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   2422篇
  免费   347篇
  国内免费   170篇
化学   1520篇
晶体学   22篇
力学   70篇
综合类   7篇
数学   195篇
物理学   584篇
无线电   541篇
  2024年   6篇
  2023年   53篇
  2022年   66篇
  2021年   72篇
  2020年   69篇
  2019年   95篇
  2018年   82篇
  2017年   60篇
  2016年   102篇
  2015年   118篇
  2014年   133篇
  2013年   178篇
  2012年   209篇
  2011年   220篇
  2010年   143篇
  2009年   131篇
  2008年   167篇
  2007年   144篇
  2006年   156篇
  2005年   121篇
  2004年   102篇
  2003年   69篇
  2002年   83篇
  2001年   27篇
  2000年   27篇
  1999年   47篇
  1998年   30篇
  1997年   33篇
  1996年   39篇
  1995年   19篇
  1994年   14篇
  1993年   9篇
  1992年   14篇
  1991年   10篇
  1990年   12篇
  1989年   7篇
  1988年   10篇
  1987年   9篇
  1985年   7篇
  1984年   10篇
  1981年   3篇
  1979年   2篇
  1978年   4篇
  1977年   4篇
  1976年   3篇
  1974年   3篇
  1969年   2篇
  1968年   2篇
  1960年   1篇
  1938年   1篇
排序方式: 共有2939条查询结果,搜索用时 18 毫秒
61.
A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.  相似文献   
62.
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   
63.
A highly sensitive and specific enzyme-linked immunosorbent assay (ELISA) method has been developed for the determination of 20(S)-protopanaxatriol (PPT), one of the major aglycones of dammarane-type ginseng saponins. Polyclonal antibodies raised against ginsenoside F1 (GF1)-bovine serum albumin showed high reactivities to PPT and GF1, whereas they exhibited minor or even no cross-reactivities to other ginsenosides and protopanaxadiol (0.19%). The working range of this method extends from 50 pg ml−1 to 20 ng ml−1 of PPT. The assay reported here has been validated against an HPLC technique using PPT-containing samples and was shown to correlate closely (γ=0.993). This ELISA could be a useful tool for the determination of PPT contained in biological fluids and plant materials.  相似文献   
64.
基于SnO2为修饰层的Au-Pt / SnO2 / Au复合电极研究   总被引:1,自引:0,他引:1  
用真空镀膜法在Au电极上沉积SnO2薄膜,在HAuCl4和H2PtCl4的混合溶液中利用直接还原法,将Au-Pt双金属纳米颗粒组装在SnO2 / Au电极上,得到Au-Pt / SnO2 / Au复合电极。采用SEM、TEM、XPS及CV曲线测定对Au-Pt / SnO2 / Au复合电极进行了表征。结果表明:复合电极上双金属纳米颗粒分布均匀,粒子粒径约为25 nm左右。SnO2作为修饰层以配位键与双金属纳米粒子结合。Au-Pt / SnO2 / Au复合电极具有良好对甲醇氧化的电化学性能。  相似文献   
65.
A simple method of solid-phase derivatization and sequencing of tryptic peptides has been developed for rapid and unambiguous identification of spots on two-dimensional gels using post-source decay (PSD) matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The proteolytic digests of proteins are chemically modified by 4-sulfophenyl isothiocyanate. The derivatization reaction introduces a negative sulfonic acid group at the N-terminus of a peptide, which can increase the efficiency of PSD fragmentation and enable the selective detection of only a single series of fragment ions (y-ions). This chemically assisted method avoids the limitation of high background normally observed in MALDI-PSD spectra, and makes the spectra easier to interpret and facilitates de novo sequencing of internal fragment. The modification reaction is conducted in C(18) microZipTips to decrease the background and to enhance the signal/noise. Derivatization procedures were optimized for MALDI-PSD to increase the structural information and to obtain a complete peptide sequence even in critical cases. The MALDI-PSD mass spectra of two model peptides and their sulfonated derivatives are compared. For some proteins unambiguous identification could be achieved by MALDI-PSD sequencing of derivatized peptides obtained from in-gel digests of phosphorylase B and proteins of hepatic satellite cells (HSC).  相似文献   
66.
