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   1915篇
  免费   113篇
  国内免费   23篇
化学   1494篇
晶体学   23篇
力学   41篇
数学   144篇
物理学   349篇
  2023年   12篇
  2022年   5篇
  2021年   48篇
  2020年   44篇
  2019年   41篇
  2018年   27篇
  2017年   37篇
  2016年   70篇
  2015年   59篇
  2014年   88篇
  2013年   129篇
  2012年   192篇
  2011年   175篇
  2010年   115篇
  2009年   82篇
  2008年   125篇
  2007年   120篇
  2006年   110篇
  2005年   88篇
  2004年   83篇
  2003年   67篇
  2002年   61篇
  2001年   42篇
  2000年   49篇
  1999年   22篇
  1998年   23篇
  1997年   15篇
  1996年   7篇
  1995年   8篇
  1994年   7篇
  1993年   10篇
  1992年   7篇
  1991年   5篇
  1990年   3篇
  1989年   9篇
  1988年   4篇
  1987年   6篇
  1986年   5篇
  1985年   3篇
  1983年   7篇
  1982年   3篇
  1981年   4篇
  1979年   4篇
  1978年   4篇
  1977年   2篇
  1976年   4篇
  1975年   2篇
  1974年   5篇
  1973年   5篇
  1933年   2篇
排序方式: 共有2051条查询结果,搜索用时 234 毫秒
81.
Glutamic acid is readily converted into N-butenyl-2-pyrrolidi-none-5-carboxaldehyde. The novel butenyl protecting group allows the synthesis of this aldehyde which can be olefinated using standard Wittig methodology.  相似文献   
82.
Dialkyl, diaryl, and aryl alkyl sulfoxides can be rapidly converted to the corresponding sulfides with a WCl6/In system in excellent yields under mild conditions.  相似文献   
83.
Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs.  相似文献   
84.
The reactions of FeCl3 · 6H2O and 2‐(2′‐hydroxyphenyl)‐2‐thiazoline as a bidentate O‐N donor thiazoline ligand (thoz) afford a five‐coordinate FeIII complex [Fe(thoz)2Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz)2Cl] was isolated as air‐stable crystalline solids and fully characterized, including by single‐crystal X‐ray structure analysis. Complex [Fe(thoz)2Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air.  相似文献   
85.
We have developed a simple and powerful method, which is called ‘angled sample holder method’, to characterize a topographic structured sample such as microsized via hole of ball grid array using time‐of‐flight SIMS. The diameter of via holes was 100 µm and the depth was 70 µm. To remove the shaded area by incidence primary ion beam and to extract secondary ions from the bottom of a via hole, several types of angled sample holders with compensation steering plate were applied on the basis of simulation results using SIMION code. And the analyses using angled sample holder method enabled us to characterize the bottom and side wall of a via hole in clear. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
86.
A series of small molecules that contained identical π‐spacers (ethyne), a central diketopyrrolopyrrole (DPP) unit, and different aromatic electron‐donating end‐groups were synthesized and used in organic solar cells (OSCs) to study the effect of electron‐donating groups on the device performance. The three compounds, DPP‐A‐Ph , DPP‐A‐Na , and DPP‐A‐An , possessed intense absorption bands that covered a wide range, from 350 to 750 nm, and relatively low HOMO energy levels, from ?5.50 to ?5.55 eV. DPP‐A‐An , which contained anthracene end‐groups, demonstrated a stronger absorbance and a higher hole mobility than DPP‐A‐Ph , which contained phenyl groups, and DPP‐A‐Na , which contained naphthalene units. The power‐conversion efficiencies (PCEs) of OSCs based on organic:PC71BM blends (1:1, w/w) with a processed DIO additive were 3.93 % for DPP‐A‐An , 3.02 % for DPP‐Na , and 2.26 % for DPP‐A‐Ph . These findings suggest that a DPP core that is functionalized with electron‐donating capping groups constitutes a promising new class of solution‐processable small molecules for OSC applications.  相似文献   
87.
Plasma Chemistry and Plasma Processing - CF4 is commonly used in semiconductor industries, and its removal requires a large amount of energy because it is a highly stable perfluorinated compound....  相似文献   
88.
Scientists all over the world are facing a challenging task of finding effective therapeutics for the coronavirus disease (COVID-19). One of the fastest ways of finding putative drug candidates is the use of computational drug discovery approaches. The purpose of the current study is to retrieve natural compounds that have obeyed to drug-like properties as potential inhibitors. Computational molecular modelling techniques were employed to discover compounds with potential SARS-CoV-2 inhibition properties. Accordingly, the InterBioScreen (IBS) database was obtained and was prepared by minimizing the compounds. To the resultant compounds, the absorption, distribution, metabolism, excretion and toxicity (ADMET) and Lipinski's Rule of Five was applied to yield drug-like compounds. The obtained compounds were subjected to molecular dynamics simulation studies to evaluate their stabilities. In the current article, we have employed the docking based virtual screening method using InterBioScreen (IBS) natural compound database yielding two compounds has potential hits. These compounds have demonstrated higher binding affinity scores than the reference compound together with good pharmacokinetic properties. Additionally, the identified hits have displayed stable interaction results inferred by molecular dynamics simulation results. Taken together, we advocate the use of two natural compounds, STOCK1N-71493 and STOCK1N-45683 as SARS-CoV-2 treatment regime.  相似文献   
89.
90.
Although our previous study revealed that gamma-irradiated chrysin enhanced anti-inflammatory activity compared to intact chrysin, it remains unclear whether the chrysin derivative, CM1, produced by gamma irradiation, negatively regulates toll-like receptor (TLR) signaling. In this study, we investigated the molecular basis for the downregulation of TLR4 signal transduction by CM1 in macrophages. We initially determined the appropriate concentration of CM1 and found no cellular toxicity below 2 μg/mL. Upon stimulation with lipopolysaccharide (LPS), CM1 modulated LPS-stimulated inflammatory action by suppressing the release of proinflammatory mediators (cytokines TNF-α and IL-6) and nitric oxide (NO) and downregulated the mitogen-activated protein kinase (MAPK) and nuclear factor-κB (NF-κB) signaling pathways. Furthermore, CM1 markedly elevated the expression of the TLR negative regulator toll-interacting protein (Tollip) in dose- and time-dependent manners. LPS-induced expression of cell surface molecules (CD80, CD86, and MHC class I/II), proinflammatory cytokines (TNF-α and IL-6), COX-2, and iNOS-mediated NO were inhibited by CM1; these effects were prevented by the knockdown of Tollip expression. Additionally, CM1 did not affect the downregulation of LPS-induced expression of MAPKs and NF-κB signaling in Tollip-downregulated cells. These findings provide insight into effective therapeutic intervention of inflammatory disease by increasing the understanding of the negative regulation of TLR signaling induced by CM1.  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