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   49653篇
  免费   3976篇
  国内免费   4036篇
化学   28220篇
晶体学   275篇
力学   1094篇
综合类   673篇
数学   6890篇
物理学   20513篇
  2023年   639篇
  2022年   787篇
  2021年   1660篇
  2020年   1264篇
  2019年   1276篇
  2018年   965篇
  2017年   1230篇
  2016年   1463篇
  2015年   1453篇
  2014年   2021篇
  2013年   3219篇
  2012年   2562篇
  2011年   3069篇
  2010年   2605篇
  2009年   3312篇
  2008年   3274篇
  2007年   3635篇
  2006年   3025篇
  2005年   1919篇
  2004年   1734篇
  2003年   1594篇
  2002年   1463篇
  2001年   1372篇
  2000年   1048篇
  1999年   859篇
  1998年   848篇
  1997年   699篇
  1996年   703篇
  1995年   604篇
  1994年   580篇
  1993年   604篇
  1992年   607篇
  1991年   406篇
  1990年   348篇
  1989年   264篇
  1988年   296篇
  1987年   238篇
  1986年   229篇
  1985年   338篇
  1984年   248篇
  1983年   148篇
  1982年   309篇
  1981年   484篇
  1980年   438篇
  1979年   468篇
  1978年   373篇
  1977年   285篇
  1976年   243篇
  1974年   78篇
  1973年   159篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
21.
The combinatorial object named t-spontaneous emission error design (t-SEED) was proposed by Beth et al. in 2003 in order to correct errors caused by quantum jumps. The newly rising category of t-SEEDs has been studied extensively in recent years. Especially, the maximal possible dimensions for 2-SEEDs with block size 3 were determined completely; lower bounds on 2-SEEDs were established by applying affine groups. In this paper we utilize the action of twisted affine groups on finite fields and obtain new lower bounds on the dimensions of 2-(q2,k;m) SEEDs, some of which outperform the known ones.  相似文献   
22.
Oxidative dehydrogenation (ODH) of n-octane was carried out over a vanadium–magnesium oxide catalyst in a continuous flow fixed bed reactor. The catalyst was characterized by ICP–OES, powder XRD and SEM. The catalytic tests were carried out at different gas hourly space velocities (GHSVs), viz. 4000, 6000, 8000, and 10,000 h?1. The best selectivity for octenes was obtained at the GHSV of 8000 h?1, while that for C8 aromatics was attained at the GHSV of 6000 h?1 at high temperatures (500 and 550 °C). The catalytic testing at the GHSV of 10,000 h?1 showed the lowest activity, while that at the GHSV of 4000 h?1 consistently showed the lowest ODH selectivity. Generally, the best ODH performance was obtained by the catalytic testing at the GHSVs of 6000 and 8000 h?1. No phasic changes were observed after the catalytic testing.  相似文献   
23.
Tuning fluorescence colour of solid-state materials has become a topic of increasing interest for both fundamental mechanism study and practical applications such as sensors, optical recording and security printing. In this work, a fluorescent colour tuneable molecule BA-C16 is rationally designed and facilely synthesized by attaching flexible long alkyl chains to 2-hydroxybenzophenone azine ( BA ), which shows both aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. Compared to BA , the simple introduction of long alkyl chains in BA-C16 leads to an emission wavelength redshift from 542 to 558 nm. This strategy of extending emission wavelength is rarely reported, and is ascribed to the enlarged through-space π-conjugation between interplanar molecules in the aggregate of BA-C16 . Three crystals of BA-C16 are obtained with green, yellowish green and yellow emission. According to characterization by X-ray crystallography, X-ray powder diffraction and differential scanning calorimetry, alkyl chains play an important role in inducing different stacking modes of the three crystals, which further leads to polymorph-dependent fluorescence colour. BA-C16 exhibits tuneable solid-state fluorescence upon vapor fumigation, or annealing based on a transition between a “near-monomer” crystalline state and a “dimer” crystalline state. BA-C16 is further applied for rewritable fluorescence printing tuned by vapor- and thermal-treatment.  相似文献   
24.
The radius of spatial analyticity for solutions of the KdV equation is studied. It is shown that the analyticity radius does not decay faster than t?1/4 as time t goes to infinity. This improves the works of Selberg and da Silva (2017) [30] and Tesfahun (2017) [34]. Our strategy mainly relies on a higher order almost conservation law in Gevrey spaces, which is inspired by the I-method.  相似文献   
25.
A series of new tetrakis(dialkoxyphenyl) dicyanotetraoxapentacene derivatives ( 1 a – c ) were prepared by reaction of the appropriate terphenyl diols with tetrafluoroterephthalonitrile in good yields. Compounds 1 b and 1 c , which bear hexyloxy and decyloxy side chains, exhibited columnar hexagonal mesophases, as shown by polarized optical microscopy, variable-temperature powder X-ray diffraction, and differential scanning calorimetry. Single-crystal X-ray diffraction of methoxy-substituted 1 a revealed that the dicyanotetraoxapentacene core is highly planar, consistent with the notion that these molecules are able to stack in columnar mesophases. A detailed photophysical characterization showed that these compounds exhibit aggregation-induced emission in solution, emission in nonpolar solvents, weak emission in polar solvents, and strong emission in the solid state both as powder and in thin films. These observations are consistent with a weakly emissive charge-transfer state in polar solvents and a more highly emissive locally excited state in nonpolar solvents.  相似文献   
26.
We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways.  相似文献   
27.
28.
Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO2, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO2, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO2 under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO2]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO2), 365.8 K (TCCA-DMF)/NaNO2, and 358 K (TCCA-DMA)/NaNO2. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction.  相似文献   
29.
Investigating the dilatancy, acoustic emission and failure characteristics of fissured rock are significant to ensure their geotechnical stability. In this paper, the uniaxial and triaxial compression experiments with AE monitoring under different loading rates were carried out on fissured rock specimens with the same geometrical distribution of two pre-existing flaws. The dilatancy and AE activity of these specimens were discussed, and the effects of the confining pressure and loading rate on the mechanical parameters and failure characteristics were analyzed. The results show that the exponential strength criterion is more suitable than the Mohr–Coulomb strength criterion to characterize the strength characteristics of fissured rock. The crack evolution and failure characteristics of fissured rock specimens are more complicated than those of intact rock specimens. The failure characteristics of the fissured rock follow the tensile shear coalescence model, crack branching occurs with increasing the loading rate, and the multi-section coalescence model is verified with increasing the confining pressure. The phenomena of stress drop and yield platform usually occur after the dilatancy onset, the specimen does not fail instantaneously, and the propagation and coalescence of cracks cause a sharp increase in the AE signals, circumferential strain, and volumetric strain.  相似文献   
30.
A zinc-selective probe based on a set of rare earth complexes of a modified DO3A macrocyclic ligand incorporating a tris-pyridylamine (TPA) moiety has been structurally characterised in solution and in the solid-state. One pyridine group possesses a tert-butyl substituent to serve as an NMR reporter group. The mono-capped square-antiprismatic Dy complex has a long bond (2.83 Å) to an apical N atom (pKa 5.70 Eu) and binds to one water molecule on zinc binding. Zinc binding is reversible and involves all of the exocyclic ligand N donors; it is signalled by large (ratiometric) changes in Eu emission intensity, and by dramatic changes in the size (>50 ppm) and sign of the chemical shift of the paramagnetically shifted tBu resonances in Tb, Dy and Tm complexes. Slow trans-metallation was observed, leading to formation of an unusual di-zinc species in which one zinc ion is seven-coordinate and the other is six-coordinate.  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