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   2129篇
  免费   154篇
  国内免费   125篇
化学   1649篇
晶体学   11篇
力学   61篇
综合类   9篇
数学   355篇
物理学   323篇
  2023年   20篇
  2022年   28篇
  2021年   36篇
  2020年   41篇
  2019年   46篇
  2018年   34篇
  2017年   28篇
  2016年   66篇
  2015年   81篇
  2014年   83篇
  2013年   106篇
  2012年   141篇
  2011年   156篇
  2010年   87篇
  2009年   96篇
  2008年   151篇
  2007年   153篇
  2006年   131篇
  2005年   125篇
  2004年   118篇
  2003年   101篇
  2002年   116篇
  2001年   73篇
  2000年   43篇
  1999年   43篇
  1998年   23篇
  1997年   21篇
  1996年   22篇
  1995年   19篇
  1994年   19篇
  1993年   8篇
  1992年   12篇
  1991年   10篇
  1990年   14篇
  1989年   5篇
  1988年   8篇
  1987年   8篇
  1986年   9篇
  1985年   12篇
  1984年   10篇
  1983年   7篇
  1982年   13篇
  1981年   11篇
  1980年   10篇
  1979年   12篇
  1978年   12篇
  1977年   5篇
  1976年   7篇
  1975年   4篇
  1974年   9篇
排序方式: 共有2408条查询结果,搜索用时 78 毫秒
221.
应用动态应变测试方法对悬挂式残膜回收机悬挂架进行实地动应力测 试,通过数据处理及其分析,得到悬挂架在工作条件下的应力状态,以及不同工作状态下各 构件的应力情况,并对悬挂架进行了疲劳强度分析,为进一步改进设计提供必要的理论依据.  相似文献   
222.
Short α‐peptides with less than 10 residues generally display a low propensity to nucleate stable helical conformations. While various strategies to stabilize peptide helices have been previously reported, the ability of non‐peptide helical foldamers to stabilize α‐helices when fused to short α‐peptide segments has not been investigated. Towards this end, structural investigations into a series of chimeric oligomers obtained by joining aliphatic oligoureas to the C‐ or N‐termini of α‐peptides are described. All chimeras were found to be fully helical, with as few as 2 (or 3) urea units sufficient to propagate an α‐helical conformation in the fused peptide segment. The remarkable compatibility of α‐peptides with oligoureas described here, along with the simplicity of the approach, highlights the potential of interfacing natural and non‐peptide backbones as a means to further control the behavior of α‐peptides.  相似文献   
223.
224.
225.
The association of Mg2+ and H2PO4? in water can give insights into Mg:phosphate interactions in general, which are very widespread, but for which experimental data is surprisingly sparse. It is studied through molecular dynamics simulations (>100 ns) by using the polarizable AMOEBA force field, and the association free energy is computed for the first time. Explicit consideration of outer‐sphere and two types of inner‐sphere association provides considerable insight into the dynamics and thermodynamics of ion pairing. After careful assessment of the computational approximations, the agreement with experimental values indicates that the methodology can be extended to other inorganic and biological Mg:phosphate interactions in solution.  相似文献   
226.
The quantum chemical method was applied for screening functional monomers in the rational design of salbutamol‐imprinted polymers. Salbutamol was the template molecule, and methacrylic acid was the single functional monomer. The LC‐WPBE/6–31G(d,p) method was used to investigate the geometry optimization, active sites, natural bond orbital charges, binding energies of the imprinted molecule, and solvation energy. The mechanism of action between salbutamol and methacrylic acid was also discussed. The theoretical results show that salbutamol interacts with functional monomers by hydrogen bonds, and the salbutamol‐imprinted polymers with a ratio of 1:4 (salbutamol/methacrylic acid) in acetonitrile had the highest stability. The salbutamol‐imprinted polymers were prepared by precipitation polymerization. The experimental results indicated that the maximum adsorption capacity for salbutamol toward molecularly imprinted polymers was 7.33 mg/g, and the molecularly imprinted polymers had a higher selectivity for salbutamol than for norepinephrine and terbutaline sulfate. Herein, the studies can provide theoretical and experimental references for the salbutamol molecular imprinted system.  相似文献   
227.
228.
Daphenylline, a novel daphniphyllum alkaloid, boasts a fused and bridging ring system coupled with six stereogenic centers. Here we present a direct and short construction of the ACDE ring system of daphenylline from the known 3‐(2‐bromophenyl)propanal in 10 steps and 17 % overall yield. The synthesis features an iron(III)‐catalyzed aza‐Cope‐Mannich reaction, a self‐terminating 6‐exo‐trig aryl radical‐alkene cyclization and an intramolecular Friedel–Crafts acylation.  相似文献   
229.
The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two‐step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β‐alanine betaine G5 , which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea‐based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen‐bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self‐associate. Remarkably, host 6 is able to perform solid–liquid as well as liquid–liquid extraction of G5 . Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.  相似文献   
230.
The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O2 has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN3) served as a clean high‐temperature source of NCN radicals. NCN concentration–time profiles have been detected by narrow‐bandwidth laser absorption at cm?1. The experiments behind incident shock waves have been performed with up to 17% O2 in the reaction gas mixture. At such high O2 mole fractions, it was necessary to take O2 relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN3 and collision‐induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100‐μs timescale. This delayed NCN formation was attributed to a fast recombination of 1NCN with O2 forming a 3NCNOO adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O2 have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar.  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