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   4805篇
  免费   587篇
  国内免费   442篇
化学   3516篇
晶体学   51篇
力学   273篇
综合类   36篇
数学   499篇
物理学   1459篇
  2024年   17篇
  2023年   76篇
  2022年   135篇
  2021年   176篇
  2020年   156篇
  2019年   173篇
  2018年   159篇
  2017年   132篇
  2016年   223篇
  2015年   188篇
  2014年   237篇
  2013年   338篇
  2012年   331篇
  2011年   384篇
  2010年   256篇
  2009年   254篇
  2008年   280篇
  2007年   253篇
  2006年   260篇
  2005年   188篇
  2004年   175篇
  2003年   153篇
  2002年   179篇
  2001年   134篇
  2000年   104篇
  1999年   110篇
  1998年   95篇
  1997年   84篇
  1996年   52篇
  1995年   71篇
  1994年   60篇
  1993年   50篇
  1992年   52篇
  1991年   31篇
  1990年   36篇
  1989年   16篇
  1988年   18篇
  1987年   14篇
  1986年   26篇
  1985年   25篇
  1984年   19篇
  1983年   15篇
  1982年   19篇
  1981年   13篇
  1980年   6篇
  1979年   10篇
  1978年   5篇
  1976年   5篇
  1974年   8篇
  1973年   8篇
排序方式: 共有5834条查询结果,搜索用时 0 毫秒
971.
The effect of EO side chain functionalization on the transport and electrochemical properties of polysiloxane electrolytes has been examined in this report. First, a study of the electrochemical stability of the electrolytes by linear sweep voltammetry shows that the polymer electrolytes have a negligible effect on the electrolyte stability windows. In addition, the parameters of cation mobility in polysiloxane electrolytes, such as ionic transference numbers and diffusion coefficients, were increased by increasing the lengths of the EO side chain. However, cation mobility in polymer structures is quite different compared to liquid-based systems and is probably suppressed, resulting in their polymer structure. Therefore, Positron Annihilation Lifetime Spectroscopy (PALS) was used to study the relationship between orthopositronium (o-Ps) lifetime, free volume radius, free volume of micro voids and EO side chain affection at different temperatures. Finally, a battery application with LiCoO2 and LiFePO4/polymer electrolyte/lithium metal electrode was monitored for its potential use in the future.  相似文献   
972.
The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.  相似文献   
973.
Pyridotriazol-1-yloxypyrimidine 3 reacts with arylboronic acids under palladium-free, Cs2CO3, (0.8%) H2O2, and DME conditions to produce heteroaryl ethers 4-16 in good yields comparable to the oxidative palladium-catalyzed reaction. The yields of aryl ethers 17-19 from quinazoline 2 with (0.8%) H2O2 were modest. Hydrogen peroxide is superior to dioxygen as an oxidant in these reactions.  相似文献   
974.
Penguins live in the extremely cold Antarctic. Understanding the thermal radiative properties of penguin down may help us to develop super insulating materials. In this study, Fourier transform infrared spectroscopy (FTIR) was applied to measure the thermal radiative properties of penguin down and compare them with those of other fibrous materials. It was found that penguin and duck down are superior to other fibrous materials, such as polyester, Thinsulate and wool, at the same fibre volume fraction, in shielding the radiative heat transmission, largely due to their fine fibre diameter. There is an optimum fibre diameter at which the fibrous materials are at their best in blocking thermal radiation. The fibre diameter of penguin down is very close to this optimum value. The study further found that the relationship between the effective thermal radiative conductivity and fibre fineness may be better fitted with a quadratic curve.  相似文献   
975.
The synthesis of an extended globo-H (MBr1 antigen) in the form of a glycosylamino acid is reported. By careful NMR analysis, we found an interesting conformational "flip" on the E ring of some synthetic intermediates. An explanation offered for the successful [3+3] coupling of ABC acceptor 11 and DEF donor 10 possessing a C4 free hydroxyl to produce β-galactoside in azaglycosidations is reinforced.  相似文献   
976.
