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   1981篇
  免费   241篇
  国内免费   211篇
化学   1206篇
晶体学   33篇
力学   88篇
综合类   43篇
数学   200篇
物理学   863篇
  2024年   7篇
  2023年   33篇
  2022年   58篇
  2021年   54篇
  2020年   58篇
  2019年   80篇
  2018年   70篇
  2017年   46篇
  2016年   77篇
  2015年   64篇
  2014年   78篇
  2013年   105篇
  2012年   149篇
  2011年   146篇
  2010年   103篇
  2009年   114篇
  2008年   108篇
  2007年   93篇
  2006年   94篇
  2005年   109篇
  2004年   93篇
  2003年   73篇
  2002年   64篇
  2001年   93篇
  2000年   48篇
  1999年   53篇
  1998年   51篇
  1997年   40篇
  1996年   33篇
  1995年   36篇
  1994年   25篇
  1993年   23篇
  1992年   16篇
  1991年   16篇
  1990年   33篇
  1989年   18篇
  1988年   10篇
  1987年   8篇
  1986年   19篇
  1985年   8篇
  1984年   3篇
  1983年   3篇
  1981年   2篇
  1979年   4篇
  1978年   4篇
  1977年   2篇
  1976年   1篇
  1975年   1篇
  1974年   4篇
  1973年   1篇
排序方式: 共有2433条查询结果,搜索用时 46 毫秒
991.
The medium-chain-length polyhydroxyalkanoate (PHAMCL) produced by Pseudomonas putida PGA1 using saponified palm kernel oil as the carbon source could degrade readily in water taken from Kayu Ara River in Selangor, Malaysia. A weight loss of 71.3% of the PHA film occurred in 86 d. The pH of the river water medium fell from 7.5 (at d 0) to 4.7 (at d 86), and there was a net release of CO2. In sterilized river water, the PHA film also lost weight and the pH of the water fell, but to lesser extents. The C8 monomer of the PHA was completely removed after 6 d of immersion in the river water, while the proportions of the other monomers (C10, C12, and C14) were reversed from that of the undegraded PHA. By contrast, the monomer composition of the PHA immersed in sterilized river water did not change significantly from that of the undegraded PHA. Scanning electron microscopy showed physical signs of degradation on the PHA film immersed in the river water, but the film immersed in sterilized river water was relatively unblemished. The results thus indicate that the PHAMCL was degraded in tropical river water by biologic as well as nonbiologic means. A significant finding is that shorter-chain monomers were selectively removed throughout the entire PHA molecule, and this suggests enzymatic action.  相似文献   
992.
The (0001) surface of alpha-Al(2)O(3) single crystals has been imaged by atomic force microscopy in water. The observed hexagonal lattice arrangement has a period of 4.7 A, in good agreement with the known bulk unit cell. The sample cleaning procedure was found to be crucial in obtaining clean terraces and achieving lattice resolution.  相似文献   
993.
设计开发了一个大学化学综合性实验,合成了2-羟基-1-萘甲醛缩邻苯二胺席夫碱及其铜(Ⅱ)配合物,分别采用化学分析法和仪器分析法对配合物的组成进行了测定,并结合红外光谱、核磁共振氢谱对产物的结构进行了表征,取得了满意的实验结果。该实验一定程度上弥补了大学化学教学实验中合成有机金属配位化合物教学资源的匮乏。通过该实验的实施,可使学生进一步巩固回流、纯化、离心等基本操作技能,掌握摩尔比法测定配合物配位数及稳定常数的原理和方法,同时掌握运用有机波谱技术推断和鉴定分子结构的方法。本实验有利于培养学生综合运用有机化学、无机化学、化学分析及仪器分析等知识解决具体问题的能力,同时有利于学生了解席夫碱及其金属配合物的性质、研究动态等,激发学生对科学研究的热情,培养学生系统的科学思维和研究能力。  相似文献   
994.
The photoassisted charge behavior of hydrogen storage alloy modified with TiO2/Pt nanocomposites (HSA-TiO2/Pt electrode) was investigated. The HSA-TiO2/Pt electrode can be photocharged under current. The mechanism of photoassisted behavior of the HSA-TiO2/Pt electrode was explained through the results of cyclic voltammogram and impedance measurements of the HSA-TiO2/Pt electrode. Upon illumination, the photogenerated electrons can charge the electrode, but the photogenerated holes may oxidize the hydrogen storage alloy to form a layer of metal oxide. Because the current could keep the electrode active, the H atoms produced by photogenerated electrons diffused to the hydrogen storage alloy and a metal hydride formed. The electrode delivered a higher discharge capacity due to the assistance of photocharge.  相似文献   
995.
