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21.
Dipl.‐Chem. Alexander Rupp Dr. Nataliya Roznyatovskaya Dr. Harald Scherer Dr. Witali Beichel Petra Klose Carola Sturm Dr. Anke Hoffmann Dr. Jens Tübke Prof. Dr. Thorsten Koslowski Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9794-9804
Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium‐sized [NTf2]? (0.230 nm3; Tf=CF3SO3?) and the large [Al(hfip)4]? (0.581 nm3; hfip=OC(H)(CF3)2) anions were synthesized and characterized. Their temperature‐dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel–Fulcher–Tammann (VFT) behavior. Ion‐specific self‐diffusion constants were measured at room temperature by pulsed‐gradient stimulated‐echo (PGSTE) NMR experiments. In general, self‐diffusion constants of both cations and anions in [Al(hfip)4]?‐based ILs were higher than in [NTf2]?‐based ILs. Ionicities were calculated from self‐diffusion constants and measured bulk conductivities, and showed that [Al(hfip)4]?‐based ILs yield higher ionicities than their [NTf2]? analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)4]?‐based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)4]?. Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions. 相似文献
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Lubov' V. Snegur Yury S. Nekrasov Nataliya S. Sergeeva Zhanna V. Zhilina Vera V Gumenyuk Zoya A. Starikova Alexander A. Simenel Nataliya B. Morozova Irina K. Sviridova Valery N. Babin 《应用有机金属化学》2008,22(2):139-147
The toxicity of ferrocenylethyl benzotriazole ( 1 ) and other ferrocene compounds including ferrocenylmethyl benzimidazoles ( 4,5,6,11 ), ferricenium salts ( 3,9,10 ) and ferrocenylmethyl adenine ( 7 ), was studied. All ferrocene complexes under investigation showed low or medium toxicities. On the basis of an earlier model of chemical carcinogenesis, the antitumor activity of ferrocenylalkyl azoles 1, 8 and ferricenium salts 9, 10 was studied in vivo in the so‐called sub‐capsular test on human tumors. This effectiveness was compared with that of cisplatin. A series of ferrocenylalkyl azoles were synthesized by interacting azoles either with α‐hydroxyalkyl ferrocenes FcC(OH)R1R2 in organic solvent in the presence of aqueous HBF4 in quantitative yields or with trimethyl(aminomethyl)ferrocene iodide in an aqueous‐basic medium in good yields. The X‐ray determinations of molecular and crystal structures of α‐(1‐benzotriazolyl)ethylferrocene ( 1 ) and α‐(1‐naphthatriazolyl)ethylferrocene ( 12 ) were performed. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
25.
V. P. Zhelezny Yu. V. Semenyuk S. N. Ancherbak N. V. Emel’yanenko 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2009,83(2):182-186
The results obtained in studying the temperature dependence of parachor are presented. The concepts of the parachor at the critical point and reduced parachor are introduced. The approach based on scaling principles and the assumption of a universal character of changes in crossover functions at critical exponents was used to obtain a universal temperature dependence of the reduced parachor. The dependence of the parachor at the critical point on the critical molar volume was established. The constituents of parachor were determined for halogenated hydrocarbons. 相似文献
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Eric M. Galimov Vyacheslav S. Sevastyanov Nataliya E. Babulevich Ekaterina N. Tyurina 《Rapid communications in mass spectrometry : RCM》2009,23(16):2461-2466
The application of a high‐temperature electrochemical reactor based on stabilized zirconium dioxide (0.9 ZrO20.1 Y2O3) for organic gas sampling in continuous‐flow isotope‐ratio mass spectrometry (CF‐IRMS) has been found to be efficient. This solid electrolyte reactor (SER) can also be used as a chromatographic detector for the quantitative measurements of organic gases. A three‐electrode SER system was studied. Complete stoichiometric oxidation of organic gases has been achieved at 900–950°C due to the large catalytic surface area of the porous platinum coating. At this temperature, the oxygen ions formed from the oxygen of ambient air on the outer surface of the reactor migrate through the solid electrolyte under the action of the applied electric field and allow combustion of gases being analyzed to be effected. It should be noted that oxygen gas was not introduced into the gas‐carrier flow. Similar results for the measurements of carbon isotope ratios were obtained at the oxidation of hydrocarbon gases in both the standard and the solid electrolyte reactors. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
28.
Gladis G. Zakirova Dmitrii Yu. Mladentsev Nataliya E. Borisova 《Tetrahedron letters》2017,58(35):3415-3417
Bis(diphenylphosphine oxides) and bis(tert-butyl(phenyl)phosphine oxides) of 1,10-phenanthroline, 2,2′-bipyridine and pyridine were synthesised in good yields via the Pd(OAc)2/dppf mediated cross-coupling reactions between 6,6′-dichloro-2,2′-bipyridine, 2,9-dichloro-1,10-phenanthroline, or 2,6-dichloropyridine and the corresponding secondary phosphine oxides. These compounds represent potential tetradentate chelating ligands for ions of f-block elements. 相似文献
29.
Ardanova LI Get'man EI Loboda SN Prisedsky VV Tkachenko TV Marchenko VI Antonovich VP Chivireva NA Chebishev KA Lyashenko AS 《Inorganic chemistry》2010,49(22):10687-10693
Polycrystalline hydroxyapatites Ca(10-x)REE(x)(PO(4))(6)(OH)(2-x)O(x) were synthesized and studied by X-ray powder diffraction, infrared absorption, diffuse-reflectance spectroscopy, and thermogravimetry. The solubility limits x(max) of rare earth elements (REE) in Ca hydroxyapatites decreases with an increasing REE atomic number from x(max) = 2.00 for La, Pr, and Nd to x(max) = 0.20 for Yb at 1100 °C. Refinements of X-ray diffraction patterns by the Rietveld method show that REE atoms substitute for Ca preferentially at the Ca(2) sites of the apatite structure. The substitution decreases the Ca(2)-O(4) atomic distances in the calcium coordination polyhedra and increases the Ca(2)-O(1,2,3) distances. This observation shows that interatomic distances depend not only on radii of the ions involved in the substitution but also on their charges. 相似文献
30.
Franz Weitzer Masaaki Naka Nataliya Krendelsberger Frank Stein Cuiyun He Yong Du Julius C. Schuster Prof. Dr. 《无机化学与普通化学杂志》2010,636(6):982-990
The constitution of the ternary system Ni/Si/Ti is investigated over the entire composition range using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDS), differential thermal analysis (DTA), and metallography. The solid state phase equilibria are determined for 900 °C. Eight ternary phases are found to be stable. The crystal structures for the phases τ1NiSiTi, τ2Ni4Si7Ti4, τ3Ni40Si31Ti13, τ4Ni17Si7Ti6, and τ5Ni3SiTi2 are corroborated. For the remaining phases the compositions are determined as Ni6Si41Ti53 (τ6), Ni16Si42Ti42(τ7), and Ni12Si45Ti43 (τ8). The reaction scheme linking the solid state equilibria with the liquidus surface is amended to account for these newly observed phases. The discrepancies between previous experimental conclusions and modeling results are addressed. The liquidus surface is dominated by the primary crystallisation field of τ1NiSiTi, the only congruently melting phase. 相似文献