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   1991篇
  免费   113篇
  国内免费   19篇
化学   1529篇
晶体学   31篇
力学   49篇
数学   105篇
物理学   409篇
  2024年   18篇
  2023年   42篇
  2022年   182篇
  2021年   172篇
  2020年   70篇
  2019年   92篇
  2018年   78篇
  2017年   72篇
  2016年   122篇
  2015年   76篇
  2014年   92篇
  2013年   121篇
  2012年   143篇
  2011年   142篇
  2010年   83篇
  2009年   61篇
  2008年   76篇
  2007年   79篇
  2006年   66篇
  2005年   70篇
  2004年   49篇
  2003年   38篇
  2002年   24篇
  2001年   9篇
  2000年   10篇
  1999年   6篇
  1997年   3篇
  1996年   4篇
  1995年   5篇
  1994年   9篇
  1993年   5篇
  1992年   6篇
  1991年   5篇
  1990年   5篇
  1989年   9篇
  1988年   5篇
  1987年   6篇
  1986年   5篇
  1985年   5篇
  1984年   6篇
  1983年   6篇
  1982年   3篇
  1981年   12篇
  1980年   6篇
  1979年   3篇
  1973年   2篇
  1970年   2篇
  1969年   2篇
  1968年   3篇
  1967年   2篇
排序方式: 共有2123条查询结果,搜索用时 46 毫秒
21.
A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10?6?1.0×10?4 M and 5.0×10?7 to 1.0×10?4 M, respectively. The detection limits were determined to be of 1.0×10?6 M and 9.0×10?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples.  相似文献   
22.
The electroosmotic peristaltic flow of modified hybrid nanofluid in presence of entropy generation has been presented in this thermal model. The Hall impact and thermal radiation with help of nonlinear relations has also been used to modify the analysis. The assumed flow is considered due to a non-uniform trapped channel. The properties of modified hybrid nanofluid model are focused with interaction of three distinct types of nanoparticles namely copper (Cu), silver (Ag) and aluminum oxide (Al2O3). The mathematical modeling and significances of entropy generation and Bejan number are identified. With certain flow assumptions, the governing equations are attained for optimized peristaltic electroosmotic problem. Widely used assumptions of long wave length and low Reynolds number reduced the governing equations in ordinary differential equations. The ND solver is flowed for the solution process. The physical significant of results is observed by assigning the numerical values to parameters.  相似文献   
23.
Chen X  Fazal MA  Dovichi NJ 《Talanta》2007,71(5):1981-1985
Two-dimensional capillary electrophoresis was used for the separation of proteins and biogenic amines from the mouse AtT-20 cell line. The first-dimension capillary contained a TRIS–CHES–SDS–dextran buffer to perform capillary sieving electrophoresis, which is based on molecular weight of proteins. The second-dimension capillary contained a TRIS–CHES–SDS buffer for micellar electrokinetic capillary chromatography. After a 61-s preliminary separation, fractions from the first-dimension capillary were successively transferred to the second-dimension capillary, where they further separated by MECC. The two-dimensional separation required 60 min.  相似文献   
24.
Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os3(CO)9(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os3(CO)12] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me3NO in moderate yields. Compounds [Os3(CO)9(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os3(CO)9(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh3; 6, L′ = P(OMe)3; 7, L′ = tBuNC; 8, L′ = C5H5N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms.  相似文献   
25.
Hydration of short-chain poly(oxyethylene)s, CH(3)(OCH(2)CH(2))(m)OCH(3) (abbreviated as C(1)E(m)()C(1)) (m = 1-3), in carbon tetrachloride has been studied by infrared spectroscopy. The O-H stretching vibrations of water in ternary solutions with H(2)O:C(1)E(m)C(1):CCl(4) mole ratios of 0.000418:0.005:0.995 to 0.000403:0.04:0.96 were analyzed. Two types of hydrogen bonds are formed in the interaction between water and C(1)E(m)C(1) in carbon tetrachloride; one is a monodentate hydrogen bond, in which only one of the O-H bonds of a water molecule participates in hydrogen bonding, and the other is a bidentate hydrogen bond, in which both of the O-H bonds of a water molecule participate in hydrogen bonding by bridging oxygen atoms separated by two or more monomer units on the polymer chain. An important finding is that the bidentate hydrogen-bond bridge is not formed between the nearest-neighbor oxygen atoms. This experimental observation supports the results of previous molecular dynamics simulations. The shortest oligomer of poly(oxyethylene), i.e., CH(3)OCH(2)CH(2)OCH(3) (1,2-dimethoxyethane) with a single monomer unit, is suggested not to be an adequate model for this polymer with respect to hydrogen bonding to water. The hydrogen bonding in a 1:1 C(1)E(m)C(1)-water adduct in carbon tetrachloride represents primitive incipient hydration of poly(oxyethylene). The present results indicate that both monodentate and bidentate hydrogen bonds are important and the latter is destabilized more rapidly than the former with increasing temperature. This dehydration process can be a potential mechanism of the poly(oxyethylene)-water phase separation.  相似文献   
26.
