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911.
L. Costa G. Camino A. Chiotis G. Clouet J. Brossas M. Bert A. Guyot 《Polymer Degradation and Stability》1984,6(3):177-188
On heating at volatilisation temperatures, polystyrene (PS) and telechelic chloromethoxyphosphonated polystyrene (TPPS) behave differently in the very early stage of the process. The initial rate of volatilisation of PS is zero and increases with conversion whereas TPPS polymers volatilise at an initial high rate which decreases with conversion. However, in the main stage of volatilisation (from 10–20 to 70% weight loss) both polymers liberate the same volatile products through the same basic mechanism of depolymerisation. Nevertheless, the overall rate of volatilisation of TPPS polymers in this stage is much lower than that of PS. This is attributed to the creation in degrading TPPS polymers of less reactive chain carriers of the depolymerisation process which are stabilised by the phosphoryl group. 相似文献
912.
The use of X-ray elemental analysis tools like energy dispersive X-ray (EDS) is described in the context of the investigation of nuclear materials. These materials contain radioactive elements, particularly alpha-decaying actinides that affect the quantitative EDS measurement by producing interferences in the X-ray spectra. These interferences originating from X-ray emission are the result of internal conversion by the daughter atoms from the alpha-decaying actinides. The strong interferences affect primarily the L X-ray lines from the actinides (in the typical energy range used for EDS analysis) and would require the use of the M lines. However, it is typically at the energy of the actinide's M lines that the interferences are dominant. The artifacts produced in the X-ray analysis are described and illustrated by some typical examples of analysis of actinide-bearing material. 相似文献
913.
Hanson EL Schwartz J Nickel B Koch N Danisman MF 《Journal of the American Chemical Society》2003,125(51):16074-16080
A new method is described to prepare strongly bonded, compact monolayer films of alkyl- or arylphosphonates on the native oxide surface of Si (SiO(2)/Si). This method is illustrated for octadecyl- and alpha-quarterthiophene-2-phosphonates. For both cases, AFM shows comprehensive coverage of the SiO(2)/Si surface. The thickness of the continuous film of 4TP/SiO(2)/Si was measured both by AFM and by X-ray reflectivity to be ca. 18 A. Direct gravimetric analysis shows surface coverage by alpha-quarterthiophene-2-phosphonate to be about 0.66 nmol/cm(2), which corresponds to molecular packing in the film close to that of crystalline alpha-quarterthiophene. Coverage by octadecylphosphonate was ca. 0.90 nmol/cm(2), corresponding to a cross-sectional area of about 18.5 A(2)/molecule, consistent with close-packed alkyl chains. 相似文献
914.
Maarten B J Roeffaers Bert F Sels Davey Loos Christopher Kohl Klaus Müllen Pierre A Jacobs Johan Hofkens Dirk E De Vos 《Chemphyschem》2005,6(11):2295-2299
Fluorescence spectroscopy is employed to follow the ion exchange of an emissive dye--a carboxylated perylene imide--on a layered double hydroxide. The exchange of the carboxylate ions starts at the edges of the layered double hydroxide crystals and is followed by diffusion to the basal plane. Such space-resolved observations provide a solid basis for modelling and studying the mechanisms of exchange. 相似文献
915.
In the 1980s, capillary electrophoresis (CE) developed rapidly into a first-class analytical separation technique. Its advances in instrumentation and method development will not only enhance or complement existing mature separation techniques such as liquid chromatography and conventional slab gel electrophoresis, but will also severely challenge these separation methods. A brief overview of the most striking achievements of CE in the 1980s is given. which illustrates the challenges to liquid chromatography and conventional slab gel electrophoresis, and some detailed discussions are presented to highlight the advantages of CE. New developments in CE that can be expected for the 1990s include especially column technology, separation chemistry and instrumentation, which will serve further to diversify and improve the applicability of this technique in areas which are poorly addressed by other separation methods. This paper considers and speculates on the technological advancements that can be expected to emerge for CE in the 1990s. 相似文献
916.
