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991.
Adaptivity is an essential trait of life. One type of adaptivity is the reconfiguration of a functional system states by correlating sensory inputs. We report polymer transformers, which can adaptively reconfigure their composition from a state of a mixed copolymer to being enriched in either monomer A or B. This is achieved by embedding and hierarchically interconnecting two chemically fueled activation/deactivation enzymatic reaction networks for both monomers via a joint activation pathway (network level) and an AB linker monomer reactive to both A and B (species level). The ratio of enzymes governing the individual deactivation pathways (our external signals) control the enrichment behavior in the dynamic state. The method shows high programmability of the reconfigured state, rejuvenation of transformation cycles, and quick in situ adaptation. As a proof‐of‐concept, we showcase this dynamic reconfiguration for colloidal surface functionalities.  相似文献   
992.
Controlling the solution‐state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid‐state microstructures through temperature‐controlled solution‐state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field‐effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution‐state aggregation to reveal the relationship between solution‐state aggregation and solid‐state microstructures of conjugated polymers.  相似文献   
993.
Molybdenum complexes are versatile and efficient for liquid phase olefin epoxidation reactions. Rational design of catalysts is critical to achieve high atom efficiency during epoxidation processes. Although liquid phase epoxidation has been a popular topic for decades, three key issues, (a) rational control of morphology of molybdenum nanoparticles, (b) manipulating metal‐support interaction and (c) altering electronic configuration at molybdenum center remains unsolved in this area. Therefore, in this paper, we have critically revised recent research progress on heterogeneous molybdenum catalysts for facile liquid phase olefin epoxidation in terms of catalyst synthesis, surface characterization, catalytic performance and structure‐function relationship. Furthermore, plausible reaction mechanisms will be systematically discussed with the aim to provide insights into fundamental understanding on novel epoxidation chemistry.  相似文献   
994.
Detection and determination of many known/unknown compounds in traditional Chinese medicines have always been challenging. To comprehensively identify compounds in Qishen granule, which is a widely prescribed herbal formula for treating chronic heart failure, a pseudotargeted screening method was proposed based on compound biosynthetic correlation using ultra high‐performance liquid chromatography coupled with high‐resolution mass spectrometry. Firstly, all possible compounds of Qishen granule were classified into nine types according to their core skeletons, and potential analogue molecular formulas were predicted according to core compound‐related biosynthetic correlations, such as methylation, hydroxylation, and glucosidation. Secondly, nine pseudocompound databases consisting of core compounds, deduced biosynthetic correlations, and predicted analogue molecular formulas were established. Then, compounds of interest were directly located by pseudotargeted screening of high resolution mass spectrometry data and further verified by target tandem mass spectrometry. As a result, 213 constituents were identified and 21 of them were determined as potential new compounds. This demonstrated that pseudotargeted screening based on compound biosynthetic correlations significantly facilitated the processing of extremely large information data and improved the efficiency of compound identification. This research provided essential data for exploration of effective substances in Qishen granule and enriched the methodology for comprehensive characterization of constituents in complex traditional Chinese medicines.  相似文献   
995.
Science China Chemistry -  相似文献   
996.
The present research has demonstrated that selective C?S bond cleavages of dibenzothiophene and its derivatives are feasible by thia‐Baeyer–Villiger type oxidation, i. e. the oxygen insertion process within a sulfoxide‐carbon linkage, in the presence of porphyrin iron (III) and by ultraviolet irradiation originating from sunlight, high pressure Hg‐lamp or residentially germicidal ultraviolet lamp under very mild conditions. This reaction with tert‐butylhydroperoxide at 30.0 °C leads to dibenzo[1,2]oxathiin‐6‐oxide ( PBS ) in 83.2 % isolated yield or its hydrated products, 2‐(2‐hydroxyphenyl)‐benzenesulfinic derivatives ( HPBS ) in near 100 % yield based HPLC data. PBS and HPBS are a type of biological products detected on the C?S bond cleavage step through various oxidative biodesulfurization ( OBDS ) pathways, and are useful synthetic intermediates and fine chemicals. These observations may contribute on understanding delicately molecular aspect of OBDS in the photosynthesis system, expanding the C‐S cleavage chemistry of S‐heterocyclic compounds and approaching toward biomemic desulfurization with respect to converting sulfur contaminants to chemically beneficial blocks as needed and performing under the ambient conditions.  相似文献   
997.
A facile hybrid assembly between Ti3C2Tx MXene nanosheets and (3‐aminopropyl) triethoxylsilane‐modified Si nanoparticles (NH2?Si NPs) was developed to construct multilayer stacking of Ti3C2Tx nanosheets with NH2?Si NPs assembling together (NH2?Si/Ti3C2Tx). NH2?Si/Ti3C2Tx exhibits a significantly enhanced lithium storage performance compared to pristine Si, which is attributed to the robust crosslinking architecture and considerably improved electrical conductivity as well as shorter Li+ diffusion pathways. The optimized NH2?Si/Ti3C2Tx anode with Ti3C2Tx: NH2?Si mass ratio of 4 : 1 displays an enhanced capacity (864 mAh g?1 at 0.1 C) with robust capacity retention, which is significantly higher than those of NH2?Si NPs and Ti3C2Tx anodes. Furthermore, this work demonstrates the important effect of the MXene‐based electrode architecture on the electrochemical performance and can guide future work on designing high‐performance Si/MXene hybrids for energy storage applications.  相似文献   
998.
999.
Hyperbranched polymers have garnered much attention due to attractive properties and wide applications, such as drug‐controlled release, stimuli‐responsive nano‐objects, photosensitive materials and catalysts. Herein, two types of novel hyperbranched poly(ester‐enamine) (hb‐PEEa) were designed and synthesized via the spontaneous amino‐yne click reaction of A2 monomer (1, 3‐bis(4‐piperidyl)‐propane (A2a) or piperazine (A2b)) and B3 monomer (trimethylolpropanetripropiolate). According to Flory's hypothesis, gelation is an intrinsic problem in an ideal A2+B3 polymerization system. By controlling the polymerization conditions, such as monomer concentration, molar ratio and rate of addition, a non‐ideal A2+B3 polymerization system can be established to avoid gelation and to synthesize soluble hb‐PEEa. Due to abundant unreacted alkynyl groups in periphery, the hb‐PEEa can be further functionalized by different amino compounds or their derivates. The as‐prepared amphiphilic PEG‐hb‐PEEa copolymer can readily self‐assemble into micelles in water, which can be used as surfactant to stabilize Au nanoparticles (AuNPs) during reduction of NaBH4 in aqueous solution. As a demonstration, the as‐prepared PEG‐hb‐PEEa‐supported AuNPs demonstrate good dispersion in water, solvent stability and remarkable catalytic activity for reduction of nitrobenzene compounds.  相似文献   
1000.
This paper studies the contact vibration problem of an elastic half-space coated with functionally graded materials (FGMs) subject to a rigid spherical punch. A static force superimposing a dynamic time-harmonic force acts on the rigid spherical punch. Firstly, we give the static contact problem of FGMs by a least-square fitting approach. Next, the dynamic contact pressure is solved by employing the perturbation method. Lastly, the dynamic contact stiffness with different dynamic contact displacement conditions is derived for the FGM coated half-space. The effects of the gradient index, coating thickness, internal friction, and punch radius on the dynamic contact stiffness factor are discussed in detail.  相似文献   
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