首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   10327篇
  免费   1642篇
  国内免费   1140篇
化学   7647篇
晶体学   112篇
力学   589篇
综合类   70篇
数学   1204篇
物理学   3487篇
  2024年   29篇
  2023年   240篇
  2022年   444篇
  2021年   446篇
  2020年   553篇
  2019年   496篇
  2018年   425篇
  2017年   333篇
  2016年   506篇
  2015年   531篇
  2014年   628篇
  2013年   753篇
  2012年   942篇
  2011年   1009篇
  2010年   649篇
  2009年   603篇
  2008年   576篇
  2007年   514篇
  2006年   527篇
  2005年   411篇
  2004年   302篇
  2003年   252篇
  2002年   298篇
  2001年   171篇
  2000年   182篇
  1999年   203篇
  1998年   146篇
  1997年   130篇
  1996年   149篇
  1995年   119篇
  1994年   101篇
  1993年   70篇
  1992年   71篇
  1991年   61篇
  1990年   50篇
  1989年   45篇
  1988年   40篇
  1987年   19篇
  1986年   26篇
  1985年   21篇
  1984年   13篇
  1983年   4篇
  1981年   6篇
  1957年   3篇
  1937年   1篇
  1935年   1篇
  1931年   1篇
  1930年   3篇
  1928年   1篇
  1922年   1篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Through a two-step vacuum-filtration process, WSe2 and MoS2 nanosheets were sequentially deposited onto a polymeric nanoporous support, forming WSe2/MoS2 bi-layered heterostructure. Highly rectified ion transport phenomenon is observed through the heterogeneous 2D layered membranes.  相似文献   
992.
The asymmetric intramolecular Friedel–Crafts type Michael reaction of α,β-unsaturated aldehyde with pyrrole, catalyzed by a spiropyrrolidine (SP)-type organocatalyst, has been accomplished, which allows the construction of a series of azepine and indolizine frameworks with high to excellent enantioselectivities (up to 98% ee). Moreover, the substrate scope could be extended to generate a quaternary center in indolizine frameworks (up to 96% ee).  相似文献   
993.
Nowadays, there is a demand for fast liquid chromatography (LC) of biogenic amines in food with the equipment available in the average laboratory. To this end, high-temperature liquid chromatography (HTLC) is presented in this study as a viable option, working on a conventional LC platform at moderately high temperatures up to 80 °C. The LC platform was adapted by including an appropriate length of stainless-steel microbore tubing as a preheater. Biogenic amines as benzoyl derivatives showed good thermostability on a thermally rugged column (150?×?4.6 mm, 5 µm). As a model application the HTLC conditions were developed for wine separation. The separation selectivity changed considerably with temperature in the range 36–84 °C, and baseline resolution was obtained only at temperatures well above ambient. At 73 °C oven temperature, the system allowed a flow rate as high as 3 mL min?1 with the backpressure not exceeding 195 bar (2800 psi). The separation took less than 5 min, comparably fast to documented fast LC separations, and typically at least three to five times faster than a conventional separation.  相似文献   
994.
Five new diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene] tyrosinates, R2Sn[2‐O‐3‐MeOC6H3CH=NCH (CH2C6H4OH‐4)COO] (R = Me, 1 ; Et, 2 ; Bu, 3 ; Cy, 4 ; Ph, 5 ), have been synthesized and characterized by elemental analysis, IR, NMR (1H, 13C and 119Sn) spectra, and the X‐ray single crystal diffraction. In non‐coordinated solvent, complexes 1 – 5 have penta‐coordinated tin atom. In the solid state, 1 – 3 are centrosymmetric dimmers in which each tin atom is seven‐coordinated in a distorted pentagonal bipyramid, and 4 displays discrete molecular structure with distorted trigonal bipyramidal geometry, and the tin atom of 5 is hexa‐coordinated and possess the distorted octahedral geometry with a coordinational methanol molecule. The intermolecular O‐H???O hydrogen bonds in 1 – 4 link molecules into the different one‐dimensional supramolecular chain with R22 (30) or R22 (20) macrocycles, and the molecules of 5 are joined into a two‐dimensional supramolecular network containing R44 (24) and R44 (28) two macrocycles. Bioassay results against human tumour cell HeLa indicated that 3 ‐ 5 belonged to the efficient cytostatic agents and the activity decreased in the order 4 > 3 > 5 > 2 > 1. The fluorescence determinations show the complexes may be explored for potential luminescent materials.  相似文献   
995.
