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   22204篇
  免费   1213篇
  国内免费   3302篇
化学   21461篇
晶体学   483篇
力学   145篇
综合类   112篇
数学   862篇
物理学   3656篇
  2024年   96篇
  2023年   221篇
  2022年   452篇
  2021年   463篇
  2020年   553篇
  2019年   1325篇
  2018年   564篇
  2017年   1217篇
  2016年   760篇
  2015年   677篇
  2014年   834篇
  2013年   1838篇
  2012年   1381篇
  2011年   1390篇
  2010年   993篇
  2009年   1199篇
  2008年   1347篇
  2007年   1378篇
  2006年   1305篇
  2005年   1170篇
  2004年   1176篇
  2003年   931篇
  2002年   794篇
  2001年   692篇
  2000年   643篇
  1999年   496篇
  1998年   446篇
  1997年   386篇
  1996年   305篇
  1995年   315篇
  1994年   237篇
  1993年   202篇
  1992年   200篇
  1991年   147篇
  1990年   91篇
  1989年   79篇
  1988年   66篇
  1987年   41篇
  1986年   36篇
  1985年   42篇
  1984年   25篇
  1983年   13篇
  1982年   31篇
  1981年   37篇
  1980年   19篇
  1979年   35篇
  1978年   15篇
  1977年   16篇
  1976年   13篇
  1973年   10篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
The precursors with a low manganese content ≤ 0.07% Mn were synthesized by spontaneous crystallization from Zn2+, Mn2+ and C2O4 2−-containing solutions. The initial ratio Zn2+:C2O4 2− = 1:1 and 1:2 influences the morphology and prevailing orientations of the crystallites in the oxalate samples. The presence of such small Mn content in the samples does not change the morphology or size of the crystals. The ZnO and Mn/ZnO oxides with manganese content from 0.51×10−2 to 15.1×10−2 Wt % are obtained after thermal decomposition of the oxalates. The oxides preserved the morphology of the precursors. The catalytic tests show that the pure ZnO has a poor activity for CO oxidation reaction. Its doping with Mn promotes the catalytic activity (up from twice to five times) in spite of the very low contents of the dopants. The observed increase of the activity depends on both dopant concentration and Zn2+:C2O4 2− ratio, probably due to the different mechanism of the manganese inclusion and different morphology of the oxides. The catalysts of the 1:2 series are more active in CO oxidation reaction.   相似文献   
62.
A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I2 (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.  相似文献   
63.
在铝酸盐体系中,利用微等离体氧化脉冲电源在Ti-6Al-4V合金表面制备了以Al2TiO5为主晶相的陶瓷膜层,然后采用钛酸四丁酯/乙醇和硅酸钠溶液的封孔方法对微弧氧化陶瓷膜进行封孔后处理。通过SEM及高温氧化测试,分析比较了陶瓷膜层在封孔前后的表面形貌以及抗高温氧化性能的变化情况。结果表明:封孔后膜层孔洞明显变小。经700℃高温氧化测试,采用钛酸四丁酯/乙醇溶液封孔方法不仅没有带来抗高温氧化性能的提高反而下降,而硅酸钠溶液的封孔方法提高了抗高温氧化性能。  相似文献   
64.
New derivatives obtained by the combination of unique 1,2,4,5-tetrazine and 4H-1,2,4-triazole rings have great application potential in many fields. Therefore, two synthetic few-step methodologies, which make use of commercially available 4-cyanobenzoic acid (method A) and ethyl diazoacetate (method B), were applied to produce two groups of the aforementioned heterocyclic conjugates. In both cases, the target compounds were obtained in various combinations, by introducing electron-donating or electron-withdrawing substituents into the terminal rings, together with aromatic or aliphatic substituents on the triazole nitrogen atom. Synthesis of such designed systems made it possible to analyze the influence of individual elements of the structure on the reaction course, as well as the absorption and emission properties. The structure of all products was confirmed by conventional spectroscopic methods, and their luminescent properties were also determined.  相似文献   
65.
标题化合物是一个重要的精细化工中间体,可用于制备嘧啶类、吡唑类等产品.本文利用红外光谱(IR)、质谱(MS)、核磁共振氢谱(1 H NMR)、核磁共振碳谱(13 C NMR)和X-射线单晶衍射对此化合物进行了表征,并在B3LYP/6-311G(d,p)模式下使用密度泛函理论(DFT)计算了此化合物的最稳定晶体结构以及最...  相似文献   
66.
以处理后的脱硫石膏为原料,在H2SO4-H2O体系中以Cu(NO3)2为晶形控制剂采用水热法制备脱硫石膏晶须,探讨了Cu(NO3)2对脱硫石膏晶须生长的影响机理。结果表明:Cu(NO3)2对脱硫石膏有明显促溶作用,其中Cu2+可减小溶液中各离子的活度系数,使溶液中的Ca2+浓度增大。NO-3通过静电作用在Ca2+周围聚集并对SO2-4产生屏蔽作用,导致脱硫石膏继续溶解并使Ca2+和SO2-4的浓度处于相对稳定状态,有利于半水脱硫石膏晶体的形核与生长。此外,Cu2+还可在晶须的生长过程中选择性吸附在晶须表面,生成CuSO4,促进了脱硫石膏的结晶生长,最终在Cu(NO3)2用量为2.0%(质量分数)时制备的脱硫石膏晶须长径比约为73。  相似文献   
67.
A series of 1,7-diphenyl-1,4-heptadien-3-ones with various substituents (HO-, CH3O-, CH3-, Cl-) on the phenyl rings were synthesized and evaluated for anti-neuroinflammatory effects in LPS-stimulated BV2 microglia. The pharmacological results showed that the target compounds bearing methoxy groups greatly inhibited LPS-induced NO release, and that the active compounds CU-19 and CU-21 reduced the level of NO, TNF-α, IL-6 and PGE-2, downregulated the expression of COX-2 and iNOS in LPS-stimulated BV2 cells. A study of the mechanism of action revealed that CU-19 and CU-21 inhibited the nuclear translocation of NF-κB and phosphorylation of MAPKs (ERK, JNK, and p38). A preliminary pharmacokinetic study in rats revealed that the pharmacokinetic properties of CU-19 and CU-21 were dramatically ameliorated in comparison with the pharmacokinetic properties of curcumin.  相似文献   
68.
Considering the important damage caused by the reactive oxygen (ROS) and nitrogen (RNS) species in the human organism, the need for new therapeutic agents, with superior efficacy to the known natural and synthetic antioxidants, is crucial. Quinazolin-4-ones are known for their wide range of biological activities, and phenolic compounds display an important antioxidant effect. Linking the two active pharmacophores may lead to an increase of the antioxidant activity. Therefore, we synthesized four series of new hybrid molecules bearing the quinazolin-4-one and phenol scaffolds. Their antioxidant potential was evaluated in vitro, considering different possible mechanisms of action: hydrogen atom transfer, ability to donate electrons and metal ions chelation. Theoretical quantum and thermodynamical calculations were also performed. Some compounds, especially the ortho diphenolic ones, exerted a stronger antioxidant effect than ascorbic acid and Trolox.  相似文献   
69.
Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m−2∙h−1.  相似文献   
70.
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