全文获取类型
收费全文 | 18069篇 |
免费 | 1113篇 |
国内免费 | 34篇 |
专业分类
化学 | 13633篇 |
晶体学 | 96篇 |
力学 | 355篇 |
综合类 | 1篇 |
数学 | 2709篇 |
物理学 | 2422篇 |
出版年
2023年 | 128篇 |
2022年 | 86篇 |
2021年 | 165篇 |
2020年 | 255篇 |
2019年 | 311篇 |
2018年 | 187篇 |
2017年 | 185篇 |
2016年 | 625篇 |
2015年 | 668篇 |
2014年 | 694篇 |
2013年 | 1250篇 |
2012年 | 1275篇 |
2011年 | 1178篇 |
2010年 | 803篇 |
2009年 | 677篇 |
2008年 | 1143篇 |
2007年 | 1057篇 |
2006年 | 1045篇 |
2005年 | 948篇 |
2004年 | 835篇 |
2003年 | 698篇 |
2002年 | 702篇 |
2001年 | 324篇 |
2000年 | 313篇 |
1999年 | 169篇 |
1998年 | 141篇 |
1997年 | 154篇 |
1996年 | 195篇 |
1995年 | 136篇 |
1994年 | 133篇 |
1993年 | 153篇 |
1992年 | 132篇 |
1991年 | 90篇 |
1990年 | 94篇 |
1989年 | 85篇 |
1988年 | 81篇 |
1986年 | 98篇 |
1985年 | 127篇 |
1984年 | 132篇 |
1983年 | 93篇 |
1982年 | 125篇 |
1981年 | 125篇 |
1980年 | 135篇 |
1979年 | 129篇 |
1978年 | 126篇 |
1977年 | 119篇 |
1976年 | 123篇 |
1975年 | 102篇 |
1974年 | 102篇 |
1973年 | 79篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
181.
José Fernández Bertrán Boris La Serna Klaus Doerffel Klaus Dathe Gunther Kabish 《Journal of Molecular Structure》1982
The Fermi doublet V2?V3 + V4 of CH3CN in basic, inert and acidic solvents has been studied by IR and Raman spectroscopy. The values of W, the Fermi coupling coefficient, obtained from IR spectra varies with the nature of the solvent while W evaluated from Raman data remains constant at 12.5 ± 0.5 cm?1. The similar effects of Bronsted and Lewis acids on the band frequencies and intensities is evidence that the CN group complexes with acids via the N atom “n” electron pair and not the π bond. 相似文献
182.
The molecular energy of the complex (η5-C5H5)2TiCl2 has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol?1. This difference is sufficiently high to explain the difficulty of the inversion process. 相似文献
183.
In this work, two partial differential equation-based models have been proposed for the quantitative analysis of temperature-programmed desorption (TPD) thermograms when the adsorption cell can be modeled as a well-mixed reactor, using the Langmuir equation as the adsorption isotherm and including the effect of diffusional resistance. One model considers pore diffusion, and the other considers surface diffusion. For both models, the rate of adsorption is proportional to the gas pressure. By nondimensionalizing these models, the range of design parameters for which the accumulation in the gas cell, diffusional resistance, and readsorption have an important effect on the TPD signal is proposed. An important conclusion is that the dimensionless numbers accounting for the diffusional resistance and the corresponding range of parameters are quite different for both mechanisms. The models have been validated with two systems where surface and pore diffusion are the relevant mechanisms: (i) CO2-Na-mordenite and (ii) CO2-Na-mordenite pellets. 相似文献
184.
Top S el Hafa H Vessiéres A Huché M Vaissermann J Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(22):5241-5249
In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha. 相似文献
185.
Barry SJ Carr RM Lane SJ Leavens WJ Monté S Waterhouse I 《Rapid communications in mass spectrometry : RCM》2003,17(6):603-620
A simple method has been developed for the pre-column derivatisation of low molecular weight primary and secondary amines and carboxylic acids using quaternary nitrogen compounds to enhance their detection by liquid chromatography/electrospray ionisation mass spectrometry (LC/ESI-MS). The synthesis of seven novel quaternary nitrogen reagents is described. The derivatives are designed to be relatively small molecules to avoid some of the steric hindrance problems that may be associated with larger derivatisation reagents. The compounds have amine and carboxylic acid functional groups with which to derivatise carboxylic acids and amines, respectively. Two of the compounds contain a bromine atom in order to assess the advantages of a bromine isotope pattern in the mass spectra. This acts as a simple marker for derivatisation and enables data processing by cluster analysis.Activation of the carboxylic acid group was achieved by the use of either 1-chloro-4-methylpyridinium iodide (CMPI) or the more reactive 1-fluoro-4-methylpyridinium p-toluenesulphonate (FMP).1 Using both of these active reagents, the degree of nucleophilic substitution was investigated for the derivatisation of a variety of small molecules. Whilst giving some increase in the ESI-MS response for the derivatised compounds, the FMP itself acted as a derivatising reagent in a competing reaction. In the light of this finding, FMP was reacted with the test compounds separately and gave positive results as a derivatising reagent. Detection of the 'pre-charged' derivatives of amines and carboxylic acids by LC/ESI-MS was investigated with respect to their ESI response and chromatography. 相似文献
186.
Urs P. Wild Hans J. Griesser Vo Dinh Tuan Jean F.M. Oth 《Chemical physics letters》1976,41(3):450-455
The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S2 → S0 emission. In addition, fluorescence from the S1 state can be observed in monofluoro [13] annulene by exciting into the S2 or directly into the S1 absorption. 相似文献
187.
Complexes of TiCl4, VCl4 and SnX4 (X = Cl or Br) with Schiff bases derived from 2-aminobenzimidazole
Agueda Arquero Pilar Souza José A. García-Vázquez José R. Masaguer 《Transition Metal Chemistry》1985,10(11):424-426
Summary The reactions of anhydrous titanium(IV), tin(IV) and vanadium(IV) halides with Schiff bases derived from 2-aminobenzimidazole and 4-methylbenzaldehyde (abimbz) and salicylaldehyde (abisal), yield hexacoordinated complexes M(abimbz)Cl4 and M(abisal)2X4 (M = Ti, Sn or V; X = Cl or Br).The compounds have been characterized by elemental analyses, magnetic measurements, e.p.r., electronic and i.r. spectral studies. I.r. spectra suggest that the Schiff base (abimbz) is coordinated as a bidentate ligand with the metal ion and the (abisal) base acts as a monodentate ligand. 相似文献
188.
RuCl2(PPh3)3 catalyzes oxidation of alcohols to carbonyi compounds by iodosylbenzene and that of aldehydes to carboxylic acids. Catalyzed oxidation of primary alcohols with phenyliodosodiacetate affords aldehydes. 相似文献
189.
We describe the synthesis of 3-(2-thienyl)pyridazine and of some of its derivatives substituted on the 6 position eg., ethoxy, hydrazino and azido. Some of these compounds have lead to condensed rings systems, namely, triazolo- and tetrazolopyridazines. 相似文献
190.
The optically active methylphenyl-α-naphthylsilane racemises quickly in tetrahydrofuran in the presence of LiAlH4.Kinetic results show a different behaviour of the hydride depending on its concentration. Activation parameters have been obtained and mechanisms proposed. 相似文献