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1.
Hans Jagusch Markus Werner Oliver Werz Georg Pohnert 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17805-17809
Arachidonic‐acid‐derived prostaglandins (PGs), specifically PGE2, play a central role in inflammation and numerous immunological reactions. The enzymes of PGE2 biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic‐acid‐derived oxylipins including PGs that may account for food poisoning. Described here is the analysis of PGE2 biosynthesis in the red macroalga Gracilaria vermiculophylla that led to the identification of 15‐hydroperoxy‐PGE2, a novel precursor of PGE2 and 15‐keto‐PGE2. Interestingly, this novel precursor is also produced in human macrophages where it represents a key metabolite in an alternative biosynthetic PGE2 pathway in addition to the well‐established arachidonic acid‐PGG2‐PGH2‐PGE2 route. This alternative pathway of mammalian PGE2 biosynthesis may open novel opportunities to intervene with inflammation‐related diseases. 相似文献
2.
Julia Holz Camilla Pfeffer Hualiang Zuo Dennis Beierlein Gunther Richter Elias Klemm Ren Peters 《Angewandte Chemie (International ed. in English)》2019,58(30):10330-10334
Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent. 相似文献
3.
Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates 下载免费PDF全文
Dr. Johannes Moritz Bauer Dr. Wolfgang Frey Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5767-5777
The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β‐ and γ‐aminoalcohols as well as α‐ and β‐aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N‐tosylisocyanate in a single step into highly enantioenriched N‐tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation‐induced [3,3]‐rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl‐protected allylic amines, which can be deprotected under non‐reductive conditions. 相似文献
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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
8.
Enantiodivergent [4+2] Cycloaddition of Dienolates by Polyfunctional Lewis Acid/Zwitterion Catalysis
M. Sc. Vukoslava Miskov-Pajic M. Sc. Felix Willig M. Sc. Daniel M. Wanner Dr. Wolfgang Frey Prof. Dr. René Peters 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20045-20049
Diels–Alder reactions have become established as one of the most effective ways to prepare stereochemically complex six-membered rings. Different catalysis concepts have been reported, including dienophile activation by Lewis acids or H-bond donors and diene activation by bases. Herein we report a new concept, in which an acidic prodiene is acidified by a Lewis acid to facilitate deprotonation by an imidazolium–aryloxide entity within a polyfunctional catalyst. A metal dienolate is thus formed, while an imidazolium–ArOH moiety probably forms hydrogen bonds with the dienophile. The catalyst type, readily prepared in few steps in high overall yield, was applied to 3-hydroxy-2-pyrone and 3-hydroxy-2-pyridone as well as cyclopentenone prodienes. Maleimide, maleic anhydride, and nitroolefin dienophiles were employed. Kinetic, spectroscopic, and control experiments support a cooperative mode of action. High enantioselectivity was observed even with unprecedented TONs of up to 3680. 相似文献
9.
A conspicuous detail of the so-called brown-ring test (the analytical test on nitrate) is the reddish color of the bottom layer of concentrated sulfuric acid, which develops upon the bleeding of the brown layer into the acid. Crystals of the same color form from a solution of ferrous sulfate in concentrated sulfuric acid on saturation with gaseous nitric oxide. The structure of this H3O[{Fe(NO)(μ4-SO4)(μ2-SO4)0.5}n/n] ( 1a ) is made up from infinite chessboard-type layers with sulfur on the field junctions and Fe(NO) moieties below the black and above the white fields. An Fe–N–O angle of about 160° causes disorder in the tetragonal space group I4/mmm. A similar crystal pathology was found in the related [{Fe(MeOH)(NO)(μ4-SO4)}n/n] ( 1b ) in the same crystal class. A one-dimensional coordination polymer is formed in crystals of a third compound that comprises the Fe(NO)O5 coordination pattern, namely the brown oxalato species [{Fe(H2O)(NO)(μ2-ox)}n/n · H2O] ( 2 ). A still larger NO tilt of about 156° is not obscured by disorder in the triclinic crystals of 2 . 相似文献
10.
Khanna Vikram Monroe Jacob I. Doherty Michael F. Peters Baron 《Journal of computer-aided molecular design》2020,34(6):641-646
Journal of Computer-Aided Molecular Design - The decoupling approach to solvation free energy calculations requires scaling the interactions between the solute and the solution with all... 相似文献