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   41615篇
  免费   4203篇
  国内免费   7268篇
化学   35273篇
晶体学   1909篇
力学   2246篇
综合类   329篇
数学   2651篇
物理学   10678篇
  2024年   83篇
  2023年   355篇
  2022年   719篇
  2021年   838篇
  2020年   1160篇
  2019年   1069篇
  2018年   923篇
  2017年   1142篇
  2016年   1580篇
  2015年   1520篇
  2014年   1902篇
  2013年   2967篇
  2012年   3394篇
  2011年   2378篇
  2010年   2040篇
  2009年   2574篇
  2008年   2760篇
  2007年   2871篇
  2006年   2622篇
  2005年   2424篇
  2004年   2376篇
  2003年   2021篇
  2002年   2163篇
  2001年   1376篇
  2000年   1421篇
  1999年   1136篇
  1998年   1007篇
  1997年   822篇
  1996年   818篇
  1995年   726篇
  1994年   680篇
  1993年   518篇
  1992年   535篇
  1991年   316篇
  1990年   260篇
  1989年   199篇
  1988年   194篇
  1987年   135篇
  1986年   124篇
  1985年   133篇
  1984年   108篇
  1983年   86篇
  1982年   81篇
  1981年   74篇
  1980年   71篇
  1979年   72篇
  1978年   54篇
  1977年   56篇
  1974年   43篇
  1973年   50篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
971.
SynthesisandStructureof[(C_2H_5)_4N][Mo_3(μ_3-O)(μ-Cl)_3(μ-CH_3CH_2COO)_3Cl_3]ZhuangHong-Hui;WuDing-Ming;HuangJian-Quan;HuangJin-L...  相似文献   
972.
Proteins may be rigid or flexible to various degrees as required for optimal function. Flexibility of large parts of a protein, which rearrange or move, is particularly interesting and will be discussed in this article. We differentiate between several categories, although the boundaries between them are diffuse: flexibility of peptide segments, order–disorder transitions of spatially contiguous regions, and domain motions. The domains may be flexibly linked to allow rather unrestricted motions or the motions may be constrained to certain modes. The various categories of large-scale flexibility will be illustrated with the following examples: (1) Small protein proteinase inhibitors are rather rigid molecules which provide binding surfaces complementary to their cognate proteases but show also limited segmental flexibility and adaptation. (2) Large plasma proteinase inhibitors exhibit large conformational changes after interaction with proteases probably for regulatory purposes. (3) Pancreatic serine proteases employ a disorder–order transition of their activation domain as a means to regulate enzymic activity. (4) Immunoglobulins show rather unrestricted and also hinged domain motions in different parts of the molecule probably to allow binding to antigens in different arrangements. (5) Citrate synthase adopts open and closed forms by a hinged domain motion to bind substrates and release products and to perform the catalytic condensation reaction, respectively. (6) Riboflavin synthase, a bifunctional multienzyme complex, catalyzes two consecutive reactions by means of two subunits, α and β. The β-subunits form a shell, in which the α-subunits are enclosed. Diffusional motion of the catalytic intermediates is therefore restricted. In addition, rearrangement of the N-terminal segment occurs during the assembly of the β-subunit. In contrast, rigidity is dominant in the structures of the light-harvesting complexes and the photosynthetic reaction centers involved in photosynthetic light reactions. These are large protein–pigment complexes in which the proteins serve as matrices to hold the pigments in the appropriate conformation and relative arrangement. Since motion would contribute to deactivation of the photoexcited states of the pigments and diminish the efficiency of light-energy and electron transfer, the functional role of rigidity is easy to rationalize for these proteins.  相似文献   
973.
