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   2455篇
  免费   97篇
  国内免费   171篇
化学   926篇
晶体学   12篇
力学   25篇
综合类   22篇
数学   160篇
物理学   1578篇
  2024年   5篇
  2023年   56篇
  2022年   48篇
  2021年   51篇
  2020年   65篇
  2019年   73篇
  2018年   98篇
  2017年   68篇
  2016年   91篇
  2015年   72篇
  2014年   96篇
  2013年   148篇
  2012年   150篇
  2011年   202篇
  2010年   127篇
  2009年   132篇
  2008年   163篇
  2007年   144篇
  2006年   128篇
  2005年   91篇
  2004年   85篇
  2003年   82篇
  2002年   83篇
  2001年   63篇
  2000年   79篇
  1999年   67篇
  1998年   50篇
  1997年   24篇
  1996年   19篇
  1995年   23篇
  1994年   21篇
  1993年   14篇
  1992年   11篇
  1991年   11篇
  1990年   8篇
  1989年   15篇
  1988年   7篇
  1987年   10篇
  1986年   12篇
  1985年   7篇
  1984年   10篇
  1981年   4篇
  1979年   2篇
  1977年   1篇
  1976年   2篇
  1974年   2篇
  1973年   1篇
  1972年   1篇
  1967年   1篇
排序方式: 共有2723条查询结果,搜索用时 62 毫秒
51.
王群  谢去病 《中国物理 C》1994,18(8):702-705
从强子化过程的两个基本性质出发,在夸克随机组合框架上,得出了包括所有激发态在内的重子产生权重的一组基本关系.解释了“自旋抑制”和单态重子产额大的原因.最后,讨论了进一步确定激发态重子产生比例的条件和方法.  相似文献   
52.
本文用自旋捕捉-ESR技术研究了二茂戊铁、环二烯和胺甲基类取代二茂铁的紫外光解过程中的活泼自由基。结果表明,二茂铁光解初级过程中生成的自由基为(C_5H_5Fe)·和C_5H_5·,其衍生物光解则生成(C_5H_5Fe)·和RC_5H_4·,而(C_5H_5Fe)·还可以进一步分解给出C_5H_5和Fe。  相似文献   
53.
The 1,2-diphcnylethyl radical and derivatives were generated from photolysis of tran-f-stilbene and its derivatives 1–13 with secondary amines as quenchers. The 1,2-diphenylelhyl radicals that escaped from the solvent cage were trapped by 2-methyl-2-nitrosopropane (MNP) and were detected by the HPLCEPR method. The yield of the spin adduct is greater for tertiary amines. The smaller yields of the spin adduct formed from secondary amines are ascribed to greater reactivities of the 1,2-diphenylethyl and dialkylamino radicals within the solvent cage.  相似文献   
54.
One of the most important trends in the spin crossover (SCO) field is focused on the synthesis of new molecule-based functional materials in which the SCO properties may be combined with other physical or chemical properties in a synergic fashion. The current stage of investigations regarding interplay and synergic effects between SCO, magnetic coupling, liquid crystalline properties, host-guest interactions, non-linear optical properties, electrical conductivity, and ligand isomerization is highlighted and discussed.  相似文献   
55.
Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(2--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and 2--CyD. GUG--CyD and 2--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and 2--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and 2--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs.  相似文献   
56.
The complex [Ru(II)(dcbpyH2)(bdmpp)NCS](PF6) (1) (where dcbpyH2 is 2,2′-bipyridine-4,4′-dicarboxylic acid, bdmpp is 2,6-bis(3,5-dimethyl-N-pyrazoyl)pyridine,) is synthesized and characterized extensively by 1H NMR and 13C NMR 1D and 2D, mass spectroscopy, cyclic voltammetry, electronic absorption spectroscopy and IR. The half-wave potential of the Ru(II)/Ru(III) redox couple was measured at E1/2=+0.795 V versus Ag/AgCl in CH3CN. The complex presents three intense metal-to-ligand charge transfer (MLCT) (dM→πL*) absorption bands centered at 383 (=21 300 M−1 cm−1), 432 (=22 400 M−1 cm−1) and 475 nm (=23 400 M−1 cm−1), respectively. The absorbance is extremely strong between 400 and 500 nm and even at 620 nm, the extinction coefficient is still high (=3768 M−1 cm−1). The strong π-acceptor property of the trans-isothiocyanate ligand compared with the Cl ligand is probably the cause of the blue-shift observed in complex 1. These properties make the complex potentially promising for the photosensitization process. The incorporation of TiO2 photoelectrodes derivatized with this complex into a solar cell using a composite polymer/inorganic oxide solid-state electrolyte confirmed its sensitizing ability. Incident monochromatic photon-to-current conversion efficiency (IPCE) values of about 30% and overall energy conversion efficiency (η) of 1.7% were obtained.  相似文献   
57.
We investigate then limit of then-vector model single-spin and pairspin correlation functions. In this limit we show that the correlation functions become those of the corresponding spherical model.  相似文献   
58.
A new ion-pair complex, [1-(4′-chlorobenzyl)-4-aminopyridinium](+)bis(maleonitrile-dithiolato)nickel(−),[ClbzPyNH2][Ni(mnt)2] (1), has been prepared and characterized. X-ray single crystal structure conforms that the Ni(mnt)2 anions and [ClbzPyNH2]+ cations of 1 form completely segregated uniform stacking columns with the Ni?Ni distance 3.944 Å in the Ni(mnt)2 stacking column. The temperature dependence of the magnetic susceptibility reveals that 1 undergoes a magnetic transition, and exhibits ferromagnetic interaction in the high-temperature phase and spin gap system in the low-temperature phase.  相似文献   
59.
The complexing (in CHCl3) and extracting abilities of 18-crown-6 type compounds (1–15) were measured with Li, Na, K and NH4 cations. The substituents on the sugar part affected these properties significantly (K a=103–107). Some substituents, like acetyloxy groups (3) decreased whereas others, like tosyloxy groups (10, 11) significantly increased the complexing ability and thus changed the selectivity. The compound with four tosyloxy groups (11) shows an excellent picrate salt extracting ability in a CH2Cl2-water system.  相似文献   
60.
The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5–2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed.  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