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   886篇
  免费   25篇
  国内免费   38篇
化学   746篇
晶体学   3篇
力学   28篇
综合类   3篇
数学   38篇
物理学   131篇
  2024年   8篇
  2023年   69篇
  2022年   18篇
  2021年   20篇
  2020年   27篇
  2019年   30篇
  2018年   25篇
  2017年   33篇
  2016年   23篇
  2015年   24篇
  2014年   51篇
  2013年   32篇
  2012年   29篇
  2011年   47篇
  2010年   18篇
  2009年   45篇
  2008年   34篇
  2007年   38篇
  2006年   23篇
  2005年   19篇
  2004年   23篇
  2003年   17篇
  2002年   19篇
  2001年   10篇
  2000年   9篇
  1999年   23篇
  1998年   39篇
  1997年   13篇
  1996年   9篇
  1995年   12篇
  1994年   6篇
  1993年   9篇
  1992年   11篇
  1991年   9篇
  1990年   7篇
  1989年   8篇
  1988年   8篇
  1987年   6篇
  1986年   7篇
  1985年   4篇
  1984年   12篇
  1981年   4篇
  1979年   6篇
  1978年   8篇
  1977年   7篇
  1976年   5篇
  1975年   8篇
  1974年   9篇
  1967年   8篇
  1966年   4篇
排序方式: 共有949条查询结果,搜索用时 15 毫秒
1.
In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.  相似文献   
2.
Summary A novel approach to solid phase extraction, based on the use of a highly selective molecularly imprinted polymer, is presented. The versatility of this type of sorbent for solid phase extraction was demonstrated in a model batch-wise pre-concentration of sameridine prior to gas chromatography. Problems associated with leakage of remaining imprint molecules during the desorption phase could be eliminated by the use of a close structural analogue of sameridine as the imprint species. It was found that a major benefit of the imprinted polymer was its specificity, which lead to distinctly cleaner chromatographic traces and ability to improve sensitivity by extracting sameridine from larger sample volumes.  相似文献   
3.
Alkenylidenes R2C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.  相似文献   
4.
This paper deals with the existence of curved front solution of a partial differential equation coming from a mathematical model of stroke. The equation is of reaction-diffusion type in a cylinder of radius R and of diffusion and absorption type outside of the cylinder. We prove the nonexistence of a travelling front when R is small enough and the existence if R is large enough using a recent energy method. We construct the travelling front as the limit in time of a solution with a well-chosen initial condition, in a travelling referential.  相似文献   
5.
Enantioselective biocatalysis in nonaqueous media is becoming increasingly important in preparative synthetic chemistry. This article discusses (1) the general catalytic properties of enzymes in nonaqueous environments, (2) the basic principles that govern lipase-catalyzed enantioselective esterification and transesterification reactions in organic media for the preparation of optically active acids and alcohols, (3) the determination of kinetic and thermodynamic parameters, and (4) the quantitative analysis of published data.  相似文献   
6.
The syntenic distance between two species is the minimum number of fusions, fissions, and translocations required to transform one genome into the other. The linear syntenic distance, a restricted form of this model, has been shown to be close to the syntenic distance. Both models are computationally difficult to compute and have resisted efficient approximation algorithms with non-trivial performance guarantees. In this paper, we prove that many useful properties of syntenic distance carry over to linear syntenic distance. We also give a reduction from the general linear synteny problem to the question of whether a given instance can be solved using the maximum possible number of translocations. Our main contribution is an algorithm exactly computing linear syntenic distance in nested instances of the problem. This is the first polynomial time algorithm exactly solving linear synteny for a non-trivial class of instances. It is based on a novel connection between the syntenic distance and a scheduling problem that has been studied in the operations research literature.  相似文献   
7.
Most adhesives and binders, including bitumen for asphalt mixture production, are presently produced from petrochemicals after the refining of crude oil. The fact that crude oil reserves are a finite resource means that in the future, it may become necessary to produce these materials from alternative and probably renewable sources. Suitable resources of this kind may include polysaccharides, plant oils and proteins. This paper deals with the synthesis of polymer binders from monomers that could, in future, be derived from renewable resources. These binders consist of polyethyl acrylate (PEA) of different molecular weight, polymethyl acrylate (PMA) and polybutyl acrylate (PBA), which were synthesised from ethyl acrylate, methyl acrylate and butyl acrylate, respectively, by atom transfer radical polymerisation. The rheological properties of these binders were determined by means of oscillatory testing using a dynamic shear rheometer and combinations of stress/strain, temperature and frequency sweeps. The results indicate that PEA can be produced to have rheological properties similar to that of ‘soft’ 100/150 penetration grade bitumen, PMA with similar rheological properties to that of ‘hard’ 10/20 penetration grade bitumen, while PBA, due to its highly viscous nature and low dynamic moduli, cannot be used on its own as a binder. The synthetic polymers were found to be thermo-rheologically simple, and the shift factors, used to produce the dynamic moduli master curves, were found to fit an Arrhenius function.  相似文献   
8.
北京同步辐射装置3B1B生物光谱实验站   总被引:1,自引:0,他引:1  
本文介绍北京同步辐射装置(BSRF)3B1B光束线、生物光谱实验站和圆二色谱仪的基本情况。报道北京正负电子对撞机(BEPC)同步辐射专用光期间,我们在站测量了11种手征性生物和药物样品的圆二色(CD)谱,首次在国内利用同步辐射光获取了D-苯丙氨酸等样品的CD谱和D-及L-亮氨酸对称的CD曲线。  相似文献   
9.
我国法定可使用的合成食用色素主要有5种。即苋菜红、胭脂红、柠檬黄、日落黄和亮蓝。根据调色需要,它们常被混合配置应用.目前一般采用高效液相色谱和层析分离法分析,但尚缺少可靠的同时测定此5组分的化学计量学方法,Loosbroek曾用卡尔曼滤波光度法鉴  相似文献   
10.
Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.  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