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911.
    
Aqueous zinc‐ion batteries (ZIBs) have become the highest potential energy storage system for large‐scale applications owing to the high specific capacity, good safety and low cost. In this work, a NASICON‐type Na3V2(PO4)3 cathode modified by a uniform carbon layer (NVP/C) has been synthesized via a facile solid‐state method and exhibited significantly improved electrochemical performance when working in an aqueous ZIB. Specifically, the NVP/C cathode shows an excellent rate capacity (e. g., 48 mAh g?1 at 1.0 A g?1). Good cycle stability is also achieved (e. g., showing a capacity retention of 88% after 2000 cycles at 1.0 A g?1). Furthermore, the Zn2+ (de)intercalation mechanism in the NVP cathode has been determined by various ex‐situ techniques. In addition, a Zn||NVP/C pouch cell has been assembled, delivering a high capacity of 89 mAhg?1 at 0.2 A g?1 and exhibiting a superior long cycling stability.  相似文献   
912.
    
Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11‐hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co3HITP2 and Ni3HITP2 are compared. Unpaired 3d electrons in Co3HITP2 result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co3HITP2, showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four‐electron for Co3HITP2 to two‐electron for Ni3HITP2. Rechargeable zinc–air batteries using Co3HITP2 as the air cathode catalyst demonstrate excellent energy efficiency and stability.  相似文献   
913.
    
The iridium half‐sandwich complex [Ir(η51‐C5Me4CH2py)(2‐phenylpyridine)]PF6 is highly cytotoxic: 15–250× more potent than clinically used cisplatin in several cancer cell lines. We have developed a correlative 3D cryo X‐ray imaging approach to specifically localize and quantify iridium within the whole hydrated cell at nanometer resolution. By means of cryo soft X‐ray tomography (cryo‐SXT), which provides the cellular ultrastructure at 50 nm resolution, and cryo hard X‐ray fluorescence tomography (cryo‐XRF), which provides the elemental sensitivity with a 70 nm step size, we have located the iridium anticancer agent exclusively in the mitochondria. Our methodology provides unique information on the intracellular fate of the metallodrug, without chemical fixation, labeling, or mechanical manipulation of the cells. This cryo‐3D correlative imaging method can be applied to a number of biochemical processes for specific elemental localization within the native cellular landscape.  相似文献   
914.
    
Fluorescent materials exhibiting two‐photon induction (TPI) are used for nonlinear optics, bioimaging, and phototherapy. Polymerizations of molecular chromophores to form π‐conjugated structures were hindered by the lack of long‐range ordering in the structure and strong π–π stacking between the chromophores. Reported here is the rational design of a benzothiadiazole‐based covalent organic framework (COF) for promoting TPI and obtaining efficient two‐photon induced fluorescence emissions. Characterization and spectroscopic data revealed that the enhancement in TPI performance is attributed to the donor‐π‐acceptor‐π‐donor configuration and regular intervals of the chromophores, the large π‐conjugation domain, and the long‐range order of COF crystals. The crystalline structure of TPI‐COF attenuates the π–π stacking interactions between the layers, and overcomes aggregation‐caused emission quenching of the chromophores for improving near‐infrared two‐photon induced fluorescence imaging.  相似文献   
915.
    
We report a RhIII‐catalyzed regio‐ and diastereoselective synthesis of δ‐lactams from readily available acrylamide derivatives and unactivated alkenes. The reaction provides a rapid route to a diverse set of δ‐lactams in good yield and stereoselectivity, which serve as useful building blocks for substituted piperidines. The regioselectivity of the reaction with unactivated terminal alkene is significantly improved by using Cpt ligand on the RhIII catalyst. The synthetic utility of the reaction is demonstrated by the preparation of a potential drug candidate containing a trisubstituted piperidine moiety. Mechanistic studies show that the reversibility of the C?H activation depends on the choice of Cp ligand on the RhIII catalyst. The irreversible C?H activation is observed and becomes turnover‐limiting with [CptRhCl2]2 as catalyst.  相似文献   
916.
    
