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   5486篇
  免费   316篇
  国内免费   277篇
化学   3570篇
晶体学   87篇
力学   156篇
综合类   39篇
数学   1007篇
物理学   1220篇
  2023年   22篇
  2022年   82篇
  2021年   128篇
  2020年   99篇
  2019年   125篇
  2018年   96篇
  2017年   119篇
  2016年   179篇
  2015年   167篇
  2014年   202篇
  2013年   381篇
  2012年   283篇
  2011年   330篇
  2010年   217篇
  2009年   251篇
  2008年   310篇
  2007年   280篇
  2006年   255篇
  2005年   233篇
  2004年   270篇
  2003年   221篇
  2002年   263篇
  2001年   190篇
  2000年   134篇
  1999年   113篇
  1998年   65篇
  1997年   74篇
  1996年   77篇
  1995年   56篇
  1994年   58篇
  1993年   58篇
  1992年   51篇
  1991年   43篇
  1990年   50篇
  1989年   38篇
  1988年   34篇
  1987年   35篇
  1986年   24篇
  1985年   50篇
  1984年   48篇
  1983年   34篇
  1982年   33篇
  1981年   40篇
  1980年   32篇
  1979年   28篇
  1978年   23篇
  1977年   38篇
  1976年   21篇
  1975年   17篇
  1974年   18篇
排序方式: 共有6079条查询结果,搜索用时 46 毫秒
901.
Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn3O4 and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn3O4 and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 μWh cm−2 with power density of 14.1 mW cm−2 (156.7 mW cm−3) at 1.4 V.  相似文献   
902.
The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)2 ⋅ DABCOH2](X)2 (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF4, ClO4) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3221 and P3121. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed.  相似文献   
903.
Poly (ether ether ketone) was irradiated with gamma rays or electron beam to investigate the radical process. The generated paramagnetic species were observed by electron spin resonance spectroscopy at ambient temperature and in liquid nitrogen. The effect of microwave power on saturation of the particular spectra and thermal annealing effects were determined. The following radicals were identified: radical anion, phenoxyl radical, and phenylperoxy radical. Despite the fact that the intermediates were formed as a result of backbone cleavage causing degradation, the macroscopic features were almost unaffected by irradiation up to dose of 1500 kGy.  相似文献   
904.
905.
The article presents the impact of long-term (10 years of maintenance) use of polymer material, with the result of a gradual loss of primary physical and chemical properties and degradation. Under the influence of factors such as heat, water, sunlight, stress forces, sulfur oxides, nitrogen oxides, oxygen, metals, and microorganisms, polymers experience irreversible structural changes that cause a decrease in molecular weight or change in chemical composition. The problems mentioned in this article are known worldwide because of many possible applications for wide-area covers, roofing and others.  相似文献   
906.
The crystal structure of an orthorhombic polymorph of the title compound, crystallized by sublimation, has been determined. Dehydroepiandrosterone, C19H28O2, space groupP212121 witha=6.6408(4)b=11.4423(11)c=22.085(2)Å,V=1678.2(4)Å3,Z=4. The structure was refined toR=0.051 for 2645 observed reflections. The conformation of the molecule is similar to that found in other polymorphs and solvates, with a chair A ring, an 8, 9 half-chair B ring, a chair C ring, and a 14 envelope D ring. Molecules are linked in chains by OH...O hydrogen bonds involving the carbonyl oxygen atom. The O...O distance is 2.855(3) Å, and the angle about H is 171(2)o.  相似文献   
907.
Eosin Y, a well‐known economical alternative to metal catalysts in visible‐light‐driven single‐electron transfer‐based organic transformations, can behave as an effective direct hydrogen‐atom transfer catalyst for C?H activation. Using the alkylation of C?H bonds with electron‐deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y‐based photocatalytic hydrogen‐atom transfer strategy is promising for diverse functionalization of a wide range of native C?H bonds in a green and sustainable manner.  相似文献   
908.
In search of magneto‐optic materials, the mononuclear compounds LnIII(depma)(NO3)3(hmpa)2 (Ln=Dy, Gd) were synthesized. The anthracene moieties undergo [4+4] dimerization when irradiated at 365 nm without loss of crystallinity. The Dy compound switches from a single‐ion to a single‐molecule magnet with doubling of the spin reversal barrier energy and from yellow‐green to blue‐white emission. The dimerization is reversed by heating at 100 °C or partially on light irradiating at 254 nm. The results suggest that lanthanide phosphonates with anthracene are promising smart materials displaying synergistic magneto‐optic property.  相似文献   
909.
In this work, a new polymer resin with a functional groups capable of holding trace metals has been synthesized. The structure of polymer resin has been examined by BET-N2 method analyzer, IR spectrometer, scanning electron microscope (SEM) and elemental microanalyser. The synthesized polymer resin was used for the simultaneous separation and preconcentration of the trace metals from various tea and herbal plants samples. After extraction process, flame atomic absorption spectrometry (FAAS) was used to determine the trace metals. The analytical parameters and solid phase extraction (SPE) performance such as pH, sample volume, flow rates of sample, flow rates of eluent, concentration, volume and type of eluent and effect of interference ions, were investigated. The limits of detection (DL) of the SPE procedure for trace metals, were calculated to be (3s) in the range of 0.9?4.0 μg L?1 (n = 21) and the factors of preconcentration (PF) were obtained at 200 for Cd, Co, Cu, Fe, Ni and Zn, and at 50 for Cr, Mn and Pb ions and the relative standard deviation (RSD) at ≤ 2% (n = 11).  相似文献   
910.
Two types of bicyclic N-cyclopropyl glycine ester derivatives have been prepared and put under scrutiny as possible precursors of azomethine ylides. The results demonstrate that they can indeed participate in 1,3-dipolar cycloaddition reactions with dipolarophiles, as illustrated in the cases of phenyl vinyl sulfone, N-phenylmaleimide, diethyl fumarate and diethyl maleate. The relative configurations of the major diastereoisomers produced are consistent with the predicted generation of azomethine ylide species, reacting in concerted cycloaddition processes. This unprecedented way of generating such 1,3-dipoles provides access to functionalised pyrrolizidine and pyrrolidine derivatives, that would be difficult to make directly by more classic methods. It was also found that using phenyl vinyl sulfone or N-phenylmaleimide as the dipolarophile reactant, a domino nucleophilic conjugate addition/1,3-dipolar cycloaddition process may operate competitively.  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