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   4147篇
  免费   215篇
  国内免费   41篇
化学   2684篇
晶体学   38篇
力学   135篇
数学   446篇
物理学   1100篇
  2024年   10篇
  2023年   40篇
  2022年   59篇
  2021年   225篇
  2020年   177篇
  2019年   172篇
  2018年   172篇
  2017年   136篇
  2016年   205篇
  2015年   147篇
  2014年   216篇
  2013年   379篇
  2012年   314篇
  2011年   314篇
  2010年   245篇
  2009年   192篇
  2008年   220篇
  2007年   187篇
  2006年   140篇
  2005年   75篇
  2004年   100篇
  2003年   55篇
  2002年   60篇
  2001年   33篇
  2000年   30篇
  1999年   31篇
  1998年   20篇
  1997年   29篇
  1996年   23篇
  1995年   10篇
  1994年   26篇
  1993年   17篇
  1992年   19篇
  1991年   11篇
  1990年   20篇
  1989年   13篇
  1988年   15篇
  1987年   16篇
  1985年   23篇
  1984年   23篇
  1983年   15篇
  1982年   20篇
  1981年   13篇
  1980年   37篇
  1979年   11篇
  1977年   15篇
  1976年   10篇
  1973年   12篇
  1969年   9篇
  1968年   8篇
排序方式: 共有4403条查询结果,搜索用时 968 毫秒
991.
In this paper we report the effect of poly(vinyl alcohol) (PVA) on the silver nanoparticles formation of different morphologies by using silver nitrate and citric acid as the oxidant and reductant, respectively, for the first time. Our transmission electron microscopy (TEM) results suggest that the presence of PVA has significant impact on the size, shape, and the size distribution of the silver nanoparticles. The reaction follows a zero-order kinetics in [citric acid] as well as in [silver(I)] in the absence and presence of PVA. It was found that PVA and cetyltrimethylammonium bromide (CTAB) concentrations show no significant effects on the rate of CTAB-stabilized silver nanoparticles formation, whereas in presence of PVA, the reaction rate increases with (CTAB). Both spectrophotometric and TEM measurement demonstrated that the orange silver sol consists of aggregates, whereas the purple sol does not contain the aggregated arrangement. On the basis of various observations, the most plausible mechanism has been envisaged.  相似文献   
992.
<正>In the present work,a three-dimensional molecular dynamics simulation is carried out to perform the nanoindentation experiment on Ni single crystal.The substrate indenter system is modeled using hybrid interatomic potentials including the many-body potential embedded atom method(EAM),and two-body morse potential.To simulate the indentation process,a spherical indenter(diameter = 80 A,1 A=0.1 nm) is chosen.The results show that the mechanical behaviour of a monolithic Ni is not affected by crystalline orientation.To elucidate the effect of a heterogeneous interface, three bilayer interface systems are constructed,namely Ni(100)/Cu(111),Ni(110)/Cu(111),and Ni(111)/Cu(111).The simulations along these systems clearly describe that mechanical behaviour directly depends on the lattice mismatch. The interface with the smaller mismatch between the specified crystal planes is proved to be harder and vice versa.To describe the relationship between film thickness and interface effect,we choose various values of film thickness ranging from 20 A to 50 A to perform the nanoindentation experiment.It is observed that the interface is significant only for the relatively small thickness of film and the separation between interface and the indenter tip.It is shown that with the increase in film thickness,the mechanical behaviour of the film shifts more toward that of monolithic material.  相似文献   
993.
The present work proposes the application of bar adsorptive micro-extraction (BAµE) coated with an N-vinylpyrrolidone polymer (NVP) combined with micro-liquid desorption (200 µL) followed by high-performance liquid chromatography with diode array detection (BAµE(NVP)-µLD/HPLC-DAD) for the determination of trace levels of emerging organic micro-pollutants in environmental water matrices. The model compounds selected include an antibacterial/antifungal agent (triclosan), two pharmaceuticals (carbamazepine and diclofenac) and two steroid hormones (17α-ethinylestradiol and 17β-estradiol), in which the latter three were recently included in the European Union watch list of substances to be monitored in the field of water policy. Assays performed on 25 mL of ultrapure water samples spiked at the 8.0 µg L?1 level yielded average recoveries ranging from 81.9 to 102.4% for the compounds studied using optimised experimental conditions. The proposed analytical methodology demonstrated suitable detection limits (0.02–0.10 µg L?1) and good linear dynamic ranges (0.1–20.0 µg L?1) with determination coefficients higher than 0.9909. Using the standard addition method (SAM), the present analytical approach was applied on environmental water matrices, including surface, sea, river and groundwaters. The proposed method proved to be a suitable and alternative sorption-based static micro-extraction technique for monitoring trace levels of organic micro-pollutants in environmental water matrices.  相似文献   
994.
An organic‐inorganic material (NH4)2(MimAM)40[Mo132O372(CH3COO)30(H2O)72] have been synthesized by reacting [(NH4)42[MoVI72 MoV60O372(CH3COO)30(H2O)72] with the ionic liquid 3‐Aminoethyl‐1‐methylimidazolium bromide. The catalyst showed remarkably a high catalytic performance in the oxidation of dibenzothiophene (DBT) derivatives with H2O2 35% as a safe and green oxidant. The main parameters affecting the process including catalyst, acid additive, hydrogen peroxide amounts and temperature have been investigated in detail. Sulfur removal of DBT in n‐heptane reached to 98.3% yield at 40 °C using 2.5 mmol H2O2 and 100 mg of (NH4)2(MimAM)40[Mo132O372(CH3COO)30(H2O)72] after 90 min. Under the optimal conditions, BT (benzothiophene), DBT (dibenzothiophene) and 4,6‐DMDBT (4,6‐dimethyl‐dibenzothiophene) achieved high desulfurization efficiency. Our results showed that the reactivity order of different model sulfur compounds are thiophene <4,6‐dimethyl dibenzothiophene< dibenzothiophene. The catalysts could be easily separated from the reaction solution by simple filtration and recycled for several times without loss of activity.  相似文献   
995.