The effects of organic solvents on the ammoximation of cyclohexanone to cyclohexanone oxime with H2O2and NH3 over TS-1 were studied. To investigate the effects of ammonia and organic solvents on the structure stability of the catalyst, TS-1 samples were pretreated under severe conditions in ammonia solution or ammonia solution plus methanol, toluene or t-butanol, respectively, and then characterized bySEM, XRD, FTIR, etc. The results revealed that t-butanol is the best solvent for the ammoximation reaction; ammonia tends to destroy the active sites, -Ti-O-Si- structure in TS-1, but the presence of organic solvents remarkably limits this damaging effect of ammonia.  相似文献   
67.
Hu  Chuanjiang  Duan  Chunying  Meng  Qingjin  Liu  Yongjiang  Lu  Changsheng  Reng  Xiaoming  Chen  Yijun  Cao  Mi 《Transition Metal Chemistry》2000,25(2):141-144
The mixed-valence molybdovanadate compound Na2(NH4)4[VIVVV 8Mo)O28] · 10H2O [Vanadata(6-)tetradeca--oxotetra-3-oxodi-6-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH2OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO6 octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.  相似文献   
68.
In this work, an integral equation approach to investigate the atactic polystyrene (aPS) melt based on polymer reference interaction site model (PRISM) theory is proposed. The intramolecular structure factors, required as input to PRISM theory, are obtained from the semiflexible chain model. With a novel coarse-graining procedure and the explicit-atom molecular-dynamics (MD) simulations for aPS, the parameters needed for the coarse-grained model are obtained by using an automatic simplex optimization. These parameters can be used to describe the structure and thermodynamic properties of the complex aPS melt and good agreement is obtained between the theory and MD simulations. The proposed integral equation approach provides a basis for describing the structure and properties of PS nanocomposites where the application of molecular simulation is difficult.  相似文献   
69.
EPO检测技术的研究进展   总被引:3,自引:0,他引:3  
王杉  宓捷波  常文保 《化学进展》2003,15(2):117-122
促红细胞生成素(EPO)是一种临床上广泛应用的重要药物,也是近年来兴奋剂检测的热点。本文主要从EPO的产生和应用出发,对EPO的结构、特性及其检测方法进行了介绍及评价,重点探讨了竞技体育中EPO的检测技术,并对检测前景作了展望。  相似文献   
70.
Pt‐nanoparticles were synthesized and introduced into a carbon paste electrode (CPE), and the resulting modified electrode was applied to the anodic stripping voltammetry of copper(II) ions. The synthesized Pt‐nanoparticles were characterized by cyclic voltammetry, scanning electron microscopy and X‐ray photoelectron spectroscopy techniques to confirm the purity and the size of the prepared Pt‐nanoparticles (ca. 20 nm). This incorporated material seems to act as catalysts with preconcentration sites for copper(II) species that enhances the sensitivity of Cu(II) ions to Cu(I) species at a deposition potential of ?0.6 V in an aqueous solution. The experimental conditions, such as, the electrode composition, pH of the solution, pre‐concentration time, were optimized for the determination of Cu(II) ion using as‐prepared electrode. The sensitivity changes on the different binder materials and the presence of surfactants in the test solution. The interference effect of the coexisted metals were also investigated. In the presence of surfactants, especially TritonX‐100, the Cu(II) detection limit was lowered to 3.9×10?9 M. However, the Pt‐nanoparticle modified CPE begins to degrade when the period of deposition exceeds to 10 min. Linear response for copper(II) was found in the concentration range between 3.9×10?8 M and 1.6×10?6 M, with an estimated detection limit of 1.6×10?8 M (1.0 ppb) and relative standard deviation was 4.2% (n=5).  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