全文获取类型
收费全文 | 682篇 |
免费 | 22篇 |
国内免费 | 2篇 |
专业分类
化学 | 546篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 77篇 |
物理学 | 77篇 |
出版年
2022年 | 5篇 |
2020年 | 10篇 |
2019年 | 13篇 |
2017年 | 8篇 |
2016年 | 16篇 |
2015年 | 17篇 |
2014年 | 17篇 |
2013年 | 32篇 |
2012年 | 21篇 |
2011年 | 28篇 |
2010年 | 21篇 |
2009年 | 23篇 |
2008年 | 33篇 |
2007年 | 30篇 |
2006年 | 42篇 |
2005年 | 37篇 |
2004年 | 35篇 |
2003年 | 26篇 |
2002年 | 26篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 12篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1993年 | 6篇 |
1990年 | 10篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1985年 | 7篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 10篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1976年 | 8篇 |
1975年 | 12篇 |
1974年 | 19篇 |
1973年 | 11篇 |
1972年 | 3篇 |
1971年 | 4篇 |
1970年 | 6篇 |
1955年 | 4篇 |
1937年 | 3篇 |
1934年 | 3篇 |
1930年 | 3篇 |
1925年 | 4篇 |
排序方式: 共有706条查询结果,搜索用时 125 毫秒
31.
Benijts T Günther W Lambert W De Leenheer A 《Rapid communications in mass spectrometry : RCM》2003,17(16):1866-1872
A sonic spray ionization liquid chromatography/mass spectrometry (LC/SSI-MS) procedure combined with off-line solid-phase extraction was optimized for the analysis of 20 endocrine-disrupting chemicals (EDCs) in water samples. Method development included a comparison of the novel sonic spray ionization (SSI) with more traditional ion sources, i.e. pneumatically assisted electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). It was demonstrated that SSI and ESI spectra were very similar, but were more prone to the formation of solvent cluster ions as compared with APCI spectra. This phenomenon was most prominent for SSI and resulted in an increased chemical background in full-scan mass spectra. However, this chemical noise did not affect the overall sensitivity of SSI and ESI. After optimization of LC and MS parameters, the LC/SSI-MS method was validated. Recoveries ranged from 76.3 up to 113.4% for all compounds. Limits of detection (LOD) and quantitation (LOQ) were established between 3.0 and 11.5 ng/L and 9.9 and 38.0 ng/L, respectively. Within-day (n = 5) and between-day (n = 5) reproducibility were investigated at three levels and ranged from 3.3-16.5% and 7.6-19.2%, respectively. Eight-point calibration curves were established and showed linearity for all compounds (r(2) > 0.987) over a linear dynamic range of 10-10 000 ng/L. 相似文献
32.
Cano Sierra J Hüerländer D Hill M Kehr G Erker G Fröhlich R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3618-3622
The titanium complex [(C(5)H(4)bond;allyl)TiCl(3)] (2) undergoes olefin metathesis coupling when treated with 3 mol % of [Cl(2)(L(1))(L(2))Ru=CHPh] (L(1)=L(2)=PCy(3), 4 a; L(1)=PCy(3), L(2)=(H(2)IMes), 4 b) to yield the dimetallic complex [Cl(3)Ti(C(5)H(4))-CH(2)CH=CHCH(2)-(C(5)H(4))TiCl(3)] (5). The allyl-substituted titanocene complex [Cp(C(5)H(4)bond;allyl)TiCl(2)] (3) analogously yields the dimetallic system 6 when treated with 4. The ansa-zirconocene complex [Me(2)Si(C(5)H(4))(C(5)H(3)bond;allyl)ZrCl(2)] (7) cleanly yields the analogous dimetallic coupling product 8 (>95 % isomerically pure), when treated with catalytic amounts of 4 b in toluene. Complex 8 gives an active homogeneous ethene or propene polymerization catalyst, especially at elevated temperatures, when treated with excess methylalumoxane. 相似文献
33.