由于介孔二氧化硅单晶规整的外观形貌和有序的内部孔道结构性能, 使其在微激光器件领域具有十分重要的潜在应用. 试着用高电荷密度的阳离子三头季铵盐表面活性剂(C18-2-3-1)作模板剂, 用正硅酸四乙酯作无机前驱体, 在硫酸介质中通过调变有机-无机物种之间的协同组装作用, 成功地合成了具有简单立方相Pm3n结构的介孔二氧化硅单晶. 扫描电子显微镜(SEM)观察到这种介孔二氧化硅单晶具有菱形十二面体形貌, X射线衍射(XRD)和透射电子显微镜(TEM)测试结果证实这种介孔单晶属于简单立方Pm3n对称结构. 氮气吸附数据测得这种单晶具有较大的BET比表面积(550 cm2/g), 较大的孔体积(BJH 0.20 cm3/g)和孔径(BJH 2.4 nm).  相似文献   
977.
An electrochemical sensor was developed for the detection of organophosphate pesticides based on electrodeposition of gold nanoparticles on a multi-walled carbon nanotubes modified glassy carbon electrode. Cyclic voltammetry was employed in the process of electrodeposition. Field emission scanning electron microscope and X-ray diffraction techniques were used for characterization of the composite. Organophosphate pesticides (e.g. parathion) were determined using linear scan voltammetry. A highly linear response to parathion in the concentration range from 6.0?×?10?5 to 5.0?×?10?7 M was observed, with a detection limit of 1.0?×?10?7 M estimated at a signal-to-noise ratio of 3. The method has been applied to the analysis of parathion in real samples.  相似文献   
978.
Yi Wan  Dun Zhang  Baorong Hou 《Talanta》2009,80(1):218-401
An impedimetric immunosensor was fabricated for rapid and non-labeled detection of sulfate-reducing bacteria, Desulforibrio caledoiensis (SRB) by immobilizing lectin-Concanavalin A using an agglutination assay. The immobilization of lectin was conducted using amine coupling on the surface of a gold (Au) electrode assembled with 11-Mercaptoundecanoic acid. Electrochemical impedance spectroscopy (EIS) was used to verify the stepwise assembly of the sensor system. The work conditions of the impedimetric immunosensor, such as pH of the buffer solutions and the incubation time of lectin, were optimized. Faradic impedance spectra for charge transfer for the redox probe Fe(CN)63−/4−were measured to determine SRB concentrations. The diameter of the Nyquist diagram that is equal to the charge-transfer resistance (Rct) increased with increasing SRB concentration. A linear relationship between Rct and SRB concentration was obtained in SRB concentration range of 1.8 to 1.8 × 107 cfu/ml. The variation of the SRB population during the growth process was also monitored using the impedimetric immunosensor. This approach has great potential for simple, low-cost, and time-saving monitoring of microbial populations.  相似文献   
979.
Highly ordered honeycomb-patterned polystyrene (PS)/poly(ethylene glycol) (PEG) films were prepared by a water-assisted method using an improved setup, which facilitated the formation of films with higher regularity, better reproducibility, and larger area of honeycomb structures. Surface aggregation of hydrophilic PEG and adsorption of bovine serum albumin (BSA) on the honeycomb-patterned films were investigated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to observe the surface morphologies of the films before and after being rinsed with water. As confirmed by the FESEM images and the AFM phase images, PEG was enriched in the pores and could be gradually removed by water. The adsorption of fluorescence-labeled BSA on the films was studied in visual form using laser scanning confocal microscopy. Results clearly demonstrated that the protein-resistant PEG was selectively enriched in the pores. This water-assisted method may be a latent tool to prepare honeycomb-patterned biofunctional surfaces. Supported by the National Natural Science Foundation of China (Grant No. 50803053), the National Natural Science Foundation of China for Distinguished Young Scholars (Grant No. 50625309), the National Postdoctoral Science Foundation of China (Grant Nos. 20070421172 & 20081466) and the National Undergraduate Innovative Test Program  相似文献   
980.
Ionic liquid, 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl), was used as solvent for the polymerization of acrylonitrile (AN) and the resulting polymer solution was directly applied for spinning to produce polyacrylonitrile (PAN) fiber for the first time. Acrylic polymers with high content of AN, large molecular weight, and low polydispersity index (PDI) were prepared. The PAN macromolecules have little degradation during dissolution of PAN in [BMIM]Cl, which is completely different from the dissolution of biopolymers such as cellulose in ionic liquids. The PAN fiber with round profile and good mechanical properties was successfully spun from the PAN/[BMIM]Cl solution using dry–jet wet spinning technology. It suggests that an environmental friendly process for the acrylic fiber would be developed and the high performance PAN fiber would be obtained when the spinning conditions are optimized further. Copyright © 2008 John Wiley & Sons, Ltd.  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