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   4670篇
  免费   661篇
  国内免费   393篇
化学   3352篇
晶体学   52篇
力学   239篇
综合类   24篇
数学   537篇
物理学   1520篇
  2024年   9篇
  2023年   114篇
  2022年   180篇
  2021年   188篇
  2020年   173篇
  2019年   154篇
  2018年   146篇
  2017年   110篇
  2016年   209篇
  2015年   213篇
  2014年   259篇
  2013年   290篇
  2012年   357篇
  2011年   402篇
  2010年   244篇
  2009年   240篇
  2008年   285篇
  2007年   262篇
  2006年   243篇
  2005年   206篇
  2004年   168篇
  2003年   153篇
  2002年   130篇
  2001年   104篇
  2000年   90篇
  1999年   115篇
  1998年   101篇
  1997年   90篇
  1996年   90篇
  1995年   78篇
  1994年   55篇
  1993年   33篇
  1992年   37篇
  1991年   32篇
  1990年   23篇
  1989年   18篇
  1988年   20篇
  1987年   20篇
  1986年   13篇
  1985年   10篇
  1984年   15篇
  1983年   4篇
  1982年   4篇
  1981年   3篇
  1980年   9篇
  1978年   2篇
  1976年   7篇
  1975年   3篇
  1974年   2篇
  1972年   2篇
排序方式: 共有5724条查询结果,搜索用时 15 毫秒
61.
Eu8(NCN)4.95I6.10 is the first compound with discrete tritetrahedral Eu8 clusters which are interconnected by coordinating NCN2- carbodiimide anions on their triangular faces to form separated layers, the latter being bridged by iodide and carbodiimide anions.  相似文献   
62.
Diclobutrazol的合成及其生物活性研究张洪奎,廖联安,陈明德,叶向阳,郭奇珍(厦门大学化学系厦门361005)关键词:Diclobutrazol,相转移催化,合成,生物活性Diclobutrazol(1)俗名粉锈清,是一种广谱内吸性杀菌剂,...  相似文献   
63.
固-液相转移催化1,2,4-三唑N-烷基化的研究   总被引:1,自引:0,他引:1  
本文研究了相转移催化条件下的1,2,4-三唑烷基化反应。评价了几种相转移催化剂,结果表明PEG是合适的固-液相转移催化剂。在相转移催化剂作用下,用不同的烷基化剂制备了一系列N-1取代的1,2,4-三唑,并对实验的结果进行了讨论。  相似文献   
64.
Four new NiII–NiII–NiII homotrinuclear complexes namely [Ni(-BD)2{NiL2}](ClO4)2 [L = 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (5-NO2-phen), 2,2-bipyridyl (bpy) or 4,4-dimethyl-2,2bipyridyl (Me2bpy) and (-BD)– = -benzyldioximato ion] have been prepared and characterized. Based on elemental analyses, i.r. spectra, conductivity measurements, extended -benzyldioximato-bridged systems consisting of three nickel(II) ions in which the central nickel(II) ion has a square-planar environment and the end capped two nickel(II) ions have a distorted octahedral environment are proposed for these structures. The temperature dependence of the magnetic susceptibility for complexes (1) (phen), (2) (5-NO2-phen), (3) (bpy) and (4) (Me2bpy) were measured over the 77–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator (H^ = –2JS^1S^2), giving the exchange integral J = –13.31 cm–1 for (1), J = –7.37 cm–1 for (2), J = –8.96 cm–1 for (3) and J = –7.33 cm–1 for (4) These results indicate a weak antiferromagnetic spin exchange interaction between the two terminal nickel(II) io  相似文献   
65.
[Reaction: see text]. The potential dual behavior as dienes and dienophiles of the diene moieties of masked o-benzoquinones (MOBs) 10a-e-12a-e, generated upon oxidation of 2-methoxyphenols 1-3 with BTIB in the presence of appropriate dienols, in their intramolecular Diels-Alder (IMDA) reactions has been examined. The IMDA reactions of MOBs 10a-d, 11a,b,d, and 12a,b,d resulted in highly functionalized oxatricyclic compounds 18a-d, 19a,b,d, and 20a,b,d, respectively, with concomitant formation of cis-decalin derivatives 21a-d, 22a,b,d, and 23a,b,d in a highly regio- and stereoselective manner. However, the MOBs 10e-12e provided exclusively oxatricyclic compounds 18e-20e. The formation of cis-decalins in these IMDA reactions illustrates the dienophilic character of MOBs, in addition to their behavior as dienes. The ratio of the two cycloadducts obtained in each reaction as a result of the dual character of MOBs depends on the nature and/or position of the substituents on both the cyclohexadienone moiety and the added 2,4-dienol. The majority of the cycloadducts resulted from the diene property of MOBs in intramolecular Diels-Alder reactions smoothly underwent Cope rearrangement to furnish cis-decalins as sole products in excellent to quantitative yields that provides a short and efficient entry to polyfunctionized cis-decalins from 2-methoxyphenols. Furthermore, the variation of dienophilic and diene characters of MOBs in the IMDA reactions with the electron-donating or electron-withdrawing substituent of both cyclohexadienone moiety and the added conjugated acyclic diene or 2,4-dienol has been studied in detail.  相似文献   
66.
