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   429篇
  免费   17篇
  国内免费   5篇
化学   273篇
晶体学   6篇
力学   4篇
数学   90篇
物理学   78篇
  2023年   3篇
  2020年   7篇
  2019年   6篇
  2018年   3篇
  2016年   7篇
  2015年   8篇
  2014年   16篇
  2013年   22篇
  2012年   22篇
  2011年   19篇
  2010年   22篇
  2009年   14篇
  2008年   28篇
  2007年   18篇
  2006年   22篇
  2005年   12篇
  2004年   17篇
  2003年   13篇
  2002年   13篇
  2001年   5篇
  2000年   3篇
  1999年   5篇
  1997年   6篇
  1996年   6篇
  1995年   5篇
  1994年   4篇
  1993年   8篇
  1992年   4篇
  1987年   3篇
  1986年   3篇
  1985年   9篇
  1984年   7篇
  1983年   8篇
  1982年   7篇
  1981年   8篇
  1980年   7篇
  1979年   3篇
  1978年   7篇
  1977年   6篇
  1976年   3篇
  1974年   6篇
  1968年   3篇
  1967年   9篇
  1966年   4篇
  1963年   2篇
  1962年   6篇
  1956年   2篇
  1955年   2篇
  1954年   2篇
  1953年   2篇
排序方式: 共有451条查询结果,搜索用时 15 毫秒
1.
The main result is that to any even integer q in the interval 0 ≤ q ≤ 2n+1-2log(n+1), there are two perfect codes C1 and C2 of length n = 2m − 1, m ≥ 4, such that |C1C2| = q.  相似文献   
2.
The conformations and dynamic processes in two bicyclophanes have been analysed on the basis of temperature-dependent 1H NMR spectra. Both bicyclophanes are suggested to have a lowest-energy conformation of D3 symmetry in which the substituents at all ethylene bridges are gauche+ (or gauche?) oriented. The interconversion of the mirror image conformers of each bicyclophane equilibrates the two hydrogens in each methylene group, the barriers being ca 36 and 37 kJ mol?1, respectively, as determined by line-shape analysis.  相似文献   
3.
The complex forming properties of the thiazole azo dyestuffs and related compounds have been studied in order to try to ascertain the role of importance of the donor atoms present in thiazolylazo-resorcinol. Potentiometric titrations were employed for these determinations, although in many cases meaningful stability constants could not be obtained because of reagent instability or insolubility of the complexes formed on chelation.  相似文献   
4.
Tetracyanoethylene (TCNE) reacts with indolizines ( 1a-c ) to give mixtures of 1- and 3-sub-stituted tricyanovinylindolizines, respectively. The isomers are identified by nmr spectroscopy. The occurrence of intramolecular charge-transfer bands in the visible spectra is discussed.  相似文献   
5.
6.
Aromatic compounds including phenols, carboxylic acids and aldehydes, can be rapidly separated on pellicular anion-exchange resins in the acetate form by elution with a sodium acetate solution. Like the aromatic carboxylic acids, hydroxybenzaldehydes are held as counter ions in the resin. The affinity of the resin for corresponding anions as well as that for sorbed non-electrolytes is largely influenced by the aromatic ring and non-polar aliphatic substituents. Formation of hydrogen bonds between the resin and phenolic groups is less important.  相似文献   
7.
The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged.  相似文献   
8.
Quenching of the 3MLCT excited state of [Ru(bpy)3]2+ (bpy=bipyridine) by the reduction products (MV*+ and MV0) of methyl viologen (MV2+) was studied by a combination of electrochemistry with laser flash photolysis or femtosecond pump-probe spectroscopy. Both for the bimolecular reactions and for the reactions in an Ru(bpy)3(2+)-MVn+ dyad, quenching by MV*+ and MV0 is reductive and gives the reduced ruthenium complex [Ru(bpy)3]+, in contrast to the oxidative quenching by MV2+. Rate constants of quenching (kq), and thermal charge recombination (krec) and cage escape yields (phi(ce)) were determined for the bimolecular reactions, and rates of forward (kf) and backward (kb) electron transfer in the dyad were measured for quenching by MV2+, MV*+, and MV0. The reactions in the dyad are very rapid, with values up to kf = 1.3 x 10(12) s(-1) for *Ru(bpy)3(2+)-MV*+. In addition, a long-lived (tau = 15 ps) vibrationally excited state of MV*+ with a characteristically structured absorption spectrum was detected; this was generated by direct excitation of the MV*+ moiety both at 460 and 600 nm. The results show that the direction of photoinduced electron transfer in a Ru(bpy)3-MV molecule can be switched by an externally applied bias.  相似文献   
9.
Summary The interstitial volume in ion-exchange columns packed with beads of gel-type is a well defined quantity. The retention volumes of dextran and high relative molecular mass polyethylene glycols are identical. For macroreticular resins and cross linked polyvinylpyrrolidone the retention volume depends on the structure and relative molecular mass of the polymer indicating that no strict borderline exists between the resin phase and the mobile phase.  相似文献   
10.
Neutral half‐sandwich organometallic ruthenium(II) complexes of the type [(η6‐cymene)RuCl2(L)] ( H1 – H10 ), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single‐crystal X‐ray diffraction confirming a piano‐stool geometry with η6 coordination of the arene ligand. Hydrogen bonding between the N? H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metal–ligand interaction. Complexes coordinated to a mercaptobenzothiazole framework ( H1 ) or mercaptobenzoxazole ( H6 ) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1‐phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non‐intercalative fashion and cause unwinding of plasmid DNA in a cell‐free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase IIα activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen‐bond donor on the heterocycle reduces the cytotoxicity.  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