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71.
Bidyut B. Sarma Jonglack Kim Jonas Amsler Giovanni Agostini Claudia Weidenthaler Norbert Pfnder Raul Arenal Patricia Concepcin Philipp Plessow Felix Studt Gonzalo Prieto 《Angewandte Chemie (International ed. in English)》2020,59(14):5806-5815
Realizing the full potential of oxide‐supported single‐atom metal catalysts (SACs) is key to successfully bridge the gap between the fields of homogeneous and heterogeneous catalysis. Here we show that the one‐pot combination of Ru1/CeO2 and Rh1/CeO2 SACs enables a highly selective olefin isomerization‐hydrosilylation tandem process, hitherto restricted to molecular catalysts in solution. Individually, monoatomic Ru and Rh sites show a remarkable reaction specificity for olefin double‐bond migration and anti‐Markovnikov α‐olefin hydrosilylation, respectively. First‐principles DFT calculations ascribe such selectivity to differences in the binding strength of the olefin substrate to the monoatomic metal centers. The single‐pot cooperation of the two SACs allows the production of terminal organosilane compounds with high regio‐selectivity (>95 %) even from industrially‐relevant complex mixtures of terminal and internal olefins, alongside a straightforward catalyst recycling and reuse. These results demonstrate the significance of oxide‐supported single‐atom metal catalysts in tandem catalytic reactions, which are central for the intensification of chemical processes. 相似文献
72.
Philipp Wilhelm Dominik Blank Prof. John M. Lupton Dr. Jan Vogelsang 《Chemphyschem》2020,21(10):961-965
Controlling the morphology of π-conjugated polymers for organic optoelectronic devices has long been a goal in the field of materials science. Since the morphology of a polymer chain is closely intertwined with its photophysical properties, it is desirable to be able to change the arrangement of the polymers at will. We investigate the π-conjugated polymer poly(9,9-dioctylfluorene) (PFO), which can exist in three distinctly different structural phases: the α-, β-, and γ-phase. Every phase has a different chain structure and a unique photoluminescence (PL) spectrum. Due to its unique properties and the pronounced spectral structure-property relations, PFO can be used as a model system to study the morphology of π-conjugated polymers. To avoid ensemble averaging, we examine the PL spectrum of single PFO chains embedded in a non-fluorescent matrix. With single-molecule spectroscopy the structural phase of every single chain can be determined, and changes can be monitored very easily. To manipulate the morphology, solvent vapor annealing (SVA) was applied, which leads to a diffusion of the polymer chains in the matrix. The β- and γ-phases appear during the self-assembly of single α-phase PFO chains into mesoscopic aggregates. The extent of β- and γ-phase formation is directed by the solvent-swelling protocol used for aggregation. Aggregation unequivocally promotes formation of the more planar β- and γ-phases. Once these lower-energy more ordered structural phases are formed, SVA cannot return the polymer chain to the less ordered phase by aggregate swelling. 相似文献
73.
Burkart Philipp 《Nachrichten aus der Chemie》1994,42(12):1256-1258
74.
Two samples of mussels (Mytilus edulis) were collected from the southwest of Ireland. One sample contained domoic acid, the other sample contained okadaic acid,
dinophysistoxin-2 and azaspiracid-1, -2 and -3. Wet and freeze-dried reference materials were prepared from each of the two
samples to test for differences in homogeneity, stability and extractability of the analytes in either condition. Wet materials
were homogenised, aliquoted and hermetically sealed under argon and subsequently frozen at −80 °C. Dry materials were similarly
homogenised but frozen in flat cakes prior to freeze-drying. After grinding, sieving and further homogenisation, the resulting
powder was aliquoted and hermetically sealed. Domoic acid materials were characterised using HPLC–UV, while LC–MS was used
for the determination of lipophilic toxins. The extractabilities of all phycotoxins studied were comparable for wet and freeze-dried
materials once a sonication step had been carried out for reconstitution of the freeze-dried materials prior to extraction.
Homogeneity was assessed through replicate analysis of the phycotoxins (n = 10), and was found to be similar for wet and freeze-dried materials, for both hydrophilic and lipophilic toxins. Water
contents were determined for both wet and freeze-dried materials, and particle size was determined for the freeze-dried materials.
Stability was evaluated isochronously over eight months at four temperatures (−20, +4, +20 and +40 °C). The freeze-dried material
containing domoic acid was stable over the whole duration at all temperatures, while in the wet material domoic acid degraded
to some extent at all temperatures except −20 °C. In freeze-dried and wet materials containing lipophilic toxins, okadaic
acid, dinophysistoxin-2, azaspiracid-1 and azaspiracid-2 were stable over the whole duration at all conditions, while concentrations
of azaspiracid-3 changed significantly in both materials at some storage temperatures.
Figure Aliquots of freeze-dried and wet mussel tissue reference materials containing the various shellfish toxins examined in the
study 相似文献
75.
The heterogeneously catalyzed liquid phase Fries rearrangement reaction of phenyl acetate was carried out on Beta zeolites reexchanged with different amounts of metal cations. The aim of this work was to determine the influence of the amount of Brønsted acid sites as the catalytic active centers on the conversion. Sodium and potassium ions as well as divalent calcium and zinc ions were used in the reexchange procedure. The conversion shows a linear dependency on the degree of ion reexchange following the theoretically expected values. So the results prove that the bridged hydroxyl groups are indeed the dominating active centers and that their strength seems to be independent of the degree of reexchange; consequently, their acidic strength should be identical. A special emphasis was placed on the reexchange with divalent metal ions. It was shown that one divalent ion is not able to replace two protons as is supposed to be necessary for the charge balance—so a 1:1 stoichiometry is needed to assume to explain the catalytic results. 相似文献
76.
Synthesis and characterisation of the SrxBa1−xFeO3−y-system and the fluorinated phases SrxBa1−xFeO2F
Oliver Clemens Robert Haberkorn Peter R. Slater Horst Philipp Beck 《Solid State Sciences》2010,12(8):1455-1463
Compounds in the system SrxBa1?xFeO3?y have been prepared under different partial pressures of oxygen. In this system, different perovskite-type structures are found depending highly on the values of x and y. Fluorination using polyvinylidenedifluoride (PVDF) gives oxyfluoride materials of composition SrxBa1?xFeO2F, which normally crystallize in the cubic perovskite structure. Rietveld refinement results provide information about the packing density for oxide and oxyfluoride samples and allow a general comparison between these two different types of materials. Furthermore, the determination of the average iron oxidation state also showed that the oxygen deficiency, y, depends significantly on the value of x and the structure determined by the Sr/Ba ratio. 相似文献
77.
78.
We improve a recent result of Mauduit and Sárk?zy (2000) on the well-distribution measure of pseudorandom sequences and complement
another of their results on the correlation measure. 相似文献
79.
We report on the temperature and electric field strength dependence of the conductivity of iodine-doped polyacetylene in the metallic regime. The experimental results are discussed in terms of Sheng model of fluctuation induced tunneling and characteristic dimensions of the tunneling zones between fibres are deduced from a fit between this theory and our experiments. 相似文献
80.