Six known metabolites, two new isocoumarins 4 and 8, and one new highly substituted benzoic acid derivative 9 were isolated from the ethyl acetate culture extract of a fungal endophyte, Scytalidium sp. In addition, another new benzoic acid 10 with an unusual 1,2-dicarbonyl side chain was indirectly identified from its methylated derivatives 10a-10d.  相似文献   
27.
Investigations of the thermal stability of detonating fuse containing 10 g pentaerythrol tetranitrate (PETN) revealed that the cord burnt under unconfinement at 403 K. Under confinement in a steel pipe or copper tube there was a partial detonation at 403 K. In order to characterize the thermal stability of PETN and pyrotechnic composition used in fuse head of electric detonators differential thermal analysis (DTA) was used.The electric detonators of aluminium cell and copper cell were heated from ambient temperature to 373 K at an average rate of 0.4 deg/min. The rate of heating was increased gradually to 1.5 deg/min till explosion. The detonation temperature varied between 373 K and 375 K.The impact and friction sensitivity of detonating fuse was poor. There was no detonation when a 5 kg hammer was repeatedly hit over the fuse from a height of one metre. There was no detonation when the detonating fuse was rubbed by a blunt edge of steel plate till it was smashed.
Zusammenfassung Untersuchungen der thermischen Stabilität von Sprengschnuren mit 10 gm–1 PETN zeigten, daß die Schnur frei bei 403 K verbrennt. Unter Abschluß in einem Stahloder Kupferrohr tritt bei 403 K eine partielle Detonation auf. Zur Charakterisierung der thermischen Stabilität von PETN und von pyrotechnischen Mischungen, die in Zünderköpfen von elektrischen Sprengkapseln verwendet werden, wurde Differentialthermoanalyse (DTA) angewendet. Die elektrischen Sprengkapseln von Aluminium- und Kupferzellen wurden mit einer durchschnittlichen Aufheizgeschwindigkeit von 0.4 Grad/min von Raumtemperatur auf 373 K erhitzt. Die Aufheizgeschwindigkeit wurde bis zur Explosion allmählich auf 1,5 Grad/min erhöht. Die einzelnen Detonationen erfolgten bei einer Temperatur zwischen 373 und 375 K. Die Stoß- und Reibempfindlichkeit der Sprengschnur war gering. Bei einem mehrmaligen Einwirken eines 5 kg-Hammers aus einer Höhe von 1 m erfolgte keine Detonation. Bei Reiben mit der unscharfen Kante einer Stahlplatte bis zur Zerstörung erfolgte keine Detonation.

, 10 –1 PETN, , 403 , 403 . PETN , , . 373 0,4°/. 1,5°/ . 373 375 . . 5 1 . , .


The authors are indebted to the Director, Central Mining Research Station for giving permission to publish this paper. The views expressed in the paper are those of the authors and not necessarily of the institute which they belong to.  相似文献   
28.
N-Bromosuccinimide-dibenzoyl peroxide/azobisisobutyronitrile is used to carry out several types of Z- to E-alkene isomerizations. The NBS-bromination conditions are sufficient for both allylic bromination and alkene isomerization. When the allylic hydrogens are not available in substrates, only the isomerization of the alkene takes place. The present conditions for isomerization of carbon-carbon double bonds are mild and efficient.  相似文献   
29.
The polymerization of acrylonitrile initiated by an ascorbic acid–peroxodisulfate redox system was studied in an aqueous solution at 35°C in the presence of air. Molecular oxygen was found to have no effect on the polymerization reaction. An increase in ionic strength slightly increased the rate. The overall rate of polymerization, Rp, showed a square dependence on [monomer] and a half-order dependence on [peroxodisulfate]. A first-order dependence on [ascorbic acid] at low concentrations (<3.0 × 10?3 mol L?1) followed by a decrease in Rp at higher concentrations of ascorbic acid (>3.0 × 10?3 mol L?1) was also noted. Rp remained unchanged up to 40°C and showed a decline thereafter. Addition of catalytic amounts of cupric ions decreased the rate whereas ferric ions were found to increase the rate. Added sulfuric acid in the range (6.0?50.0) × 10?5 mol L?1 decreased the Rp.  相似文献   
30.
A new strain of the fungusMorchella nov. ES-1 (ATCC 20951) that produces blue pigment in submerged culture has been isolated. The blue pigment was extracted by chloroform or ethyl acetate treatment. The crude extract when chromatographed yielded three fractions; a blue one has been identified by mass spectrometry as indigotin. Fermentation studies using enriched media revealed that maximum accumulation of indigotin in culture was approx 24 mg/L in 168 h.  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