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81.
HgI2 crystallizes under ambient conditions from various solvents and by sublimation into three concomitant polymorphs whose colors are red, orange, and yellow. The orange and yellow phases are metastable and transform into the red phase when touched. A phase transition from red to yellow occurs at 400 K. The reverse transition from yellow to red shows a huge hysteresis. We established that the structures of the metastable yellowM phase (determined by single‐crystal X‐ray diffraction) and the high‐temperature yellowHT phase (determined by powder synchrotron X‐ray diffraction and second‐harmonic generation) are different, albeit closely related. Both show analogous packings of I? Hg? I molecules, which are straight in the first and bent with an angle of ca. 160° in the second. The red and orange phases are tetrahedral semiconductor structures that sublime even at room temperature. The growth of the yellowM phase from 2‐chloroethanol and the kinetics of the reconstructive phase transition red to yellowHT and back were studied by optical microscopy, Raman spectroscopy in solution, luminescence, and powder synchrotron X‐ray diffraction as a function of time at various temperatures. Both yellow phases grow by accretion of HgI2 molecules, present in the solution or liberated from the red crystals, on the surface of the crystal. In contrast, the reverse transformation from yellow to red occurs in the bulk of the crystal, presumably by migration of Hg in the packing of I and subsequent rearrangement of I. The displacement parameters of Hg in both structures are considerably larger than those of I and apparently not dominated by disorder effects. 相似文献
82.
Walrand J Lengelé M Blanquet G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(14):3299-3303
Using diode-laser spectroscopy, the intensities of 58 lines of the v(1) + v(1/2) - v(1/2) band and 36 lines of the 2v(1) - v(1) band of OCS have been measured. The corresponding band strengths S(0)(v) and the vibrational transition dipoles micro(v) have been derived through least squares fitting of these individual intensities. The band strengths values have been determined with a precision better than 2.5%. 相似文献
83.
Siemeling U Bausch K Fink H Bruhn C Baldus M Angerstein B Plessow R Brockhinke A 《Dalton transactions (Cambridge, England : 2003)》2005,(14):2365-2374
The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state. 相似文献
84.
June E. Reitz W. Sean McGivern M. Clark Church Marc D. Wilson Simon W. North 《国际化学动力学杂志》2002,34(4):255-261
Rate constants for several intermediate steps in the OH‐initiated oxidation of isoprene were determined using laser‐photolysis/laser‐induced fluorescence of OH radicals at total pressures between 3 and 4 Torr at 295 K. The rate constant for decomposition of the hydroxyalkoxy radical was determined to be (3.0 ± 0.5) × 104 s?1 in this pressure range, which is in fair agreement with previous work. The presence of a prompt alkoxy decomposition pathway was also investigated and found to contribute less than 10% to the total hydroxyalkoxy radical decomposition. The rate constant for the reaction of the hydroxyperoxy radical with NO was determined to be (2.5 ± 0.5) × 10?11 cm3 molecule?1 s?1, which is moderately higher than previously reported. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 255–261, 2002 相似文献
85.
Muller A Zhou Y Zhang L Bogge H Schmidtmann M Dressel M Slageren J 《Chemical communications (Cambridge, England)》2004,(18):2038-2039
The highly charged nanocontainer capsule of the type [pentagon]12[linker]30 identical with [(Mo)Mo5O21(H2O)6]12[Mo2O4(SO4)]30 with 20 nanosized pores and channels allows the entrance of cations like Pr3+: the latter are positioned at two different sites and have two different coordination shells, corresponding to a coordination chemistry under confined conditions; a fascinating aspect is that capsule encapsulated water shells fixed by hydrogen bonds act formally as polydentate ligands. 相似文献
86.
Micellar shape change and internal segregation induced by chemical modification of a tryptych block copolymer surfactant 总被引:1,自引:0,他引:1
Zhou Z Li Z Ren Y Hillmyer MA Lodge TP 《Journal of the American Chemical Society》2003,125(34):10182-10183
We report the detailed characterization of micelles formed by two nonionic, amphiphilic ABC triblock copolymers. Poly(ethylene oxide)-b-poly(styrene)-b-1,2-poly(butadiene) (PEO-b-PS-b-PB) triblock copolymer "OSB" forms core-corona spherical micelles in aqueous solution, and the two hydrophobic blocks S and B are mixed homogeneously within the micelle core. PEO-b-PS-b-PB:C6F13I triblock copolymer "OSF" was prepared by selective fluorination of the B block in OSB with n-perfluorohexyl iodide. Fluorination of the B block induces internal segregation into an inner F core and an intermediate S shell. Furthermore, the strong incompatibility that results from fluorination drives a shape change into an oblate ellipsoid. These micellar morphologies are confirmed by combined light, neutron, and X-ray scattering measurements, as well as TEM imaging. 相似文献
87.
