全文获取类型
收费全文 | 5401篇 |
免费 | 275篇 |
国内免费 | 56篇 |
专业分类
化学 | 3738篇 |
晶体学 | 35篇 |
力学 | 149篇 |
数学 | 961篇 |
物理学 | 849篇 |
出版年
2023年 | 49篇 |
2022年 | 103篇 |
2021年 | 143篇 |
2020年 | 131篇 |
2019年 | 100篇 |
2018年 | 102篇 |
2017年 | 91篇 |
2016年 | 195篇 |
2015年 | 187篇 |
2014年 | 229篇 |
2013年 | 379篇 |
2012年 | 347篇 |
2011年 | 471篇 |
2010年 | 311篇 |
2009年 | 249篇 |
2008年 | 349篇 |
2007年 | 372篇 |
2006年 | 292篇 |
2005年 | 255篇 |
2004年 | 225篇 |
2003年 | 174篇 |
2002年 | 173篇 |
2001年 | 81篇 |
2000年 | 54篇 |
1999年 | 64篇 |
1998年 | 40篇 |
1997年 | 49篇 |
1996年 | 54篇 |
1995年 | 38篇 |
1994年 | 31篇 |
1993年 | 35篇 |
1992年 | 33篇 |
1991年 | 13篇 |
1990年 | 19篇 |
1989年 | 15篇 |
1988年 | 15篇 |
1987年 | 19篇 |
1986年 | 16篇 |
1985年 | 28篇 |
1984年 | 30篇 |
1983年 | 20篇 |
1982年 | 21篇 |
1981年 | 14篇 |
1979年 | 16篇 |
1978年 | 11篇 |
1977年 | 10篇 |
1975年 | 9篇 |
1974年 | 9篇 |
1973年 | 17篇 |
1972年 | 10篇 |
排序方式: 共有5732条查询结果,搜索用时 15 毫秒
841.
842.
We report a DFT study on the self‐assembly of the fullerene derivative PCBM on the Au(111) surface. Recent STM experiments (Angew. Chem. 2007 , 119, 8020–8023[1]) show a coverage‐dependent transition of the adsorption and self‐assembly of PCBM on this surface. To understand the origin of this observation, we compute the geometries and relative energies of ten PCBM dimers and four tetramers. The calculations show that the self‐assembly of PCBM at high coverage is mainly controlled by hydrogen bonding between the PCBM tails. Due to the large size of the fullerene cage, the hydrogen bonds are formed far away from the surface; hence they are very similar to those found in the gas phase. This picture successfully explains the observed site‐insensitive adsorption at high coverage and the 2D arrangement of PCBM on the surface. 相似文献
843.
Juan Manuel Ortiz‐Sánchez Ricard Gelabert Dr. Miquel Moreno Dr. José M. Lluch Prof. 《Chemphyschem》2008,9(14):2068-2076
The two isoelectronic bipyridyl derivatives [2,2′‐bipyridyl]‐3,3′‐diamine and [2,2′‐bipyridyl]‐3,3′‐diol are experimentally known to undergo very different excited‐state double‐proton‐transfer processes, which result in fluorescence quantum yields that differ by four orders of magnitude. In a previous study, these differences were explained from a theoretical point of view, because of topographical features in the potential energy surface and the presence of conical intersections (CIs). Here, we analyze the photochemical properties of a new molecule, [2,2′‐bipyridyl]‐3‐amine‐3′‐ol [BP(OH)(NH2)], which is, in fact, a hybrid of the former two. Our density functional theory (DFT), time‐dependent DFT (TDDFT), and complete active space self‐consistent field (CASSCF) calculations indicate that the double‐proton‐transfer process in the ground and first singlet π→π* excited state in BP(OH)(NH2) presents features that are between those of their “parents”. The presence of two CIs and the role they may play in the actual photochemistry of BP(OH)(NH2) and other bipyridyl derivatives are also discussed. 相似文献
844.
