献
125.
Dr. Jean-François Ayme Dr. Sébastien Dhers Prof. Dr. Jean-Marie Lehn 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12584-12592
Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self-sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the CuI complex. 相似文献
126.
We report a simple and highly stereocontrolled strategy toward the total synthesis of isoprostanes based on a bicyclic alpha,beta-epoxy ketone intermediate 6. Bicyclo[3.3.0]octene scaffold permitted stereodirection of reagents allowing stereoselective epoxidation, diastereoselective ketone reduction, and regioselective epoxide opening otherwise not accessible with a simple cyclopentene framework. 相似文献
127.
The epimeric sesquiterpene alcohols (14R)-beta-oplopenol and (14S)-beta-oplopenolwere obtained by LiAlH(4) reduction of beta-oplopenone. The complete (1)H- and (13)C-NMR assignments of these two new sesquiterpene alcohols have been made using 1D and 2D NMR techniques, including COSY, NOESY, HSQC, HMBC experiments. 相似文献
128.
Polyunsaturated fatty acids (PUFAs) are important constituents in all organisms. They fulfil many functions, ranging from modulating the structure of membranes to acting as precursors of physiologically important molecules, such as the prostaglandins, which for a long time were the most prominent cyclic PUFA metabolites. However, since the beginning of the 1990s a large variety of cyclic metabolites have been discovered that form under autoxidative conditions in vivo to a much larger extent than do prostaglandins. These compounds--isoprostanes, neuroprostanes, phytoprostanes, and isofurans--proved subsequently to be ubiquitous in nature. They display a wide range of biological activities, and isoprostanes have become the currently most reliable indicators of oxidative stress in humans. In a relatively short time, the structural variety, properties, and applications of the autoxidatively formed cyclic PUFA derivatives have been uncovered. 相似文献
129.
De Schutter DP Saison D Delvaux F Derdelinckx G Rock JM Neven H Delvaux FR 《Journal of chromatography. A》2008,1179(2):75-80
The aim of this study was to create a simple, solventless technique without derivatisation in order to analyze a broad range of volatiles in beer wort. A method was developed using headspace solid-phase microextraction coupled with gas chromatography and mass spectrometry. The procedure was optimised by selection of the appropriate fibre and optimisation of extraction temperature, extraction time, and salting-out. The detection limits were well below the actual wort concentrations of the selected volatiles, ranging from 12 ng/l for linalool to 0.53 microg/l for furfural. Moreover, the procedure showed a good linearity and was applied to the analysis of wort samples taken from a wort boiling process in an industrial brewery. 相似文献
130.
Nardello-Rataj V Caron L Borde C Aubry JM 《Journal of the American Chemical Society》2008,130(45):14914-14915
A series of "Balanced Catalytic Surfactants" (BCS) [(Cn)2N(C1)2]2MoO4 (n = 8, 9, 10, 12) based on amphiphilic double-tailed quaternary ammonium with molybdate as a counterion has been developed for the dark singlet [4 + 2] cyclooxygenation of organic substrates in three-liquid-phase microemulsion systems. These cationic surfactants form three-liquid-phase microemulsion systems at room temperature in the presence of an appropriate organic solvent and water without addition of any cosurfactant or electrolyte. Comparative peroxidation of rubrene points out the specific advantages of these three-phase media over phase transfer catalysis in two phase systems and on conventional one-phase microemulsions based on sodium molybdate: (i) only three constituents, (ii) low amounts of surfactants, (iii) insensitivity to water dilution, (iv) fast separation of the three phases, (v) straightforward recovery of the product and the surfactant from the oil and microemulsion phases, respectively. The preparative peroxidation of alpha-terpinene and 1,4,5-trimethylnaphtalene was performed in the ternary systems [(C8)2N(C1)2]2MoO4/water/tert-butyl acetate or benzene. The reusability of the catalyst, the catalytic nature of the BCS, and the ability of the systems to oxidize poorly reactive substrates were demonstrated showing the broadness of the applicability of such systems. 相似文献