Zhang  Li  Liu  Lang  Jia  Dianzeng  Yu  Kaibei 《Structural chemistry》2004,15(4):327-331
A novel mixed-ligand nickel complex, [Ni(PMBP—PNH) (Py)3], [PMBP—PNH=N-(1-phenyl-3-methyl-4-benzylidene-5-pyrazolone) p-nitrobezoylhydrazide; Py = pyridine], has been synthesized by the hydrothermal method and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The X-ray diffraction reveals that the nickel (II) ion in the title complex is in a slightly distorted octahedral arrangement of the ONO donor atoms of primary ligand PMBP-PNH and three N-donor atoms in the secondary ligand pyridine.  相似文献   
974.
IntroductionTheadvantageofmacrocyclicoligomersasprecursorsforthepreparationofhighperformancepolymersviaring openingpolymerization (ROP)hassparkedmuchinterestintheareaofadvancedthermoplasticcomposites.1 3Andaseriesofcyclicoligomerssuchascarbonates,4 arylesters ,5,6 ethers,7amides8andsulfides9,10 hasbeensuccessfullysynthesized .Recently ,Nishikuboetal.11reportedakindofnovelmacro cyclicoligomerscontainingthioestergroupspreparedbycon densationofbis(4 mercaptophenyl)sulfidewitharomaticaciddichlo…  相似文献   
975.
新型尾式硫代苯并噻唑基卟啉化合物的合成与表征   总被引:1,自引:0,他引:1  
通过不对称的单羟基卟啉化合物、溴代烷烃和巯基苯并噻唑合成了一系列新型硫代苯并噻唑基尾式卟啉化合物, 并采用核磁共振氢谱、碳谱、红外光谱、质谱和元素分析对卟啉化合物的结构进行了表征.  相似文献   
976.
Synthesis and Crystal Structure of Hydronium-tris-ethylenediamine-cobalt(rhodium)-μ-trichloro-nonachlorotrirhenate(III)-chloride, H3O[MEn3][Re3Cl12]Cl (M=Co, Rh) The chlorides H3O[MEn3][Re3Cl12]CI (M = Co, 1 ; Rh, 2 ) crystallize from hydrochloric acid solutions of ReCl3 and MEn3 · 3H2O as deep red hexagonal columns. They are isotypic and crystallize with the hexagonal system (P6 , Z = 1; 1: a = 1010.87(3); c = 794.30(4) pm, R = 0.023, Rw = 0.016; 2: a = 1018.58(3); c = 794.74(4) pm, R = 0.026, Rw = 0.018). The anions [Re3Cl12]3? are connected via H3O+ cation (C.N. 3). The large channels that run in the [001] direction contain, alternatively, the cations [MEn3]3+ and the lonesome Cl?-anions  相似文献   
977.
Preparation and Crystal Structure of LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr3 LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl3Br12, PrAl3Br12, and NdAl3Br12 were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3112, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl3Br12 (Ln = Nd) to the corresponding lanthanoide tribromide is described.  相似文献   
978.
1INTRoDUCTIoNIntenseinterestintransition-metalclusterscontinuesbecausetheyrepresentpos-sibleconceptualbridgesbetweenhomogeneousandheterogeneouscatalystsmoreoveralsobecausetheyrepresentsyntheticchallenges.TheuseofelementsofGroup16ofthePeriodicTableassingleatomligandsforclustergrowthandstabilizationofthemetalcorearenowwellestablished[1i.ThereisanincreasinginterestintheuseofSe-bridgrdclusters,manyofthereactionsofSe2Fe2(CO),andSe2Fe,(CO),havebeenreported"';however,therehasbeenverylittlewor…  相似文献   
979.
A new neutral -arene complex of trivalent uranium, (6-C6H5Me)U(AlCl4)3 (1), was obtained by the reductive Freidel-Crafts reaction. The crystal structure of 1 was determined by single crystal X-ray diffraction analysis. The U atom in 1 is bound to the C6H5Me group by the 6 mechanism and is linked to the three AICl4 groups through two g-CI bridges. The coordination of the U atom is a distorted pentagonal bipyramid in which the center of the arene ring is in one apical position, and the bridging Cl atoms occupy the other vertices.Translated from Izvestiva Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 469–472, February, 1996.  相似文献   
980.
In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.  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