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   2008篇
  免费   240篇
  国内免费   211篇
化学   1209篇
晶体学   33篇
力学   107篇
综合类   43篇
数学   198篇
物理学   869篇
  2024年   7篇
  2023年   33篇
  2022年   63篇
  2021年   56篇
  2020年   60篇
  2019年   81篇
  2018年   73篇
  2017年   48篇
  2016年   79篇
  2015年   64篇
  2014年   80篇
  2013年   106篇
  2012年   150篇
  2011年   147篇
  2010年   105篇
  2009年   117篇
  2008年   108篇
  2007年   94篇
  2006年   94篇
  2005年   109篇
  2004年   93篇
  2003年   73篇
  2002年   64篇
  2001年   93篇
  2000年   48篇
  1999年   53篇
  1998年   51篇
  1997年   40篇
  1996年   33篇
  1995年   36篇
  1994年   25篇
  1993年   23篇
  1992年   16篇
  1991年   16篇
  1990年   33篇
  1989年   17篇
  1988年   10篇
  1987年   8篇
  1986年   19篇
  1985年   8篇
  1984年   3篇
  1983年   3篇
  1981年   2篇
  1979年   4篇
  1978年   4篇
  1977年   2篇
  1976年   1篇
  1975年   1篇
  1974年   3篇
  1973年   1篇
排序方式: 共有2459条查询结果,搜索用时 15 毫秒
91.
This paper addresses a previously unexplored regime of three-dimensional dissipative chaotic flows in which all but one of the nonlinearities are quadratic. The simplest such systems are determined, and their equilibria and stability are described. These systems often have one or more infinite lines of equilibrium points and sometimes have stable equilibria that coexist with the strange attractors, which are sometimes hidden. Furthermore, the coefficient of the single nonquadratic term provides a simple means for scaling the amplitude and frequency of the system.  相似文献   
92.
Four polycyclic norditerpenoids, cephalotanins A–D ( 1 – 4 ) representing three unprecedented carbon skeletons with highly rigid ring systems, were isolated from Cephalotaxus sinensis and structurally characterized by a combination of various methods. Compounds 1 and 2 are new skeletal norditerpenoid trilactones, while 3 and 4 are two norditerpenoids featuring different new carbon skeletons. Biosynthetic pathways for 1 – 4 were proposed by involving diverse and very fascinating chemical events with the coexisting cephalotane troponoids as the precursors. Compound 1 exhibited good NF‐κB inhibition with an IC50 value of 4.12±0.61 μΜ.  相似文献   
93.
A new nonporous Zn-based metal-organic framework (NPMOF) synthesized from a high nitrogen-containing rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sources. A series of NPMOF-derived porous carbons with very high N/O contents (24.1% for NPMOF-700, 20.2% for NPMOF-800, 15.1% for NPMOF-900) were prepared by adjusting the pyrolysis temperatures. The NPMOF-800 fabricated electrode exhibits a high capacitance of 220 F/g and extremely large surface area normalized capacitance of 57.7 μF/cm2 compared to other reported MOF-derived porous carbon electrodes, which could be attributed to the abundant ultramicroporosity and high N/O co-doping. More importantly, symmetric supercapacitor assembled with the MOF-derived carbon manifests prominent stability, i.e., 99.1% capacitance retention after 10,000 cycles at 1.0 A/g. This simple preparation of MOF-derived porous carbon materials not only finds an application direction for a variety of porous or even nonporous MOFs, but also opens a way for the production of porous carbon materials for superior energy storage.  相似文献   
94.
A strategy to reversibly switch the parallel/antiparallel helical conformation of aromatic double helices through the formation/breakage of a disulfide bond is presented. Single-crystal X-ray structures, NMR, and circular dichroism spectroscopy demonstrate that the double helices with terminal thiol groups favor an antiparallel helical arrangement both in the solid state and in solution, while the P/M bias of helicity induced by chiral segments from another extremity of the sequence is weak in this structural motif. The antiparallel helices can be rearranged to parallel helices through the disulfide connection of the sequences. This change enhances the bias of helical handedness and results in absolute chirality control of the double helices. The handedness-mediated process can be governed by the oxidation-reduction cycle, thereby switching the structural arrangement and the enhancement of chiral bias. In addition, we find that the sequences can dimerize into an intermolecular double helix with the disulfide connection. And the helical handedness is also fully controlled due to the head-to-head structural motif.  相似文献   
95.
