全文获取类型
收费全文 | 7555篇 |
免费 | 269篇 |
国内免费 | 52篇 |
专业分类
化学 | 5617篇 |
晶体学 | 71篇 |
力学 | 191篇 |
综合类 | 1篇 |
数学 | 941篇 |
物理学 | 1055篇 |
出版年
2023年 | 54篇 |
2022年 | 78篇 |
2021年 | 150篇 |
2020年 | 142篇 |
2019年 | 125篇 |
2018年 | 102篇 |
2017年 | 86篇 |
2016年 | 208篇 |
2015年 | 184篇 |
2014年 | 225篇 |
2013年 | 380篇 |
2012年 | 532篇 |
2011年 | 582篇 |
2010年 | 328篇 |
2009年 | 241篇 |
2008年 | 488篇 |
2007年 | 509篇 |
2006年 | 516篇 |
2005年 | 504篇 |
2004年 | 425篇 |
2003年 | 350篇 |
2002年 | 278篇 |
2001年 | 100篇 |
2000年 | 80篇 |
1999年 | 71篇 |
1998年 | 68篇 |
1997年 | 76篇 |
1996年 | 117篇 |
1995年 | 61篇 |
1994年 | 64篇 |
1993年 | 65篇 |
1992年 | 46篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 25篇 |
1988年 | 40篇 |
1987年 | 25篇 |
1986年 | 32篇 |
1985年 | 64篇 |
1984年 | 39篇 |
1983年 | 25篇 |
1982年 | 50篇 |
1981年 | 27篇 |
1980年 | 22篇 |
1979年 | 26篇 |
1978年 | 32篇 |
1977年 | 28篇 |
1976年 | 22篇 |
1975年 | 19篇 |
1974年 | 22篇 |
排序方式: 共有7876条查询结果,搜索用时 15 毫秒
201.
Amanda B. Lima Eric O. Faria Rodrigo H. O. Montes Rafael R. Cunha Eduardo M. Richter Rodrigo A. A. Munoz Wallans T. P. dos Santos 《Electroanalysis》2013,25(7):1585-1588
The electrochemical oxidation of ibuprofen at a boron‐doped diamond electrode (BDDE) and its voltammetric determination is reported for the first time. A well‐defined oxidation peak was observed at around 1.6 V in 0.1 mol L?1 H2SO4 solution with 10 % (v/v) ethanol at the BDDE surface activated by either cathodic or anodic pretreatments. A differential‐pulse voltammetric method for the determination of ibuprofen in pharmaceutical formulations was optimized with a detection limit of 5 µmol L?1 and compared with the British Pharmacopeia method. 相似文献
202.
The performance of a range density functional theory functionals combined in a quantum mechanical (QM)/molecular mechanical (MM) approach was investigated in their ability to reliably provide geometries, electronic distributions, and relative energies of a multicentered open‐shell mechanistic intermediate in the mechanism 8R–Lipoxygenase. With the use of large QM/MM active site chemical models, the smallest average differences in geometries between the catalytically relevant quartet and sextet complexes were obtained with the B3LYP* functional. Moreover, in the case of the relative energies between 4II and 6II , the use of the B3LYP* functional provided a difference of 0.0 kcal mol–1. However, B3LYP± and B3LYP also predicted differences in energies of less than 1 kcal mol–1. In the case of describing the electronic distribution (i.e., spin density), the B3LYP*, B3LYP, or M06‐L functionals appeared to be the most suitable. Overall, the results obtained suggest that for systems with multiple centers having unpaired electrons, the B3LYP* appears most well rounded to provide reliable geometries, electronic structures, and relative energies. © 2012 Wiley Periodicals, Inc. 相似文献
203.
Sekar P Greyson EC Barton JE Odom TW 《Journal of the American Chemical Society》2005,127(7):2054-2055
This communication describes a new synthetic approach to one- (1D) and two-dimensional (2D) NbSe2 nanoscale materials using soft chemical methods. Our one-pot synthesis provides a direct route to control the morphology of nanostructures that can exhibit complex electronic properties, and can produce layered, nanocrystalline materials in high yield. 相似文献
204.
Antoine Tiya Djowe Samuel Laminsi Daniel Njopwouo Elie Acayanka Eric M. Gaigneaux 《Plasma Chemistry and Plasma Processing》2013,33(4):707-723
Smectite clay from Sabga (west-Cameroon) was treated in aqueous suspension by gliding arc plasma to modify its surface properties. The evolution of the modifications was followed with the exposure time and post-discharge duration using Fourier transformed infra red spectroscopy and scanning electron microscopy. X-ray diffraction and nitrogen physisorption analyses were also performed to evaluate if both crystalline and textural properties of the material are affected by the treatment. The results obtained show that the plasma treatment causes the breakdown of structural bounds at the clay surface and induces the formation of new hydroxyl groups (Si–OH and Al–OH) on the clay edges. Crystallinity, sheet structure and textural properties are not significantly affected by the plasma treatment. However, it should be noted that an intensive treatment of the clay lowers the pH of the suspension, which subsequently induces an acid attack of the clay. In such case, the specific surface area of the clay increases. This study demonstrates that gliding arc plasma treatments can be used to activate clay minerals for environmental application. 相似文献
205.
