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   504篇
  免费   15篇
  国内免费   3篇
化学   412篇
晶体学   2篇
力学   7篇
数学   46篇
物理学   55篇
  2023年   3篇
  2022年   15篇
  2021年   13篇
  2020年   11篇
  2019年   15篇
  2018年   7篇
  2017年   5篇
  2016年   16篇
  2015年   14篇
  2014年   11篇
  2013年   34篇
  2012年   32篇
  2011年   30篇
  2010年   21篇
  2009年   9篇
  2008年   20篇
  2007年   19篇
  2006年   31篇
  2005年   20篇
  2004年   18篇
  2003年   15篇
  2002年   25篇
  2001年   11篇
  2000年   6篇
  1999年   8篇
  1998年   6篇
  1997年   4篇
  1996年   6篇
  1995年   4篇
  1994年   3篇
  1993年   8篇
  1992年   6篇
  1991年   3篇
  1990年   6篇
  1989年   5篇
  1988年   4篇
  1987年   3篇
  1986年   6篇
  1985年   10篇
  1984年   3篇
  1983年   4篇
  1982年   2篇
  1981年   6篇
  1978年   3篇
  1974年   2篇
  1973年   3篇
  1972年   3篇
  1971年   2篇
  1956年   1篇
  1935年   1篇
排序方式: 共有522条查询结果,搜索用时 15 毫秒
1.
2.
In this paper, we study the central limit theorem and its weak invariance principle for sums of a stationary sequence of random variables, via a martingale decomposition. Our conditions involve the conditional expectation of sums of random variables with respect to the distant past. The results contribute to the clarification of the central limit question for stationary sequences. Magda Peligrad is supported in part by a Charles Phelps Taft research support grant at the Univeristy of Cincinnati and the NSA grant H98230-05-1-0066.  相似文献   
3.
The growth and oxygen consumption of a variety of thermophilic, acidophilic bacteria in the presence of thiophene-2-carboxylate (T2C) and dibenzothiophene (DBT) have been determined. T2C was extremely toxic to the acidophiles in comparison with neutrophiles, but appeared to be degraded by a heterotrophicSulfolobus- like thermophile. DBT proved to be unstable at high temperatures, even in the absence of bacteria, and was not a substrate for the thermophiles.  相似文献   
4.
The results of magnetic resonance studies on ferrimagnetic (GdxY1?x)Co2 compounds, both below and above the Curie points, are presented. The ferrimagnetic resonance measurements show that the effective g values can be described by using the Wangsness relation. The spectroscopic splitting factors of cobalt atoms are not composition dependent. In the paramagnetic range the thermal variation of the linewidth is not linear and the g values are a function of temperature. This behavior is analyzed in correlation with the magnetic data.  相似文献   
5.
The spectrophotometric and thermodynamic properties of different substituted methylnaphthalenes charge transfer (CT) complexes with tetracyanoethylene have been studied in carbon tetrachloride. The spectral characteristics of the CT bands have also been discussed in relation to the positions of methyl groups. The formation constants and the spectral properties of the complexes are markedly affected with the substitution position of the methyl groups. The ionization potentials of the donors are determined.  相似文献   
6.
Complexes of Co(II), Ni(II) and Cu(II) with substituted phenylazo-6-aminouracils containing (-H, p-OH, p-CH(3), p-OCH(3) p-COOH) have been synthesized and characterized by elemental analysis, magnetic measurements and spectral measurements (IR, UV-Vis, ESR). Infrared spectra assigned the fundamental bands of the major groups, O-H, N-H, C-H, C=O, C=N, N=N, C-N and C-O (nu, delta and gamma modes of vibrations). The absence of nu(OH) and the appearance of nu(C=O) in the infrared spectra of the free ligands of 5-(p-tolyl and p-anisylazo)-6-aminouracil, assigned the keto structure, whereas in cases of 5-(phenyl, p-hydroxyphenyl and p-carboxyphenylazo)-6-aminouracil ligands, the data showed strong nu(OH) and nu(C=O) bands to assign keto-enol tautomerisms. The modes of interactions between the ligands and the metals were discussed, where oxygen and nitrogen atoms (of amino-amide groups) are involved in chelation. The azo group was not involved in chelation for all the prepared complexes except those of copper complexes derived from 5-(phenyl, p-tolyl, p-hydroxyphenyl and p-carboxyphenylazo)-6-aminouracils. The room temperature effective magnetic moment values, the Nujol mull spectra and ESR proved that all the prepared complexes were of octahedral geometry, except the nickel complex derived from 5-(phenylazo)-6-aminouracil and cobalt complex derived from 5-(p-carboxy-phenylazo)-6-aminouracil were square planar.  相似文献   
7.
