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1.
Robin F. Weitkamp Beate Neumann Hans‐Georg Stammler Berthold Hoge 《Angewandte Chemie (International ed. in English)》2020,59(14):5494-5499
We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization. 相似文献
2.
Robin van der Veer 《Discrete Mathematics》2019,342(9):2680-2693
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Isaiah R. Speight Dr. Igor Huskić Dr. Mihails Arhangelskis Dr. Hatem M. Titi Dr. Robin S. Stein Prof. Timothy P. Hanusa Prof. Tomislav Friščić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1811-1818
The “disappearing polymorph” phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal–organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C−H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs. 相似文献
5.
Robin M. Bär Dr. Patrick J. Gross Dr. Martin Nieger Prof. Dr. Stefan Bräse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(19):4242-4245
Herein, we present the synthesis of the bench-stable sodium bicyclo[1.1.1]pentanesulfinate (BCP-SO2Na) and its application in the synthesis of bicyclo[1.1.1]pentyl (BCP) sulfones and sulfonamides. The salt can be obtained in a four-step procedure from commercially available precursors in multigram scale without the need for column chromatography or crystallization. Sulfinates are known to be useful precursors in radical and nucleophilic reactions and are widely used in medicinal chemistry. This building block enables access to BCP sulfones and sulfonamides avoiding the volatile [1.1.1]propellane which is favorable for the extension of SAR studies. Further, BCP-SO2Na enables the synthesis of products that were not available with previous methods. A chlorination of BCP-SO2Na and subsequent reaction with a Grignard reagent provides a new route to BCP sulfoxides. Several products were analyzed by single-crystal X-ray diffraction. 相似文献
6.
Daoyong Zhu Zhiwei Jiao Yonggui Robin Chi Tho P. Gonalves Kuo‐Wei Huang Jianrong Steve Zhou 《Angewandte Chemie (International ed. in English)》2020,59(13):5341-5345
Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5‐aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines. 相似文献
7.
Shenghan Teng Dr. Zhiwei Jiao Prof. Dr. Yonggui Robin Chi Prof. Dr. Jianrong Steve Zhou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(6):2266-2270
Palladium-catalyzed three-component carboetherification of cyclic alkenes proceeded to give trans adducts exclusively with excellent enantioselectivity through a Wacker-type pathway. The reaction is also applicable to other oxygen nucleophiles, such as water, phenols, and carboxylic acids, as well as some electron-poor aryl amines. 相似文献
8.
Dr. Qaisar Nadeem Dr. Giuseppe Meola Dr. Henrik Braband Robin Bolliger Dr. Olivier Blacque Daniel Hernández-Valdés Prof. Dr. Roger Alberto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1213-1216
The labeling of (bio)molecules with metallic radionuclides such as 99mTc demands conjugated, multidentate chelators. However, this is not always necessary since phenyl rings can directly serve as integrated, organometallic ligands. Bis-arene sandwich complexes are generally prepared by the Fischer–Hafner reaction. In extension of this, we show that [99mTc(η6-C6R6)2]+-type complexes are directly accessible from water and [99mTcO4]−, even using arenes incompatible with Fischer–Hafner conditions. To unambiguously confirm the nature of these unprecedented 99mTc complexes, their rhenium homologous have been prepared by substituting naphthalene ligands in [Re(η6-C10H8)2]+ with the corresponding phenyl groups. The ease with which highly stable [99mTc(η6-C6R6)2]+ complexes are formed under standard labeling conditions enables a multitude of new potential imaging agents based on commercial pharmaceuticals or lead structures. 相似文献
9.
Dr. N. Kodiah Beyeh Dr. Fangfang Pan Dr. Sandip Bhowmik Toni Mäkelä Prof. Robin H. A. Ras Acad. Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1355-1361
N‐Alkyl ammonium resorcinarene salts (NARYs, Y=triflate, picrate, nitrate, trifluoroacetates and NARBr) as tetravalent receptors, are shown to have a strong affinity for chlorides. The high affinity for chlorides was confirmed from a multitude of exchange experiments in solution (NMR and UV/Vis), gas phase (mass spectrometry), and solid‐state (X‐ray crystallography). A new tetra‐iodide resorcinarene salt (NARI) was isolated and fully characterized from exchange experiments in the solid‐state. Competition experiments with a known monovalent bis‐urea receptor ( 5 ) with strong affinity for chloride, reveals these receptors to have a much higher affinity for the first two chlorides, a similar affinity as 5 for the third chloride, and lower affinity for the fourth chloride. The receptors affinity toward chloride follows the trend K1?K2?K3≈ 5 >K4, with Ka=5011 m ?1 for 5 in 9:1 CDCl3/[D6]DMSO. 相似文献
10.