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51.
Bingham RJ Findlay JB Hsieh SY Kalverda AP Kjellberg A Perazzolo C Phillips SE Seshadri K Trinh CH Turnbull WB Bodenhausen G Homans SW 《Journal of the American Chemical Society》2004,126(6):1675-1681
In the present study we examine the thermodynamics of binding of two related pyrazine-derived ligands to the major urinary protein, MUP-I, using a combination of isothermal titration calorimetry (ITC), X-ray crystallography, and NMR backbone (15)N and methyl side-chain (2)H relaxation measurements. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than the classical entropy-driven hydrophobic effect. Unfavorable entropic contributions from the protein backbone and side-chain residues in the vicinity of the binding pocket are partially offset by favorable entropic contributions at adjacent positions, suggesting a "conformational relay" mechanism whereby increased rigidity of residues on ligand binding are accompanied by increased conformational freedom of side chains in adjacent positions. The principal driving force governing ligand affinity and specificity can be attributed to solvent-driven enthalpic effects from desolvation of the protein binding pocket. 相似文献
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Merlin A. Fox Fang-Jie Zhao Steve P. McGrath 《International journal of environmental analytical chemistry》2013,93(5):323-329
A new method for the determination of the 34S/32S ratio of water-extractable sulphate in soil is described. Soils are extracted directly with deionized water, which is evaporated down. The remaining residue is then rehydrated and transferred to tin cups containing an adsorbent and mixed with an oxygen donor (V2O5). Samples are then analysed using a continuous flow isotope ratio mass spectrometer. The new method requires around 10?g soil per determination, compared to much larger amounts (up to kilograms) of soil required for the previous methods. Sample preparation and subsequent analysis is quick and efficient. The method is demonstrated using a number of soils collected from around the world to provide a range of determined δ34S values. The δ34S values of water-extractable sulphur were broadly similar to those of the soil total sulphur. 相似文献
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Alejandro Ortega Moñux Steve Greedy Ginés Lifante 《Optical and Quantum Electronics》2013,45(4):307-307
56.
Steve Scheiner 《International journal of quantum chemistry》2013,113(11):1609-1620
The characteristics of the pnicogen bond are explored using a variety of quantum chemical techniques. In particular, this interaction is compared with its halogen and chalcogen bond cousins, as well as with the more common H‐bond. In general, these bonds are all of comparable strength. More specifically, they are strengthened by the presence of an electronegative substituent on the electron‐acceptor atom, and each gains strength as one moves down the appropriate column of the periodic table, for example, from N to P to As. These noncovalent bonds owe their stability to a mixture in nearly equal parts of electrostatic attraction and charge transfer, along with a smaller dispersion component. The charge transfer arises from the overlap between the lone pair of the electron donor and a σ* antibond of the acceptor. The angular characteristics of the equilibrium geometry result primarily from a compromise between electrostatic and induction forces. Angular distortions of the H‐bond are typically less energetically demanding than comparable bends of the other noncovalent bonds. © 2012 Wiley Periodicals, Inc. 相似文献
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Georgia W. Hodges Deborah Tippins J. Steve Oliver 《School science and mathematics》2013,113(6):263-274
Science teacher retention, attrition, and migration continue to perplex educational scholars, political entities, as well as the general public. This study utilized an interpretive methodological design to generate assertions regarding career choice made by highly qualified science teachers in the deep, rural South through analysis of documents, interviews, focus groups, and observation. Generally considered “difficult to staff” because of location, socioeconomics, and demographics, Wilson County High School is an exemplar in science teacher retention and student achievement. Findings presented include how the science department at Wilson County improved student learning outcomes as well as the reasons why two of the highly qualified science teachers at this school were considering leaving the profession they love. 相似文献
59.
Peng Yang Yaxin Sun Kaiyue Fu Li Zhang Guang Yang Jieyu Yue Yu Ma Jianrong Steve Zhou Bo Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202111778
We report a stereoselective conversion of terminal alkynes to α-chiral carboxylic acids using a nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction. A simple nickel/BenzP* catalyst displayed high activity in both steps of regioselective hydrocarboxylation of alkynes and subsequent asymmetric transfer hydrogenation. The reaction was successfully applied in enantioselective preparation of three nonsteroidal anti-inflammatory profens (>90 % ees) and the chiral fragment of AZD2716. 相似文献
60.
Heinz J. Robota Laura A. Richard Soumitra Deshmukh Steve LeViness Daniele Leonarduzzi Diarmid Roberts 《Catalysis Surveys from Asia》2014,18(4):177-182
Each process configuration for practicing the Fischer–Tropsch synthesis places demands particular to that configuration on the catalyst to be used. We discuss how a particular catalyst, prepared by the OMX (organic matrix combustion) method, when used in conjunction with the Velocys microchannel reactor system, results in a very stable, high performance Fischer–Tropsch synthesis system. With the ability to remove heat far more effectively than a conventional reactor system, this microchannel reactor requires a catalyst with much higher volumetric reactive site density. Further, with such a high volumetric reaction rate, mass transfer effects will be important in both the observed activity and selectivity of the operating catalyst. Nevertheless, the catalyst prepared using the OMX method exhibits an apparent turnover frequency which is considerably higher than reported for other catalysts in the literature. In addition to high activity, an economically useful catalyst must exhibit a stable, high selectivity for liquid products and be able to recover near-fresh performance using a regeneration approach which can be carried out with the catalyst in-place. An example of such a stable, multiply regenerated catalyst is given. Finally, further development has focused on a catalyst with even higher C5+ selectivity. 相似文献