全文获取类型
收费全文 | 5033篇 |
免费 | 207篇 |
国内免费 | 33篇 |
专业分类
化学 | 3597篇 |
晶体学 | 17篇 |
力学 | 123篇 |
数学 | 865篇 |
物理学 | 671篇 |
出版年
2023年 | 41篇 |
2022年 | 52篇 |
2021年 | 91篇 |
2020年 | 116篇 |
2019年 | 110篇 |
2018年 | 68篇 |
2017年 | 55篇 |
2016年 | 154篇 |
2015年 | 139篇 |
2014年 | 177篇 |
2013年 | 277篇 |
2012年 | 312篇 |
2011年 | 358篇 |
2010年 | 252篇 |
2009年 | 200篇 |
2008年 | 313篇 |
2007年 | 314篇 |
2006年 | 301篇 |
2005年 | 300篇 |
2004年 | 236篇 |
2003年 | 207篇 |
2002年 | 212篇 |
2001年 | 82篇 |
2000年 | 69篇 |
1999年 | 70篇 |
1998年 | 59篇 |
1997年 | 64篇 |
1996年 | 69篇 |
1995年 | 44篇 |
1994年 | 38篇 |
1993年 | 23篇 |
1992年 | 19篇 |
1991年 | 31篇 |
1990年 | 19篇 |
1989年 | 30篇 |
1988年 | 18篇 |
1986年 | 19篇 |
1985年 | 28篇 |
1984年 | 30篇 |
1983年 | 27篇 |
1982年 | 33篇 |
1981年 | 23篇 |
1980年 | 25篇 |
1979年 | 18篇 |
1978年 | 33篇 |
1977年 | 20篇 |
1976年 | 15篇 |
1975年 | 12篇 |
1974年 | 18篇 |
1973年 | 10篇 |
排序方式: 共有5273条查询结果,搜索用时 15 毫秒
71.
A new result on products of matrices is proved in the following theorem: let Mi (i=1,2,…) be a bounded sequence of square matrices, and K be the l.u.b. of the spectral radii ρ(Mi). Then for any positive number ε there is a constant A and an ordering p(j) (j = 1,2,…) of the matrices such that . The ordering is well defined by p(j), a one-to-one mapping on the set of positive integers. In general the inequality does not hold for any ordering p(j) (a counterexample is provided); however, some sufficient conditions are given for the result to remain true irrespective of the order of the matrices. 相似文献
72.
73.
Addition of stabilized Horner-Wadsworth-Emmons (HWE) phosphonates to substituted 1,2-dioxines leads to diastereomerically pure di- and trisubstituted cyclopropanes in high yields and represents a viable alternative to ylides in the cyclopropanation reaction involving 1,2-dioxines. While yields are comparable, reaction times with these stabilized phosphonates were accelerated and the diastereoselectivity for this cyclopropanation reaction was significantly greater than for the previously reported examples employing ylides. 相似文献
74.
Jacques Darriet Marc Drillon Gérard Villeneuve Paul Hagenmuller 《Journal of solid state chemistry》1976,19(3):213-220
The cationic ordering in the oxides which crystallize with the 6H structure gives rise to Ru5+Ru5+ pairs in (Ru2O9) clusters. The magnetic properties have been analyzed on the basis of the Heisenberg-Dirac-Van Vleck model: The d electrons are localized on each Ru5+ ion and interact strongly through antiferromagnetic exchange. The susceptibility curves agree with the H.D.V.V. model. The values of the exchange integrals have been determined by fitting the experimental values. 相似文献
75.
Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures. 相似文献
76.