Preparation and photochromic behavior of ormosil containing encapsulated AgTCNQ molecules were studied in this paper. The ormosil resulted from hydrolysis and polycondensation of glycidoxypropyltrimethoxysilane, dimethyldimethoxysilane and methyltrimethoxysilane. The time to add AgNO3 water solution into the resultant sol was a key factor to synthesize AgTCNQ molecules inside ormosil matrix. AgTCNQ molecules encapsulated in the ormosil showed different photochromic behavior compared with pure AgTCNQ film: normal photochromic reaction can be realized, while reverse photochromic reaction can not. The “cage” model was used to explain this phenomenon.  相似文献   
996.
某些苯二醛类双Schiff碱及其双铜(Ⅱ)配合物研究   总被引:1,自引:0,他引:1  
用2-甲氧基-5-氯-1,3-苯二甲醛与含有不同取代基团X的邻氨基酚缩合,合成了一系列双Schiff碱L-X(X=OMe,diMe,Me,t-Bu,H,Cl,NO2),它们与乙酸铜(Ⅱ)作用生成了一系列的双核配合物Cu2L-X(OEt).用红外、紫外、磁天平、顺磁共振等手段对配合物进行了表征,并通过量化计算(CNDO/2法)探讨了配合物的成键性质。研究结果表明,该类配合物是一个较大的共轭体系,配合物中Cu(Ⅱ).Cu(Ⅱ)之间有较强的反铁磁性交换作用,其共轭程度和交换作用强弱皆随X基团的不同而呈现某种变化规律。  相似文献   
997.
Two new azo dyes of alpha-isoxazolylazo-beta-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.  相似文献   
998.
Yang  Tao  Dong  Mengqi  Cui  Juqing  Gan  Lu  Han  Shuguang 《Analytical and bioanalytical chemistry》2019,411(21):5455-5464

The preparation and fractionation of oligomeric proanthocyanidins (OPCs) are particularly important for the application of tannins in the biomedical field. By use of two different methods—gel filtration chromatography (GFC) with Sephadex LH-20 and progressive solvent precipitation—the OPCs were prepared and fractionated from mangosteen pericarp. The fractions were compared by reversed-phase and normal-phase high-performance liquid chromatography–electrospray ionization mass spectrometry and gel permeation chromatography. GFC directly purified oligomers (monomer to pentamer) with polydispersity values close to 1 and generated fractions with a higher level of total phenols (800.59 mg gallic acid equivalents per gram) but a lower yield (7.72%). Progressive solvent precipitation rapidly prepared and fractionated OPCs with a lower level of total phenols (609.57 mg gallic acid equivalents per gram) but a higher yield (24.74%) and higher polydispersity. Additionally, we found pronounced structural and quantitative differences among different tannin-rich fractions, and fractions obtained by GFC better reflected the structural diversity and complexity of OPCs from mangosteen pericarp. This study presents different ways of preparing and fractionating OPCs in the biomedical field.

  相似文献   
999.
甘峰  龚范 《分析化学》1998,26(1):51-54
将序贯为九论优化法,结合采用约束背影双线性比模型用于多组分“灰色”体系同时测定,且对SNTO的收缩比和收敛判据进行了改进。结果表明,SNTO法是一种实用的全局优化方法,收缩比和收敛判据的改进可大大缩短计算时间。  相似文献   
1000.
The reactions of pyrimidine‐phosphine ligand N‐[(diphenylphosphino)methyl]‐2‐pyrimidinamine ( L ) with various metal salts of PtII, PdII and CuI provide three new halide metal complexes, Pt2Cl4(μ‐L)2·2CH2Cl2 ( 1 ), Pd2Cl4(μ‐L)2 ( 2 ), and [Cu2(μ‐I)2L2]n ( 3 ). Single crystal X‐ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve‐membered ring structure, while complex 3 consists of one‐dimensional polymeric chains, which are further connected into a 2‐D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2 , the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3 , both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1 ‐ 3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal‐to‐ligand charge‐transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively.  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