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991.
The total experimental electron density rho(r), its Laplacian inverted delta(2)rho(r), the molecular dipole moment, the electrostatic potential phi(r), and the intermolecular interaction energies have been obtained from an extensive set of single-crystal X-ray diffracted intensities, collected at T = 70(1) K, for the fungal metabolite austdiol (1). The experimental results have been compared with theoretical densities from DFT calculations on the isolated molecule and with fully periodic calculations. The crystal structure of (1) consists of zigzag ribbons extended along one cell axis and formed by molecules connected by both OH...O and CH...O interactions, while in a perpendicular direction, adjacent molecules are linked by short CH...O intermolecular contacts. An extensive, quantitative study of all the intra- and intermolecular H...O interactions, based not only on geometrical criteria, but also on the topological analysis of rho(r), as well as on the evaluation of the pertinent energetics, allowed us (i) to assess the mutual role of OH...O and CH...O interactions in determining molecular conformation and crystal packing; (ii) to identify those CH...O contacts which are true hydrogen bonds (HBs); (iii) to determine the relative hydrogen bond strengths. An experimental, quantitative evidence is given that CH...O HBs are very similar to the conventional OH...O HBs, albeit generally weaker. The comparison between experimental and theoretical electric dipole moments indicates that a noticeable charge rearrangement occurs upon crystallization and shows the effects of the mutual cooperation of HBs in the crystal. The total intermolecular interaction energies and the electrostatic energy contribution obtained through different theoretical methods are reported and compared with the experimental results. It is found that the new approach proposed by Spackman, based on the use of the promolecular charge density to approximate the penetration contribution to intermolecular electrostatic energies, predicts the correct relative electrostatic interaction energies in most of the cases.  相似文献   
992.
Fiorentino G  Spaccini R  Piccolo A 《Talanta》2006,68(4):1135-1142
A selective removal of humic constituents involved in ester groups was conducted by a boron trifluoride-methanol transesterification reaction after removal of structurally unbound lipids. An analytical separation of subfractions containing specific classes of compound liberated from the humic matrix simplifies their identification by gas chromatography-mass spectrometry. We compared the traditional liquid-liquid separation into phenolic and aliphatic fractions with the modern and versatile fractionation technique using solid-phase extraction (SPE) on aminopropyl-bonded phases. Our results showed that both methods ensured separation of the same compounds, such as di- and tri-hydroxyalkanoic acids, α-, β- and ω-hydroxy fatty acids, alkanoic acids, α,ω-alkanedioic acids, n-alkanols, phenolic acids and sterols. Moreover, the SPE method not only provided a larger recovery of compounds, but involved smaller sample and solvent requirements, and larger ease and rapidity of sample handling than the traditional liquid-liquid separation. The SPE method should be thus recommended in structural studies of natural organic matter.  相似文献   
993.
The orientational order parameters and conformational behavior of five relatively large rodlike molecules, biphenyl, trans-stilbene, 1,3-diphenyl-butadiene, 1,3,5-diphenyl-hexatriene, and 1,3,5,7-diphenyl-octatetraene, dissolved in the thermotropic liquid crystal ZLI-1167, have been studied using an integrated approach combining (13)C NMR measurements and quantum mechanical computations of carbon chemical shift tensors. Besides biphenyl, the phenyl moiety of all structures has been found to have a high rotational mobility in the temperature range of the present experiments. The rank-two order parameter in the nematic phase is found to increase steadily from the shortest to the longest term of the series at any temperature within the nematic range. The molecular biaxiality order parameter is found to be small and essentially constant with temperature, giving further support to the common assumption of effective uniaxiality for these probes.  相似文献   
994.
This paper deals with the lack of compactness in the nonlinearelliptic problem – u + u = |u|p–2u in , u > 0in , u = 0 on , when is un unbounded domain in n and 2 <p < 2n/(n–2). In particular, a domain is provided where non-converging Palais–Smale sequences existat every energy level. Nevertheless, it is proved that the problemhas infinitely many solutions on .  相似文献   
995.