Fluorination of chlorofluorinated telomers of general formula Cl(CFClCF2)nCCl3 (n ? 7) was studied using potassium fluoride in dimethylsulfoxide as fluorinating agent. The reaction leads to a mixture of perfluorinated linear olefins having 15 to 30 carbon atoms : CF3(CF2)pCFCF(CF2)mCF3 (p + m = 2n?3).We perfected a method to determine molecular weights of the telomers by gel permeation chromatography (G.P.C.). The olefins obtained by fluorination are analyzed both by vapor phase chromatography (V.P.C.) and by 19F nuclear magnetic resonance (N.M.R.). 相似文献
34.
35.
In this work, the effect of addition of kaolinite and rice husk microparticles on the water vapor permeability of polylactic acid (PLA) was evaluated. The PLA-composites materials were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and optical microscopy. For the composite preparation, an experimental design was established using two factors: additive type and concentration. When evaluating the water vapor permeability of the composites, it was found that the incorporation of kaolinite at 1% and 5% reduced the permeability coefficient of PLA. Furthermore, the inclusion of 5% kaolinite showed an increase on the tensile strength of the material. By contrast, the addition of rice husk produced an increase on water vapor permeability of the material and a decrease of both the tensile strength and ductility (percent of elongation at fracture). The higher dispersion and more regular morphology of the kaolinite particles could explain the enhancement of the gas barrier. A similar thermal behavior was observed for both PLA and composite materials, confirming that no damage of these properties was caused with the incorporation of the filler particles. 相似文献
36.
37.
38.
Prof. Miguel A. Sierra Prof. Luis Casarrubios Dr. María C. de la Torre 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7232-7242
Overuse and misuse of antibacterial drugs has resulted in bacteria resistance and in an increase in mortality rates due to bacterial infections. Therefore, there is an imperative necessity of new antibacterial drugs. Bio-organometallic derivatives of antibacterial agents offer an opportunity to discover new active antibacterial drugs. These compounds are well-characterized products and, in several examples, their antibacterial activities have been studied. Both inhibition of the antibacterial activity and strong increase in the antibiotic activity of the parent drug have been found. The synthesis of the main classes of bio-organometallic derivatives of these drugs, as well as examples of the use of structure–activity relation (SAR) studies to increase the activity and to understand the mode of action of bio-organometallic antimicrobial peptides (BOAMPs) and platensimicyn bio-organometallic mimics is presented in this article. 相似文献
39.
Prof. Dr. Javier A. Cabeza Dr. Pablo García-Álvarez Prof. Dr. Mar Gómez-Gallego Laura González-Álvarez Alba D. Merinero Prof. Dr. Miguel A. Sierra 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8635-8642
The reactivity of amidinatotetrylenes of the type E(tBu2bzm)R1 (E=Si, Ge; tBu2bzm=N,N′-bis(tertbutyl)benzamidinate; R1=alkyl or aryl) with the chromium Fischer alkynylcarbene complexes [Cr{C(OEt)C2R2}(CO)5] (R2=Ph; ferrocenyl, Fc) has been studied. At room temperature, two different reaction pathways have been identified: (a) attack of the amidinatotetrylene to the alkynyl C2 atom (γ-attack), which leads to σ-allenyl complexes in which the original Ccarbene atom maintains its attachment to the Cr(CO)5 and OEt groups (compounds 3 ), and (b) attack of the amidinatotetrylene to the Ccarbene atom (α-attack), which ends in σ-allenyl complexes in which the original Ccarbene atom is not attached to the metal atom and has been inserted into an E−N bond of the amidinatotetrylene forming an E-C-N-C-N five-membered ring (compounds 4 ). It has been found that compounds 3 are thermodynamically less stable than their corresponding 4 isomers and that some of the former (E=Ge; R1=CH2SiMe3) can be transformed into the latter upon heating. At high temperatures (>70 °C) the reactions involving bulky amidinatotetrylenes (R1=Mes, tBu) end in the carbene-substitution products [Cr{E(tBu2bzm)R1}(CO)5]. 相似文献
40.
We define the hyperbolic order of any locally injective holomorphic function between arbitrary hyperbolic domains of the complex plane and study the relation between the hyperbolic order and the Schwarzian derivative for locally injective holomorphic functions from the unit disk into itself. 相似文献