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   5518篇
  免费   350篇
  国内免费   766篇
化学   5082篇
晶体学   102篇
力学   47篇
综合类   19篇
数学   100篇
物理学   1284篇
  2024年   21篇
  2023年   85篇
  2022年   173篇
  2021年   190篇
  2020年   236篇
  2019年   190篇
  2018年   124篇
  2017年   121篇
  2016年   191篇
  2015年   184篇
  2014年   237篇
  2013年   434篇
  2012年   286篇
  2011年   227篇
  2010年   218篇
  2009年   289篇
  2008年   286篇
  2007年   362篇
  2006年   262篇
  2005年   288篇
  2004年   279篇
  2003年   287篇
  2002年   216篇
  2001年   132篇
  2000年   180篇
  1999年   159篇
  1998年   132篇
  1997年   109篇
  1996年   119篇
  1995年   132篇
  1994年   115篇
  1993年   69篇
  1992年   91篇
  1991年   35篇
  1990年   23篇
  1989年   22篇
  1988年   23篇
  1987年   21篇
  1986年   12篇
  1985年   7篇
  1984年   11篇
  1983年   4篇
  1981年   7篇
  1980年   11篇
  1979年   4篇
  1978年   6篇
  1977年   6篇
  1976年   4篇
  1974年   2篇
  1973年   9篇
排序方式: 共有6634条查询结果,搜索用时 343 毫秒
41.
An investigation was made of the gelation of dimethacrylate‐type crosslinking agents in view of an application for separation media. The study mainly centered on a crosslinking agent, glycerol dimethacrylate (GDMA), which is relatively hydrophilic because of a hydroxyl group in the middle of its structure. The gelation of GDMA was compared with that of other hydrophobic crosslinking agents such as ethylene glycol dimethacrylate and 1,6‐hexanediol dimethacrylate. The diluents used in the study were toluene, toluene with methanol, and cyclohexanol. The gelation was observed in real time with a charge coupled device camera and dynamic light scattering (DLS). Also, the separated dry gels were extensively characterized with scanning electron microscopy, BET (N2 absorption and desorption isotherm), and Fourier transform infrared. DLS analysis showed a stronger molecular interaction of GDMA gelation in toluene, whereas this interaction was much weaker in an alcoholic solvent such as toluene with methanol or cyclohexanol. This indicated that GDMA gelation might proceed through hydrogen bonding as well as a crosslinking reaction of vinyl groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 949–958, 2006  相似文献   
42.
The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, 1H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006  相似文献   
43.
44.
The reactions of phosphine derivatives of diallyl isocyanurates with palladium(ii) dichloride lead to the formation of complexes, whose structure, composition, and stability depend on the length of the methylene chain between the isocyanurate and diphenylphosphine fragments in the ligand. 1,3-Diallyl-5-[5′-(diphenylphosphino)pentyl and 10′-(diphenyl-phosphino)decyl] isocyanurates with PdCl2 form monomeric L2PdCl2 trans-complexes in which P atoms of the ligands participate in coordination with the metal. 1,3-Diallyl-5-[2′-(diphenylphosphino)ethyl] isocyanurate with PdCl2 forms a dimeric (LPdCl2)2 complex, which decomposes in a solution to the monomer including solvent molecule into the coordination sphere of the metal. The reactions of 1,3-diallyl-5-[4′-(diphenylphosphino)butyl] isocyanurate and 1,3-diallyl-5-[6′-(diphenylphosphino)hexyl] isocyanurate with PdCl2 give monomeric chelate LPdCl2 complexes in which one of the allyl groups of the isocyanurate cycle participates in coordination with the central ion along with the phosphorus atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1859–1865, September, 1998.  相似文献   
45.
采用两种方法制得了尖晶石结构纯相MgFe2O4样品.Moessbauer分析发现,一种样品表现出了完全的超顺磁性,另一种表现出了部分超顺磁性.这揭示出了样品具有很小的粒子尺度.首次在实验上发现了MgFe2O4IR-V2谱带的劈裂现象,报导了拉曼光谱,通过ESR分析,进一步揭示了两样品的结构特征,并讨论了性质之间的相关性。  相似文献   
46.
钯II催化CO/乙烯共聚加压原位红外光谱研究   总被引:1,自引:1,他引:1  
聚酿以其优良的物理、化学性能及原料(CO乙烯)简单易得的优点,在世界范围内已引起人们的普遍关注.为寻找价廉的催化剂或改良高效或(11)一双磷催化剂以推动聚酮的工业化进程,必须对共聚机理进行深入的研究.S;,n[’,’1、DrentP]等人根据对产品主链和端基的分析首先  相似文献   
47.
ZnO粉体的两种不同制备途径   总被引:14,自引:0,他引:14       下载免费PDF全文
本文用沉淀法和气相沉积法两种方法制备了ZnO粉体,对所得样品用粉末X射线衍射(XRD)、透射电镜(TEM)和红外吸收光谱(IR)进行了鉴定和表征,初步探讨了气相沉积法制备的ZnO微粒的生长机理,并对所用的两种制备方法作了简要的比较。  相似文献   
48.
Quantum-chemical calculations and IR spectroscopy were used to study the conformations as well as the energy and spectral characteristics of 2,3-trimethylene- and 2,3-pentamethylene-3,4-dihydro-4-quinazolinones. The shift of -electron density from the heterocyclic system to the carbonyl group and, thus, the proton affinity of the oxygen atom of this group increase with expansion of the bond angle at the nitrogen atom in going from a five-membered to seven-membered ring.  相似文献   
49.
The vibrational wavenumbers and the fundamental modes of 2,2′-biquinoline were obtained by density functional theory (DFT) with the B3LYP functional using the 6-31G(d,p) basis set. The calculated wavenumbers were scaled by a single factor of 0.965 to correct them for vibrational anharmonicity, but the force constants were overestimated. Normal coordinate analysis of the molecule was also carried out by using the force field of the quinoline molecule and the force field parameters of quinoline are shown to be transferable to 2,2′-biquinoline. The potential energy distribution associated with the normal modes is also given. The theoretical wavenumbers are found to be in good agreement with the experimental data.  相似文献   
50.
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes.  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