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   646篇
  免费   131篇
  国内免费   83篇
化学   420篇
晶体学   7篇
力学   38篇
综合类   1篇
数学   100篇
物理学   294篇
  2024年   3篇
  2023年   6篇
  2022年   18篇
  2021年   26篇
  2020年   32篇
  2019年   20篇
  2018年   21篇
  2017年   31篇
  2016年   36篇
  2015年   25篇
  2014年   49篇
  2013年   46篇
  2012年   70篇
  2011年   75篇
  2010年   35篇
  2009年   36篇
  2008年   25篇
  2007年   53篇
  2006年   37篇
  2005年   35篇
  2004年   15篇
  2003年   19篇
  2002年   24篇
  2001年   21篇
  2000年   13篇
  1999年   6篇
  1998年   2篇
  1997年   12篇
  1996年   8篇
  1995年   3篇
  1994年   4篇
  1993年   7篇
  1992年   4篇
  1991年   2篇
  1990年   16篇
  1989年   9篇
  1987年   3篇
  1986年   1篇
  1985年   1篇
  1982年   2篇
  1981年   3篇
  1979年   1篇
  1977年   2篇
  1976年   1篇
  1975年   2篇
排序方式: 共有860条查询结果,搜索用时 31 毫秒
851.
We investigate experimentally the linear viscoelastic properties of a lamellar liquid foam as a function of the cell size and spatial organisation. The system consists of multilamellar vesicles generated by a simple shear flow on a lyotropic lamellar phase. The vesicles can be prepared either in an amorphous or a spatially ordered state. Their size is easily tunable in the range R = 0.5-15 μm. Whereas the shear modulus of the amorphous lamellar foam is alike that of usual liquid foams or concentrated emulsions and scales linearly with 1/R, the elastic modulus of the ordered foam is almost independent of the cell size. This result --probably the first describing the elasticity of an ordered foam-like system-- remains unexplained. Received 7 August 2000  相似文献   
852.
介绍了用石墨炉原子吸收分光光度法测定大气颗粒物中的锡,并进行了全程序空白值的测定、精密度测定,准确度测定,以及加标回收率实验,各项指标均符合实际要求。  相似文献   
853.
The crystal structure of the title complex, [Cu(C7H8N4)2(H2O)2](ClO4)2, consists of a discrete centrosymmetric [Cu(C7H8N4)2(H2O)2]2+ cation and two perchlorate anions. The CuII centre is six‐coordinated by four N donors from the two pyrazole rings [Cu—N 1.998 (2) and 2.032 (3) Å] and two O atoms from the water mol­ecules occupying the apical sites [Cu—O 2.459 (3) Å]. The coordination geometry of the complex can be described as octahedral. There is a unique three‐dimensional network in which the perchlorate units are linked by a combination of strong O—H?O and weak C—H?O hydrogen bonds.  相似文献   
854.
The crystal structure of the title complex, [Cd(C20H25­N2­O2)­Cl], reveals a hydrogen‐bonded dimer composed of neutral molecules. The CdII center is five‐coordinated by two O atoms of the pendant arms, two nitro­gen donors of the 1,5‐di­aza­cyclo­octane ring and a chloride anion. The coordination geometry of the complex could be described as a distorted square pyramid. The 1,5‐di­aza­cyclo­octane backbone adopts a boat/chair configuration and the two phenol/phenolato groups have a dihedral angle of 101.3 (2)° between them. The coordinated phenolate and phenolic groups of inversion‐related mol­ecules form strong intermolecular O—H?O hydrogen bonds.  相似文献   
855.
Electrorheological (ER) fluid is one of the popular materials used in smart materials and structures. The material properties of ER fluid can be changed markedly while an external electric field is imposed on ER fluid domain. In this paper, the optical properties of ER suspensions consisting of composite particles dispersed in silicone oil are investigated. Both dc and ac electric fields are utilized to be imposed on ER fluid. The transmissivity of light through ER fluid under various electric fields is detected and analyzed. It is shown that the transmissivity of light increases with the increasing electric field strength and time. The change of transmissivity is caused by the formation of particle chains. The higher the particle concentration, the faster the change occurs. When an ac electric field is applied, the transmissivity can be affected by the frequency of electric field.  相似文献   
856.
