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   1529篇
  免费   176篇
  国内免费   177篇
化学   1116篇
晶体学   13篇
力学   83篇
综合类   11篇
数学   183篇
物理学   476篇
  2024年   10篇
  2023年   43篇
  2022年   70篇
  2021年   73篇
  2020年   87篇
  2019年   68篇
  2018年   63篇
  2017年   70篇
  2016年   75篇
  2015年   67篇
  2014年   95篇
  2013年   117篇
  2012年   134篇
  2011年   130篇
  2010年   84篇
  2009年   70篇
  2008年   80篇
  2007年   75篇
  2006年   76篇
  2005年   69篇
  2004年   30篇
  2003年   36篇
  2002年   24篇
  2001年   29篇
  2000年   26篇
  1999年   30篇
  1998年   15篇
  1997年   15篇
  1996年   24篇
  1995年   14篇
  1994年   19篇
  1993年   7篇
  1992年   17篇
  1991年   10篇
  1990年   4篇
  1989年   2篇
  1988年   3篇
  1987年   6篇
  1986年   7篇
  1985年   2篇
  1984年   1篇
  1983年   1篇
  1982年   1篇
  1970年   1篇
  1965年   1篇
  1958年   1篇
排序方式: 共有1882条查询结果,搜索用时 15 毫秒
111.
A novel ligand: 2,2′‐(1,3‐phenylenedivinylene)bis‐8‐hydroxyquinoline (m‐B8QPH) ( 4 ) and the corresponding polymeric metal complex Zn ( m‐B8QPH ) ( 5 ) were designed and synthesized in a convenient way. The luminescence properties of the compounds Zn ( m‐B8QPH ) ( 5 ) and Zn(p‐B8QPH) ( 9 ) were investigated by UV‐vis and fluorescence spectra in DMF at room temperature. The experimental results showed that the polymeric complexes 5 and 9 emitted yellow luminescence at 578 and 554 nm in DMF solution. The polymeric complex 5 has demonstrated good solubility in common organic solvents and good thermal stability with high Tg: 261°C. Furthermore, the molecular interactions of 5 with fullerene (C60) and fulleropyrrolidine containing 3,5‐bis(trifluoromethyl)benzene ( 11 ) were also investigated, which indicated the metal dye 5 can be used as new fluorescent probe.  相似文献   
112.
Series of new 2-aryl-6-styryl-2,3-dihydropyridin-4(1H)-one derivatives were synthesized in acceptable to good yields by treatment of the curcuminoids with aqueous ammonia,the mechanism was proposed.By modification of the primary products,total 13 new compounds were obtained.The structures of all products were elucidated by spectroscopy analysis including HR-MS,~1H NMR and ~(13)C NMR.  相似文献   
113.
A novel, simple, and rapid detector using a fluorescent sensor array for discrimination and quantification of different concentrations (ppb level) of pesticides was proposed in this paper. Employing porphyrin, porphyrin derivatives, and chemically responsive dyes as the sensing elements, the developed sensor array based on a cross-responsive mechanism showed a unique pattern of fluorescence changes upon the reaction that lasted just 10 min. The eigenvalues from raw fluorescence spectra were analyzed via a pattern recognition algorithm, including hierarchical cluster analysis (HCA), principal component analysis (PCA), and back-propagation neural network (BPNN). The results showed that HCA, which were used to assess the feasibility and effectiveness of discrimination of the fluorescent sensor array, revealed a distinct separation between different pesticides. PCA and BPNN were used for automatically predicting the concentration of pesticides, and the recovery was 91.29–109.81 % while the lowest relative standard deviation was up to 3.12 %. It indicates a detector based on the fluorescent sensor array is a rapid and feasible sensing platform for the discrimination and quantitative analysis of pesticides, and also shows the possibilities in the related fields of pesticides identification and detection.  相似文献   
114.
Nanoporous (NP) PtRu alloys with three different bimetallic components were straightforwardly fabricated by dealloying PtRuAl ternary alloys in hydrochloric acid. Selective etching of aluminum from source alloys generates bicontinuous network nanostructures with uniform size and structure. The as‐made NP‐PtRu alloys exhibit superior catalytic activity toward the hydrolytic dehydrogenation of ammonia borane (AB) than pure NP‐Pt and NP‐Ru owing to alloying platinum with ruthenium. The NP‐Pt70Ru30 alloy exhibits much higher specific activity toward hydrolytic dehydrogenation of AB than NP‐Pt30Ru70 and NP‐Pt50Ru50. The hydrolysis activation energy of NP‐Pt70Ru30 was estimated to be about 38.9 kJ mol?1, which was lower than most of the reported activation energy values in the literature. In addition, recycling tests show that the NP‐Pt70Ru30 is still highly active in the hydrolysis of AB even after five runs, which indicates that NP‐PtRu alloy accompanied by the network nanoarchitecture is beneficial to improve structural stability toward the dehydrogenation of AB.  相似文献   
115.
