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   245篇
  免费   7篇
  国内免费   7篇
化学   154篇
晶体学   1篇
力学   15篇
数学   40篇
物理学   49篇
  2022年   2篇
  2021年   3篇
  2020年   6篇
  2019年   14篇
  2018年   11篇
  2017年   13篇
  2016年   20篇
  2015年   15篇
  2014年   16篇
  2013年   30篇
  2012年   18篇
  2011年   28篇
  2010年   18篇
  2009年   17篇
  2008年   12篇
  2007年   12篇
  2006年   2篇
  2005年   5篇
  2004年   3篇
  2003年   3篇
  2002年   1篇
  1994年   1篇
  1993年   1篇
  1992年   2篇
  1990年   1篇
  1982年   1篇
  1980年   2篇
  1979年   1篇
  1978年   1篇
排序方式: 共有259条查询结果,搜索用时 15 毫秒
71.
Colloidal silver nanoparticles were synthesized by γ-irradiation-induced reduction method of an aqueous solution containing silver nitrate as a precursor in various concentrations between 7.40×10?4 and 1.84×10?3 M, polyvinyl pyrrolidone for capping colloidal nanoparticles, isopropanol as radical scavenger of hydroxyl radicals and deionised water as a solvent. The irradiations were carried out in a 60Co γ source chamber at doses up to 70 kGy. The optical absorption spectra were measured using UV–vis spectrophotometer and used to study the particle distribution and electronic structure of silver nanoparticles. As the radiation dose increases from 10 to 70 kGy, the absorption intensity increases with increasing dose. The absorption peak λmax blue shifted from 410 to 403 nm correspond to the increase of absorption conduction electron energy from 3.02 to 3.08 eV, indicating the particle size decreases with increasing dose. The particle size was determined by photon cross correlation spectroscopy and the results showed that the particle diameter decreases exponentially with the increase of dose. The transmission electron microscopy images were taken at doses of 20 and 60 kGy and the results confirmed that as the dose increases the diameter of colloidal silver nanoparticle decreases and the particle distribution increases.  相似文献   
72.
Various aryl aldehydes underwent prompt one pot conversion into the corresponding nitriles in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation in the presence of ammonium acetate as catalyst.  相似文献   
73.
The 1:1 adduct of N,N′‐bis(2‐chlorobenzylidene)ethylenediamine (cb2en) with copper(I) chloride proves to be an ionic compound with CuI‐centred cations and anions, [Cu(C16H14Cl2N2)2][CuCl2]·CH3CN. In the cation, the CuI atom has a flattened tetrahedral coordination geometry, with a small bite angle for the chelating ligands, which form a double‐helical arrangement around the metal centre. The anion is almost linear, as expected. The packing of the cations involves intermolecular π–π interactions, which lead to columns of translationally related cations along the shortest unit‐cell axis, with anions and solvent molecules in channels between them.  相似文献   
74.
The 4-chloromethyl styrene (CMS) was copolymerized with different styrenic monomers such as methyl styrene, 4-methoxy styrene and α-methyl styrene by free radical polymerization method at 70 ± 1 °C using α,α-azobis(isobutyronitrile) (AIBN) as an initiator and the copolymers I, II and III collected respectively. The very bulky tris(trimethylsilyl)methyl {trisyl} substituents were covalently attached to the obtained copolymers with replacement of all the chlorine atoms in CMS units. The polymers, obtained in quantitative yields, were characterized by FT-IR, 1H NMR and 13C NMR spectroscopy; differential scanning calorimetry (DSC) and GPC studies. All the polymers containing trisyl groups showed a high glass transition temperature (in the range 150-190 °C) in comparison with copolymers I-III (in the range 90-95 °C). The increase of the glass transition temperature reflects the substantial increase in rigidity of new polymers bearing very bulky substituents in side chains.  相似文献   
75.
The interaction of 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (Kryptofix5) with alkali-metal cations (Li+, Na+, K+) in aprotic medium (acetonitrile) has been investigated. Conductance measurements demonstrated that 1:1 metal cation:ligand stoichiometries are found with these cations in this solvent. 7Li and 23Na NMR experiments were carried out by titration of the metal cation solutions with Kryptofix5 solution in CD3CN + CH3CN at 298 K. Thermodynamic parameters of complexation for this ligand and alkali-metal cations in acetonitrile at 278–308 K were derived from titration conductometry. The highest stability is found for sodium complex. The complexation sequence, based on the value of log K at 278–308 K was found to be Na+ > K+ > Li+.  相似文献   
76.
77.
Benzyl chloride was treated with (Me3Si)3CLi to give (Me3Si)3CCH2Ph (1). A new styrene derivative, (Me3Si)3CCH2C6H4(CHCH2-p) (2), was synthesized by reaction of p-vinylbenzyl chloride with (Me3Si)3CLi in the presence of CuCl. Addition and oxidation reactions on 2 gave a series of new compounds (Me3Si)3CCH2C6H4X-p (X = CH2CH3, CHBrCH2Br, CHClCH2I, CHBrCH2I, cyclo-C3H3Cl2, CHOHCH2OH, COOH, CH2OH).  相似文献   
78.
The compound (Me3Si)3CSiPh2F loses Me3SiF under reflux or on passage through a tube at 450°C to give three products, A, B, and C, in approximately 20/20/60 ratio. Products A and B, which are solids, were shown by X-ray crystallographic analysis to be the diastereoisomeric forms of 1-dimethylsila-2-trimethylsilyl-3-[(methyl)(phenyl)sila]indane. From its mass and 1H NMR spectra, C (a liquid) was tentatively identified as 1,3-bis(dimethylsila)-2-[(dimethyl)(phenyl)silyl]indane. All three products are isomers of the sila-olefin (Me3Si)2CSiPh2, and it is suggested that the latter is first formed by loss of Me3SiF from (MeSi)3CSiPh2F, and the equilibrium (Me3Si)2CSiPh2 ? (Me3Si)(Ph2MeSi)CSiMe2 ? (Me3Si)(PhMe2Si)CSiMePh ? (Me2PhSi)2CSiMe2 is then rapidly established; internal cyclizations involving addition of aryl CH bonds across SiC bonds then occur to give the observed products. Consistent with this is the observation that a mixture of silicon alkoxides, thought to be (Me3Si)2CHSiPh2OMe and its isomers (which would be formed by addition of methanol across the SiC bonds of the four sila-olefins) is produced when methanol is passed through the hot tube with the (Me3Si)3CSiPh2F.Full structural details are given for compounds A and B. Some features of interest are: (a) the conformation of the 5-membered ring is different in the two diastereoisomers; (b) the exocyclic SiCSiMe3 bond angles, of ca. 120° are unusually large; and (c) there is a little distortion of the fused benzene ring, which is attributed to the effect of silicon substituents on the hybridization of carbon atoms to which they are attached.  相似文献   
79.
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