King'ondu CK Iyer A Njagi EC Opembe N Genuino H Huang H Ristau RA Suib SL 《Journal of the American Chemical Society》2011,133(12):4186-4189
Short reaction times and morphology control in the synthesis of inorganic materials under nonthermal conditions remain a challenge. Herein we report a rapid, self-templating, and nonthermal method based on ultraviolet light to prepare metal oxide hierarchical structures. With this method, the morphology of the metal oxides was controlled readily without using templates. 相似文献
206.
Graham M. Lee Eric G. Bowes Christopher M. Vogels Andreas Decken Stephen A. Westcott 《Tetrahedron》2019,75(14):2106-2112
In this study we have studied the synthesis, characterization and catalytic activity of phosphinocopper(I) complexes [Cu(PPh3)3(NCCH3)][B(O2C6H4-4-R)2] (3a: R?=?H; 3b: R?=?Me; 3c: R?=?NO2) and [Cu(PPh3)3(NCCH3)][B(O2C6H3-3,5-di-tBu)2] (3d) containing weakly coordinating arylspiroborate ligands bearing various electronic and sterically defined characteristics. All new compounds have been characterized fully including single crystal X-ray diffraction studies for 3a and 3c and confirm that the arylspiroborate ligands do not coordinate to the copper atoms. Using these new metal complexes as precatalysts in the cyclisation of short chain alkynoic acids gave the corresponding exo-dig cyclic lactones exclusively. 相似文献
207.
The structures of aggregates formed in aqueous solutions of an anionic surfactant, sodium dodecyl sulfate (SDS), with the addition of a cationic hydrotropic salt, p-toluidine hydrochloride (PTHC), have been investigated by small angle neutron scattering (SANS). The SANS spectra exhibit a pronounced peak at low salt concentration, indicating the presence of repulsive intermicellar interactions. Model-independent real space information about the structure is obtained from a generalized indirect Fourier transformation (GIFT) technique in combination with a suitable model for the interparticle structure factor. The interparticle interaction is captured using the rescaled mean spherical approximation (RMSA) closure relation and a Yukawa form of the interaction potential. Further quantification of the geometrical parameters of the micelles was achieved by a complete fit of the SANS data using a prolate ellipsoidal form factor and the RMSA structure factor. The present study shows that PTHC induces a decrease in the fractional charge of the micelles due to adsorption at the micellar surface and consequent growth of the SDS micelles from nearly globular to rodlike as the concentration of PTHC increases. 相似文献
208.
Host 1 was designed and synthesized as a fluorescent sensor for 2,3-bisphosphoglycerate (BPG, 3). The design features a tris-functionalized triethylbenzene core to preorganize binding groups. The three cationic moieties, a tetra-N-oxide bipyridine-europium complex and two ammonium groups, were included to complement the three anionic functionalities on the guest. Beyond acting as a binding site, the europium complex was used to signal binding of the guest through modification of the charge transfer emission. A 1:1 complex with BPG was determined in 50 % methanol/acetonitrile with a K(a) of 6.7 x 10(5) mol(-1) by monitoring the reduction of the fluorescence signal upon guest addition. In the titration of related glycolytic intermediates lacking a second phosphate (4-6) into host 1, 2:1 host to guest binding was observed. Similarly, control compound 2, which lacks the ammonium groups, binds BPG and 4-6 in a 2:1 fashion. Also, phenylphosphate 7 binds to host 1 in a 1:1 stoichiometry with a K(a) over three times less than 3. 相似文献
209.
Steve Scheiner Paul Redfern Eric A. Hillenbrand 《International journal of quantum chemistry》1986,29(4):817-827
Results of quantum mechanical calculations are presented that suggest a number of mechanisms whereby protons may be shifted from one group to another along an H bond. The first factor to be considered is a stretching of the bond that drastically raises the energy barrier to transfer. It is possible to predict barriers for an arbitrary system based only on results for a simple system and knowledge of the relevant bond length in the isolated subsystems. Factors that increase the intrinsic basicity of the B group in A-H-B lead not only to a lowering of the energy of the A-HB state relative to AH-B but also to a reduction in the barrier to transfer of the proton from A to B. Ions in the vicinity of the H bond exert a powerful influence and can shift the proton to the less basic group across a gradient of several pK units. Rather than shielding the proton from the external ion, the H bond acts instead to amplify the effects of the electric field. Reorientation of the A and B groups relative to one another, i.e., bends of the H bond, also produce surprisingly large changes in the relative energies of the AH-B and A-HB states. Such bends are capable of pushing the proton across to the normally less basic group, providing a mechanism of coupling conformational changes to proton ‘pumping’ activity. It is found that the high and low pH states of a given H bond can have dramatically differnt relative populations of the AH-B and A-HB configurations. These observations are explained in terms of fundamental concepts involving electrostatic interaction energies. 相似文献
210.
Charles Eric Brown Charles A. Wilkie Jeffrey Smukalla Robert B. Cody James A. Kinsinger 《Journal of polymer science. Part A, Polymer chemistry》1986,24(6):1297-1311
The reaction of red phosphorus with poly(methyl methacrylate) under pyrolysis conditions was investigated with a number of physical techniques. A random methyl methacrylate/cyclic anhydride copolymer is formed from atatic PMMA, whereas a random methyl methacrylate/methacrylic acid copolymer is obtained with isotactic PMMA. The backbones of both these copolymers are more stable toward depolymerization than that of PMMA. The flame-retardant activity of red phosphorus with PMMA may arise in part from stabilization of the polymer toward depolymerization via modification of the sidechains. 相似文献