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   1741篇
  免费   65篇
  国内免费   5篇
化学   1163篇
晶体学   18篇
力学   67篇
数学   186篇
物理学   377篇
  2023年   9篇
  2022年   38篇
  2021年   45篇
  2020年   26篇
  2019年   41篇
  2018年   56篇
  2017年   21篇
  2016年   55篇
  2015年   52篇
  2014年   59篇
  2013年   116篇
  2012年   125篇
  2011年   129篇
  2010年   93篇
  2009年   69篇
  2008年   106篇
  2007年   127篇
  2006年   96篇
  2005年   81篇
  2004年   57篇
  2003年   59篇
  2002年   52篇
  2001年   21篇
  2000年   18篇
  1999年   18篇
  1998年   16篇
  1997年   21篇
  1996年   9篇
  1995年   7篇
  1994年   9篇
  1993年   9篇
  1992年   5篇
  1991年   8篇
  1990年   7篇
  1989年   7篇
  1988年   5篇
  1987年   8篇
  1986年   7篇
  1985年   12篇
  1984年   10篇
  1983年   13篇
  1982年   8篇
  1980年   9篇
  1979年   9篇
  1978年   5篇
  1977年   11篇
  1976年   4篇
  1975年   4篇
  1973年   8篇
  1972年   4篇
排序方式: 共有1811条查询结果,搜索用时 203 毫秒
71.
Using tools from set-valued and variational analysis, we propose a mathematical formulation for a power DC-DC Buck converter. We prove the existence of trajectories for the model. A stability and asymptotic stability results are established. The theoretical results are supported by some numerical simulations with a discussion about explicit and implicit schemes.  相似文献   
72.
An efficient building block-based synthetic protocol has been developed for the synthesis of 3-ketosphingoids with various chain lengths using cross metathesis of a Garner’s aldehyde-derived α,β-unsaturated ketone as the key step. Stereoselective reduction of the biomimetic precursors thus obtained provided d-erythro-sphingosine and truncated anaogues in good overall yields.  相似文献   
73.
The synthesis and characterization of highly ordered three‐dimensional photonic crystals have been the subjects of intense study over the past two decades due to the unique ability of these structures to control light at the nanoscale. Building on that work in recent years, increasing interest is now focused on the unique optical properties of disordered and quasi‐ordered photonic structures. We present a study of the effects of shape anisotropy and disorder on the specular reflection properties of polymer‐based colloidal films comprised of rod‐shaped subunits of varying aspect ratio. We characterize the specular reflectance properties of these films as a function of their increasing levels of disorder, demonstrating progressive transition from resonant reflection to diffuse reflection. The onset of the diffuse reflection is governed by particle size. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys. 2014 , 52, 611–617  相似文献   
74.
Convergent routes to a variety of indolines, indoles, oxindoles, and their aza analogues involving radical additions of xanthates are described. Three approaches are summarized. The first is the least general and relies on the generation of aryl or heteroaryl radicals starting from diazonium salts. The second involves radical addition to N-allylanilines followed by ring-closure onto the aromatic core. A large variety of indolines and azaindolines can thus be obtained and, in many cases, converted into the corresponding indoles and azaindoles by various methods. The synthesis of novel fluoroazaindolines and fluoroazaindoles by a rare homolytic ipso-substitution of fluorine atoms is particularly noteworthy. The last approach hinges on the direct modification of indoles by radical addition to the pyrrole subunit of the indole nucleus. Application of this methodology to the total synthesis of melatonin and the alkaloids mersicarpine, caulerpine, and the pentacyclic skeleton of tronocarpine is briefly discussed. Most of the compounds described herein would be difficult to obtain by more traditional routes.  相似文献   
75.
76.
Lipotoxicity is defined as deposition of excess fat associated with an inflammatory response. Metabolomic analysis of fatty acids (FAs) can be a marker of silent inflammation. ω3-Enriched diet, celecoxib, and safranal may have a protective anti-inflammatory role. In this work, total FAs extracted from red blood cells and arachidonic acid-to-eicosapentaenoic acid (AA-to-EPA) ratios were assessed using GC–MS assay in single-ion monitoring mode. The study was conducted on 64 male rats divided into eight groups: I, controls; II, rats received high-fat diet (HFD), III, rats received ω-6-enriched HFD; IV, rats received ω-3-enriched HFD; V, rats received celecoxib with HFD; VI, rats received safranal with HFD; VII and VIII, rats received celecoxib and safranal with ω-3 HFD, respectively. GC–MS Gas chromatography Mass spectrometry was performed for analysis of fatty acid methyl ester. Enzyme-linked immunosorbent assay was used to analyze serum interleukin-6 (IL-6) and transforming growth factor-beta 1 (TGF-β1) concentrations. A statistically significant decrease of AA-to-EPA ratio was observed in group VII when compared with the groups receiving HFDs. This group also showed the lowest serum IL-6 level and highest TGF-β1 level. In conclusion, ω3-enriched diet along with drugs (e.g. celecoxib) and herbal medications (e.g. safranal) may have an anti-inflammatory effect in lipotoxicity. GC–MS with single-ion monitoring is valid for the analysis of FAs.  相似文献   
77.
This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2SiC6H4PPh2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2]. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.  相似文献   
78.
A simple CE method was developed and validated for the simultaneous determination of chlordiazepoxide (CHL), amitriptyline, and nortriptyline (mixture I) or the determination of CHL and imipramine (mixture II) using the same BGE. Sertraline and amitriptyline were used as internal standards for the first and second mixtures, respectively. The method allows amitriptyline to be completely separated from its impurity and main metabolite nortriptyline, which can be quantified from 0.2 μg/mL. The separation was achieved using 20 mM potassium phosphate buffer pH 5 containing 12 mM β‐cyclodextrin and 1 mM carboxymethyl‐β‐cyclodextrin. UV detection was performed at 200 nm and a voltage of 15 kV was applied on an uncoated fused‐silica capillary at 25°C. These experimental conditions allowed separation of the compounds to be obtained in 7 min. Calibration graphs proved the linearity up to 40 μg/mL for CHL, up to 100 μg/mL for amitriptyline and imipramine, and up to 5 μg/mL for nortriptyline. The accuracy and precision of the method have been determined by analyzing synthetic mixtures and pharmaceutical formulations. The analytical results were quite good in all cases indicating that the method was linear, sensitive, precise, accurate, and selective for both mixtures.  相似文献   
79.
Abstract

In continuing our efforts to develop new potent anticancer candidates, a new series of 9-ethylcarbazoles carrying at position 3 various heterocyclic substituents such as 2-imino-2H-chromenes 5a–e, 2-oxo-2H-chromenes 6a–e, 3-imino-3H-benzo[f]chromene 8, 3-oxo-3H-benzo[f]chromene 9, 2-pyridones 11, 14, pyrazole 19, pyrimidine 23, pyrido[1,2-a]pyrimidine 27, 2H-pyran-2-one 30, and pyrano[2,3-d]pyrimidinetrione 34 were efficiently synthesized, characterized and evaluated for their in vitro antitumor activity. The mechanism for the synthesis of compounds was also discussed. Most of the synthesized compounds were displayed the considerable anticancer activities against three human tumor cells lines, in particular, colon carcinoma (HCT-116), hepatocellular carcinoma (HepG-2) and breast cancer (MCF-7). Compound 6d proves as most active molecule in this study with special effectiveness against the human HCT-116 and HepG-2 as its IC50 values are 1.50, 0.90?μM, respectively, when doxorubicin is compared. Compound 34 was also found to have high activity against HepG-2, HCT-116 and moderate activity against MCF-7.  相似文献   
80.
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