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91.
Nicolas P. Cheval Barbara Hoffmann Anna Dikova Fatih Sirindil Philippe Bertus Aurélien Blanc Jean-Marc Weibel Patrick Pale 《Tetrahedron》2018,74(50):7111-7119
Vinyl nosylates, readily obtained from β-dicarbonyl derivatives, could be efficiently engaged in Sonogashira cross-coupling reactions, either cocatalyzed by copper or silver salts. The para-nitrobenzenesulfonate (nosylate) group allows this coupling to be performed under very mild conditions (room temperature). These new leaving group and mild conditions could be applied to the synthesis of acetylenic coumarinyl derivatives and to the total synthesis of an acetylenic monoterpene natural product, named cleviolide. 相似文献
92.
Dr. David Martin Dr. Nicolas Lassauque Florian Steinmann Gerald Manuel Prof. Guy Bertrand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14895-14901
Experimental and computational investigations of anti‐Bredt amidinium salts are presented. Calculations show that the pyramidalization of an amino group can significantly destabilize the formal carbocation center of amidiniums, due to the decreased π donation. In some cases, the unfavorable ‐I effect of nitrogen surpasses its beneficial +M effect, and amidiniums become less stable than iminiums. It is shown that although 1‐aza‐3‐azonia[3.3.1]bicyclo‐non‐2‐enes can be isolated, they feature a nonclassical reactivity, which is more typical for iminium than amidinium salts, such as pronounced electrophilicity and azomethineylide instead of carbene formation. 相似文献
93.
Dr. Yuwei Zhang Caiyun Zhang Prof. Yirong Mo Prof. Zexing Cao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1402-1409
Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN4C8H8) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3pz leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3pz results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si. 相似文献
94.
Dr. Dai Wu Xiu-Fang Mo Prof. Piao He Dr. Hai-Ru Li Prof. Xiao-Yi Yi Prof. Chao Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(40):10313-10322
Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH4][(UO2)3(HTTDS)(H2O)] ( 1 ), [(UO2)4(HTTDS)2](HIM)6 ( 2 , IM=imidazole), [(UO2)4(TTDS)(H2O)2(Phen)2] ( 3 , Phen=1,10-phenanthroline), [Zn(H2O)4]0.5[(UO2)3(HTTDS)(H2O)4] ( 4 ), and {(UO2)2[Zn(H2O)3]2(TTDS)} ( 5 ), {Zn(UO2)2(H2O)(Dib)0.5(HDib)(HTTDS)} ( 6 , Dib=1,4-di(1H-imidazol-1-yl)benzene) and [Na]{(UO2)4[Cu3(u3-OH)(H2O)7](TTDS)2} ( 7 ) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5-dicarboxyphenyl)silicon(H8TTDS). These UOFs have different 3D self-assembled structures as a function of co-ligands, structure-directing agents and transition metals. The structure of 1 has an infinite ribbon formed by the UO7 pentagonal bipyramid bridged by carboxylate groups. With further introduction of auxiliary N-donor ligands, different structure of 2 and 3 are formed, in 2 the imidazole serves as space filler, while in 3 the Phen are bound to [UO2]2+ units as co-ligands. The second metal centers were introduced in the syntheses of 4–7 , and in all cases, they are part of the final structures, either as a counterion ( 4 ) or as a component of framework ( 5 − 7 ). Interesting, in 7 , a rare polyoxometalate [Cu3(μ3-OH)O7(O2CR)4] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO2)2(O2CR)4] unit. Those uranyl carboxylates were sufficiently determined by single crystal X-ray diffraction, and their topological structures and luminescence properties were analyzed in detail. 相似文献
95.
Alejandro Ortega Moñux Steve Greedy Ginés Lifante 《Optical and Quantum Electronics》2013,45(4):307-307
96.
97.
Dr. Aurélien Adenot Dr. Lucile Anthore-Dalion Dr. Emmanuel Nicolas Jean-Claude Berthet Dr. Pierre Thuéry Dr. Thibault Cantat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18047-18053
An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule. 相似文献
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