Trujillo C Lamsabhi AM Mó O Yáñez M Salpin JY 《Organic & biomolecular chemistry》2008,6(20):3695-3702
The structures and relative stabilities of the complexes formed by uracil and its sulfur derivatives, namely, 2-thio-, 4-thio, and 2,4-dithio-uracil when interacting with Ca(2+) in the gas phase have been analyzed by means of density functional theory (DFT) calculations carried out at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) level. For uracil and 2,4-dithiouracil, where the two basic sites are the same, Ca(2+) attachment to the heteroatom at position 4 is preferred. However, for the systems where both types of basic centers, a carbonyl or a thiocarbonyl group, are present, Ca(2+)-oxygen association is favored. The most stable complexes correspond to structures with Ca(2+) bridging between the heteroatom at position 2 of the 4-enol (or the 4-enethiol) tautomer and the dehydrogenated ring nitrogen, N3. The enhanced stability of these enolic forms is two-fold, on the one hand Ca(2+) interacts with two basic sites and on the other triggers a significant aromatization of the ring. Besides, Ca(2+) association has a clear catalytic effect on the tautomerization processes which connect the oxo-thione forms with the enol-enethiol tautomers. Hence, although the enol-enethiol tautomers of uracil and its thio derivatives should not be observed in the gas phase, the corresponding Ca(2+) complexes are the most stable species and should be accessible, because the tautomerization barriers are smaller than the Ca(2+) binding energies. 相似文献
845.
Benbrahim N Rahmouni A Ruiz-López MF 《Physical chemistry chemical physics : PCCP》2008,10(36):5624-5632
alpha-Aminophosphonic acids are analogues of natural alpha-aminoacids and very promising agents for use in various pharmaceutical applications. However, in contrast to the numerous theoretical investigations on the structure of natural alpha-aminoacids, only very few studies on alpha-aminophosphonic acids have been performed. In the present work, we report a detailed investigation of the simplest compound, the glycine analogue aminomethylphosphonic acid (AMPA), by means of quantum mechanical calculations at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) and MP2/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) levels. We focus on the structure of the neutral species looking at the evolution of non-ionized and ionized forms from gas phase to non-polar solvents and aqueous media. Continuum and discrete-continuum solvent models have been employed to account for the effects of the environment. The discussion is centered on: (1) the geometry and relative stability of possible conformers in gas phase and aqueous solution, (2) the free energy of tautomerization in different media, (3) the role of hydrogen bonds in liquid water, and (4) the free energy of transfer from water to a hydrophobic solvent such as cyclohexane. Systematic comparison between AMPA and Gly is performed. Though both systems exhibit many similarities, some important differences have also been found that may be explained, at least in part, by the higher acidity of phosphonic acids compared to carboxylic acids. In particular, in solvents lacking hydrogen-bond formation capability, Gly derivatives should mainly exist as non-ionized molecules while the equivalent AMPA derivatives should adopt a zwitterionic structure in media with dielectric constant above 10. This might have significant environmental or biological consequences that will need to be addressed. 相似文献
846.
A computer-controlled manifold allowing the automatic generation of concentration profiles is described. For this purpose, the sample or standard solution is placed inside a semi-closed loop to which diluent is incorporated at a given flow rate, while the solution is removed at the same flow rate and directed towards the detector. The flow manifold, which works in a similar way to the tank model, includes a membrane micropump to recirculate the solution in the semi-closed loop. For simplicity purposes in the assessment of the system, a flame atomic absorption spectrometer is used for both withdrawing liquid and detection, although the basic idea can easily be extended to other detectors. The experimental data, verified by measuring the calcium, magnesium, sodium and potassium contents of some soft drinks demonstrate that the approach is reliable and may be a basis for developing portable instruments of reduced-size. 相似文献
847.
Wavelet neural networks to resolve the overlapping signal in the voltammetric determination of phenolic compounds 总被引:1,自引:0,他引:1
Three phenolic compounds, i.e. phenol, catechol and 4-acetamidophenol, were simultaneously determined by voltammetric detection of its oxidation reaction at the surface of an epoxy-graphite transducer. Because of strong signal overlapping, Wavelet Neural Networks (WNN) were used in data treatment, in a combination of chemometrics and electrochemical sensors, already known as the electronic tongue concept. To facilitate calibration, a set of samples (concentration of each phenol ranging from 0.25 to 2.5mM) was prepared automatically by employing a Sequential Injection System. Phenolic compounds could be resolved with good prediction ability, showing correlation coefficients greater than 0.929 when the obtained values were compared with those expected for a set of samples not employed for training. 相似文献
848.