用单纵模Nd:YAG激光(波长1.06μm,脉宽9ns,线宽0.003cm-1)泵浦氢气中的受激喇曼散射,产生很强的后向一级斯托克斯.当泵浦能量为120mJ,压力为1.5MPaH2时,后向和前向喇曼的光子转化效率分别为66%和15%,而在4MPa时两个数值分别为46%和39%.由于后向喇曼与前向喇曼和泵浦光的传播方向相反,二者的相互竞争产生了张弛振荡,使得后向和前向喇曼的时间波形都分裂为两个峰,后向喇曼的两个峰都被压窄到1ns,使峰值功率达到了泵浦光功率的二倍,这在前向喇曼是不可能的.而且后向喇曼的光束质量要大大优于泵浦光和前向喇曼的光束质量,在4MPaH2和脉冲重复频率为10Hz时,喇曼过程的放热使前向喇曼的光束质量变坏,但对后向喇曼的光束质量影响不大.计算表明,该实验条件下受激喇曼过程没有达到稳态,所有实验结果都可以而且只能用相关的瞬态受激喇曼理论解释.  相似文献   
857.
稀土元素对磷钼钒杂多酸催化氧化活性的影响   总被引:1,自引:0,他引:1  
讨论了镧的置換度和稀土元素对含氧有机化合物在杂多酸催化剂上的氧化反应的影响,并与催化剂的结构进行了关联。镧的引入不影响氧化脱氢反应,而明显削弱插入氧反应。其它稀土元素的影响与镧相同。  相似文献   
858.
Mitomycin has a unique chemical structure and contains densely assembled functionalities with extraordinary antitumor activity. The previously proposed mitomycin C biosynthetic pathway has caused great attention to decipher the enzymatic mechanisms for assembling the pharmaceutically unprecedented chemical scaffold. Herein, we focused on the determination of acyl carrier protein (ACP)-dependent modification steps and identification of the protein–protein interactions between MmcB (ACP) with the partners in the early-stage biosynthesis of mitomycin C. Based on the initial genetic manipulation consisting of gene disruption and complementation experiments, genes mitE, mmcB, mitB, and mitF were identified as the essential functional genes in the mitomycin C biosynthesis, respectively. Further integration of biochemical analysis elucidated that MitE catalyzed CoA ligation of 3-amino-5-hydroxy-bezonic acid (AHBA), MmcB-tethered AHBA triggered the biosynthesis of mitomycin C, and both MitB and MitF were MmcB-dependent tailoring enzymes involved in the assembly of mitosane. Aiming at understanding the poorly characterized protein–protein interactions, the in vitro pull-down assay was carried out by monitoring MmcB individually with MitB and MitF. The observed results displayed the clear interactions between MmcB and MitB and MitF. The surface plasmon resonance (SPR) biosensor analysis further confirmed the protein–protein interactions of MmcB with MitB and MitF, respectively. Taken together, the current genetic and biochemical analysis will facilitate the investigations of the unusual enzymatic mechanisms for the structurally unique compound assembly and inspire attempts to modify the chemical scaffold of mitomycin family antibiotics.  相似文献   
859.
采用密度泛函理论对硫醚与2-甲基-1,5-己二烯的反应机理进行了详细的理论探究.计算结果表明,该反应历程主要包含活性物种的生成、2-甲基-1,5-己二烯的插入、另一分子的硫醚的碳氢键活化三部分.在2-甲基-1,5-己二烯插入步骤中,发现其采用6-5-re-插入时需要克服的活化能垒最低,反应时更为占优,在进行烯烃分子内碳碳双键插入完成闭环反应时相对比较容易.通过能量对比探明硫醚的C-H键活化需要克服的能垒最高,为该反应的速控步.  相似文献   
860.
A series of novel phosphonodipeptides containing a uracil or thymine group was synthesized in 54.2–74.1% yields by means of a peptide coupling reaction with DCC as the dehydrating agent and 1‐hydroxybezotriazole as the activating agent of the carboxyl group. All products were characterized by 1H NMR, 31P NMR and IR spectra, and by elemental analyses. The crystal and molecular structure of compound 6c has been determined by X‐ray diffraction. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:422–427, 2000  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