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   475篇
  免费   70篇
  国内免费   71篇
化学   287篇
晶体学   5篇
力学   14篇
综合类   8篇
数学   44篇
物理学   141篇
无线电   117篇
  2024年   3篇
  2023年   13篇
  2022年   14篇
  2021年   28篇
  2020年   17篇
  2019年   22篇
  2018年   13篇
  2017年   21篇
  2016年   21篇
  2015年   24篇
  2014年   25篇
  2013年   41篇
  2012年   47篇
  2011年   24篇
  2010年   15篇
  2009年   26篇
  2008年   33篇
  2007年   25篇
  2006年   26篇
  2005年   13篇
  2004年   18篇
  2003年   17篇
  2002年   15篇
  2001年   9篇
  2000年   10篇
  1999年   10篇
  1998年   9篇
  1997年   11篇
  1996年   11篇
  1995年   7篇
  1994年   7篇
  1993年   7篇
  1992年   4篇
  1991年   11篇
  1990年   3篇
  1989年   4篇
  1988年   1篇
  1987年   1篇
  1985年   2篇
  1984年   4篇
  1983年   2篇
  1979年   1篇
  1957年   1篇
排序方式: 共有616条查询结果,搜索用时 305 毫秒
11.
Poor sensitivity and low phase ratio are the main drawbacks of open tubular capillary electrochromatography (OTCEC). The poor sensitivity results from the use of narrow bore size capillary, whereas the low phase ratio, which limits the separation capability, is caused by the limited surface area of conventional capillary. Two strategies may be useful to overcome these disadvantages. First, an extended light path (ELP) capillary, which has a bubble cell at the detection point, is used to improve the sensitivity. Secondly, an etched capillary of a 1,000-fold increased surface area is used to enhance the phase ratio. In this work, use of an ELP capillary and an etched capillary in OTCEC was evaluated with a chiral stationary phase of avidin prepared with the physical adsorption method. With a 20 microm I.D. ELP capillary with a 150 microm bubble cell, the peak height was enhanced by 4-10-fold and the corrected peak area was increased by 12-fold relative to a 20 microm I.D. conventional capillary. However, the peak efficiency and resolution decreased noticeably. The phase ratio on the etched capillary was slightly enhanced, by a factor of 1.64 relative to an unetched capillary. Consequently, the separation capability was slightly improved. The increase in the phase ratio was much lower than that expected from the increase in surface area, the reason for which is probably the reduced density of surface silanol group and the generation of nitrogen-containing groups due to the etching process.  相似文献   
12.
13.
<正> 聚甲基丙烯酸己磺酸钠(PSSHMA)是我们最近合成的,具有较好的抗凝血性能。对于带磺酸基聚合物抗凝血性能的研究,文献报道还不多。我们用羟基己磺酸钠与甲基丙烯酸反应制备了甲基丙烯酸己磺酸钠(SSHMA)新单体,在此异相酯化反应中,使用了四丁基硫酸氢铵(TBAB)作为催化剂,使反应较顺利的进行,得纯单体。经复钙时  相似文献   
14.
Electrothermal stirring for heterogeneous immunoassays   总被引:1,自引:0,他引:1  
A technique is proposed to enhance microfluidic immuno-sensors, for example, immunoassays, in which a ligand immobilized on a microchannel wall specifically binds analyte flowing through the channel. These sensors can be limited in both response time and sensitivity by the diffusion of analyte to the sensing surface. In certain applications, the sensitivity and response of these heterogeneous immunoassays may be improved by using AC electrokinetically-driven microscale fluid motion to enhance antigen motion towards immobilized ligands. Specifically, the electrothermal effect is used to micro-stir analyte near the binding surface. Numerical simulations of antigen in a microchannel flow subjected to the electrothermal effect show that 6 V(rms) applied to electrodes near a binding region can increase binding in the first few minutes by a factor of seven. The effectiveness of electrothermal stirring is a strong function of the Damk?hler number. The greatest binding enhancement is possible for high Damk?hler numbers, where the reaction is limited by diffusion. Based on these results, the utility of this technique for diffusion-limited microfluidic sensor applications is demonstrated.  相似文献   
15.
Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH4][(UO2)3(HTTDS)(H2O)] ( 1 ), [(UO2)4(HTTDS)2](HIM)6 ( 2 , IM=imidazole), [(UO2)4(TTDS)(H2O)2(Phen)2] ( 3 , Phen=1,10-phenanthroline), [Zn(H2O)4]0.5[(UO2)3(HTTDS)(H2O)4] ( 4 ), and {(UO2)2[Zn(H2O)3]2(TTDS)} ( 5 ), {Zn(UO2)2(H2O)(Dib)0.5(HDib)(HTTDS)} ( 6 , Dib=1,4-di(1H-imidazol-1-yl)benzene) and [Na]{(UO2)4[Cu3(u3-OH)(H2O)7](TTDS)2} ( 7 ) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5-dicarboxyphenyl)silicon(H8TTDS). These UOFs have different 3D self-assembled structures as a function of co-ligands, structure-directing agents and transition metals. The structure of 1 has an infinite ribbon formed by the UO7 pentagonal bipyramid bridged by carboxylate groups. With further introduction of auxiliary N-donor ligands, different structure of 2 and 3 are formed, in 2 the imidazole serves as space filler, while in 3 the Phen are bound to [UO2]2+ units as co-ligands. The second metal centers were introduced in the syntheses of 4–7 , and in all cases, they are part of the final structures, either as a counterion ( 4 ) or as a component of framework ( 5 − 7 ). Interesting, in 7 , a rare polyoxometalate [Cu33-OH)O7(O2CR)4] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO2)2(O2CR)4] unit. Those uranyl carboxylates were sufficiently determined by single crystal X-ray diffraction, and their topological structures and luminescence properties were analyzed in detail.  相似文献   
16.
A methacrylate‐based crosslinking hyperbranced polymers have been synthesized through initiator‐fragment incorporation radical polymerization and used for the temperature stable electro‐optic (EO) polymer application. This polymer consists of methyl methacrylate, 2‐metacryloxyethyl isocyanate, and ethylene glycol dimethacrylate (EGDMA) monomers. The use of EGDMA as a bifunctional unit resulted in the solvent‐soluble crosslinking hyperbranched chain, so that the EO polymer enhanced glass transition temperatures. A phenyl vinylene thiophene vinylene bridge nonlinear optical chromophore was attached to the polymer backbone as the side‐chain by a post‐functionalization reaction. The loading concentration of the chromophore was varied between 30 and 50 wt % by simply changing the mixing ratio of the precursor polymer to the chromophore. The synthesized EO polymers produced optical quality films with a light propagation loss of 0.61 dB/cm in a slab waveguide at 1.31 μm. The electrically poled film had an EO coefficient (r33) of 139 pm/V at 1.31 μm. The EO crosslinking hyperbranced polymer had a high‐glass transition temperature of 170 °C, and exhibited excellent temporal stability of the EO activity at 85 °C for 500 h. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   
17.
The assembly of two tripyridinium-tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane-like interlocking of tricyclic cages. The MOFs show tripyridinium-afforded and metal-modulated photoresponsive properties. The MOFs with d10 metal centers ( 1-Cd , 1-Zn , 2-Cd , 2-Zn ) show fast and reversible photochromism and concomitant fluorescence quenching, 1-Ni displays slower photochromism but does not fluoresce, and 1-Co and 2-Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor-acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal-centered d-d transitions. In addition, 1-Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO22+ in water.  相似文献   
18.
A double asymmetric induction has been observed in allylation of the imines derived from (+)-camphor, (+)- and (-)- 2-hydroxypinan-3-ones with (+)- and (-)-menthyl glycinates. After hydrolysis of the allylated intermediates, (R)- and (S)-α-allylglycines are obtained in 3–90% optical yields.  相似文献   
19.
Zhao  Qiang  Piao  Mingwei 《Russian Physics Journal》2021,64(3):427-435
Russian Physics Journal - The lateral vibration coupling mechanism is the basic law describing the current vibration behavior of a high-speed train. The main reason is that there are design defects...  相似文献   
20.
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