Hansjürgen Mattausch Dr. Manuel C. Schaloske Constantin Hoch Chong Zheng Arndt Simon 《无机化学与普通化学杂志》2008,634(3):491-497
Rare Earth Halides Ln4X5Z. Part 1: C and/or C2 in Ln4X5Z The compounds Ln4X5Cn (Ln = La, Ce, Pr; X = Br, I and 1.0 < n < 2.0) are prepared by the reaction of LnX3, Ln metal and graphite in sealed Ta‐ampoules at temperatures 850 °C < T < 1050 °C. They crystallize in the monoclinic space group C2/m. La4I5C1.5: a = 19.849(4) Å, b = 4.1410(8) Å, c = 8.956(2) Å, β = 103.86(3)°, La4I5C2.0: a = 19.907(4) Å, b = 4.1482(8) Å, c = 8.963(2) Å, β = 104.36(3)°, Ce4Br5C1.0: a = 18.306(5) Å, b = 3.9735(6) Å, c = 8.378(2) Å, β=104.91(2)°, Ce4Br5C1.5: a = 18.996(2) Å, b = 3.9310(3) Å, c = 8.282(7) Å, β = 106.74(1)°, Pr4Br5C1.3: a = 18.467(2) Å, b = 3.911(1) Å, c = 8.258(7) Å, β = 105.25(1)° and Pr4Br5C1.5: a = 19.044(2) Å, b = 3.9368(1) Å, c = 8.254(7) Å, β = 106.48(1)°. In the crystal structure the lanthanide metals are connected to Ln6‐octahedra centered by carbon atoms or C2‐groups. The Ln6‐octahedra are condensed via opposite edges to chains and surrounded by X atoms which interconnect the chains. A part n of isolated C‐atoms is substituted by 1‐n C2‐groups. The C‐C distances range between 1.26 and 1.40Å. In the ionic formulation (Ln3+)4(X?)5(C4?)n(C2m?)1?n·e? with 0 < n < 1 and m = 2, 4, 6 (C22?, C24? C26?), there are 1 < e? < 5 electrons centered in metal‐metal bonds. 相似文献
849.
Protein extraction from Phoenix dactylifera L. leaves, a recalcitrant material, for two-dimensional electrophoresis 总被引:1,自引:0,他引:1
This work was aimed at optimizing a protein extraction procedure for date palm (Phoenix dactylifera L.) leaves, a highly recalcitrant plant tissue for 2-DE. Five protein extraction protocols based on different protein precipitation agents (TCA/acetone vs. phenol (Ph) methods) and protein resolubilization methods (physical treatments, e.g., sonication, shaking and/or heating) were tested. Ph/SDS extraction with methanol/ammonium acetate precipitation, followed by DOC preincubation and TCA/acetone precipitation and, finally, solubilization by shaking in rehydration solution was found to be the best protein extraction method. We conclude that DOC with TCA/acetone precipitation step eliminates interfering compounds, thus allowing efficient resolubilization of date palm leaf proteins. This method could be appropriate for proteomic studies such as date palm colonization by entomopathogenic fungi. 相似文献
850.
Cantó-Mirapeix A Herrero-Martínez JM Mongay-Fernández C Simó-Alfonso EF 《Electrophoresis》2008,29(18):3858-3865
Acrylate-ester-based monoliths for CEC using peroxodisulfate as a chemical initiator were prepared. The influence of two ternary porogenic solvents on the physical and chromatographic properties of butyl acrylate monolithic stationary phases was investigated. The composition and the ratio of porogenic solvent were adjusted to obtain highly permeable rigid monoliths with adequate column efficiency. Among the prepared butyl acrylate monoliths, those polymerized from a ternary porogenic solvent of acetonitrile/ethanol/water exhibited the most promising performance with a minimum plate height for naphthalene of 10.5 microm and a bed permeability of 7.3 x 10(-14) m(2). A comparison in terms of efficiency and permeability with thermal and UV initiation using alpha,alpha'-AIBN was also performed. The resulting monolithic stationary phases were evaluated in terms of reproducibility, giving RSD values below 5.1% in the electrochromatographic properties studied. 相似文献