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   5285篇
  免费   684篇
  国内免费   524篇
化学   3912篇
晶体学   58篇
力学   279篇
综合类   36篇
数学   554篇
物理学   1654篇
  2024年   11篇
  2023年   87篇
  2022年   90篇
  2021年   172篇
  2020年   197篇
  2019年   215篇
  2018年   192篇
  2017年   152篇
  2016年   249篇
  2015年   227篇
  2014年   278篇
  2013年   375篇
  2012年   395篇
  2011年   435篇
  2010年   286篇
  2009年   275篇
  2008年   325篇
  2007年   290篇
  2006年   301篇
  2005年   215篇
  2004年   194篇
  2003年   176篇
  2002年   188篇
  2001年   149篇
  2000年   110篇
  1999年   120篇
  1998年   105篇
  1997年   88篇
  1996年   64篇
  1995年   82篇
  1994年   63篇
  1993年   54篇
  1992年   51篇
  1991年   33篇
  1990年   38篇
  1989年   18篇
  1988年   17篇
  1987年   11篇
  1986年   25篇
  1985年   24篇
  1984年   17篇
  1983年   14篇
  1982年   12篇
  1981年   12篇
  1980年   6篇
  1979年   10篇
  1977年   4篇
  1974年   7篇
  1973年   7篇
  1969年   4篇
排序方式: 共有6493条查询结果,搜索用时 442 毫秒
81.
The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.  相似文献   
82.
新型含氟聚芳醚酮的合成与表征   总被引:10,自引:0,他引:10  
聚芳醚酮具有很高的热稳定性和优良的电性能及机械性能 ,已经被广泛应用于宇航、电子及核能等高技术领域 [1] .氟元素的引入可以降低材料介电常数、折光指数和吸水率 ,提高热稳定性、溶解性和阻燃性 ,增加材料透明度 ,使这类聚合物在光电子、光学和微电子等应用领域的研究倍受关注 [2~ 4 ] .本文在合成含三氟甲基苯侧基的聚芳醚酮 [5] 的基础上 ,设计并合成了新型的含氟量更高的单体和聚合物 ,并对其性能进行了初步研究 .1 实验部分1 .1 试剂与仪器  [3,5 -二 (三氟甲基 ) ]苯代对苯醌 (自制 ) ;锌粉 ,A.R.级 ,天津化学试剂一厂产品 ;…  相似文献   
83.
本文合成了部分烷基化三氟乙酰化的β-环糊精手性固定相(DP-TFA-β-CD),并把它与普通聚硅氧烷OV-7混合制备出了柱效高、热稳定性好的手性石英毛细管柱。与直接涂DP-TFA-β-CD相比,混合固定相能在较短分析时间内对卤代烃、醇、酯、γ-内酯、胺等对映体有更好的拆分。  相似文献   
84.
In this work, we used the solution precipitation route to synthesize Eu3+-doped YPO4·nH2O nanowires. The structure, morphology, composition, thermal behavior, and photoluminescence of as-synthesized product were characterized by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopic (FE-SEM) and photoluminescence (PL) spectra. The dependence of the structure, morphology, composition and luminescent properties on the thermal treatment was investigated. The results indicate that the aqueous synthesis has a better control on the structure, morphology, composition of the products, and that the heat treatment induces the transitions of the structure, composition, and luminescent properties.  相似文献   
85.
采用水辅助方法(water-assisted fabrication method),分别以4-十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)和聚2-甲氧基-5-(2′-乙烯基-己氧基)苯乙炔(MEH-PPV)两种功能高聚物为成膜材料,冷凝水滴为模板,利用水滴在聚合物溶液表面的自组装,制备出了两种纳米层次以上的蜂窝状有序多孔聚合物薄膜.通过原子力显微镜和共聚焦荧光显微镜对其形貌、电学性质和荧光图像进行了表征.  相似文献   
86.