铈、镨二乙基磷酸盐的晶体结构   总被引:1,自引:0,他引:1  
合成了Ce[PO_2(OC_2H_5)_2]_3和Pr[PO_2(OC_2H_5)_2]_3(简称Ce(DEP)_3和Pr(Pr(DEP)_3)。用四圆衍射仪测定了其晶体结构。它们均属三斜晶系,空间群P1。晶胞参数,对Ce(DEP)_3:α=10.324(4)A,b=12.861(4)A,c=13.998(5)A,x=106.49(3)°,β=112.83(4)° γ=115.61(3)°,V=1296(1)A~3,Z=2;对Pr(DEP)_3:α=10.27(1)A,b=11.81(1)A,c=12.51(1)A,x=109.93(9)°,β=111.9(9)°,γ=93.0(1)°,V=1293(3)A~3,Z=2。用Patterson法并经分块全矩阵最小二乘法修正,最后的R值,Ce的为0.1071,Pr的为0.1066。结构分析指出,两种配合物结构类似,Ce和Pr原子均由二乙基磷酸根的六个氧原子配位形成八面体构型。  相似文献   
67.
A 3D graphical representation of DNA sequences, which has no circuit or degeneracy, is derived for mathematical denotation of DNA sequence. Based on this graphical representation, we propose a new sequence distance measure. We make use of the corresponding similarity matrix to construct a phylogenic tree by virtue of the fuzzy theory. The examination of phylogenic tree belong to eight species illustrates the utility of our approach. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006  相似文献   
68.
A new tocopherol derivative, 7a‐methoxy‐α‐tocopherol ( 1 ), and a new taraxastane triterpene, taraxast‐1,20(30)‐dien‐3‐one ( 5 ), together with four known compounds, β‐tocopherol ( 2 ), α‐tocopherol ( 3 ), α‐tocospiro B ( 4 ) and taraxasterone ( 6 ) were isolated from the whole plant of Sida acuta. Their structures were elucidated by spectral analysis including MS, 1D and 2D‐NMR spectroscopy. Among those compounds, compounds 1 , 2 , and 3 showed significant antioxidant effect (EC50 = 86.9, 68.2, and 70.9 μM, respectively) in the DPPH radicals scavenging activity assay.  相似文献   
69.
Samples of poly[1-(3-sulfopropyl)-2-vinyl-pyridinium-betaine] (PSPV) have been synthesized to high conversion by free radical polymerization in aqueous solution of the zwitterionic monomer SPV with several concentrations of the crosslinker N,N′-methylene-bis-acrylamide (MBA). The densities of the resultant xerogels increased regularly with the content of MBA. Hydrogels obtained by swelling them in water and aqueous KSCN solution were examined by gravimetric and dimensional analysis. The water contents increased with decreasing content of MBA, the value of 92.7 wt% at the lowest MBA content being higher than that for other zwitterionic hydrogels. Enhanced swelling occurred in 1 M aq. KSCN at each MBA content, the total swelling being 98.1 wt% at the lowest crosslinker content. Swelling increased with increasing temperature. An approximate procedure to formulating swelling equilibrium in term of the volume fraction of water in hydrogel, in conjunction with the van’t Hoff equation, yields a small positive value for the enthalpy of swelling. This is compared with values derived similarly for other hydrogels.  相似文献   
70.
The first total syntheses of siphonarienolone and siphonarienedione are described. The development of a stereoselective synthesis of beta-diketones facilitated the synthesis of the latter compound. The synthesis of the structures proposed for the natural products afforded compounds whose spectral data did not match those of the natural products. However, the synthesis of compounds isomeric to the proposed structures at C(4) and C(5) afforded compounds identical to the natural products, thereby reassigning the stereochemistry of the natural products.  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