Zusammenfassung Es wurden 34 neue Komplexsalze durch doppelte Umsetzung aus wäßr.-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)4(m-xylidin)2], [Cr(NCS)4(p-xyl)2] und Hexammin-, Monoacido-pentammin- und Diacido-tetramminkobalt(III)-komplexsalze erhalten. Es wurden in einigen Fällen Unterschiede in physiko-chemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR f-Werte, bei den stellungsisomeren Salzen vom Typus: Kation · [Cr(NCS)4(xyl)2] und auch bei den Koordinationsisomerpaaren: [Co(DH)2(m-xyl)2] [Cr(NCS)4(p-xyl)2] und [Co(DH)2(p-xyl)2] [Cr(NCS)4(m-xyl)2] usw. beobachtet.
Cobalt(III)ammine derivatives of some reineckate analogues with xylidines
34 new complex salts were prepared by double conversion of the reineckate analogues [Cr(NCS)4(m-xylidine)2], [Cr(NCS)4(p-xyl)2], with the hexammine-, monoacido-pentammine- and diacidotetrammine-complexes of Co(III). In some of the position and coordination isomeres differences of the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR f-values were observed.
  相似文献   
8.
Reaction of 2-acetonyl-4,5-dimethoxy-3′-chlorobenzophenone (1) with ethylenediamine afforded the imidazo[2,1-a]isoquinoline 2, whereas 6-(3-chlorophenyl)-8,9-dimethoxybenzo[b]phenazine (3) and naphthol 4 were obtained with ortho-phenylenediamine.  相似文献   
9.
The silver-assisted ligand metathesis reaction involving a platinum(II) complex of formula [PtClMe(N,N-chelate)] with acetonitrile has been investigated. By using a suitably hindered N,N-chelate, an otherwise hardly detectable trinuclear species has been isolated and characterized through X-ray diffractometry. The trinuclear cation consists of two nearly orthogonal [PtCl(Me)(N,N-chelate)] square-planar units entrapping an Ag(+) cation through the chloride ligands that, acting as bidentate, form a linear AgCl(2) unit with two nonequivalent Ag-Cl bonds. The residual acidity of the silver cation is satisfied by one secondary Ag-Pt interaction [Ag-Pt(1) = 2.82 A] in which the platinum atom acts as a donor. Kinetic studies have demonstrated that the silver assistance operates both through a simple associative step and through a pathway in which the above trinuclear complex is an active intermediate. In a noncoordinating solvent the latter species evolves with AgCl loss and formation of a dinuclear Pt,Pt complex showing a rare single chloride bridge.  相似文献   
10.
The mixed crystals of 1,2-bis(diethylaminomethyl)-3,6-di- and 3,4,6-trichloro-benzene perchlorate at 0.5:0.5 ratio have been studied using X-ray diffraction and FT-IR spectroscopy. The molecules of di- and tri-chloro derivatives are distributed randomly in the crystal lattice; however, this disorder manifested mainly by a partial occupation of the chlorine atom at C(4) and by relatively big atomic temperature parameters even at 99 K, particularly for the oxygens of the perchlorate anion. The proton in the [NHN]+ bond refined close to the equidistant position between the nitrogens. The conformations of the diethylaminomethyl substituents are pseudo-symmetrical relative to the plane and twofold axis passing through the midpoint of the hydrogen bond. The IR spectrum of the crystals shows a broad intense band and an intense continuous absorption indicating relatively high proton polarizability in the intramolecular hydrogen bond. In acetonitrile and in chloroform, the proton in the intramolecular hydrogen bond also shows a very high proton polarizability demonstrated by the continuous absorption in the IR spectrum.  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