Dimethylformamide (DMF) acts as an efficient source of carbon monoxide and dimethylamine in the palladium-catalyzed aminocarbonylation (Heck carbonylation) of p-tolyl bromide to provide the dimethylamide. Addition of amines to the reaction mixture in excess delivers the corresponding aryl amides in good yields. The amines employed, benzylamine, morpholine, and aniline, all constitute good reaction partners. The reaction proceeds smoothly with bromobenzene and more electron-rich aryl bromides, but electron-deficient aryl bromides fail to undergo aminocarbonylation. The reactions are conducted at 180-190 degrees C for 15-20 min with microwave heating in a reaction mixture containing imidazole and potassium tert-butoxide: the latter is required to promote decomposition of the DMF solvent at a suitable rate. The beneficial effects of controlled microwave irradiation as an energy source for the rapid heating of the carbonylation reaction mixture are demonstrated. The carbonylation procedure reported herein, which relies on the in situ generation of carbon monoxide, serves as a convenient alternative to other carbonylation methods and is particularly applicable to small-scale reactions where short reaction times are desired and the direct use of carbon monoxide gas is impractical.  相似文献   
87.
IntroductionInthcsclcctivcoxidationofalkanes.suchas'theoxidativccouplingofmcthanc(0CM)andthcoxidativcdch}'drogenationofcthanc(0DE)t0prcparccth}'lene.bothoxidcionsofthelatticeandtheox}'genspeciesovercataIystsuffocepla}'animportantrole.Althoughcxtcnsivcinvcstigationshavcbeengivcntothecharactcrizationofox}'gcnspccicsandthcreactionofox}'gcnspecicsx`ithalkanes,itisstilldifficulttosayt`hichoncsofox}'gcnspcciesarcthcactivcspecicsinthcactivation0falkancs.bccauscthenaturcofcatal}'stsandthecxperimcntc…  相似文献   
88.
Magnusson J  Wan H  Blomberg LG 《Electrophoresis》2002,23(17):3013-3019
Determination of enantiomeric purity is most often done under overload conditions, which leads to deformed peaks. In general, the best resolutions are obtained when the small peak appears before the large peak in the electropherogram. To be able to determine the R(+)-impurity in the S(-)-form as well as the S(-)-impurity in the R(+)-form the elution orders have to be reversed. The present paper describes reversal of enantiomeric elution order for the basic analyte propranolol and the acidic analyte ibuprofen. For propranolol, a charged heptakis-(6-sulfo)-beta-cyclodextrin (CD) is used in the background electrolyte. For ibuprofen, a mix of the charged heptakis-(6-sulfo)-beta-CD and the uncharged heptakis-(2,3,6-tri-O-methyl)-beta-CD is used in the background electrolyte. The use of a coated capillary and reversal of the polarity shift the elution order, buffer composition is unchanged in both cases. The enantiomers of propranolol and ibuprofen are well separated on both the coated and uncoated capillaries. Detection limits of enantiomer impurities are investigated using spiked samples of both propranolol and ibuprofen.  相似文献   
89.
Dispersion of MoO3, NiO, ZnO on rutile TiO2 with low specific surface area was studied with Mercury Porosimeter, SEM, XPS and Ammonia Extraction method. The dispersion thresholds of MoO3, NiO, ZnO on three rutile TiO2 carriers were obtained with XPS, and com-pared with those on anatase TiO2 with high specific surf are area. Ammonia Extraction method was used to identify the surface oxide species interarting with support surface in different strength and it was found that the proportions of oxides that can not be extracted by ammonia extraction are different for MoO3, NiO and ZnO which are supported on rutile TiO2.  相似文献   
90.
A series of chiral aromatic imides and diimides were synthesized and their electrochemical, absorption, fluorescent, and chiroptical properties were examined for their potential application as molecular chiroptical switches. These compounds exhibit strong UV-vis absorptions, and can be electrochemically reduced to radical anions that absorb in the near infrared (NIR) region. Further reduction to the dianionic states results in new absorptions in the visible region. The changes in circular dichroism upon redox switching were apparent in the UV-vis region but were absent in the NIR region.  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