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   6248篇
  免费   1148篇
  国内免费   1142篇
化学   5391篇
晶体学   61篇
力学   262篇
综合类   81篇
数学   778篇
物理学   1965篇
  2024年   19篇
  2023年   102篇
  2022年   111篇
  2021年   148篇
  2020年   231篇
  2019年   272篇
  2018年   231篇
  2017年   177篇
  2016年   286篇
  2015年   320篇
  2014年   353篇
  2013年   482篇
  2012年   537篇
  2011年   516篇
  2010年   431篇
  2009年   422篇
  2008年   441篇
  2007年   407篇
  2006年   385篇
  2005年   352篇
  2004年   324篇
  2003年   305篇
  2002年   361篇
  2001年   230篇
  2000年   194篇
  1999年   193篇
  1998年   125篇
  1997年   106篇
  1996年   75篇
  1995年   59篇
  1994年   59篇
  1993年   34篇
  1992年   37篇
  1991年   43篇
  1990年   30篇
  1989年   22篇
  1988年   17篇
  1987年   11篇
  1986年   18篇
  1985年   20篇
  1984年   9篇
  1983年   9篇
  1982年   9篇
  1981年   4篇
  1979年   4篇
  1977年   2篇
  1975年   2篇
  1974年   2篇
  1968年   3篇
  1936年   2篇
排序方式: 共有8538条查询结果,搜索用时 15 毫秒
131.
李英奇  杨斌盛 《中国化学》2004,22(10):1153-1157
The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site.  相似文献   
132.
The aqueous dispersion of polyurethaneurea-acrylate (PUA) including small amount of fluorinated block copolymers containing carboxyl groups (PATF), which can be dissolved in water, was used to make films and the surface properties of these films were examined. The experimental data show that the modified PUA film exhibits a hydrophobic surface property, although the original surface of PUA film is hydrophilic. The surface composition of the modified PUA film was measured by ATR and XPS. The results indicate that there is a concentration gradient of the fluorine groups along the lines of thickness of the modified film and towards the outmost surface layer, resulting from the migration of fluorinated blocks to the air side surface of the modified PUA film during the film formation process. However, the PUA film can not be modified effectively by adding the sodium salt of PATF, since the urethane groups in the system are easy to occupy on the surface of the film.  相似文献   
133.
油菜花粉十二肽的二维核磁共振研究   总被引:4,自引:0,他引:4  
用核磁共振方法对油菜花粉十二肽溶液构象进行了研究。利用2D COSY和NOESY归属了^1H NMR谱的全部共振峰。用Karplus方程从肽键N-H质子与α-H质子的偶合常数计算出了所有肽键的二面角θ及Φ,并对其进行不同温度及不同溶剂条件下的观测。结果表明,在水溶液中该肽链为无规卷曲结构,个别肽段存在γ-turn构象。  相似文献   
134.
The addition of suitable cross-linking agents with norbornene-based monomers has significant effects on the thermal properties of the resulting polymers formed by olefin metathesis. Ethylidene norbornene (ENB) and endo-dicyclopentadiene (endo-DCPD) were mixed separately with various loadings of three different cross-linking agents and then polymerized with the addition of Grubbs’ catalyst. The polymerization kinetics and resulting glass transition temperature (T g) of the systems were evaluated by differential scanning calorimetry (DSC). The addition of the first cross-linking agent, norbornadiene (CL-1), to both endo-DCPD and ENB resulted in decreasing glass transition temperatures with increasing concentrations. In contrast, the addition of the other two cross-linking agents (CL-2 and CL-3), which were both custom synthesized bifunctional norbornyl systems, to both endo-DCPD and ENB resulted in a monotonic increases in T g with cross-linker concentration. By tailoring the loading of these custom cross-linking agents, the properties of these polymer systems can be controlled for various applications, including self-healing composites.  相似文献   
135.
分子筛体系的氢溢出效应李晓燕,盛太成,杨孔章(山东大学化学院,济南250100)关键词铂/分子筛催化剂,氢溢出,程序升温脱附负载型金属催化剂的表面氢溢出效应近年来引起了人们的重视.人们采用不同的实验方法对此进行了广泛的研究,但对以分子筛为担体的负载型...  相似文献   
136.
CompoundsformedfromCu ,AgandAuwithdithio lateligands ,suchasthedialkyldithiocarbamate (DTC) ,mercaptothiazoline (HMT)anddialkyldithiophosphates(DDP) ,haveplayedanimportantroleintechnology .1Cu(I) Sclustersalsohavebeenimplicatedinbiologyasan ti oxidants .2Thecuban…  相似文献   
137.
A theoretical study using density functional theory was performed to understand the structure/property relationship of the cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined.  相似文献   
138.
考察了反应温度、气体空速和进料中CH4:O2比值对Mo2C/Al2O3催化的POM反应制合成气的影响.结果发现较高的温度具有较高的甲烷转化率、CO和H2的选择性;而在较低的温度下,对CO的选择性比对H2的影响更大.反应气体的空速较小时对于甲烷的转化率、CO和H2的选择性是有利的;而在较高的气体空速下,氢气的选择性则更低.进料中CH4:O2比值稍高于2:1时有利于获得高的甲烷转化率、CO和H2的选择性.并且还可以增加催化剂的稳定性.当CH4:O2比值低于2:1时.甲烷转化率、CO和H2选择性随反应的进行急剧下降.而当此比值调整到高于2:1时.转化率和选择件都可以得到恢复。  相似文献   
139.
许多三唑类化合物具有优良的杀菌和植物生长调节活性 ,如三唑酮、三唑醇、烯效唑、烯唑醇等 ,对常见真菌病害具有很好的防治效果 ,并具有增产、抗倒和生长调节作用 ,已成为重要的杀菌剂类型 [1] .为筛选新型高活性三唑类杀菌剂和探讨其活性与结构间的关系 ,我们利用生物等排体理论以常规三唑类杀菌剂三唑酮为先导物设计合成了 1 6个含芳硫基的新三唑类化合物 ,其合成路线如下 :RCCH2 BrO+HNNNB NRCCH2O NNHAC-Na ACBr2NRCCHOBrNN(1 ) (2 ) (3 )3 +SH  R′B NRCCHOS R′NN  (4 )RCCH2 CH2 NMe2 .HClO+HNNNH2 O…  相似文献   
140.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation.  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