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   3484篇
  免费   550篇
  国内免费   596篇
化学   2905篇
晶体学   47篇
力学   147篇
综合类   74篇
数学   361篇
物理学   1096篇
  2024年   6篇
  2023年   60篇
  2022年   98篇
  2021年   123篇
  2020年   146篇
  2019年   178篇
  2018年   125篇
  2017年   142篇
  2016年   187篇
  2015年   175篇
  2014年   213篇
  2013年   231篇
  2012年   303篇
  2011年   322篇
  2010年   236篇
  2009年   224篇
  2008年   251篇
  2007年   227篇
  2006年   193篇
  2005年   173篇
  2004年   159篇
  2003年   115篇
  2002年   136篇
  2001年   119篇
  2000年   85篇
  1999年   66篇
  1998年   44篇
  1997年   33篇
  1996年   42篇
  1995年   42篇
  1994年   30篇
  1993年   19篇
  1992年   14篇
  1991年   27篇
  1990年   15篇
  1989年   19篇
  1988年   9篇
  1987年   9篇
  1986年   8篇
  1985年   7篇
  1983年   7篇
  1982年   1篇
  1981年   1篇
  1980年   1篇
  1979年   2篇
  1977年   1篇
  1975年   3篇
  1961年   1篇
  1957年   1篇
  1936年   1篇
排序方式: 共有4630条查询结果,搜索用时 687 毫秒
61.
The determination of cysteine and homocysteine levels is of great current interest for the monitoring of desease states. A new colorimetric method for the simultaneous detection of l-cysteine and l-homocysteine has been developed. A fluorescein derivative reacts with the above amino acids, producing their respective thiazolidines resulting in color changes. Interference from other amino acids and proteins is minimal.  相似文献   
62.
Soap-flee P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and theparticle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.  相似文献   
63.
Two novel sesquiterpene dimers, compounds 1 and 2 , were isolated from the rhizome of Ligularia virgaurea, together with the six known sesquiterpenoids 3 – 8 . Their structures were established by physico‐chemical and spectroscopic methods, especially by means of 1D‐ and 2D‐NMR as well as HR‐MS analyses. A mechanism based on a classical Diels–Alder cyclization is proposed for the formation of the dimer 1 from the precursors 8 and the quinone form of 6 (Scheme).  相似文献   
64.
富氧条件下乙炔选择催化还原NOx   总被引:1,自引:0,他引:1  
于姗姗  王新平  王崇  徐岩 《中国化学》2006,24(5):598-602
Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 (C2H2-SCR) was investigated over a series 08% C2H2, and 9.95% O2 (volume percent) in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.  相似文献   
65.
The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique.  相似文献   
66.
A novel coordination polymer of [Sr2(4-CPOA)2(H2O)5]n (where 4-CPOA2- is 4-carboxylphenoxyacetate) has been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex belongs to monoclinic system with space group C2/c, a=2.563 9(5) nm, b=1.162 7(2) nm, c=0.742 96(15) nm, β=99.64(3)°. V=2.183 5(7) nm3, Z=4, Mr=653.60, Dc=1.988 g·cm-3, R=0.027 8, wR=0.058 1. The strontium atom has a bicapped triangular prismatic coordination geometry, involving four oxoacetate oxygen atoms, one ether oxygen atom from different 4-CPOA2- ligands and three water molecules. The strontium(Ⅱ) ions are linked by 4-CPOA2- ligands and water molecules to form a 3D network structure. CCDC: 223313.  相似文献   
67.
Dinuclear silver (I) six‐membered ring complex [Ag2 (bta)2 ‐(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement.  相似文献   
68.
A novel 1-D Cd(Ⅱ) coordination polymer, [Cd(p-BDOA)·2H2O]n(I) ( p-BDOA2-=benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR, PL, TG and X-ray single crystal diffraction. The Crystal crystallizes in monoclinic system, the space group is C2/c, with the crystal cell parameters a=1.175 1(1) nm, b=0.551 0(1) nm, c=1.827 7(2) nm, β=96.14(2)°, and V=1.176 6(3) nm3,, Mr=372.60, R=0.045 9, wR=0.127 9. The Cd(Ⅱ) ion has a trigonal prism coordination configuration that defined by four carboxyl O atoms from two different p-BDOA2- ligands and two water molecules. Adjacent Cd(Ⅱ) ions are linked by carboxylate groups with the bidentate coordination mode, giving rise to a chain structure with the adjacent Cd…Cd distance of 1.526 3(5) nm. Furthermore, such chains are linked by hydrogen bonds to form supramolecular network. The results of PL and TG show that the complex exhibits intense fluorescent emissions and its chain skeleton is thermally stable up to 419 K. CCDC: 220443.  相似文献   
69.
In the title compound, poly[μ5‐pyrazine‐2,3‐dicarboxyl­ato‐cadmium(II)], [Cd(C6H2N2O4)]n or [Cd(pdc)]n, where pdc is the pyrazine‐2,3‐dicarboxyl­ate anion, the CdII atom is six‐coordinated by five carboxyl­ate O atoms and one N atom from five different pdc ligands in a distorted octa­hedral CdO5N coordination geometry. Two CdII atoms are bridged by carboxyl­ate groups of the pdc ligands to create a dimeric unit. The dimeric units are further connected by the pdc ligands to generate an inter­esting two‐dimensional structure.  相似文献   
70.
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