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   7458篇
  免费   1047篇
  国内免费   1144篇
化学   5932篇
晶体学   130篇
力学   369篇
综合类   136篇
数学   862篇
物理学   2220篇
  2024年   12篇
  2023年   110篇
  2022年   232篇
  2021年   208篇
  2020年   277篇
  2019年   267篇
  2018年   215篇
  2017年   199篇
  2016年   356篇
  2015年   344篇
  2014年   430篇
  2013年   550篇
  2012年   611篇
  2011年   668篇
  2010年   556篇
  2009年   480篇
  2008年   550篇
  2007年   553篇
  2006年   515篇
  2005年   371篇
  2004年   367篇
  2003年   273篇
  2002年   295篇
  2001年   226篇
  2000年   158篇
  1999年   135篇
  1998年   104篇
  1997年   90篇
  1996年   83篇
  1995年   52篇
  1994年   46篇
  1993年   50篇
  1992年   41篇
  1991年   32篇
  1990年   36篇
  1989年   20篇
  1988年   15篇
  1987年   15篇
  1986年   14篇
  1985年   14篇
  1984年   7篇
  1983年   13篇
  1982年   7篇
  1981年   5篇
  1980年   8篇
  1978年   6篇
  1974年   3篇
  1973年   3篇
  1969年   3篇
  1928年   3篇
排序方式: 共有9649条查询结果,搜索用时 15 毫秒
961.
In order to establish the hierarchical structure in multiple levels on mesoporous silica, this article reports a new strategy to prepare the monolith with the pore configuration in nanometer scale, micro-morphology in micrometer level and macroscopic shape in millimeter or larger grade. These hierarchical monoliths are synthesized in a weak acidic condition by using triblock copolymer P123, hydroxyl carboxylic acid and tetramethyl orthosilicate (TMOS), and the textural properties of the mesostructure can be facilely adjusted by simply controlling the synthesis condition without any additive. During the synthesis, the primary particles can be selectively synthesized as monodispersed sphere, noodle, prism, straight rods with different size or irregular bars, and their connection plus arrangement in 3D directions can be also regulated. Therefore, various textural properties of mesopore are able to be altered including pore size (5.5-10.6 nm), total pore volume (0.48-1.2 cm(3) g(-1)), micropore surface area (47-334 m(2) g(-1)), and pore shape (from 2D or 3D straight channel to plugged channel). Moreover, these monoliths exhibit a considerable mechanical strength; they are also applied in eliminating particulate matters and tobacco special nitrosamines (TSNA) in tobacco smoke, exhibiting various morphology-assisted functions.  相似文献   
962.
Phosphate removal from polluted water is crucial to preventing eutrophication. Herein, we present the investigation on phosphate adsorption in aqueous solutions by using lanthanum-doped activated carbon fiber (ACF-La). Various batch sorption conditions, e.g., pH, ionic strength, and temperature were tested, and the adsorption mechanisms were discussed. The sorption capacity of ACF-La was higher in acidic solutions than that in basic ones, suggesting that the Lewis acid-base interaction gradually dominated the adsorption process with the increase in pH values. The degree of phosphate removal decreased with the enhancement of the ionic strength of the solution, meaning that the adsorption of phosphate on ACF-La was strongly dependent on ionic strength. Employing the pseudo first- and second-order, and intra-particle diffusion models to evaluate the adsorption kinetics of phosphate onto ACF-La indicated that the second-order model best fits the experimental data. The presence of chloride ion in solutions increased the effect of intra-particle diffusion on the adsorption of phosphate onto ACF-La but reduced the overall rate of the adsorption. The thermodynamic parameters were determined which revealed the feasibility, spontaneity, and endothermic nature of adsorption.  相似文献   
963.
Alumina nanotubes (ANTs) with unique fusiform morphologies were synthesized via a simple electrochemical route; the fluctuation of the electronic current density during the anodization process is considered to be the main reason for the formation of such new alumina nanostructures.  相似文献   
964.
The Chaihu-Shaoyao drug pair (Bupleuri Radix and Paeoniae Radix Alba) which is a traditional Chinese drug pair, has been widely used for anti-inflammatory purposes. Saikosaponin a (SSA), saikosaponin d (SSD) and paeoniflorin are identified as the main components in the pair. The present study focused on the interaction of the main components based on investigating their intestinal absorption using a four-site perfused rat intestinal model in order to clarify the mechanism of the compatibility of Chaihu-Shaoyao. The concentrations of SSA, SSD and paeoniflorin in the intestinal perfusate were determined by LC/MS or UPLC (Ultra Performance Liquid Chromatography) methods, followed by P*(eff) (effective permeability) and 10% ABS (the percent absorption of 10 cm of intestine) calculations. The results showed that all of the three main components displayed very low permeabilities (P*(eff) < 0.4), which implied their poor absorption in the rat intestine. The absorption levels of SSA and SSD were similar in intestine and higher in ileum than those in other intestinal regions in the decreasing order: colon, jejunum and duodenum. However, there is no significant difference in the absorption of paeoniflorin in the four segments (P < 0.05). The P*(eff) values of paeoniflorin exhibited an almost 2.11-fold or 1.90-fold increase in ileum when it was co-administrated with SSA and SSD, as well as 2.42-, 2.18-fold increase in colon, respectively, whereas the absorptions of SSA and SSD were not influenced by paeoniflorin. In conclusion, SSA and SSD could promote the absorption of paeoniflorin. To some extent this might explain the nature of the compatibility mechanisms of composite formulae in TCMs.  相似文献   
965.
