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71.
Noritaka Ohtani Makoto Nakaya Kenji Shirahata Tsuyoshi Yamashita 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2677-2686
Polystyrene-based crosslinked cationic ionomers containing ammonium or phosphonium chlorides (AxRCI and PxBuCI) were reacted with decyl methanesulfonate. The kinetic data were correlated with the swelling behavior of the ionomers and the solution viscosity of the corresponding linear ionomers. The reactivity of the ionomers was independent of the particle size of the ionomer beads, indicating no diffusion control of the reaction. The solvent and the ion content of the ionomers greatly affect the reactivity. In nonpolar solvents with a low acceptor number, AN, such as toluene, the aggregation of ionic groups with an increasing ion content reduces the reactivity. A solvent with a high value of AN, such as chloroform, led a very low reactivity independent of the ion content. Aprotic polar solvent, such as acetonitrila, promoted the dissociation of the ionic groups and furnished a relatively high reactivity independent of the ion content. Several catalytic substitution reactions were carried out under liquid-solid-solid triphase conditions. The kinetic results were accounted for in terms of slow nucleophile transport and fast chemical reaction within the ionomer particles. © 1994 John Wiley & Sons, Inc. 相似文献
72.
The palladium-catalyzed regio- and diastereo-selective allylic alkylation of allyl acetates with carbon nucleophiles occurred. The stereochemistry was highly controlled by the palladium catalyst with 2-(diphenylphosphino)benzoic acid as the ligand, and vicinal quaternary and tertiary carbon centers were constructed. 相似文献
73.
Akihiko Kanazawa Tomiki Ikeda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3003-3011
Polyesters were prepared which retained phosphonium biocides as counter ions of sodium sulfonate moieties incorporated into the polymers, and surface antibacterial activity of the polyester films against Staphylococcus aureus and Escherichia coli was explored. These films exhibited a high surface antibacterial activity against S. aureus and E. coli, particularly against S. aureus, and the activity was affected by the structure and the compositional ratio of the phosphonium salts. Amount of the released phosphonium salts was very small, so that liberation of the phosphonium biocides can be expected to occur over a long period. Morphological changes of the cells of S. aureus and E. coli in contact with the polyester films were evaluated by scanning electron microscopy. It was found that the surface antibacterial activity of the polyester films was rather bacteriostatic than bactericidal as evidenced by no morphological changes of the bacterial cells in contact with the phosphonium biocides © 1993 John Wiley & Sons, Inc. 相似文献
74.
Tsuyoshi Matsumoto Junji Furukawa Hirohisa Morimura 《Journal of polymer science. Part A, Polymer chemistry》1971,9(7):1971-1981
The π-allyl nickel halide-oxygen system was found to be active as catalyst for stereospecific polymerization of butadiene. The catalyst from π-allyl nickel chloride or π-allyl nickel bromide yields the polymer of 90% cis-1,4 content with high activity, whereas the catalyst from π-allyl nickel iodide affords a polymer of 70% or less cis-1,4 content. The catalyst systems can be fractionated into two parts on the basis of solubility in benzene. It is concluded that the catalyst activity originates essentially from the benzene-insoluble nickel complex which is composed of oxygen, halogen, σ-allyl group, and nickel. The structure of growing polymer terminal is discussed in relation to the mechanism of the stereospecific polymerization. 相似文献
75.
Satoshi Ikeda 《Foundations of Physics》1983,13(6):629-636
Under the assumption that the so-called space-time fluctuationy(x) in a classical sense, attached to each point of the gravitational field at some microscopic stage, is summarized as the metrical fluctuation in the formg λκ (x)=gλκ (x)·exp2σ(y(x)), some new physical aspects induced by the conformal scalarσ(x) (≡σ(y(x))) are found: By introducing the torsionT κ λμ (x) from a general standpoint, the resulting micro-gravitational field is made to have a conformally non-Riemannian structure, where a special form ofT κ λμ (i.e.,T κ λμ =δ κ λ σμ?δ κ μ σλ(σμ=?σ/?x μ)) shows some peculiar features. An averaging process with respect toy is taken into account, by which the spatial structure of the corresponding macro-field is shown, in general, to have a somewhat “non”-Riemannian structure due to the contributions of the torsionT κ λμ . 相似文献
76.
