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   1817篇
  免费   65篇
  国内免费   3篇
化学   1103篇
晶体学   39篇
力学   69篇
数学   360篇
物理学   314篇
  2024年   3篇
  2023年   8篇
  2022年   35篇
  2021年   49篇
  2020年   59篇
  2019年   54篇
  2018年   55篇
  2017年   71篇
  2016年   97篇
  2015年   81篇
  2014年   104篇
  2013年   241篇
  2012年   127篇
  2011年   129篇
  2010年   112篇
  2009年   85篇
  2008年   108篇
  2007年   88篇
  2006年   50篇
  2005年   45篇
  2004年   53篇
  2003年   32篇
  2002年   33篇
  2001年   18篇
  2000年   16篇
  1999年   8篇
  1998年   12篇
  1997年   10篇
  1996年   12篇
  1995年   6篇
  1994年   12篇
  1993年   3篇
  1992年   4篇
  1991年   5篇
  1990年   7篇
  1987年   2篇
  1985年   4篇
  1984年   4篇
  1983年   5篇
  1982年   3篇
  1981年   4篇
  1980年   5篇
  1979年   5篇
  1977年   2篇
  1976年   6篇
  1972年   2篇
  1967年   1篇
  1965年   2篇
  1936年   1篇
  1907年   1篇
排序方式: 共有1885条查询结果,搜索用时 23 毫秒
51.
A glassy carbon electrode was modified with electropolymerized film of diphenylamine sulfonic acid (DPASA). Electropolymerization was performed by cyclic voltammetry in 0.1 M KCl solution. The modified electrode showed an excellent electrocatalytic effect towards oxidation of dopamine (DA) and ascorbic acid (AA). Electrostatic interaction between the negatively charged poly(DPASA) film and either cationic DA species or anionic AA species favorably contributed to the redox response of DA and AA. Anodic peaks of DA and AA in their mixture were well separated by ca 168 and −11.8 mV. The proposed modified electrode was utilized for selective determination of dopamine in the concentration range of 5.0 × 10t7–2.0 × 10−5 M in the presence of high concentration of ascorbic acid. Detection limit was 6.5 × 10−9 M.  相似文献   
52.
Biologically important 12 new important 3,4‐dihydropyrimidin‐2‐(1H)‐ones (‐thiones) were synthesized with in one‐pot three‐component Biginelli reaction from the corresponding aromatic aldehydes (5‐methyl‐2‐thiophenecarboxaldehyde and 2‐chloro‐5‐nitrobenzaldehyde), β‐keto esters (ethylacetoacetate, allylacetoacetate, and t‐butylacetoacetate), and urea/thiourea in the presence of catalytic amount of magnesium bromide and magnesium chloride hexahydrate as nontoxic, inexpensive, and easily available catalysts under solvent‐free conditions at 80 and 100°C. Compared with the catalyst‐free three‐component Biginelli reaction conditions, this method consistently has the advantage of short reaction time (45–100 min) and good to excellent yields (75–91%).  相似文献   
53.
A new empirical potential energy function (PEF) is proposed, which is formed from pair-interactions only, and containes the many-body contributions. The PEF satisfies bulk cohesive energy and bulk stability condition. The PEF is parameterized for copper, silver, and gold elements in fcc crystal structure. The elastic constantsC 11 andC 12 and the bulk modulus of the elements are calculated, and the structural stability and energetics of microclusters containing 3 to 7 atoms of the same elements are investigated.  相似文献   
54.
55.
An intramolecular Pauson–Khand reaction of enynes derived from homoallyl, homopropargyl, and allyl alcohols is described. 2-Heteroaryl-substituted homoallyl, homopropargyl, and allyl alcohols are easily and efficiently resolved through enzymatic resolution in high ee (91–99%) and with a known stereochemistry. Each enantiomerically enriched enyne derived from homoallyl and homopropargyl alcohols affords the conformationally most stable diastereomeric cyclopenta[c]pyran ring system as the sole product, whereas enantiomerically enriched enynes derived from allyl alcohols give a diastereomeric cis:trans mixture of the cyclopenta[c]furan ring system.  相似文献   
56.
