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991.
CE-MS has evolved into a strong alternative to LC-MS. Most of CE-MS applications deal with characterization and identification. However, quantitative aspects have gained importance in, e.g., pharmaceutical and biotechnological applications. Here we summarize and evaluate various methodological aspects in order to achieve sensitive and reproducible results. Similar to LC-MS, aspects of matrix influence on the electrospray process need to be carefully addressed when quantitative results are intended by CE-MS. Due to a more complicated coupling special emphasis needs to be put on the CE-MS interface. Generally linearity over more than three orders of magnitude can be achieved by CE-ESI-MS. Furthermore, a literature survey has been performed in order to give an overview over quantitative measurements performed by CE-MS. The precision can be doubled when changing from a structural related to an isotopically labeled internal standard. Thus a level of precision better than 5% RSD can be achieved. 相似文献
992.
Goossen LJ Koley D Hermann HL Thiel W 《Journal of the American Chemical Society》2005,127(31):11102-11114
The mechanism of the cross-coupling of phenylboronic acid with acetic anhydride, a viable model of the widely used Suzuki reaction, has been studied by DFT calculations at the BP86/6-31G level of theory. Two alternative catalytic cycles have been investigated, one starting from a neutral Pd(0)L(2) complex, the other from an anionic "Jutand-type" [Pd(0)L(2)X](-) species. The reaction profiles are in good agreement with the experimental findings, as both pathways require only moderate activation energies. Both pathways are dominated by cis-configured square-planar palladium(II)diphosphine intermediates. Despite careful investigations, we did not find in this model reaction any evidence for five-coordinate palladium(II) intermediates, which are commonly believed to cause the profound effects of counterions in palladium-catalyzed transformations. Instead, our calculations suggest that the higher catalytic activity of anionic complexes, such as [Pd(PMe(3))(2)OAc](-), may arise from their stronger ability to coordinate to carbon electrophiles. The transmetalation sequence is the same for both catalytic cycles, involving the dissociation of one phosphine ligand from the palladium. In the decisive transition state, in which the phenyl group is transferred from boron to palladium, the acetate base is found to be in a bridging coordination between these two atoms. 相似文献
993.
994.
Wolfgang Richter 《Analytical and bioanalytical chemistry》1999,365(7):569-573
As a consequence of the globalisation of trade and industry and other human activities, reliability of and confidence in measurement results is increasingly required, also in the field of chemical analysis, so that measurements made in one country will be accepted in other countries without the necessity to repeat them. The prerequisite for confidence is comparability on the basis of known uncertainties which in turn are based on traceability to recognised references. Traceability structures for chemical measurements are required which, by providing calibration means traceable to national standards, allow uncertainty statements to be made at field level, thus establishing comparability. Such traceability structures are now being developed in all industrialised countries. To ensure international comparability, mutual recognition of the national activities in metrology in chemistry is required in addition. The Mutual Recognition Agreement (MRA) for national measurement standards and calibration certificates issued by national metrology institutes, which is currently under way within the framework of the Metre Convention, aimes at providing the necessary international confidence for all kinds of measurements. The field of chemical analysis is included in the international metrological infrastructure through the new Consultative Committee for Amount of Substance (CCQM). Carefully selected key comparison measurements, which cover the most important areas where traceability is required, and which are carried out by national metrology institutes in cooperation with other national institutes entrusted with the provision of part of the national references for chemical measurements, form the basis for declarations of equivalence under the MRA. The results of the first key comparisons and studies carried out so far clearly show that the group of laboratories involved in the key comparisons is capable of establishing the international references (key comparison reference values) for chemical measurements with sufficient accuracy, also in complicated matrices. 相似文献
995.
Ohne Zusammenfassung 相似文献
996.
R. Fresenius und E. Hintz 《Fresenius' Journal of Analytical Chemistry》1896,35(1):525-544
Schlussfolgerungen Aus vorstehenden Versuchen folgt, in Uebereinstimmung mit den Schlussfolgerungen A b und , dass man bei Sachkenntniss und gutem Willen in der Zeit März bis October 1895 wesentlich reinere Thornitrate hätte darstellen können, als bei der Fabrikation der fraglichen Glühkörper benutzt wurden, und dass also das Ceroxyd den Imprägnationsflüssigkeiten entweder zugesetzt oder durch wohl absichtliche Verwendung von an Ceroxyd reichen Thornitraten in die Glühkörper gelangte. 相似文献
997.
998.
C. Voumard H. P. Weber und R. Salathe 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1978,29(4):723
Ohne Zusammenfassung 相似文献
999.
Ohne Zusammenfassung 相似文献
1000.
E. M. Richter M. A. Augelli G. H. Kume R. N. Mioshi L. Angnes 《Analytical and bioanalytical chemistry》2000,366(5):444-448
The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working ¶electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of “gold electrodes” allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5–100 μg L–1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water. 相似文献