To elucidate the structure of a compound is a necessary step for its practical applications. To study the structure and properties of metal sulfide fullerene Sc2S@C88 detected by mass spectrometry, 11 194 isomers of C88 and 33 isomers of Sc2S@C88 were systematically examined by density functional theory calculations. The calculations show that the two lowest‐energy isomers are Sc2S@C88:81 738 (IPR‐35) and Sc2S@C88:81 735 (IPR‐32), followed by Sc2S@C88:81 729 (IPR‐26), Sc2S@C88:81 712 (IPR‐9), and Sc2S@C88:81 733 (IPR‐30). Structural analysis shows that the first two energetically favored isomers are bridged by the third and fifth energetically favored isomers, which can transfer into each other via direct Stone–Wales rotation. The calculations of temperature effect show that the first two favored isomers become dominant forms of Sc2S@C88 with decreasing temperature and may coexist in the soot. This structural convertibility among favored isomers of Sc2S@C88 suggest a hidden rule that birds of a feather flock together in metal sulfide fullerenes. This rule may decrease the range of candidate cages for the structural identification of a metal sulfide fullerene. IR spectra are simulated for helping the future experimental identification of Sc2S@C88.  相似文献   
96.
A novel sandwich‐type electrochemiluminescence (ECL) immunosensor was developed to enable the sensitive detection of HIV‐1 antibodies. This system incorporated mesoporous silica (mSiO2) complexed with quantum dots (QDs) and nano‐gold particles, which were assembled to enhance signal detection. Magnetic beads were used by immobilizing the secondary anti‐IgG antibody. This was first employed to capture HIV‐1 antibody (Ab) to form a Fe3O4/anti‐IgG/Ab complex. A high loading and signal‐enhanced nanocomposite (hereafter referred to as Au‐mSiO2‐CdTe) was used as a HIV‐1 antigen label. The Au‐mSiO2‐CdTe nanocomposite was conjugated with the Fe3O4/anti‐IgG/Ab complex to form an immunocomplex (hereafter referred to as Fe3O4/anti‐IgG/Ab/HIV‐1/CdTe‐mSiO2‐Au). This complex could be further separated by an external magnetic field to produce ECL signals. Due to the large specific surface area and pore volume of mSiO2, the loading of the CdTe QDs was markedly increased. Thus, the loaded QDs released a powerful chemiluminescent signal with a concordantly increased sensitivity of the immunosensor. The immunosensor was highly sensitive, and displayed a linear range of responses for HIV‐1 antibody across a dilution range of 1 : 1500 through 1 : 50 with the detection limit of 1 : 4500. The immunoassay can be a promising candidate in early diagnosis of HIV infection.  相似文献   
97.
Different-shaped aluminas were readily prepared via hydrothermal reaction. It was found that the morphology and the electrochemical sensing properties of alumina were heavily dependent on the reaction time. When extending the reaction time from 6 h to 24 h, the obtained alumina samples changed from amorphous bumps to regular microfibers in diameter of 200 nm, as confirmed by scanning electron microscopy. Transmission electron microscopy observation revealed that longer reaction time was beneficial for the formation of porous and uniform fiber-like structures. Electrochemical tests proved that alumina microfibers were more active for the oxidation of amaranth and exhibited much higher enhancement effect, compared with alumina bumps. On the surface of alumina microfibers, the oxidation peak currents of amaranth increased remarkably. The influences of pH value, amount of alumina microfibers, and accumulation time on the signal enhancement of amaranth were discussed. As a result, a novel electrochemical method was developed for the detection of amaranth. The linear range was from 1 to 150 nM, and the detection limit was 0.75 nM after 1-min accumulation. The analytical application in drink samples was investigated, and the results consisted with the values that obtained by high-performance liquid chromatography.  相似文献   
98.
We have prepared core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT). The use of particles strongly improves the imprinting effect and leads to fast adsorption kinetics and high adsorption capacities. The functional monomer acrylamide was grafted to the surface of Fe3O4 nanospheres in two steps, and MIP layers were then formed on the surface by creating a MIP layer on the surface consisting of poly(ethyleneglycol dimethacrylate) with a TBT template. The particles were characterized in terms of morphological, magnetic, adsorption, and recognition properties. We then have developed a method for the extraction of TBT from spiked mussel (Mytilidae), and its determination by liquid chromatography-tandem mass spectrometry. The method has a limit of detection of 1.0 ng?g?1 (n?=?5) of TBT, with a linear response between 5.0 and 1,000 ng?g?1. The proposed method was successfully applied to the determination of trace TBT in marine food samples with recoveries in the range of 78.3–95.6 %.
Figure
The preparation procedures of core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT) in seafood  相似文献   
99.
A stereoselective and scalable synthesis of (1R,3S,5R)-2-(tert-butoxycarbonyl)-2-azabicyclo[3.1.0]hexane-3-carboxylic acid (3a) is described. Key to the success of the devised route was the realization that the stereoselectivity of a cyclopropanation step could be controlled by the composition of the functional group at C-α.  相似文献   
100.
Vesicles have been prepared at a constant molar ratio of L-glutamic acid/1-aminodecane/ibuprofen/H2O. The fusion dynamics of the vesicles have been directly observed and followed by using optical microscopy and freeze fracture replication-electron microscopy technologies. With time increasing up to 25 minutes, the vesicles slowly fuse to form large stable vesicles. A membrane phase transition temperature is detected at 97°C.  相似文献   
[首页] « 上一页 [5] [6] [7] [8] [9] 10 [11] [12] [13] [14] [15] 下一页 » 末  页»
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