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   25508篇
  免费   1565篇
  国内免费   3577篇
化学   19954篇
晶体学   1125篇
力学   266篇
综合类   213篇
数学   4379篇
物理学   4713篇
  2024年   12篇
  2023年   186篇
  2022年   624篇
  2021年   786篇
  2020年   584篇
  2019年   604篇
  2018年   476篇
  2017年   615篇
  2016年   639篇
  2015年   596篇
  2014年   890篇
  2013年   1917篇
  2012年   1359篇
  2011年   1593篇
  2010年   1584篇
  2009年   1773篇
  2008年   1735篇
  2007年   1746篇
  2006年   1639篇
  2005年   1420篇
  2004年   1389篇
  2003年   1174篇
  2002年   1025篇
  2001年   752篇
  2000年   740篇
  1999年   585篇
  1998年   564篇
  1997年   449篇
  1996年   412篇
  1995年   403篇
  1994年   360篇
  1993年   337篇
  1992年   323篇
  1991年   239篇
  1990年   137篇
  1989年   160篇
  1988年   141篇
  1987年   94篇
  1986年   62篇
  1985年   75篇
  1984年   100篇
  1983年   24篇
  1982年   47篇
  1981年   67篇
  1980年   54篇
  1979年   42篇
  1978年   29篇
  1977年   24篇
  1976年   12篇
  1975年   14篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
901.
We give a new minisup theorem for noncompact strategy sets. Our result is of the type of the Matthies-Strang-Christiansen minimax theorem where the hyperplane should be replaced by any closed convex set. As an application, we derive a slight generalization of the Matthies-Strang-Christiansen minimax theorem.  相似文献   
902.
Treatment of Ru3(CO)12 with dpphSe2 (dpph = 1,6-bis(diphenylphosphino)hexane) in refluxing toluene in the presence of Me3NO afforded two new compounds, Ru3(CO)7(-CO)(3-Se)(-dpph) (1) and Ru3(CO)7(3-Se)2(-dpph) (2). A similar reaction of Ru3(CO)12 with dpppeSe2 (dpppe = 1,5-bis(diphenylphosphino)pentane) gave exclusively Ru3(CO)7(3-Se)2(-dpppe) (3). Treatment of Ru3(CO)12 with dpphS2 and dpppeS2 at 110°C in the presence of Me3NO afforded Ru3(CO)7(3-S)2(-dpph) (4) and Ru3(CO)7(3-S)2(-dpppe) (5), respectively. Reactions of Fe3(CO)12 with dpphSe2 and dpppeSe2, under identical conditions, afforded Fe3(CO)7(3-Se)2(-dpph) (6) and Fe3(CO)7(3-Se)2(-dpppe) (7), respectively. Compounds 1–7 were characterized spectroscopically and the molecular structures of compounds 1–4 were determined by single crystal X-ray crystallography. The core of 1 contains an equilateral triangle of ruthenium atoms with one capping selenium, one bridging dpph, one doubly bridging carbonyl and seven terminal carbonyl ligands. Complexes 2–4 have a square-pyramidal structure with two metal and two chalcogenide atoms alternating in the basal plane and the third metal atom at the apex of the pyramid, and belong to the family of well-known nido clusters with seven skeletal electron pairs.  相似文献   
903.
胡艾希  陈平  袁帅  周勇 《合成化学》2002,10(4):333-334
室温下,6-甲氧基-2-丙酰基萘和1,3-二溴-5,5-二甲基海因的溴化反应在醇溶剂中,反应速度快、转化率高,生成5-溴-6-甲氧基-2-丙酰基萘的收率高(98.59%)。  相似文献   
904.
纳米Y2O3/钴基合金激光熔覆层的组织   总被引:6,自引:0,他引:6  
利用5 kW CO2激光器,在Ni基高温合金表面,熔覆纳米稀土氧化物(Y2O3)/钴基合金复合材料,制备了涂层.利用光学显微镜、扫描电镜及透射电镜分析了熔覆层的组织结构.结果表明: 熔覆层的主要相组成为γ-Co,ε-Co,Cr23C6和Y2O3;加入纳米Y2O3,凝固组织由细长的柱状树枝晶转变为较短的树枝晶;纳米Y2O3含量增大至1%时整个断面获得等轴晶组织;纳米Y2O3作为异质形核的核心,细化了组织;纳米Y2O3在熔覆层中分布不均匀,促进了γ-Co向ε-Co的转变;熔覆层的亚结构为堆跺层错.对熔覆层等轴组织形成机制进行了分析.  相似文献   
905.
