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   723篇
  免费   21篇
  国内免费   2篇
化学   531篇
晶体学   1篇
力学   18篇
数学   56篇
物理学   140篇
  2023年   2篇
  2022年   6篇
  2021年   8篇
  2020年   9篇
  2019年   11篇
  2018年   4篇
  2017年   7篇
  2016年   17篇
  2015年   12篇
  2014年   20篇
  2013年   29篇
  2012年   49篇
  2011年   58篇
  2010年   31篇
  2009年   40篇
  2008年   51篇
  2007年   41篇
  2006年   40篇
  2005年   42篇
  2004年   41篇
  2003年   35篇
  2002年   39篇
  2001年   9篇
  2000年   15篇
  1999年   3篇
  1998年   11篇
  1997年   8篇
  1996年   8篇
  1995年   4篇
  1994年   7篇
  1993年   5篇
  1992年   7篇
  1991年   4篇
  1990年   2篇
  1989年   7篇
  1987年   9篇
  1986年   6篇
  1985年   5篇
  1984年   6篇
  1983年   5篇
  1982年   2篇
  1981年   3篇
  1980年   3篇
  1978年   4篇
  1977年   3篇
  1975年   2篇
  1970年   2篇
  1928年   2篇
  1887年   2篇
  1880年   2篇
排序方式: 共有746条查询结果,搜索用时 701 毫秒
31.
We consider complete nonorientable minimal immersionsx(M)R 3. Assuming the double coverN ofM has finite total curvature, we generalize an argument of Lopez/Ros to give a sufficient condition for the instability ofx(M) in terms of the total curvature ofM and the genus γ of . We apply this condition to prove that if the immersion is regular thenx(M) is unstable. We also consider the case where the immersion is finitely branched, and we classify the possibilities under the assumption the is hyperelliptic.  相似文献   
32.
[structure: see text] The first enantioselective total synthesis of (-)-Centrolobine is described. The key reaction is the synthesis of the cis-disubstituted tetrahydropyran framework by intramolecular cyclization of the enantiopure hydroxyketone 3 with Et3SiH and TMSOTf. The stereoselective reduction of the beta-ketosulfoxide 4 is the source of chirality. Revision of the absolute configuration of (-)-Centrolobine is proposed.  相似文献   
33.
Serotonin or 5-hydroxytryptamine (5-HT) is a major neurotransmitter in the central nervous system. In this work, a method for analyzing 5-HT in brain microdialysis samples using a commercially available capillary electrophoresis (CE) system has been developed. A pH-mediated in-capillary preconcentration of samples was performed, and after separation by capillary zone electrophoresis, native fluorescence of 5-HT was detected by a 266 nm solid-state laser. The separation conditions for the analysis of 5-HT in standard solutions and microdialysates have been optimized, and this method has been validated on both pharmacological and analytical bases. Separation of 5-HT was performed using a 80 mmol/L citrate buffer, pH 2.5, containing 20 mmol/L hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and +30 kV voltage. The detection limit was 2.5 x 10(-10) mol/L. This method allows the in vivo brain monitoring of 5-HT using a simple, accurate CE measurement in underivatized microdialysis samples.  相似文献   
34.
The stereochemical outcome of the radical haloacetal cyclization reaction (Ueno-Stork reaction) has been examined by ab initio and other molecular orbital techniques. It was found that the stereochemistry of 5-exo- and 6-exo trig cyclizations can be accurately predicted from calculations using moderate levels of theory (UHF/6-311G** or B3LYP/6-311G**). A simplified computational procedure, easily run on a standard desktop computer, has been developed that provides excellent predictive ability for the stereochemical outcome for the reactions in question. Interestingly, a novel twist transition state has been identified for the first time in 5-exo-trig radical cyclization reactions.  相似文献   
35.
Analysis of nanoparticle size through a simple 2D plot is proposed in order to extract the correlation between length and width in a collection or a mixture of anisotropic particles. Compared to the usual statistics on the length associated with a second and independent statistical analysis of the width, this simple plot easily points out the various types of nanoparticles and their (an)isotropy. For each class of nano‐objects, the relationship between width and length (i.e., the strong or weak correlations between these two parameters) may suggest information concerning the nucleation/growth processes. It allows one to follow the effect on the shape and size distribution of physical or chemical processes such as simple ripening. Various electron microscopy pictures from the literature or from the authors′ own syntheses are used as examples to demonstrate the efficiency and simplicity of the proposed 2D plot combined with a multivariate analysis.  相似文献   
36.
This work presents an automatic system, based on an electronic tongue, for resolution of mixtures of three pesticides. Inhibition detections were performed during the steady state of biosensors response. Three biosensors were built using two enzymes, electric eel (EE), genetically-modified Drosophila melanogaster (B131), and electric eel co-immobilized with drosophila melanogaster (BH). Calibrations curves for paraoxon, dichorlvos, and carbofuran were performed in the ranges 0.4–50.4 µM, 0.01–1.01 µM, 0.01–0.41 µM with LOD of 3.91 × 10?8, 6.30 × 10?11, and 5.84 × 10?10, respectively. An artificial neural network (ANN) was used to model the combined response of three pesticides. A set of 19 mixtures were prepared in order to train the artificial neural network, the modeling was validated with a set of 6 spiked samples of river water. The error and recovery yields were found in consistent with expected values.  相似文献   
37.
Besides the well-known papain, lipolytic activity is another interesting enzymatic activity present in latex from Carica papaya. This lipolytic activity is strongly attached to the latex solid phase, resulting in a naturally immobilized biocatalyst. In this work we describe the kinetic resolution of (R,S)-2-bromophenylacetic acid octyl ester by Carica papaya crude latex and two partially purified latex fractions. Several parameters, such as substrate concentration and solvent effects were studied. The best results were obtained using decane as solvent with 50 mM of substrate and 50 mg/mL enzyme/reaction medium; under these conditions, a high enantioselectivity (E >200) was obtained with crude latex. A twofold increase of the initial rate maintaining E >200 was obtained using purified fractions without protease and without esterase. Lipase from Carica papaya latex is the most enantioselective wild-type enzyme ever described for the studied reaction.  相似文献   
38.
A novel approach to the synthesis of molecularly imprinted polymers via non-covalent linkages has been studied. It relies on the use of thermotropic side group liquid crystal polymer networks. The polysiloxane networks obtained after extraction of the template preserved the mesomorphic organization set up in the presence of the guest molecule. A first batch rebinding analysis was performed: this study revealed that the imprinted polymer has a much greater affinity for the template molecule than has the non-imprinted polymer, and a significant selectivity.  相似文献   
39.
Methane (CH4) is a potent greenhouse gas and the second highest contributor to global warming. CH4 emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH4 emissions by developing large-scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH4 (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar-driven gas phase advanced oxidation processes for CH4 removal. And (3) to propose some ideas, which may help to develop solar-driven gas phase advanced oxidation processes and make them deployable at a climate significant scale.  相似文献   
40.
The design of novel nucleoside triphosphate (NTP) analogues bearing an all-carbon quaternary center at C2′ or C3′ is described. The construction of this all-carbon stereogenic center involves the use of an intramoleculer photoredox-catalyzed reaction. The nucleoside analogues (NA) hydroxyl functional group at C2′ was generated by diastereoselective epoxidation. In addition, highly enantioselective and diastereoselective Mukaiyama aldol reactions, diastereoselective N-glycosylations and regioselective triphosphorylation reactions were employed to synthesize the novel NTPs. Two of these compounds are inhibitors of the RNA-dependent RNA polymerase (RdRp) of SARS-CoV-2, the causal virus of COVID-19.  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