Lu J Jayaprakash KN Schlueter U Fraser-Reid B 《Journal of the American Chemical Society》2004,126(24):7540-7547
A congener of the glycosylphosphatidylinositol (GPI) membrane anchor present on the cell surface of the malaria pathogen Plasmodium falciparum has been synthesized. This GPI is an example of a small number of such membrane anchors that carry a fatty acyl group at O-2 of the inositol. Although the acyl group plays crucial roles in GPI biosynthesis, it rarely persits in mature molecules. Other notable examples are the mammalian GPIs CD52 and AchE. The presence of bulky functionalities at three contiguous positions of the inositol moiety creates a very crowded environment that poses difficulties for carrying out selective chemical manipulations. Thus installations of the axial long-chain acyl group and neighboring phosphoglyceryl complex were fraught with obstacles. The key solution to these obstacles in the successful synthesis of the malarial candidate and prototype structures involved stereoelectronically controlled opening of a cyclic ortho ester. The reaction proceeds in very good yields, the desired axial diastereomer being formed predominantly, even more so in the case of long-chain acyl derivatives. The myoinositol precursor was prepared from methyl alpha-d-glucopyranoside by the biomimetic procedure of Bender and Budhu. For the glycan array, advantage was taken of the fact that (a). n-pentenyl ortho ester donors are rapidly and chemospecifically activated upon treatment with ytterbium triflate and N-iodosuccinimide and (b). coupling to an acceptor affords alpha-coupled product exclusively. A strategy for obtaining the GPI's alpha-glucosaminide component from the corresponding alpha-mannoside employed Deshong's novel azide displacement procedure. Thus all units of the glycan array were obtained from a beta-d-manno-n-pentenyl ortho ester, this being readily prepared from d-mannose in three easy, high-yielding steps. The "crowded environment" at positions 1 and 2, noted above, could conceivably be relieved by migration of the acyl group to the neighboring cis-O-3-hydroxyl in the natural product. However, study of our synthetic intermediates and prototypes indicate that the O-2 acyl group is quite stable, and that such migration does not occur readily. 相似文献
917.
[reaction: see text] Three pairs of primary-secondary diol acceptors have been exposed to armed, disarmed, and n-pentenyl ortho ester glycosyl donors in glycosidation reactions. It is shown that the regioselectivity of those glycosylations is greatly influenced by the armed, disarmed, or ortho ester nature of the glycosyl donors. The selectivities observed have been used to devise efficient in situ three-component glycosylations involving two donors and one acceptor. 相似文献
918.
van de Water LG Bergwerff JA Leliveld BR Weckhuysen BM de Jong KP 《The journal of physical chemistry. B》2005,109(30):14513-14522
Spatially resolved Raman and UV-vis-NIR microspectroscopy have been used as tools to study the preparation process of supported catalyst bodies. Detailed spectroscopic information on the local coordination geometry of two different metallic species along with their macro-distribution over the catalyst body has been obtained, enabling a good understanding of the physicochemical processes occurring during the drying process of impregnated gamma-Al(2)O(3) bodies. The formation and decomposition of the Keggin-type complex H(x)PMo(11)CoO(40)((7-)(x)-), which is considered to be a potential precursor for CoMoS(2)/gamma-Al(2)O(3) HDS catalysts, inside gamma-Al(2)O(3) bodies is shown to be a function of the composition of the impregnation solutions, the aging time, and the drying conditions applied. This knowledge has been successfully applied to prepare samples with a well-defined distribution of the bimetallic complex, that is, either egg-shell, egg-yolk, or homogeneous distributions. The Raman results are presented in a semiquantitative way by subtraction of a reference spectrum of a sample containing a known amount of H(x)PMo(11)CoO(40)((7-)(x)-) from the spectra recorded along the cross-section of the catalyst bodies. 相似文献
919.
de Groot FM Glatzel P Bergmann U van Aken PA Barrea RA Klemme S Hävecker M Knop-Gericke A Heijboer WM Weckhuysen BM 《The journal of physical chemistry. B》2005,109(44):20751-20762
1s2p resonant inelastic X-ray scattering (RIXS) spectroscopy has been measured for a series of iron oxides, including octahedral and tetrahedral Fe(II) and Fe(III) systems. Their spectral shapes have been analyzed and explained using crystal-field multiplet simulations. The RIXS planes and the K-edge and L-edge X-ray absorption spectra related to these RIXS planes will be discussed with respect to their analytical opportunities. It is concluded that the full power and possibilities of 1s2p RIXS needs an overall resolution of 0.3 eV. This will yield a technique with more detailed information than K-edge and L-edge X-ray absorption combined, obtained in a single experiment. Another major advantage is that 1s2p RIXS involves only hard X-rays, and experiments under essentially any condition and on any system are feasible. 相似文献
920.
DirkJ.A. DeRidder Kees Goubitz Henk Schenk Bert Krijnen JanW. Verhoeven 《Helvetica chimica acta》2003,86(3):799-811
The crystal structures of five N‐arylpiperidin‐4‐one derivatives 2P2, 3P2, 5P2, 1P3 , and 2P3 are presented (Fig. 2 and Tables 1–5) and discussed together with the derivatives 1P2 and 4P2 published previously. In all but one structure, 1P2 , the aryl group is in an equatorial position. The piperidine ring adopts a normal chair conformation. In 1P2 , the piperidine ring central C? C bonds are significantly elongated, which is consistent with the idea that through‐bond interaction is more pronounced in the axial conformation. Through‐bond interaction also influences the pyramidalization at the piperidine C(4)‐atom in such a way that a strong interaction is directing the ethylene C‐atom C(9) into the axial direction. 相似文献