A highly stable Q-switched laser incorporating a mechanically exfoliated tungsten sulphoselenide (WSSe) thin sheet saturable absorber (SA) is proposed and demonstrated. The SA assembly, formed by sandwiching a thin WSSe sheet between two fiber ferrules within the erbium-doped fiber laser, is used to effectively modulate the laser cavity losses. The WSSe-based SA has a saturation intensity of ~0.006 MW∕cm~2 and a modulation depth of 7.8%, giving an optimum Q-switched laser output with a maximum repetition rate of 61.81 kHz and a minimum pulse width of 2.6 μs. The laser's highest output power of 0.45 mW and highest pulse energy of 7.31 nJ are achieved at the maximum pump power of 280.5 mW. The tunability of the cavity's output at the maximum pump power is analyzed with a C-band tunable bandpass filter, giving a broad tunable range of ~40 nm, from 1530 nm to 1570 nm. The output performance of the tunable Q-switched laser correlates well with the gain spectrum of erbium-doped fibers, with the shift in the gain profile as a result of the saturated SA.  相似文献   
996.
Nano-Mg- [4-methoxy phenylsalicylaldiminemethylpyranopyrazole]Cl2 (nano-[Mg-4MSMP]Cl2) as a nano-Schiff base complex was prepared and fully characterized using some various techniques including fourier transform infrared spectroscopy (FT-IR), energy-dispersive x-ray spectroscopy (EDS), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric analysis (DTA), mass spectroscopy (MS) and scanning electron microscopy (SEM). Nano-[Mg-4MSMP]Cl2 was successfully used as an efficient catalyst for the preparation of some 1-(α-aminoalkyl) -2 -naphthols.  相似文献   
997.
A lanthanide-binding tag site-specifically attached to a protein presents a tool to probe the protein by multiple spectroscopic techniques, including nuclear magnetic resonance, electron paramagnetic resonance and time-resolved luminescence spectroscopy. Here a new stable chiral LnIII tag, referred to as C12 , is presented for spontaneous and quantitative reaction with a cysteine residue to generate a stable thioether bond. The synthetic protocol of the tag is relatively straightforward, and the tag is stable for storage and shipping. It displays greatly enhanced reactivity towards selenocysteine, opening a route towards selective tagging of selenocysteine in proteins containing cysteine residues. Loaded with TbIII or TmIII ions, the C12 tag readily generates pseudocontact shifts (PCS) in protein NMR spectra. It produces a relatively rigid tether between lanthanide and protein, which is beneficial for interpretation of the PCSs by single magnetic susceptibility anisotropy tensors, and it is suitable for measuring distance distributions in double electron–electron resonance experiments. Upon reaction with cysteine or other thiol compounds, the TbIII complex exhibits a 100-fold enhancement in luminescence quantum yield, affording a highly sensitive turn-on luminescence probe for time-resolved FRET assays and enzyme reaction monitoring.  相似文献   
998.

Fe3O4 magnetic nanoparticles (MNPs) were prepared by co-precipitation method. The nanoparticles were silica coated using TEOS, and then modified by the polymeric layers of polypropylene glycol (PPG) and polyethylene glycol (PEG). Finally, the core-shell samples were decorated with Ag, Au, and Cu nanoparticles. The products were characterized by vibrating sample magnetometry (VSM), TGA, SEM, XRD, and FTIR methods. The antibacterial activity of the prepared samples was evaluated in inactivation of E. coli and S. aureus microorganisms, representing the Gram-negative and Gram-positive species, respectively. The effect of solid dosage, bacteria concentration and type of polymeric modifier on the antibacterial activity was investigated. TEM images of the bacteria were recorded after the treatment time and according to the observed changes in the cell wall, the mechanism of antibacterial action was discussed. The prepared nanostructures showed high antibacterial activity against both Gram-negative and Gram-positive bacteria. This was due to the leaching of metal ions which subsequently led to the lysis of bacteria. A theoretical investigation was also done by studying the interaction of loaded metals with the nucleotide components of the microorganism DNA, and the obtained results were used to explain the experimental data. Finally, based on the observed inactivation curves, we explain the antibacterial behavior of the prepared nanostructures mathematically.

  相似文献   
999.
Azobenzene-based calamitic liquid crystals, 4-((4-(4-methoxymethyl-1,2,3-triazol-1-yl)phenyl)diazenyl)phenylalkanoates have been isolated and their structures were characterised. The structure–property correlation with respect to the different alkanoyloxy terminal chain (–COOCnH2n+1 where n adopts odd numbers ranging from 3 to 15) has also been given attention in the present study. In this series, all compounds exhibit smectogenic properties. The lower homologues shows enantiotropic SmA phase as well as monotropic SmC phase. The higher homologues exhibit homeotropic alignment of smectic phases. These compounds possess very high anisotropic inclination in which the mesomorphic region covers nearly 80°C.  相似文献   
1000.
New bis(pyrazolylenaminones) were prepared in good yields. Their synthetic utilities as precursors for regioselective synthesis of novel bis(hetarylpyrazoles) were also investigated. The mechanisms and selectivities observed in the studied reactions were discussed.  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