Reactive E = C(pp)π-Systems. XLII [1]. Novel Coordination Compounds of 2-(Diisopropylamino)-1-phosphaethyne: [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}], [(Ph3P)2Pt{η2-(iPr2NCP)}], and [Co2(CO)622-(iPr2NCP)}] 2-(Diisopropylamino)-phosphaethyne iPr2N? C?P ( 2 ) reacts with the Ni(0)-complexes [Ni(1,5-cyclooctadiene)2] and [Ni(CO)3(1-azabicyclo[2.2.2]octane)], respectively, to give the novel complex [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}] ( 5 ), with the 1,3-diphosphacyclobutadiene derivative and 2 (side-on) as π-ligands. The molecular structure of 5 determined by X-ray diffraction on single crystals proves the spin systems and rotational barriers deduced from NMR-data (1H, 13C-, 31P). The PC distances of the four-membered ring of 1.817(2) and 1.818(2) Å – as expected – are considerably longer than the PC bond of the η2-coordinated phosphaalkyne 2 [1.671(2) Å]. – In the reactions of 2 with [(Ph3P)2Pt(C2H4)] or [Co2(CO)8] the ligand properties of 2 resemble those of alkynes affording the complexes [(Ph3P)2Pt{η2-(iPr2NCP)}] ( 7 ) with side-on coordinated 2 and [Co2(CO)622-(iPr2NCP)}] with 2 acting as a 4e donor bridge in quantitative yield. In attempts to prepare copper(I) complexes of the aminophosphaalkyne 2 by reaction with CuCl or CuI the only isolable product formed in reasonable amounts under the influence of air and moisture is the 1 λ3, 3 λ5-diphosphetene (iPr2N) ( 10 ) (isolated yield: ca. 20%). The crystal structure analysis of 10 indicates a strong structural relationship to the diamino-2-phosphaallyl cation [Me(iPr2N)]+ ( 12 ), the 1,3-diphosphacyclobutadiene ligand (iPr2NCP)2 in the binuclear complex [{η1, μ2-(iPr2NCP)2}Ni2(CO)6] ( 3a ) as well as to the heterocycles (dme)2LiOE2′ (E′ = S, 11a ; E′ = Se, 11b ) prepared by Becker et al. [11b, 35].  相似文献   
906.
利用水和乙醇混合溶剂合成了稀土三氯醋酸盐与2份1,10-邻菲绕啉(phen)配合物RE(CCl_3COO)_3(phen)_2·nH_2O(RE=Nd,Sm,n=0;RE=Eu,n=2)的单晶.结构测定表明,Nd(CCl_3COO)_3(phen)_2为三斜晶系,每个三氯醋酸盐均以双齿配位,2个phen亦为双齿配位,故配位单元中钕为10配位;Eu(CCl_3COO)_3(phen)_2·2H_2O为单斜晶系,1个三氯醋酸根在外界,2个三氯醋酸根为单齿配位,2个phen为双齿配位,另有2分配位水,故配位单元中Eu为8配位.  相似文献   
907.
The kinetics of mesophase formation of a lyotropic aromatic polyamide from isotropic state has been studied by means of depolarized light intensity. Avrami type analysis of the data gives an exponent close to 1, which suggests the nucleation followed by one-dimensional growth. No influence of blending flexible chain from nylon 6 to the aromatic polyamide on the kinetics of mesophase formation was observed.  相似文献   
908.
Theab initio SCF method is used for computing the main electronic properties of the ribose unit of the nucleic acids. The present study is devoted to the ribose in the C3-endo,gg conformation. The properties investigated include the distribution of the electronic charges, the electrostatic molecular potential around the four oxygens of the unit, the hydration and the Na+ binding schemes studied in the supermolecule approximation. The possibilities of through-water binding of the cation to the sugar are also explored. The predictions of the computation in particular with regard to cation binding to the ribose ring are correlated with recent experimental results.  相似文献   
909.
We describe the synthesis of two functionalised p-tert-butyl calix[4]arenes: tetra(N,N-dimethyl) aminoethylamide derivative 1 and related tetramethylammonium 2. Their complexation properties towards alkali and zinc metal cations are reported along with complexation of perchlorate anion by 2.  相似文献   
910.
Synthesis and Spectroscopical Characterization of Di(halo)phthalocyaninato(1–)rhodium(III), [RhX2Pc1?] (X = Cl, Br, I) Bronze-coloured di(halo)phthalocyaninato(1–)-rhodium(III), [RhX2Pc1?] (X = Cl, Br) and [RhI2Pc1?] · I2 is prepared by oxidation of (nBu4N)[RhX2Pc2?] with the corresponding halogene. Irrespective of the halo ligands, two irreversible electrode reactions due to the first ringreduction (ER = ?0,90 V) and ringoxidation (EO = 0,82 V) are present in the cyclovoltammogram of (nBu4N)[RhX2Pc2?]. The optical spectra show typical absorptions of the Pc1?-ligand at 14.0 kK and 19.1 kK. Characteristic vibrational bands are at 1 366/1 449 cm?1 (i. r.) and 569/1 132/1 180/1 600 cm?1 (resonance Raman (r. r.)). The antisym. (Rh? X)-stretching vibration is observed at 294 cm?1 (X = Cl), 240 cm?4 (Br) and 200 cm?1 (I). Only the sym. (Rh? I)-stretching vibration at 133 cm?1 is r. r. enhanced together with a strong line at 170 cm?1, which is assigned to the (I? I)-stretching vibration of the incorporated iodine molecule. Both modes show overtones and combinationbands.  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