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21.
Emily J. Hopkins Dr. Yurii Prots Dr. Ulrich Burkhardt Dr. Yves Watier Dr. Zhiwei Hu Dr. Chang‐Yang Kuo Dr. Jen‐Che Chiang Dr. Tun‐Wen Pi Dr. Arata Tanaka Prof. Liu Hao Tjeng Dr. Martin Valldor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7938-7943
Through a solid‐state reaction, a practically phase pure powder of Ba3V2S4O3 was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P63, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated VIIIS6 and VVSO3 coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving. 相似文献
22.
Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions 下载免费PDF全文
Ing. Martin Holan Dr. Radek Pohl Dr. Ivana Císařová Dr. Blanka Klepetářová Prof. Dr. Peter G. Jones Dr. Ullrich Jahn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9877-9888
Densely functionalized cyclopentane derivatives with up to four consecutive stereocenters are assembled by a tandem Michael addition/single‐electron transfer oxidation/radical cyclization/oxygenation strategy mediated by ferrocenium hexafluorophosphate, a recyclable, less toxic single‐electron transfer oxidant. Ester enolates were coupled with α‐benzylidene and α‐alkylidene β‐dicarbonyl compounds with switchable diastereoselectivity. This pivotal steering element subsequently controls the diastereoselectivity of the radical cyclization step. The substitution pattern of the radical cyclization acceptor enables a switch of the cyclization mode from a 5‐exo pattern for terminally substituted olefin units to a 6‐endo mode for internally substituted acceptors. The oxidative anionic/radical strategy also allows efficient termination by oxygenation with the free radical 2,2,6,6‐tetramethyl‐1‐piperidinoxyl, and two C?C bonds and one C?O bond are thus formed in the sequence. A stereochemical model is proposed that accounts for all of the experimental results and allows the prediction of the stereochemical outcome. Further transformations of the synthesized cyclopentanes are reported. 相似文献
23.
Lewis Acids as Activators in CBS‐Catalysed Diels–Alder Reactions: Distortion Induced Lewis Acidity Enhancement of SnCl4 下载免费PDF全文
Dr. Alexander R. Nödling Robert Möckel Dr. Ralf Tonner Prof. Dr. Gerhard Hilt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13171-13180
The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While 2H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT‐IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ(2H) values and rate constants kDA, which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid–CBS complexes. Unexpectedly, a significant deviation was found for SnCl4 as Lewis acid. The SnCl4–CBS adduct was much more reactive than the Δδ(2H) values predicted and gave similar reaction rates to those observed for the prominent AlBr3–CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid–CBS–naphthoquinone adducts and kDA could be found. For the SnCl4–CBS–naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA‐NOCV) calculations revealed the relevant interactions and activation mode of SnCl4 as Lewis acid in Diels–Alder reactions. 相似文献
24.
Cover Picture: Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions (Chem. Eur. J. 25/2016) 下载免费PDF全文
25.
Theoretical investigations on the insertion reaction mechanisms of three- membered-ring silylenoid H2 Si Li F with GeH 3R(R = F, OH, NH2) have been systematically carried out by combined density functional theory(DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3 LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex(Q), one transition state(TS), and one intermediate(IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with Ge H3 R proceed in a concerted manner, forming H2RSi-Ge H3 and Li F. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 k J/mol, and the reaction energies for the three reactions are –127.05, –116.91, and –103.31 k J/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH 3-F GeH 3-OH GeH 3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation. 相似文献
26.
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
27.
分析和总结了催化剂催化有机化学反应的4种基本方式,包括建立电子流动通道、改变电子流动属性、加强电子流动能力和稳定电子流动结果。本文旨在揭示有机化学反应中催化剂作用的本质,以便学生更加深刻理解并掌握有机化学反应。 相似文献
28.
Daniel J. Tao Dr. Mikko Muuronen Yuriy Slutskyy Alexander Le Prof. Filipp Furche Prof. Larry E. Overman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8786-8790
The stereochemical outcome of reactions of chiral nucleophilic trisubstituted acetonide radicals with electron‐deficient alkenes is dictated by a delicate balance between destabilizing non‐bonding interactions and stabilizing hydrogen‐bonding between substituents on the α and β carbons. 相似文献
29.
Domino Staudinger/aza‐Wittig/Mannich Reaction: An Approach to Diversity of Di‐ and Tetrahydropyrrole Scaffolds 下载免费PDF全文
Dr. Anna S. Pavlova Dr. Olga A. Ivanova Dr. Alexey O. Chagarovskiy Nikolay S. Stebunov Dr. Nikolay V. Orlov Dr. Alexey N. Shumsky Dr. Ekaterina M. Budynina Dr. Victor B. Rybakov Prof. Dr. Igor V. Trushkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):17967-17971
A highly efficient and selective domino reaction producing valuable di‐ and tetrahydropyrrole‐based skeletons from azidoethyl‐substituted CH‐acids and (thio)carbonyl compounds has been developed. By involving the additional functional groups in starting compounds into the domino reaction or postmodification of the primary reaction products, the simple construction of the pharmaceutically relevant three‐ and polycyclic azaheterocyclic scaffolds was demonstrated. 相似文献
30.
Cover Picture: Mild and Low‐Pressure fac‐Ir(ppy)3‐Mediated Radical Aminocarbonylation of Unactivated Alkyl Iodides through Visible‐Light Photoredox Catalysis (Chem. Eur. J. 27/2016) 下载免费PDF全文