88.
Herv Bouchard Jean-Pierre Pulicani Marc Vuilhorgne Jean-Dominique Bourzat Alain Commer on 《Tetrahedron letters》1994,35(52):9713-9716
A new route to semisynthetic 19-nor-7β, 8β-methylene taxoids, such as compound 8, from the 7-O-trifluoromethanesulfonyl derivative 6 is reported. Evidence for a dissociation of the triflate to form a carbocation at C-7 under the reaction conditions is presented. Electrochemical reduction of the cyclopropane taxoid 8 gives, besides the expected 10-dehydroxy-cyclopropane analog 10, the 7-membered C-ring derivative 11. 相似文献
89.
Joelle Mesmar Rola Abdallah Adnan Badran Marc Maresca Abdullah Shaito Elias Baydoun 《Molecules (Basel, Switzerland)》2022,27(13)
Ziziphus nummularia, a small bush of the Rhamnaceae family, has been widely used in traditional folk medicine, is rich in bioactive molecules, and has many reported pharmacological and therapeutic properties. Objective: To gather the current knowledge related to the medicinal characteristics of Z. nummularia. Specifically, its phytochemical contents and pharmacological activities in the treatment of various diseases such as cancer, diabetes, and cardiovascular diseases, are discussed. Methods: Major scientific literature databases, including PubMed, Scopus, ScienceDirect, SciFinder, Chemical Abstracts, Medicinal and Aromatic Plants Abstracts, Henriette’s Herbal Homepage, Dr. Duke’s Phytochemical and Ethnobotanical Databases, were searched to retrieve articles related to the review subject. General web searches using Google and Google scholar were also utilized. The search period covered articles published between 1980 and the end of October 2021.The search used the keywords ‘Ziziphus nummularia’, AND (‘phytochemical content’, ‘pharmacological properties, or activities, or effects, or roles’, ‘anti-inflammatory’, ‘anti-drought’, ‘anti-thermal’, ‘anthelmintic’, ‘antidiabetic’,’ anticancer’, ‘anticholinesterase’, ‘antimicrobial’, ‘sedative’, ‘antipyretic’, ‘analgesic’, or ‘gastrointestinal’). Results: This plant is rich in characteristic alkaloids, especially cyclopeptide alkaloids such as nummularine-M. Other phytochemicals, including flavonoids, saponins, glycosides, tannins, and phenolic compounds, are also present. These phytochemicals are responsible for the reported pharmacological properties of Z. nummularia, including anti-inflammatory, antioxidant, antimicrobial, anthelmintic, antidiabetic, anticancer, analgesic, and gastrointestinal activities. In addition, Z. nummularia has anti-drought and anti-thermal characteristics. Conclusion: Research into the phytochemical and pharmacological properties of Z. nummularia has demonstrated that this plant is a rich source of novel bioactive compounds. So far, Z. nummularia has shown a varied pharmacological profile (antioxidant, anticancer, anti-inflammatory, and cardioprotective), warranting further research to uncover the therapeutic potential of the bioactives of this plant. Taken together, Z. nummularia may represent a new potential target for the discovery of new drug leads. 相似文献
90.
Joelle Mesmar Rola Abdallah Adnan Badran Marc Maresca Elias Baydoun 《Molecules (Basel, Switzerland)》2022,27(13)
Herbal medicine has been gaining special interest as an alternative choice of treatment for several diseases, being generally accessible, cost-effective and safe, with fewer side-effects compared to chemically synthesized medicines. Over 25% of drugs worldwide are derived from plants, and surveys have shown that, when available, herbal medicine is the preferred choice of treatment. Origanum syriacum (Lamiaceae) is a widely used medicinal plant in the Middle East, both as a home and a folk remedy, and in the food and beverage industry. Origanum syriacum contains numerous phytochemical compounds, including flavonoids, phenols, essential oils, and many others. Because of its bioactive compounds, O. syriacum possesses antioxidant, antimicrobial, and antiparasitic capacities. In addition, it can be beneficial in the treatment of various diseases such as cancer, neurodegenerative disorders, and peptic ulcers. In this review, the chemical compositions of different types of extracts and essential oils from this herb will first be specified. Then, the pharmacological uses of these extracts and essential oils in various contexts and diseases will be discussed, putting emphasis on their efficacy and safety. Finally, the cellular and molecular mechanisms of O. syriacum phytochemicals in disease treatment will be described as a basis for further investigation into the plant’s pharmacological role. 相似文献