A new ceramide and its glycoside were isolated from the flower of Albizia julibrissin. Their structures were established as (25,35,4R,8E)-2-[(2'R)-hydroxyhexadecanoylamino]-8-tetra-cosene-l,3,4-triol(I)and 1-O-β-D-glucopyranosy1-(2S,3S,4R,8E)-2-[(2'R)-hydroxy-hexade-canoylamino]-8-tetracosene-1,3,4-triol (II) on the basis of chemical and spectroscopic studies.  相似文献   
116.
Extinction coefficients of gold nanoparticles with core size ranging from approximately 4 to 40 nm were determined by high resolution transmission electron microscopy analysis and UV-vis absorption spectroscopic measurement. Three different types of gold nanoparticles were prepared and studied: citrate-stabilized nanoparticles in five different sizes; oleylamide-protected gold nanoparticles with a core diameter of 8 nm, and a decanethiol-protected nanoparticle with a diameter of around 4 nm. A linear relationship between the logarithms of extinction coefficients and core diameters of gold particles was found independent of the capping ligands on the particle surface and the solvents used to dissolve the nanoparticles. This linear relation may be used as a calibration curve to determine the concentration or average size of an unknown nanoparticle or nanoparticle-biomolecule conjugate sample.  相似文献   
117.
A spectrophotometric study of the kinetics and mechanism of the oxidation of malic acid (Mal) by chromium(VI) catalyzed by 2,2′-bipyridyl (bpy) in aqueous acidic medium was conducted in a temperature range of ~298 to 313 K. This reaction was found to be pseudo-first order with respect to Cr(VI) and first order with respect to malic acid. Under the conditions of the pseudo-first order ([Mal]o ? [Cr(VI)]o), the observed rate constant (k obs) increased with the increase in [H+] and [bpy]. There was a weak negative salt effect. Based on the experimental results, a possible reaction mechanism for this oxidation catalyzed by bpy is proposed. The rate equation derived from this mechanism can explain all the experimental phenomena.  相似文献   
118.
Organic phosphorescence materials demonstrate potential optoelectronic applications due to their remarkably ultralong organic phosphorescence (UOP) lifetime and abundant optical characteristics prior to the fluorescence materials. For a better insight into the intrinsic relationship among regioisomeric molecules, crystalline interactions, and phosphorescence properties, three crystalline dicarbazol-9-yl pyrazine-based regioisomers with para-, meta-, and ortho-convergent substitutions (p-DCzP, m-DCzP, and o-DCzP) were designed and presented gradually increased UOP lifetimes prolonging from 63.14, 127.93 to 350.46 ms, respectively, due to the regioisomerism effect (RIE) which would be an effective strategy for better understanding of structure-property of UOP materials.  相似文献   
119.
In this work a 1,2,4‐triazole derivative 1‐(4‐aminobenzyl)‐1,2,4‐triazole (abtz) was utilized, one new cadmium(II) coordination polymer, namely [Cd(abtz)I2]n ( 1 ) was prepared through the powerful solvo‐thermal synthetic strategy. In compound 1 , the abtz building blocks are interlinked through the central CdII ions forming the two‐dimensional (2D) layer coordination framework. Powder X‐ray diffraction (PXRD) characterization also reveals that we have prepared the pure phases of coordination polymer 1 . Optical properties have been determined, which can behave the excellent photo‐luminescent emission of coordination polymer 1 . Photo‐luminescent experiment also reveals that coordination polymer 1 can behave the highly sensitive detection for acetone molecules with high Ksv value (Ksv = 4.12 ×104 L · mol–1) in the recyclable detection fashion. Additionally, coordination polymer 1 also can behave the highly sensitive detection for pollutant dichromate with excellent quenching efficiency Ksv (Ksv = 2.12 × 104 L · mol–1) and low detection limit [38 × 10–3 mM (S/N = 3)]. UV/Vis, photo‐luminescent lifetime, and PXRD patterns also have been determined to analyze the detection mechanism.  相似文献   
120.
A new taxane glycoside was isolated from a methanol extract of the needles of Taxus cuspidata. The structure was established as 2alpha,9alpha,10beta-triacetoxytaxa-4(20),11-dien-13-one-5alpha-O-beta-D-glucopyranoside (1) on the basis of 1D- and 2D NMR and high-resolution fast atom bombardment mass spectral analyses.  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