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   225篇
  免费   6篇
化学   180篇
晶体学   1篇
力学   8篇
数学   15篇
物理学   27篇
  2023年   4篇
  2022年   13篇
  2021年   17篇
  2020年   8篇
  2019年   14篇
  2018年   5篇
  2017年   8篇
  2016年   8篇
  2015年   12篇
  2014年   7篇
  2013年   9篇
  2012年   6篇
  2011年   9篇
  2010年   13篇
  2009年   8篇
  2008年   12篇
  2007年   8篇
  2006年   8篇
  2005年   20篇
  2004年   13篇
  2003年   12篇
  2002年   5篇
  2001年   2篇
  2000年   2篇
  1999年   2篇
  1998年   1篇
  1997年   1篇
  1996年   2篇
  1995年   1篇
  1969年   1篇
排序方式: 共有231条查询结果,搜索用时 0 毫秒
21.
22.
Two different problems are proposed as approximations of the usual system modelling natural convection under the Oberbeck-Boussinesq assumptions. The error is evaluated by means of the norm of its gradient in the Hilbert space. The average Nusselt number is also estimated.  相似文献   
23.
We prove that a residually finite group G satisfying an identity \(w\equiv 1\) and generated by a commutator closed set X of bounded left Engel elements is locally nilpotent. We also extend such a result to locally graded groups, provided that X is a normal set. As an immediate consequence, we obtain that a locally graded group satisfying an identity, all of whose elements are bounded left Engel, is locally nilpotent.  相似文献   
24.
    
Hydrogenation of multiple bonds are among the most general and important organic reactions. Typical heterogeneous catalysts are based on transition metal nanoparticles, including noble metals. Data are presented here showing that metal nodes of MIL-101(Cr) and UiO-66 in the absence of occluded metal nanoparticles can promote hydrogenation of polarized X=Y double bonds of nitro and carbonyl groups. The catalytic activity is a function of the composition of the metal node and the organic linker. It is proposed that the reaction mechanism is based on the operation of frustrated Lewis acid/base pairs.  相似文献   
25.
    
Herein, we report on the use of the iron pincer complex Iron‐MACHO‐BH, in the base‐free transfer hydrogenation of esters with EtOH as a hydrogen source. More than 20 substrates including aromatic and aliphatic esters and lactones were reduced affording the desired primary alcohols and diols with moderate to excellent isolated yields. It is also possible to reduce polyesters to the diols with this method, enabling a novel way of plastic recycling. Reduction of the renewable substrate methyl levulinate proceeds to form 1,4‐pentanediol directly. The yields are largely governed by the equilibrium between the alcohol and the ethyl ester.  相似文献   
26.
    
Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ6‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.  相似文献   
27.
    
Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the MII/MIII ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.  相似文献   
28.
Measurements have been carried out on furnished orchestra platforms in four concert halls in Italy in order to describe the sound field perceived by musicians. The heterogeneous nature of the orchestra suggested a procedure able to take into account the mutual hearing between instrumental sections. The measured parameters were the early, late and total support, the reverberation time, the early decay time and the clarity index. A part of the study has been devoted to the measurement uncertainty estimation. The source directivity and the small displacements of the microphone influence the early decay time to a great extent while the on-platform spatial variability affects both the early decay time and the clarity index. Per-section early support shows differences that render the overall spatial mean inappropriate to describe the stage as a whole. For the other parameters an overall mean platform value can instead be suitable, even though, for the case of clarity a more evident group variability is observed. The values of late support, reverberation time, early decay time and clarity index, proposed in literature as suitable measures of reverberance for musicians, are not all intercorrelated, indicating that not all these parameters can be associated to the same subjective impression.  相似文献   
29.
Blood oxygenation level dependent (BOLD) response related to interictal activity was evaluated in a patient with post-traumatic focal epilepsy at repeated continuous electroencephalogram (EEG)-functional magnetic resonance imaging examinations. Lateralized interictal EEG activity induced a main cluster of activation co-localized with the anatomical lesion. Spreading of EEG interictal activity to both frontal lobes evoked bilateral clusters of activation indicating that topography of BOLD response might depend on the spatial distribution of epileptiform activity.  相似文献   
30.
Density functional theory with the B3LYP hybrid functional has been used to study the mechanisms for dioxygen activation by four families of mononuclear non-heme iron enzymes: alpha-ketoacid-dependent dioxygenases, tetrahydrobiopterin-dependent hydroxylases, extradiol dioxygenases, and Rieske dioxygenases. These enzymes have a common active site with a ferrous ion coordinated to two histidines and one carboxylate group (aspartate or glutamate). In contrast to the heme case, this type of weak field environment always leads to a high-spin ground state. With the exception of the Rieske dioxygenases, which have an electron source outside the active site, the dioxygen activation process passes through the formation of a bridging-peroxide species, which then undergoes O-O bond cleavage finally leading to the four electron reduction of O(2). In the case of tetrahydrobiopterin- and alpha-ketoacid-dependent enzymes, the O-O heterolysis yields a high-valent iron-oxo species, which is capable of performing a two-electron oxidation chemistry on various organic substrates. For the other two families of enzymes (extradiol dioxygenases and Rieske dioxygenases) the substrate oxidation and the O-O bond cleavage are found to be coupled. In the extradiol dioxygenases the product of the O-O bond cleavage is a ferric iron with an oxy-substrate with a mixture of radical and anionic character, which is essential for the selectivity of the catechol cleavage.  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