In diatoms, silica synthesis occurs by use of complex posttranslationally modified peptides, termed silaffins, and highly complex biological polyamine structures. Silaffin peptides have lysine residues that are modified to long-chain polyamine moieties of N-methyl derivatives of polypropylenimine to drive silica synthesis at slightly acidic pH conditions. Using polypropylenimine (PPI) and PAMAM amine-terminated dendrimers as a biomimetic analogue of the polyamine modifications of silaffins, we have demonstrated the condensation of silica nanospheres. We have shown that the dendrimers react in an amine concentration-dependent fashion yielding silica nanospheres with a distinct size distribution reminiscent of the structures produced from both the modified and nonmodified peptides extracted from diatoms. Additionally, the templates were encapsulated by the growing nanospheres and precipitated from solution in a manner similar to that previously described for the bioactive peptides and polyamines. 相似文献
77.
Single crystal EPR studies of the reduced active site of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F 总被引:1,自引:0,他引:1
Foerster S Stein M Brecht M Ogata H Higuchi Y Lubitz W 《Journal of the American Chemical Society》2003,125(1):83-93
In the catalytic cycle of [NiFe] hydrogenase the paramagnetic Ni-C intermediate is of key importance, since it is believed to carry the substrate hydrogen, albeit in a yet unknown geometry. Upon illumination at low temperatures, Ni-C is converted to the so-called Ni-L state with markedly different spectroscopic parameters. It is suspected that Ni-L has lost the "substrate hydrogen". In this work, both paramagnetic states have been generated in single crystals obtained from the [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F. Evaluation of the orientation dependent spectra yielded the magnitudes of the g tensors and their orientations in the crystal axes system for both Ni-C and Ni-L. The g tensors could further be related to the atomic structure by comparison with the X-ray crystallographic structure of the reduced enzyme. Although the g tensor magnitudes of Ni-C and Ni-L are quite different, the orientations of the resulting g tensors are very similar but differ from those obtained earlier for Ni-A and Ni-B (Trofanchuk et al. J. Biol. Inorg. Chem. 2000, 5, 36-44). The g tensors were also calculated by density functional theory (DFT) methods using various structural models of the active site. The calculated g tensor of Ni-C is, concerning magnitudes and orientation, in good agreement with the experimental one for a formal Ni(III) oxidation state with a hydride (H(-)) bridge between the Ni and the Fe atom. Satisfying agreement is obtained for the Ni-L state when a formal Ni(I) oxidation state is assumed for this species with a proton (H(+)) removed from the bridge between the nickel and the iron atom. 相似文献
78.
Sandra K Stals I Sandra P Claeyssens M Van Beeumen J Devreese B 《Journal of chromatography. A》2004,1058(1-2):263-272
N-Glycosylation of cellobiohydrolase I from the fungus Trichoderma reesei (strain Rut-C30) is studied using a combination of electrophoretic, chromatographic and mass spectrometric techniques. As four potential N-glycosylation sites and several uncharged and phosphorylated high-mannose glycans are present, a large number of glycoforms and phospho-isoforms can be expected. Isoelectric focusing both in gel and in capillary format was successfully applied for the separation of the phospho-isoforms. They were extracted in their intact form from the gel and subsequently analysed by nanospray-Q-TOF-MS, thereby making use of a powerful two-dimensional technique. Nano-LC/MS/MS on a Q-Trap MS further allowed the determination of the glycosylation sites. As a novel approach, an oxonium ion was used in precursor ion scanning for selective detection of glycopeptides containing phosphorylated high-mannose glycans. 相似文献
79.
80.
Database analysis and molecular mechanics were used to determine the conformational flexibility of tridentate scorpionate ligands. The tris(pyrazolyl)methane and tris(pyrazolyl)borate ligands act like molecular vises, opening their tripodal structure for larger metals and closing around smaller metal ions. Tris(3-tert-butylpyrazolyl)methane has significant preference for larger metal ions than its unsubstituted parent compound. Tris(pyrazolyl)methanes and tris(pyrazolyl)borates have similar conformational flexibilities. Placing sterically hindered groups on the central carbon or boron has only a minor effect on the geometry of the tris(pyrazolyl)methanes and tris(pyrazolyl)borates. However, it does influence the flexibility of the ligands, particularly when they have to open far from their ideal geometry, which commonly occurs. 相似文献