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   2166篇
  免费   180篇
  国内免费   125篇
化学   1151篇
晶体学   27篇
力学   89篇
综合类   8篇
数学   348篇
物理学   430篇
无线电   418篇
  2023年   41篇
  2022年   70篇
  2021年   86篇
  2020年   86篇
  2019年   87篇
  2018年   83篇
  2017年   75篇
  2016年   141篇
  2015年   94篇
  2014年   111篇
  2013年   146篇
  2012年   124篇
  2011年   139篇
  2010年   101篇
  2009年   95篇
  2008年   94篇
  2007年   94篇
  2006年   87篇
  2005年   81篇
  2004年   60篇
  2003年   46篇
  2002年   33篇
  2001年   27篇
  2000年   39篇
  1999年   31篇
  1998年   21篇
  1997年   15篇
  1996年   29篇
  1995年   34篇
  1994年   22篇
  1993年   20篇
  1992年   19篇
  1991年   28篇
  1990年   13篇
  1989年   7篇
  1988年   9篇
  1987年   7篇
  1986年   9篇
  1985年   18篇
  1984年   6篇
  1983年   16篇
  1982年   11篇
  1981年   19篇
  1980年   13篇
  1978年   15篇
  1977年   11篇
  1976年   11篇
  1975年   6篇
  1974年   6篇
  1973年   13篇
排序方式: 共有2471条查询结果,搜索用时 15 毫秒
21.
A typical planar Hall effect (PHE) sensor junction consists of two Hall bars that the bars appear normal to each other and the junction can have the required four terminals for current and voltage measurements. We are now introducing a tilted angle of the cross-junction and studying the role of the PHE therein. The results show that although there is a tilted angle of the cross-junction, the PHE voltage is remained constant. The result is interpreted by assuming the sensor material with the behavior of a basic single domain structure under the external magnetic field reversals. The calculations of the model are found to be in good concurrence with the experimental results.  相似文献   
22.
Xiang J  Li H  Yang K  Yi L  Xu Y  Dang Q  Bai X 《Molecular diversity》2012,16(1):173-181

Abstract  

Highly substituted novel 4H-pyrimido[1,6-a] pyrimidines were prepared by a trifluoromethanesulfonic acid catalyzed one-pot three-component condensation of 4-aminopyrimidines, aldehydes, and β-ketoesters. A preliminary feasibility study was undertaken on these compounds, to assess the potential production of a library of further diversified compounds by nucleophilic replacement of Cl (R1) or by reaction of electrophiles with the NH2 (R2) group.  相似文献   
23.
本文以国际性评论、文摘刊物《MathematicsReviews》(美国数学会出版)在1984-1993年间摘录文南总量和摘录中国数学研究文献量为统计样本,从分支学科文献量分布的角度,比较了中外数学研究的现状.特别结合国家自然科学基金“七五”、“八五”数学重大项目的研究成果,探讨了目前数学研究的发展趋势.  相似文献   
24.
Miniaturized liquid–liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid–liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water‐in‐decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface‐enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p‐dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min?1 for the first‐order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.  相似文献   
25.
The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π–π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation.  相似文献   
26.
We introduce a class of single-chain nanoparticles (SCNPs) that respond to visible light (λmax=415 nm) with complete unfolding from their compact structure into linear chain analogues. The initial folding is achieved by a simple esterification reaction of the polymer backbone constituted of acrylic acid and polyethylene glycol carrying monomer units, introducing bimane moieties, which allow for the photochemical unfolding, reversing the ester-bond formation. The compaction and the light driven unfolding proceed cleanly and are readily followed by size exclusion chromatography (SEC) and diffusion ordered NMR spectroscopy (DOSY), monitoring the change in the hydrodynamic radius (RH). Importantly, the folding reaction and the light-induced unfolding are reversible, supported by the high conversion of the photo cleavage. As the unfolding reaction occurs in aqueous systems, the system holds promise for controlling the unfolding of SCNPs in biological environments.  相似文献   
27.
The development of enantioselective annulation reactions using readily available substrates for the construction of structurally and stereochemically diverse heterocycles is a compelling topic in diversity-oriented synthesis. Herein, we report efficient catalytic asymmetric formal 1,3-dipolar (3 + 4) cycloadditions of azomethine ylides with 4-indolyl allylic carbonates for the construction of azepino[3,4,5-cd]-indoles fused with a challenging seven-membered N-heterocycle, a frequently occurring tricyclic indole scaffold in bioactive compounds and pharmaceuticals. Through cooperative Cu/Ir-catalyzed asymmetric allylic alkylation followed by intramolecular Friedel–Crafts reaction, an array of azepino[3,4,5-cd]-indoles were obtained in good yields with excellent diastereo-/enantioselective control. More importantly, the full stereodivergence of this transformation was established via synergistic catalysis followed by acid-promoted epimerization, and up to eight stereoisomers of the cycloadducts bearing three stereogenic centers could be predictably achieved from the same set of starting materials for the first time. Quantum mechanical computations established a plausible mechanism for the synergistic Cu/Ir catalysis to stereodivergently introduce two vicinal stereocenters whose stereochemical information is remotely delivered across the fused azepine ring to control the third chiral center. Epimerization of the last center involves protonation-enabled reversal of the thermodynamically controlled relative configuration.

A stereodivergent synthesis of azepino[3,4,5-cd]-indoles bearing three stereogenic centers was established via synergistic dual-metal catalysis followed by acid-promoted epimerization, and up to all eight stereoisomers could be predictably achieved.  相似文献   
28.
In this paper, the classical least-squares (CLS) method with molecular absorption spectrophotometric measurement was used to determine simultaneously paracetamol (PAR), ibuprofen (IBU), and caffeine (CAF) in tablets. The absorbance spectra of the standard solutions and samples were measured over a wavelength from 220 to 300 nm with a 0.5 nm step. The concentration of PAR, IBU, and CAF in the sample solutions was calculated by using Visual Basic for Applications (VBA) and a program called CLS-Excel written in Microsoft Excel 2016. The method and the CLS-Excel program were tested on mixed standard laboratory samples with different PAR, IBU, and CAF concentration ratios, and they showed only small errors and a satisfying repeatability. An analytical procedure for tablets containing PAR, IBU, and CAF was developed. The reliability of the procedure was proved via the recovery and repeatability of the analysis results with an actual tablet sample and by comparing the mean contents of active substances in the tablets obtained from the analytical procedure with the HPLC method. The procedure is simple with a reduced cost compared with the HPLC standard method.  相似文献   
29.
30.
Pyrido[3,2,1‐jk]carbazoles 1 , synthesized from carbazoles and alkyl‐ or arylmalonates, gave regioselective electrophilic substitution reactions at position 5 such as chlorination to 5‐chloro derivatives 2 , nitration to 5‐nitro compounds 3 , or hydroxylation to 5‐hydroxy derivatives 4 . 5‐Hydroxy compounds 4 gave on treatment with strong bases ring contraction to 5 , 6 or the ring opening product 7 . Exchange of the chloro group in 2 with azide or amines gave the corresponding azides 8 and the 5‐amino derivatives 9 and 10 . Alkylation of 1 with benzyl chloride or allyl bromide resulted in the formation of 5‐C‐alkylated products 11 together with 4‐alkyloxy derivatives 12 . J. Heterocyclic Chem., 48, 1039 (2011).  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