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   4357篇
  免费   716篇
  国内免费   419篇
化学   3107篇
晶体学   42篇
力学   268篇
综合类   46篇
数学   426篇
物理学   1603篇
  2024年   11篇
  2023年   122篇
  2022年   111篇
  2021年   168篇
  2020年   211篇
  2019年   161篇
  2018年   139篇
  2017年   120篇
  2016年   198篇
  2015年   171篇
  2014年   240篇
  2013年   264篇
  2012年   380篇
  2011年   364篇
  2010年   267篇
  2009年   267篇
  2008年   282篇
  2007年   273篇
  2006年   271篇
  2005年   182篇
  2004年   126篇
  2003年   110篇
  2002年   98篇
  2001年   86篇
  2000年   86篇
  1999年   101篇
  1998年   91篇
  1997年   89篇
  1996年   68篇
  1995年   91篇
  1994年   75篇
  1993年   44篇
  1992年   59篇
  1991年   45篇
  1990年   40篇
  1989年   26篇
  1988年   16篇
  1987年   14篇
  1986年   8篇
  1985年   8篇
  1984年   4篇
  1983年   1篇
  1982年   2篇
  1981年   1篇
  1980年   1篇
排序方式: 共有5492条查询结果,搜索用时 31 毫秒
151.
Reaction of either K3[Fe(CN)6] or K4[Fe(CN)6] with a macrocyclic CuII complex, [Cu(teta)](ClO4)2 (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane), in aqueous solution gave the same product as shown by spectroscopic and physicochemical characterisation. The crystal structure of the complex shows that it is a one-dimensional linear chain type heterobinuclear FeIII–CuII polymer. The unit is composed of a [Cu(teta)(H2O)2]2+ cationic complex, a FeIII–CuII alternate linear chain unit, a ClO 4 ion and four water molecules. The Cu atom is coordinated in a distorted octahedral arrangement by four nitrogen atoms from one teta ligand and two nitrogen atoms of the bridging cyanide groups. The Cu—N bond distances involving the cyanide bridges, 2.522(7) and 2.608(7)Å, respectively, indicate weak antiferromagnetic interactions between the FeIII and CuII atoms.  相似文献   
152.
莫金垣  张润建 《分析化学》1995,23(3):255-258
本文提出平行催化体系的对位叠式循环方波伏安法,并对共作了系统的研究,推导了这一方法的催化电流理论方程,并用验验证这理论的正确性,得到其各脉冲电流皆为同方向,对位叠式循环催化电流相当于将电流叠加4次,而波形不受方波幅度大小的影响,因而灵敏度和分辨率有较大提高,优于其它方波伏安法。  相似文献   
153.
Copper-catalyzed azide-alkyne cycloaddition polymerization (CuAACP) of AB2 monomers demonstrated a chain-growth mechanism without any external ligand because of the complexation of in situ formed triazole groups with Cu catalysts. In this study, we explored the use of various ligands that affected the polymerization kinetics to tune the polymers’ molecular weights and the degree of branching (DB). Eight ligands were studied, including polyethylene glycol monomethyl ether (PEG350, Mn = 350), tris(benzyltriazolylmethyl)amine (TBTA), 2,6-bis(1-undecyl-1H-benzo[d]imidazol-2-yl)pyridine (Py(DBim)2), 2,2′-bipyridyl (bpy), 4,4′-di-n-nonyl-2,2′-bipyridine (dNbpy), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), N,N,N′,N″,N″-penta(n-butyl)diethylenetriamine (PBuDETA), and N,N,N′,N″,N″-pentabenzyldiethylenetriamine (PBnDETA). All ligands except PEG350 exhibited stronger coordination with Cu(I) than the polytriazole polymer, which freed the Cu catalyst from polymers and resulted in dominant step-growth polymerization with simultaneous chain-growth feature. Meanwhile, the use of PEG350 ligand retained the confined Cu in the polymer, demonstrating a chain-growth mechanism, but lower polymer molecular weights as compared with the no-external-ligand polymerization. Results indicated that aliphatic substituent groups on ligands had little effect on the molecular weights and DB of the polymers, but rigid aromatic substituent groups decreased both values. By varying the ligand species and amounts, hyperbranched polymers with DB value ranging from 0.53 ([TBTA]0/[Cu]0 = 5) to 0.98 ([PMDETA]0/[Cu]0 = 2) have been achieved. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2238–2244  相似文献   
154.
Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H+/K+‐ATPase inhibitor via one‐pot CuI‐catalyzed three‐component click reaction of azide, secondary amine and 3‐bromopropyne under mild conditions in water. Their structures were characterized by NMR, IR, ESI‐MS, elemental analysis and single‐crystal X‐ray diffraction analysis. Most of the target compounds exhibited better H+/K+‐ATPase inhibitory activity than commercial omeprazole with IC50 values less than 15 µmol·L?1. The initial structure‐activity analysis suggested that the triazole substituted by cycloalkyl, aromatic ring or O‐containing side‐chain seemed to be beneficial for enhancing the activity.  相似文献   
155.
Nowadays sodium-based energy storage systems (Na-based ESSs) have been widely researched as it possesses the possibility to replace traditional energy storage media to become next generation energy storage system. However, due to the irreversible loss of sodium ions in the first cycle, development of Na-based ESSs is limited. Presodiation, as a strategy of adding excess sodium ions to the system in advance, accomplishes the enhancement of electrochemical performance. In this minireview, different presodiation strategies applied in sodium-based energy storage systems will be summarized in detail, their functions and corresponding mechanisms will be discussed as well. Furthermore, the current novel application of presodiation method in other aspects of Na-based ESSs will be mentioned additionally. At last, in the view of present research status of presodiation, issues that can be mitigated are put forward and guidelines are given on how to deliberate in-depth presodiation technology in the future, dedicating to promote the further development of Na-based ESSs.  相似文献   
156.
In this study, a simple and sensitive LC/MS/MS method was developed and validated for the determination of arctigenin in rat plasma. The MS detection was performed using multiple reaction monitoring at the transitions of m/z 373.2 → 137.3 for arctigenin and m/z 187.1 → 131.0 for psoralen (internal standard) with a Turbo IonSpray electrospray in positive mode. The calibration curves fitted a good linear relationship over the concentration range of 0.2–500 ng/mL. It was found that arctigenin is not stable enough at both room temperature and ?80 °C unless mixed with methanol before storage. The validated LC/MS/MS method was successfully applied for the pharmacokinetic study of arctigenin in rats. After intravenous injection of 0.3 mg/kg arctigenin injection to rats, the maximum concentration, half‐life and area under the concentration–time curve were 323 ± 65.2 ng/mL, 0.830 ± 0.166 and 81.0 ± 22.1 h ng/mL, respectively. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
157.
Dinuclear ytterbium and erbium based bifunction complexes Ln2L2(depma2)Cl2 (1-Ln, Ln = Yb and Er, H2L = N1,N3-bis(salicylideneimino)diethylenetriamine, depma2 = dimerized 9-diethyl-phosphonomethylanthracene) are reported. They undergo thermo-induced consecutive phase transitions, first the dissociation of depma2 ligand forming LnL(depma)Cl (2-Ln) and then the release of chloroethane forming LnL(epma) (3-Ln, epma = 9-ethylphosphonomethylanthrancene). The structural transformations are accompanied with synergetic switch of the luminescence in visible and NIR regions and also magnetic dynamics.  相似文献   
158.
159.
Zou  Fan  Zuo  Jing  Geng  Chao  Li  Feng  Huang  Guan  Liu  Jiaying  Jiang  Jiali  Fan  Zhihua  Li  Xinyang 《Journal of Russian Laser Research》2021,42(4):462-467
Journal of Russian Laser Research - Laser aiming is one of the key technologies of laser atmospheric transmission. The beam actually is affected by atmospheric turbulence and mechanical vibration;...  相似文献   
160.
Three new steroidal compounds with polyhydroxy groups, tupisteroide A–C (1–3), were obtained from the roots of Tupistra chinensis, together with one known compound (4) that was isolated from this plant for the first time. The structures of tupisteroide A–C were determined on the basis of one‐ and two‐dimensional NMR spectroscopy, including 1H–1H Correlation Spectroscopy, Heteronuclear Multiple Bond Correlation, and Heteronuclear Single Quantum Coherence experiments. The isolated compounds were evaluated for their cytotoxic activities against A549, HepG2, and CaSki cancer cell lines in vitro. Among them, compounds 1, 2, and 4 did not show significant inhibitory activity, but compound 3 showed cytotoxicity against A549 cancer cell lines with IC50 values of 25.0 μM. Copyright © 2012 John Wiley & Sons, Ltd.  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