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   90214篇
  免费   2567篇
  国内免费   1785篇
化学   32716篇
晶体学   899篇
力学   7537篇
综合类   88篇
数学   33399篇
物理学   19927篇
  2024年   56篇
  2023年   284篇
  2022年   484篇
  2021年   520篇
  2020年   540篇
  2019年   481篇
  2018年   10763篇
  2017年   10544篇
  2016年   6555篇
  2015年   1459篇
  2014年   1017篇
  2013年   1278篇
  2012年   4854篇
  2011年   11544篇
  2010年   6374篇
  2009年   6708篇
  2008年   7346篇
  2007年   9438篇
  2006年   879篇
  2005年   1834篇
  2004年   1911篇
  2003年   2291篇
  2002年   1310篇
  2001年   517篇
  2000年   520篇
  1999年   428篇
  1998年   450篇
  1997年   334篇
  1996年   407篇
  1995年   327篇
  1994年   257篇
  1993年   252篇
  1992年   181篇
  1991年   204篇
  1990年   192篇
  1989年   166篇
  1988年   150篇
  1987年   135篇
  1986年   117篇
  1985年   108篇
  1984年   70篇
  1983年   69篇
  1982年   67篇
  1981年   58篇
  1980年   59篇
  1979年   54篇
  1978年   42篇
  1914年   45篇
  1909年   41篇
  1908年   40篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).  相似文献   
82.
The first member of the single‐isomer, dicationic cyclodextrin (CD) family, 6A‐ammonium‐6C‐butylimidazolium‐β‐cyclodextrin chlorides (AMBIMCD), has been synthesized, analytically characterized, and used to separate a variety of acidic enantiomers and amino acids by CE. Starting from mono‐6A‐azido‐β‐cyclodextrin, the cationic imidazolium and ammonium moieties were subsequently introduced onto primary ring of β‐cyclodextrin via nucleophilic addition and Staudinger reaction. The analytically pure AC regio‐isomer CD was further obtained via column chromatography. This dicationic CD exhibited excellent enantioselectivities for selected analytes at concentration as low as 0.5 mM, which were even better than those of its mono‐imidazolium or ammonium‐substitued counterpart CDs at 10 equivalent concentrations. The effective mobilities of all studied analytes were found to decrease with the concentration of AMBIMCD. Inclusion complexation in combination with eletrostatic interactions seemed to account for the enhanced chiral discrimination process.  相似文献   
83.
84.
Commercial CaO was modified simply with benzyl bromide. The modified CaO had good water resistance, and characterization by FTIR and TG revealed the modifier was chemically bonded to the CaO surface. Commercial CaO and CaO modified with benzyl bromide were investigated as catalysts for the Henry reaction between benzaldehyde and nitromethane. It was found that the catalytic activity of the modified CaO was greatly improved, with high conversion of benzaldehyde to the (E)-phenyl nitroolefin and 1-phenyl-2-nitroethanol, and with different selectivity from commercial CaO. The effect of modification and reaction conditions on yield, selectivity, and mechanism were studied thoroughly.  相似文献   
85.
Using Fickett’s model for reactive compressible flows, i.e., the reactive form of Burgers’ equation, we address the problem of shock induced ignition by a piston in a reactive medium characterized by a 2 step induction-reaction kinetics. Owing to the model’s simplicity, the ignition and acceleration mechanism is explained using the two families of characteristics admitted by the model. The energy release along the particle paths provides the amplification of forward-traveling pressure waves. These waves pre-compress the medium in the induction layer ahead of the reaction zone, therefore changing the induction delays of successive particles. The variation of the induction delay provides the modulation of the amplification of the forward traveling pressure waves by controlling the residence time of the pressure waves in the reaction zone. A closed form analytical solution is obtained by the method of characteristics and high activation energy asymptotics. The acceleration of the reaction zone was found to be proportional to the product of the activation energy, the ratio of the induction to reaction time and the heat release. This finding provides a theoretical justification for the previous use of this non-dimensional number to characterize the ignition regimes observed experimentally in detonations and shock induced ignition phenomena. Numerical simulations are presented and analyzed. Both subsonic and supersonic internal flame propagation are observed, consistent with experiment and previous reactive Euler models.  相似文献   
86.
O-Demethylation at C-1 in the C19-diterpenoid alkaloids is very challenging. In this paper, it was firstly observed that 10-OH group in deltaline (1) is a determining factor for the O-demethylation reaction. After removal of this hydroxyl group, 1-O-methyl group in the corresponding deltaline analogs can be readily removed by treatment with HBr–HOAc. Meanwhile, the C-14 atom in bromides 18 or 20 can be extruded under basic condition probably via a sequence, including Grob fragmentation, aerobic oxidation, deformylation, and SN2 nucleophilic substitution, to give enone 21 (70%) and oxetane 22 (14%). The structure of compound 22 was confirmed by X-ray crystallographic analysis of its derivative 21.  相似文献   
87.
88.
Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported and discussed.  相似文献   
89.
The type of cooperation between antioxidants in the binary mixtures of four substituted diphenylamines and phenotiazine in the stabilization of styrene-butadiene rubber has been tested. Thermooxidation of the samples has been studied by differential scanning calorimetry under non-isothermal conditions. The protection factors of the individual stabilizers and their mixtures were determined. The synergy factors were applied to asses the type of cooperation of antioxidants in the mixtures. From their values it can be concluded that the type of cooperation depends on temperature. The highest synergistic effect has been observed for the mixture of phenotiazine and [4-(1-methyl-1-phenyl-ethyl)-phenyl]-phenylamine.  相似文献   
90.
In order to study the temperature changing rule of the crude oil in the storage tank, the wavelet finite element method, the traditional finite element method and the test were used to carry out the numerical simulation. Firstly, the thermal wavelet finite element was put forward established based on thermal finite element theory and the wavelet theory. And the computational model and three boundary conditions were established. And then the temperature changing rule of the crude oil in the storage tank in 24 h for three boundary conditions was obtained by using three methods, and the results showed that the wavelet finite element method had advantages in the numerical analysis of the temperature changing rule of the crude oil in the storage. And then the temperature distribution rule of the crude oil in the storage tank under different conditions in 5 h was obtained. And the temperature changing mechanism of the crude oil was summarized finally.  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