Iwao Hashimoto Takatoshi Kawaji Florin D. Badea Tsuyoshi Sawada Shuntaro Mataka Masashi Tashiro Gouki Fukata 《Research on Chemical Intermediates》1996,22(9):855-869
The Friedel-Crafts acylations of various aromatic compounds with cyclic anhydrides such as 2-(p-substituted phenyl)butanedioic, 3-phenylpentanedioic and homophathlic anhydrides were carried out under various conditions in order to obtain informations about the regioselectivity of the ring opening of the cyclic anhydrides and about the possible reaction pathways in the acylations. 相似文献
77.
When azulene is included in the cavity of β-cyclodextrin (β-CDx), induced circular dichroism (CD) bands are observed in the corresponding absorption bands of azulene. On the basis of the theoretical conclusions for β-CDx complexes with naphthalene derivatives of Harata and Uedaira, it is concluded from the signs of the CD bands that the first (about 455 to 715 nm), third (about 290 to 305 nm) and fifth (at about 238 nm) absorption bands have the transition dipole moments perpendicular to the long axis and the second 305 to 360 nm), fourth (about 240 to 290 nm) and sixth (shorter than 220 nm) absorption bands have the transition dipole moments parallel to the long axis of azulene. Our assignments are in complete agreement with earlier assignments. Our experimental results do not provide any information regarding two new electronic transitions suggested theoretically by Thulstrup et al. 相似文献
78.
Ohno O Ikeda Y Sawa R Igarashi M Kinoshita N Suzuki Y Miyake K Umezawa K 《Chemistry & biology》2004,11(8):1059-1070
Lipopolysaccharide (LPS) is considered to cause various inflammatory reactions. We searched among microbial secondary metabolites for compounds that could inhibit LPS-stimulated adhesion between human umbilical vein endothelial cells (HUVEC) and human myelocytic cell line HL-60 cells. In the course of our screening, we isolated a novel cyclic depsipeptide, which we named heptadepsin, from the whole culture broth of Paenibacillus sp. The addition of heptadepsin prior to LPS stimulation decreased HL-60 cell-HUVEC adhesion without showing any cytotoxicity. It also inhibited the cellular adhesion induced by lipid A, the active component of LPS, but it did not inhibit TNF-alpha or IL-1beta-induced cell adhesion. The result of surface plasmon resonance (SPR) analysis revealed that heptadepsin interacted with lipid A directly. Thus, heptadepsin, a novel naturally occurring cyclic heptadepsipeptide, was shown to inactivate LPS by direct interaction with LPS. 相似文献
79.
80.
Carbon-Fluorine Bondings of Fluorinated Fullerene and Graphite 总被引:1,自引:0,他引:1
Carbon-fluorine bondings of fluorinated fullerenes and fluorine-graphite intercalation compound CxF were investigated in detail on the basis of XPS data and the potential model using the charge distribution calculated by semiempirical method. It has been confirmed by the present study that two peaks in the C1s spectra observed for fluorinated fullerenes are assigned to carbon atoms bonded to fluorine atoms and those unbound to fluorine atoms, and the small difference in charges and Madelung potentials of fluorine atoms in different circumstances well explains the single peak in F1s spectra of fluorinated fullerenes. In the calculated structures of 1,3-C60F2 and 1,2-C60Fx (x = 2?6) used as the models of CxF, three kinds of carbon-fluorine bondings were observed corresponding to nearly ionic, semicovalent and covalent C? F bondings. The calculated result supports that the bi-intercalation structure of stage 1 CxF consists of nearly ionic and semi-covalent fluorines. 相似文献