The inhibition efficiency of 2-Pyrrolidin-1-yl-1,3-thiazole-5-carboxylic acid (PTCA) against mild steel (MS) corrosion was investigated in acidic solution by using quantum chemical calculations based on Density Functional Theory (DFT) method and electrochemical measurements. The electrochemical impedance spectroscopy (EIS), potentiodynamic, potential zero charge (pzc) analysis and electrochemical noise (EN) measurements at various concentrations (from 0.1 to 10 mM) and immersion times were utilized in experimental part. The surface analysis was achieved scanning electron microscope (SEM) and contact angle measurements in the absence and presence of 10 mM PTCA. According to DFT results, PTCA exhibited 3.737 eV band gap and 8.130 Debye dipole moment which were a signal of potentially convenient corrosion inhibitor properties. PTCA has a remarkable corrosion inhibition capability to mild steel, which inhibited both anodic and cathodic corrosion rates, relying on it's physically adsorption on the metal solution interface and protection ability was increased with increasing PTCA concentration. The obtained adsorption equilibrium constant was 11.11 × 103 M-1 and calculated standard free energy of adsorption was ?33.03 kJ mol?1. The determined activation energy values were 55.58 kJ mol?1 and 96.86 kJ mol?1 in 0.5 M HCl in the absence and presence of 10 mM PTCA, respectively. PTCA demonstrated a strong inhibition efficiency of 98.3%, after 168 h immersion, according to the EIS results. As a consequently, we recommend that PTCA is a convenient inhibitor in 0.1 M HCl for mild steel protection against corrosion.  相似文献   
57.
Journal of Inclusion Phenomena and Macrocyclic Chemistry - Newly phthalocyanine derivative which carries 2,6-dimethoxyphenoxy bioactive groups as tetrakis from non-peripheral positions of the...  相似文献   
58.
Transition Metal Chemistry - The syntheses of highly soluble asymmetrically substituted metal free and zinc phthalocyanine derivatives bearing three 4-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenoxy) and...  相似文献   
59.
An effective electrochemical sensor was constructed using an unmodified boron-doped diamond electrode for determination of genistein by square-wave voltammetry. Cyclic voltammetric investigations of genistein with HClO4 solution indicated that irreversible behavior, adsorption-controlled and well-defined two oxidation peaks at about +0.92 (PA1) & +1.27 V (PA2). pH, as well as supporting electrolytes, are important in genistein oxidations. Quantification analyses of genistein were conducted using its two oxidation peaks. Using optimized experiments as well as instrumental conditions, the current response with genistein was proportionately linear in the concentrations range of 0.1 to 50.0 μg mL−1 (3.7×10−7−1.9×10−4 mol L−1), by the detection limit of 0.023 μg mL−1 (8.5×10−8 mol L−1) for PA1 and 0.028 μg mL−1 (1.1×10−7 mol L−1) for PA2 in 0.1 mol L−1 HClO4 solution (in the open circuit condition at 30 s accumulation time). Ultimately, the developed method was effectively applied to detect genistein in model human urine samples by using its second oxidation peak (PA2).  相似文献   
60.
In the present study, controlled protein adsorption on a rigid silica microparticle is investigated numerically using classical Langmuir and two-state models under electrokinetic flow conditions. The instantaneous particle locations are simulated along a straight microchannel using an arbitrary Lagrangian−Eulerian framework in the finite element method for the electrophoretic motion of the charged particle. Within the scope of the parametric study, the strength of the external electric field (E), particle diameter (Dp), the zeta potential of the particle (ζp), and the location of the microparticle away from the channel wall (H) are systematically varied. The results are also compared to the data of pressure-driven flow having a parabolic flow profile at the inlet whose maximum magnitude is set to the particle's electrophoretic velocity magnitude. The validation studies reveal that the code developed for the particle motion in the present simulations agrees well with the experimental results. It is observed that protein adsorption can be controlled using electrokinetic phenomena. The plug-like flow profile in electrokinetics is beneficial for a microparticle at every spatial location in the microchannel, whereas it is not valid for the pressure-driven flow. The electric field strength and the zeta potential of the particle accelerate the protein adsorption. The wall shear stress and shear rate are good indicators to predict the adsorption process for electrokinetic flow.  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