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   4033篇
  免费   134篇
  国内免费   11篇
化学   3269篇
晶体学   103篇
力学   177篇
数学   115篇
物理学   514篇
  2023年   25篇
  2022年   51篇
  2021年   57篇
  2020年   75篇
  2019年   98篇
  2018年   105篇
  2017年   76篇
  2016年   138篇
  2015年   95篇
  2014年   174篇
  2013年   447篇
  2012年   274篇
  2011年   244篇
  2010年   151篇
  2009年   143篇
  2008年   234篇
  2007年   224篇
  2006年   164篇
  2005年   165篇
  2004年   154篇
  2003年   132篇
  2002年   110篇
  2001年   43篇
  2000年   44篇
  1999年   34篇
  1998年   21篇
  1997年   25篇
  1996年   42篇
  1995年   26篇
  1994年   32篇
  1993年   32篇
  1992年   29篇
  1991年   27篇
  1990年   39篇
  1989年   31篇
  1988年   25篇
  1987年   31篇
  1986年   31篇
  1985年   40篇
  1984年   41篇
  1983年   30篇
  1982年   27篇
  1981年   24篇
  1980年   23篇
  1979年   19篇
  1978年   14篇
  1977年   22篇
  1976年   16篇
  1975年   18篇
  1974年   10篇
排序方式: 共有4178条查询结果,搜索用时 31 毫秒
991.
This article deals with the web‐spline‐based finite element approximation of quasi‐Newtonian flows. First, we consider the scalar elliptic p‐Laplace problem. Then, we consider quasi‐Newtonian flows where viscosity obeys power law or Carreau law. We prove well‐posedness at the continuous as well as the discrete level. We give some error bounds for the solution of quasi‐Newtonian flow problem based on the web‐spline method. Finally, we provide the numerical results for the p‐Laplace problem. © 2014 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq31: 54–77, 2015  相似文献   
992.
 A rapid and practical green route for the N-formylation of amines with formic acid using Amberlite IR-120 as a catalyst is described. This method provides an efficient and much improved modification over the reported methods in terms of yield, reaction time, and work-up procedure. A wide variety of substituents is tolerated, which is not the case for existing procedures.  相似文献   
993.
In the present investigation, impact of nickel-impregnated silica paramagnetic particles (NSP) as biocatalyst immobilization matrices was investigated. These nanoparticles were synthesized by sol–gel route using a nonionic surfactant block co polymer [poly (ethylene glycol)-block-poly-(propylene glycol)-block-poly (ethylene glycol)]. Diastase enzyme was immobilized on these particles (enzyme-impregnated NSP) as model enzyme and characterized using Fourier-transform infrared spectroscopy and X-ray crystallography. Analysis of enzyme-binding nature with these nanoparticles at different physiological conditions revealed that binding pattern and activity profile varied with the pH of the reaction mixture. The immobilized enzyme was further characterized for its biocatalytic activity with respect to kinetic properties such as Km and Vmax and compared with free enzyme. Paramagnetic nanoparticle-immobilized enzyme showed more affinity for substrate compared to free one. The nature of silica and nickel varied from amorphous to crystalline nature and vice versa upon immobilization of enzyme. To the best of our knowledge, this is the first report of its kind for change of nature from one form to other under normal temperatures upon diastase interaction with NSP.  相似文献   
994.
Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−11-band), 15,230–14,740 cm−12-band) and 9,200–9,145 cm−13-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.  相似文献   
995.
Hydrogenated diamond-like carbon (HDLC) has an atomically smooth surface that can be deposited on high-surface area substrata and functionalized with reactive chemical groups, providing an ideal substrate for protein immobilization. A synthetic sequence is described involving deposition and hydrogenation of DLC followed by chemical functionalization. These functional groups are reacted with amines on proteins causing covalent immobilization on contact. Raman measurements confirm the presence of these surface functional groups, and Fourier transform infrared spectroscopy (FTIR) confirms covalent protein immobilization. Atomic force microscopy (AFM) of immobilized proteins is reproducible because proteins do not move as a result of interactions with the AFM probe-tip, thus providing an advantage over mica substrata typically used in AFM studies of protein. HDLC offers many of the same technical advantages as oxidized graphene but also allows for coating large surface areas of biomaterials relevant to the fabrication of medical/biosensor devices.  相似文献   
996.
