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   16689篇
  免费   1752篇
  国内免费   5222篇
化学   18228篇
晶体学   505篇
力学   495篇
综合类   167篇
数学   1978篇
物理学   2290篇
  2024年   13篇
  2023年   172篇
  2022年   236篇
  2021年   496篇
  2020年   593篇
  2019年   523篇
  2018年   470篇
  2017年   569篇
  2016年   691篇
  2015年   610篇
  2014年   876篇
  2013年   1405篇
  2012年   1674篇
  2011年   982篇
  2010年   823篇
  2009年   1057篇
  2008年   1198篇
  2007年   1263篇
  2006年   1172篇
  2005年   1139篇
  2004年   1015篇
  2003年   854篇
  2002年   744篇
  2001年   560篇
  2000年   562篇
  1999年   513篇
  1998年   439篇
  1997年   413篇
  1996年   357篇
  1995年   383篇
  1994年   337篇
  1993年   238篇
  1992年   309篇
  1991年   230篇
  1990年   178篇
  1989年   142篇
  1988年   100篇
  1987年   73篇
  1986年   74篇
  1985年   52篇
  1984年   39篇
  1983年   18篇
  1982年   25篇
  1981年   11篇
  1980年   8篇
  1979年   5篇
  1978年   5篇
  1977年   5篇
  1972年   2篇
  1936年   2篇
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
961.
WANG Yu-Fang  WANG Li-Ya 《结构化学》2007,26(12):1461-1465
A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.  相似文献   
962.
The preparation of a 1:1 complex involving-cyclodextrin (-CD) and phenylpropiolic acid (PPA) is reported. The new inclusion complex of-CD has been characterized on the basis of its chemical analysis, thermal behavior, infrared spectrum, X-ray powder pattern and13C-NMR spectrum in DMSO solution.  相似文献   
963.
复合氨基酸微量元素螯合物制备新工艺的研究   总被引:19,自引:0,他引:19  
本文报道了以废羽毛为原料,采用矿物质硫酸盐的制备与中和脱酸、螯合反应结合的新工艺,以金属盐类作催化剂和硫酸水解法,制得了复合氨基酸微量元素螯合物。复合氮基酸生成率为71.7%,微量元素螯合率达到98%以上。该工艺简单易行,生产成本低。  相似文献   
964.
宋玉民  芦小林  唐慧安  秦淑琪 《化学学报》2006,64(14):1451-1455
合成了新的O-(硫杂蒽酮-[2]-基)-氧乙酸及其稀土配合物. 通过元素分析, IR, 1H NMR, UV, DTA-TG和13C NMR谱对其结构进行了表征. 研究表明: 配体羧羰基脱质子后与金属离子配位, 2位氧原子也与金属离子配位, 配合物中含有一定量的配位水, 配合物为非电解质类型. 同时, 研究了O-(硫杂蒽酮-[2]-基)-氧乙酸稀土配合物对质粒DNA的切割作用. 结果表明: 铕的配合物对DNA的切割较明显, 且当配合物浓度增加时, 质粒DNA的超螺旋构型逐渐减少, 而缺刻、开环型构型逐渐增多. 在相同条件下, Eu(III)离子对质粒pBR322DNA几乎没有切割作用; 配体O-(硫杂蒽酮-[2]-基)-氧乙酸对质粒pBR322DNA也有切割作用, 但配合物EuL3对质粒pBR322DNA的切割作用明显强于配体, 表明稀土离子Eu(III)与配体生成配合物后有较好的协同切割作用.  相似文献   
965.
New “one-pot” protocols proposed for Pd0-catalyzed allylation of C-nucleophiles involve deprotonation of the corresponding CH acids with in situ generated dialkylamide and alkoxide anions. Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2024–2026, November, 2006.  相似文献   
966.
Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond.  相似文献   
967.
1 INTRODUCTION Nitronyl nitroxides, independently or in combina- tion with metal ions, have been one of the most wi- dely studied systems in molecular magnetism for understanding radical-radical or metal-radical inte- ractions as well as for synthesizing organic ferroma- gnets and metal-radical magnetic materials[1~4]. Up to now, lots of metal-radical complexes have been reported[5~8]. On the other hand, cooperative inter- molecular interactions, such as coordination bonds, hydrogen bon…  相似文献   
968.
A new Zn(II) complex, [Zn(pyz)(H2O)4]pht (1) (pyz=pyrazine; pht=1,2-benzenedicarboxylate) has been hydrothermally synthesized and characterized. Complex 1 features a novel polar 3D framework with a 1D polycationic chain , between which pht2− dianions are encapsulated via the supramolecular interaction. Its powder SHG is of about three times as large as that of KH2PO4.  相似文献   
969.
A new oxamato-bridged NiIICuIINiII species, [Ni(tacn)(H2O)]2[μ-Cu(pba)](ClO4)2·6H2O 1, (tacn=1,4,7-triazacyclononane; pba=1,3-propylenebis(oxamato)) has been synthesized and structurally as well as magnetically characterized. Complex 1 has a discrete trinuclear NiIICuIINiII structure: Two nickel(II) ions are bridged by [Cu(pba)]2− anion, macrocyclic ligand tacn works as terminal ligand of the nickel(II) center. The magnetic data of compound 1 was analyzed by means of
leading to gCu=2.19, gNi=2.18, J=−112.8 cm−1, D=±4.31 cm−1. The parameters are compared with the similar complexes and the irregular spin state structure of complex 1 is also described here.  相似文献   
970.
A novel one-dimensional (1D) chain coordination polymer [Mn2(2,2′-dipha)2(phen)]n has been synthesized by hydrothermal reaction, and characterized by elemental analysis, IR spectroscopy, TGA, and X-ray diffraction. Orange crystals crystallized in the monoclinic system, space group C2/c with a = 19.393(7) Å, b = 19.183(7) Å, c = 19.729(7) Å, β = 90.826(6)°, V = 7338(5) Å3, Z = 8. In the crystal structure, one manganese atom is six-coordinated with four carboxylate oxygen atoms from one pentadentate 2,2′-dipha ligand and two tetradentate 2,2′-dipha ligands, and with two nitrogen atoms of one phen ligand, giving a slightly distorted octahedral geometry. The other manganese atom is five-coordinated with five oxygen atoms from two tetradentate 2,2′-dipha ligands and two pentadentate 2,2′-dipha ligands and has a trigonal bipyramidal environment. The TGA curve shows that the compound is stable below 310°.  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