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   254篇
  免费   5篇
  国内免费   1篇
化学   202篇
晶体学   2篇
力学   1篇
数学   5篇
物理学   50篇
  2023年   3篇
  2022年   1篇
  2021年   1篇
  2019年   1篇
  2018年   4篇
  2016年   7篇
  2015年   4篇
  2014年   10篇
  2013年   24篇
  2012年   11篇
  2011年   10篇
  2010年   6篇
  2009年   5篇
  2008年   15篇
  2007年   14篇
  2006年   12篇
  2005年   15篇
  2004年   11篇
  2003年   11篇
  2002年   13篇
  2001年   3篇
  2000年   5篇
  1999年   3篇
  1998年   4篇
  1997年   6篇
  1994年   1篇
  1993年   6篇
  1992年   2篇
  1991年   2篇
  1990年   1篇
  1988年   2篇
  1985年   2篇
  1984年   3篇
  1982年   3篇
  1981年   1篇
  1980年   1篇
  1979年   3篇
  1978年   1篇
  1977年   1篇
  1976年   2篇
  1975年   3篇
  1974年   16篇
  1973年   2篇
  1972年   3篇
  1971年   2篇
  1970年   1篇
  1968年   1篇
  1967年   2篇
排序方式: 共有260条查询结果,搜索用时 15 毫秒
21.
We point out a possibility of strange giant resonances that can be excited by the (K ??) reaction on nuclear targets. Recent experimental data on40Ca are analyzed from this point of view.  相似文献   
22.
The effects of Soto's 'beta-sheet breaker peptide' and its polymer on PrPSc formation in ScN2a cells were investigated. Surface plasmon resonance study indicated that direct binding between PrP(81-145) and the 'beta-sheet breaker peptide' is not specific and may not play a major role in the inhibition of PrPSc formation.  相似文献   
23.
This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C2 symmetric catalyst produces syndiotactic polypropylene. 13C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a Tm, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene.  相似文献   
24.
An enantioselective synthesis of sterically congested 1,2-di-tert-butyl and 1,2-di-(1-adamantyl)ethylenediamines has been developed. Thus, diastereomerically pure trans-1-apocamphanecarbonyl-4,5-dimethoxy-2-imidazolidinones 6 and 7 were successfully prepared by optical resolution of (±)-trans-4,5-dimethoxy-2-imidazolidinone using apocamphanecarbonyl chloride (MAC-Cl) followed by stereospecific and stepwise substitution of the dimethoxyl groups using tert-butyl or 1-adamantyl cuprates to provide (4S,5S)-4,5-di-tert-butyl and (4R,5R)-4,5-di-(1-adamantyl)-2-imidazolidinones 12 and 15, respectively. Furthermore, N-acetyl 4,5-di-tert-butyl and 4,5-di-(1-adamantyl)-2-imidazolidinones 16a,b were enantioselectively deacetylated using a catalytic oxazaborolidine system to provide enantiopure 1-p-tolylsulfonyl-4,5-di-tert-butyl-2-imidazolidinones 12 and 19 and 1-p-tolylsulfonyl-4,5-di-(1-adamantyl)-2-imidazolidinones 18 and 20, respectively. Finally, N-p-tolylsulfonyl-2-imidazolidinones 12 and 15 were treated with 30 equiv of Ba(OH)2·8H2O to achieve ring cleavage and to provide (1S,2S)-1,2-di-tert-butylethylenediamine 3 and (1R,2R)-1,2-di-(1-adamantyl)ethylenediamine 4.  相似文献   
25.
The reaction of copolymer of N,N-dimethylacrylamide (DMAA) and bromoethyl methacrylate with potassium cinnamate produced water-soluble photosensitive polymers. Photosensitive polyDMAA films were irradiated with a 400 W high-pressure mercury lamp (λ > 280 nm) to produce crosslinked polymers, which were swollen in water. The degree of swelling was controlled by the irradiation time and content of cinnamate moieties in copolymers. Higher cinnamoylation and longer irradiation time resulted in higher yield of crosslinked polymers and less swellability. Partial degelation upon irradiation at λ ~ 254 nm was observed. The advantage of gelation via photodimerization over conventional chemical crosslinking methods is discussed in conjunction with biomedical applications. © 1992 John Wiley & Sons, Inc.  相似文献   
26.
The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl3 solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) x –(PPO) y –(PEO) x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) x –(PEO) y –(PPO) x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N2 adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h~3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles.  相似文献   
27.
Activation of aromatic C? H bonds by a transition metal catalyst has received significant attention in the synthetic chemistry community. In recent years, rapid and site‐selective extension of π‐electron systems by C–H activation has emerged as an ideal methodology for preparing organic materials with extended π‐systems. This Review focuses on recently reported π‐extending C–H activation reactions directed toward new optoelectronic conjugated materials.  相似文献   
28.
29.
In this work we obtain the thermodynamic properties of mixed (1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine) PC and (1-stearoyl-2-oleoyl-sn-glycero-3-phospho-l-serine (sodium salt)) PS monolayers. Measurements of compressibility (isotherms, bulk modulus, and excess area per molecule) and surface potential show that the properties of monolayers at the air–water interface depend on the concentration of ions (Na+ and K+) and the proportion of PS in the mixture. The dependence on PS arises because the molecule is originally bound to a Na+ counterion; by increasing the concentration of ions the entropy changes, creating a favorable system for the bound counterions of PS to join the bulk, leaving a negatively charged molecule. This change leads to an increase in electrostatic repulsions which is reflected by the increase in area per molecule versus surface pressure and a higher surface potential. The results lead to the conclusion that this mixture of phospholipids follows a non ideal behavior and can help to understand the thermodynamic behavior of membranes made of binary mixtures of a zwitterionic and an anionic phospholipid with a bound counterion.  相似文献   
30.
A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to believe that SHTS technique combined with asymmetric activation or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions.  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