Practical and convenient synthetic routes have been developed for the synthesis of a new class of pyrrolidinyl–camphor derivatives ( 7 a–h ). These novel compounds were screened as catalysts for the direct Michael addition of symmetrical α,α‐disubstituted aldehydes to β‐nitroalkenes. When this asymmetric transformation was catalyzed by organocatalyst 7 f , the desired Michael adducts were obtained in high chemical yields, with high to excellent stereoselectivities (up to 98:2 diastereomeric ratio (d.r.) and 99 % enantiomeric excess (ee)). The scope of the catalytic system was expanded to encompass various aldehydes and ketones as the donor sources. The synthetic application was demonstrated by the synthesis of a tetrasubstituted‐cyclohexane derivative from (S)‐citronellal, with high stereoselectivity.  相似文献   
997.
The compound, lithium trivanadate (LiV3O8), was synthesized by the polymer precursor method, using the polymer polyvinylpyrrolidone. The electrochemical performance of LiV3O8 was compared with LiV3O8 synthesized by the solid state reaction method. The prepared compounds were characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy techniques. The electrochemical performances were studied by cyclic voltammetry and galvanostatic cycling in the voltage range of 2.0 to 4.0 V at room temperature (25 °C). The compound prepared by the polymer precursor method was found to have a good cycling stability. A reversible capacity value of 203 mAh/g (2.18 mol of Li) and 170 mAh/g (1.83 mol of Li) was obtained at the end of the 70th cycle, at a current density of 30 and 120 mA/g, respectively.  相似文献   
998.
Microwave-assisted proteolytic digestion often yields misscleaved peptides, attributed to incomplete hydrolysis reactions between enzymes and substrates. The number of missed cleavages is an important parameter in proteome database searching. This study investigates how various factors affect digestion processes. Optimum conditions for microwave-assisted digestion (50 mM Tris buffer, 30 min at 60°C, and enzyme to protein molar ratio of 1:5) were determined. The digestion products obtained from eight standard proteins were characterized based on matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Experimental results indicate that the digestion temperature, reaction time, enzyme to substrate ratio, and digestion buffer affect the number of misscleaved peptides and incomplete digestion percentages. Although all protein molecules in a sample could be digested into peptides within a few minutes under microwave irradiation, longer reaction times or methods to maximize the enzyme activity should be considered if digestion completeness is a major concern.  相似文献   
999.
The low temperature microwave sintered NiCuZn and MgCuZn ferrites with compositions Ni0.35Cu0.05Zn0.60Fe2O4 and Mg0.35Cu0.05Zn0.60Fe2O4 were synthesized by conventional mixed oxide method. NiCuZn and MgCuZn ferrite samples obtained showed better sintered densities at 950 and 900 °C, respectively. The scanning electron micrographs of both the ferrite samples appear to be very much similar. The magnitude of initial permeability of MgCuZn ferrite samples is found to be obviously higher than those of NiCuZn ferrite samples at all sintering temperatures. This is mainly due to the fact that MgCuZn ferrite has smaller magnetocrystalline anisotropy constant and magnetostrictive constant. NiCuZn ferrites have higher saturation magnetization than MgCuZn ferrites, which is due to the higher magnetic moment of NiCuZn ferrites. Our results indicate that the microwave sintering method seems to be a potential technique in the MLCI technology.  相似文献   
1000.
In the present paper novel column solid phase extraction procedure was developed for the determination of Cd(II) and Pb(II) in cows', goats', ewes', buffalos' and humans' milk samples using newly synthesized reagent 2,2′‐DPED3P (2,2′‐{[1,2‐diphenylethane‐1,2‐diylidene]dinitrilo}diphenol) for preconcentration and separation prior to differential pulse polarography using amberlite XAD‐2 in the ranges of pH 4.0–5.0. The sorbed elements were subsequently eluted with 10 mL of 2 M HCl elutes were analysed by differential pulse polarography (DPP). The interference of foreign ions has also been studied. Effects of various instrumental parameters are investigated and received conditions are optimized. The total metal concentration of the milk samples in the study area were in the following ranges 0.030–0.090 μg L?1 of Cd(II), 0.009–0.026 μg L?1 of Pb(II) respectively. The limits of detections were found to be 0.020 and 0.024 μg L?1 for Cd(II) and Pb(II) respectively by applying a preconcentration factor ~40. The proposed enrichment method was applied successfully for the determination of metal ions in cows', goats', ewes', buffalos' and humans' milk samples.  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