Magnetic dendrites of Co x Pb1−x were fabricated through potentiostatic electrochemical deposition on Cu substrates in boric acid solution at room temperature. The as-deposited dendrites were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), electrodeposition (ED), and energy dispersive X-ray spectroscopy (EDS). SEM results indicate that the Co x Pb1−x dendrites are highly symmetrical in structures. The diameters of the branches are about 50 ~ 200 nm, and the backbones are continuous with lengths up to about 10 μm. XRD patterns show that the as-deposited dendrites are solid solutions. The annealing treatment can result in the recrystallization of these metastable alloys into two separate phases. TEM, ED, and EDS results also reveal that the backbones and the branches of the dendrites are composed of different amounts of cobalt. Magnetic measurements confirm that the as-deposited Co x Pb1−x dendrites have a softly ferromagnetic behavior, and a small coercive force (about 80 Oe). Also the saturation magnetizations of the Co x Pb1−x dendrites decrease rapidly with the temperature increasing.  相似文献   
966.
Methanol (MeOH) oxidation reaction (MOR) at Pt electrodes under potentiostatic conditions has been investigated by electrochemical in situ FTIR spectroscopy (FTIRS) in attenuated-total-reflection configuration under controlled flow conditions in 0.1 M HClO(4) with 2 M MeOH, where the mass transport effects are largely eliminated using a flow cell. Our results reveal that (i) at constant potentials, the methanol dehydrogenation rate decreases while the CO(ad) oxidation rate increases with the accumulation of CO(ad) until the maximum CO(ad) coverage (ca. 0.5 ML i.e., the steady state) is reached; (ii) at fixed CO(ad) coverage, the rates for MeOH decomposition to CO(ad) and CO(ad) oxidation increases with potential from 0.3 to 0.7 V (vs. RHE), with Tafel slopes for MeOH dehydrogenation of ca. 440 ± 30 mV/dec, which is independent of CO(ad) coverage; (iii) the current efficiency of the CO pathway in MOR at 0.6 and 0.7 V is below 20% and it decreases toward higher potentials. The mechanisms as well as the potential induced change in the kinetics of different pathways involved in MOR are briefly discussed.  相似文献   
967.
Two cyclopropyl allenylidene complexes [Ru]=CCC(R)(C3H5) ([Ru]=[RuCp(PPh3)2], Cp=Cyclopentadienyl; R=thiophene ( 2a ) and R=Ph ( 2b )) are prepared from the reactions of [Ru]Cl with the corresponding 1‐cyclopropyl‐2‐propyn‐1‐ol in the presence of KPF6. Thermal treatment, halide‐anion addition, and palladium‐catalyzed reactions of 2a and 2b all lead to a ring expansion of the cyclopropyl group, giving the vinylidene complexes 4a and 4b , respectively, each with a five‐membered ring. This ring expansion proceeds by C C bond formation between Cβ of the cumulative double bond and a methylene group of the cyclopropyl ring. In the reaction of 2a with pyrrole, consecutive formation of two C C bonds, one between C‐2 of pyrrole and Cγ of 2a and the other between C‐3 of pyrrole and Cα, results in the formation of 6a . The reaction proceeds by addition of pyrrole and 1,3‐proton shifts. The hydrogenation of 2a by NaBH4 is carried out in different solvents. The cumulative double bonds are reduced regioselectively to give a mixture of 7a and 8a . Interestingly, use of different solvents leads to different ratios of 7a and 8a . Presence of a protic solvent like methanol in dichloromethane or chloroform solution increases the yield of 8a , thus revealing that both the rates of hydroboration and deboronation increase. The structures of two new complexes 4a and 6a have been firmly established by X‐ray diffraction analysis.  相似文献   
968.
The asymmetric unit of the title compound, [InNa(C3H5O3)4]n, consists of one InIII ion, one NaI ion and four crystallographically independent l ‐lactate monoanions. The coordination of the InIII ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The NaI ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each InIII ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)4] unit, which is further linked by NaI ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.  相似文献   
969.
超空泡射弹的发射装置及射弹在制造,安装过程中存在各种不确定性.本文采用最大熵法来分析这些不确定性对射弹弹道的影响.介绍了超空泡射弹的动力学模型,对射弹的受力特性和随机参数进行了分析.根据给出的理论编制了基于最大熵法的随机参数超空泡射弹弹道随机特性分析的仿真程序,并对一个模型弹仿真计算.计算表明,与发射装置有关的随机参数...  相似文献   
970.
从迭代数列及其基本性质出发,给出单调有界定理、压缩映象原理、Cauchy收敛准则和上(下)极限四种判别迭代数列收敛的方法.  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