Let R be a real closed field and let X be an affine algebraic variety over R. We say that X is universally map rigid (UMR for short) if, for each irreducible affine algebraic variety Z over R, the set of nonconstant rational maps from Z to X is finite. A bijective map from an affine algebraic variety over R to X is called weak change of the algebraic structure of X if it is regular and φ−1 is a Nash map, which preserves nonsingular points. We prove the following rigidity theorem: every affine algebraic variety over R is UMR up to a weak change of its algebraic structure. Let us introduce another notion. Let Y be an affine algebraic variety over R. We say that X and Y are algebraically unfriendly if all the rational maps from X to Y and from Y to X are trivial, i.e., Zariski locally constant. From the preceding theorem, we infer that, if dim (X)≥1, then there exists a set of weak changes of the algebraic structure of X such that, for each t,sR with ts, and are algebraically unfriendly. This result implies the following expected fact: For each (nonsingular) affine algebraic variety X over R of positive dimension, the natural Nash structure of X does not determine the algebraic structure of X. In fact, the moduli space of birationally nonisomorphic (nonsingular) affine algebraic varieties over R, which are Nash isomorphic to X, has the same cardinality of R. This result was already known under the special assumption that R is the field of real numbers and X is compact and nonsingular. The author is a member of GNSAGA of CNR, partially supported by MURST and European Research Training Network RAAG 2002–2006 (HPRN–CT–00271).  相似文献   
996.
A synthetic route toward new 8,8-difluoro-1,6-naphthyridine-5,7-diones, which are of interest as new building blocks in pharmaceutical chemistry, is described. The key steps include a copper-mediated cross-coupling of ethyl bromodifluoroacetate and 2-bromo-3-cyanopyridine, followed by hydrolysis of the nitrile function and subsequent cyclization.  相似文献   
997.
998.
In this paper, we analyze the stability of a homogeneous self-gravitating plasma, having a non-zero resistivity. This study provides a generalization of the Jeans paradigm for determining the critical scale above which gravitational collapse is allowed.We start by discussing the stability of an ideal self-gravitating plasma embedded in a constant magnetic field. We outline the existence of an anisotropic feature of the gravitational collapse. In fact, while in the plane orthogonal to the magnetic field the Jeans length is enhanced by the contribution of the magnetic pressure, outside this plane perturbations are governed by the usual Jeans criterion. The anisotropic collapse of a density contrast is sketched in detail, suggesting that the linear evolution provides anisotropic initial conditions for the non-linear stage, where this effect could be strongly enforced.The same problem is then faced in the presence of non-zero resistivity and the conditions for the gravitational collapse are correspondingly extended. The relevant feature emerging in this resistive scenario is the cancelation of the collapse anisotropy in weakly conducting plasmas. In this case, the instability of a self-gravitating resistive plasma is characterized by the standard isotropic Jeans length in any directions. The limit of very small resistivity coefficient is finally addressed, elucidating how reminiscence of the collapse anisotropy can be found in the different values of the perturbation frequency inside and outside the plane orthogonal to the magnetic field.  相似文献   
999.
A Agnesi  L Carrà  R Piccoli  F Pirzio  G Reali 《Optics letters》2012,37(17):3612-3614
An Nd:YVO4 amplifier consisting of two modules end pumped at 808?nm at 30?W total absorbed power has been designed for efficient, diffraction-limited amplification of ultrafast pulses from low-power seeders. We investigated amplification with a 50?mW, 7?ps Nd:YVO4 oscillator, a 2?mW, 15?ps Yb fiber laser, and a 30?mW, 300?fs Nd:glass laser. Output power as high as 9.5?W with 8?ps pulses was achieved with the 250?MHz vanadate seeder, whereas the 20?MHz fiber laser was amplified to 6?W. The femtosecond seeder allowed extracting Fourier-limited 4?ps pulses at 7?W output power. To our knowledge, these are the shortest pulses from any Nd:YVO4 laser device with at least 7?W output power. This suggests a novel approach to exploit the gain bandwidth of vanadate amplifiers with high output power levels. Such amplifier technology promises to offer an interesting alternative to high-power thin disk oscillators at few picoseconds duration, as well as to regenerative amplifiers with low-repetition-rate fiber seeders.  相似文献   
1000.
A waterborne latex-based technique, in which functionalized laponite is attached to PS and acrylic latex particles, is used to prepare films containing up to 50 wt% laponite. At high laponite contents this leads to a cellular arrangement of the laponite-rich layers, concentrated at the latex particle interfaces. MDSC shows that a significant proportion of the organic matrix does not contribute to the glass transition. However, this “rigid” matrix fraction arises from intercalation of the laponite stacks, and cannot account for the large increases in global stiffness in the rubbery state (T > Tg) on laponite addition. The mechanical response for T > Tg is therefore discussed in terms of a four-phase structure, in which the intercalated laponite stacks embedded in a matrix with a relatively high rubbery modulus form a cellular structure, which is in turn embedded in a matrix whose modulus is closer to that of the bulk polymer. The importance of the cellular arrangement is underlined by the much lower rubbery modulus observed by DMA in specimens produced by deforming the original films in plane strain compression to produce oriented textures with relatively little connectivity between the laponite-rich layers.  相似文献   
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