Metal nanoparticles (NPs) are routinely stabilized by the introduction of capping agents or their distribution on supports. In this context, we report the preparation and characterization of N‐heterocyclic carbene (NHC)‐stabilized silver NPs supported on polyacrylonitrile fiber (PANF). As a result, Ag loadings of up to 8 % and particle sizes of 11.0±3.2 nm were achieved. This novel nanocomposite catalyst demonstrated high activity in addition to excellent stability and reusability in the three‐component reaction between alkynes, haloalkanes, and amines. In this system, the AgNPs were stabilized by both a support effect and a ligand effect. The unique NHC‐protected AgNP structure and the PANF support provide a synergistic effect in the deprotonation of Csp?H bonds, with turnover numbers of up to 3500. This catalyst was successfully recycled over eight runs without any significant loss in activity, and with no significant aggregation of the AgNPs. Moreover, implementation of a flow system with PANF‐NHC@Ag as catalyst leads to an efficient productivity of 57 mmol h?1.  相似文献   
996.
Hierarchical MoS2@TiO2 heterojunctions were synthesized through a one‐step hydrothermal method by using protonic titanate nanosheets as the precursor. The TiO2 nanosheets prevent the aggregation of MoS2 and promote the carrier transfer efficiency, and thus enhance the photocatalytic and electrocatalytic activity of the nanostructured MoS2. The obtained MoS2@TiO2 has significantly enhanced photocatalytic activity in the degradation of rhodamine B (over 5.2 times compared with pure MoS2) and acetone (over 2.8 times compared with pure MoS2). MoS2@TiO2 is also beneficial for electrocatalytic hydrogen evolution (26 times compared with pure MoS2, based on the cathodic current density). This work offers a promising way to prevent the self‐aggregation of MoS2 and provides a new insight for the design of heterojunctions for materials with lattice mismatches.  相似文献   
997.
The effects of a typical anti-agglomerant, sorbitan monooleate (Span80), on the interactions between cyclopentane (CyC5) hydrate particles and water droplets were investigated using a micromechanical force (MMF) apparatus. The concentration of Span80 in CyC5 was ranged from 0.01?wt% to 1?wt%, and the experimental temperature was set at 1.5°C and 7°C, respectively. The results indicate that the absorption of Span80 on the droplet surface can render the interfaces more stable, preventing hydrate agglomeration. When the preload/contact force exceeds the strength of the interface (相似文献   
998.
The synthesis and characterization is reported of (C9NH20)2SnBr4, a novel organic metal halide hybrid with a zero‐dimensional (0D) structure, in which individual seesaw‐shaped tin (II) bromide anions (SnBr42?) are co‐crystallized with 1‐butyl‐1‐methylpyrrolidinium cations (C9NH20+). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep‐red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr42? species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.  相似文献   
999.
Fluorescent probes in the second near‐infrared window (NIR‐II) allow high‐resolution bioimaging with deep‐tissue penetration. However, existing NIR‐II materials often have poor signal‐to‐background ratios because of the lack of target specificity. Herein, an activatable NIR‐II nanoprobe for visualizing colorectal cancers was devised. This designed probe displays H2S‐activated ratiometric fluorescence and light‐up NIR‐II emission at 900–1300 nm. By using this activatable and target specific probe for deep‐tissue imaging of H2S‐rich colon cancer cells, accurate identification of colorectal tumors in animal models were performed. It is anticipated that the development of activatable NIR‐II probes will find widespread applications in biological and clinical systems.  相似文献   
1000.
The light‐induced reversible and cyclic reconfiguration of constitutional dynamic networks, consisting of supramolecular nucleic acid structures as constituents and a photoisomerizable trans/cis‐azobenzene‐functionalized nucleic acid as the trigger is demonstrated. In addition, the cyclic photochemical reconfiguration of the constitutional dynamic networks guides the switchable on/off operation of an emerging hemin/G‐quadruplex DNAzyme.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号