Anion‐π catalysis functions by stabilizing anionic transition states on aromatic π surfaces, thus providing a new approach to molecular transformation. The delocalized nature of anion–π interactions suggests that they serve best in stabilizing long‐distance charge displacements. Aiming therefore for an anionic cascade reaction that is as charismatic as the steroid cyclization is for conventional cation‐π biocatalysis, reported here is the anion‐π‐catalyzed epoxide‐opening ether cyclizations of oligomers. Only on π‐acidic aromatic surfaces having a positive quadrupole moment, such as hexafluorobenzene to naphthalenediimides, do these polyether cascade cyclizations proceed with exceptionally high autocatalysis (rate enhancements kauto/kcat >104 m ?1). This distinctive characteristic adds complexity to reaction mechanisms (Goldilocks‐type substrate concentration dependence, entropy‐centered substrate destabilization) and opens intriguing perspectives for future developments.  相似文献   
917.
The kinetics of formation of the 1?:?1 complex of chromium(III) with 1,3-propanediamine-N,N′-diacetate-N,N′-di-3-propionate (1,3-pddadp) were followed spectrophotometrically at λ max?=?557?nm. The reaction was first-order in chromium(III). Increasing the 1,3-pddadp concentration from 2.2?×?10?2 to 0.11?mol?dm?3 accelerated the reaction rate. Increasing the hydrogen ion concentration from 1.995?×?10?5 to 6.31?×?10?4 mol?dm?3 retarded the reaction rate. The reaction rate was also retarded by increasing ionic strength and dielectric constant of the reaction medium. A mechanism was suggested to account for the results obtained which involves ion-pair formation between the various reactants. Values of 22?kJ?mol?1 and ?115?J?K?1 mol?1 were obtained for the energy and the entropy of activation, respectively, which indicate an associative mechanism. The logarithm of the formation constant of the 1?:?1 complex formed was 11.3.  相似文献   
918.
《Journal of Coordination Chemistry》2012,65(16-18):2767-2775
Abstract

Tetrazole-carboxylate ligands are universally considered as multi-functional candidates for the construction of coordination architectures. A 1-D [Fe(pytza)2(H2O)2]n·2nH2O (pytza = 5-(3-pyridyl)tetrazole-acetato) has been prepared. In vitro study on Hela cells show that Hpytza is naturally nontoxic while [Fe(pytza)2(H2O)2]n·2nH2O shows high toxicity with a half-maximal inhibitory concentration (IC50) of 6.3?×?10?5 M. In addition, the compound can effectively inhibit the migration of Hela cells.  相似文献   
919.
Abstract

A hybrid system involving graphene oxide (GO), magnetic oxide (Fe3O4), acrylamide and dicyandiamide was prepared via amine functionalization of GO/Fe3O4 by means of covalent bonding with acrylamide and subsequent reaction with dicyandiamide to provide a multinitrogen containing polymer on the surface of GO. This hybrid system was utilized as a heterogeneous catalyst support for immobilizing Pd nanoparticles to provide the hybrid, Pd@GO/Fe3O4/PAA/DCA. This nano-Pd composite was characterized using Fourier transform infrared, transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometer, thermogravimetric analysis, X-ray diffraction, and ICP techniques and used for promoting Sonogashira cross-coupling under mild reaction conditions. This heterogeneous and magnetic catalyst was easily separated by external magnet and was reused in a model reaction, efficiently up to six times with slight loss of catalytic activity and Pd leaching, showing the suitability of GO/Fe3O4/PAA/DCA for embedding Pd nanoparticles. To check the effect of the number of surface nitrogens of the polymeric chain on the catalytic performance, the activity of the catalyst was compared with Pd@GO/Fe3O4/PAA; increased number of the surface nitrogens on the chain polymer leads to higher loading of Pd and lower the Pd leaching.  相似文献   
920.
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