全文获取类型
收费全文 | 240篇 |
免费 | 3篇 |
专业分类
化学 | 157篇 |
数学 | 21篇 |
物理学 | 65篇 |
出版年
2021年 | 2篇 |
2019年 | 3篇 |
2015年 | 5篇 |
2014年 | 2篇 |
2013年 | 13篇 |
2012年 | 7篇 |
2011年 | 13篇 |
2010年 | 9篇 |
2009年 | 6篇 |
2008年 | 6篇 |
2007年 | 10篇 |
2006年 | 11篇 |
2005年 | 10篇 |
2004年 | 7篇 |
2003年 | 5篇 |
2002年 | 3篇 |
2001年 | 7篇 |
2000年 | 11篇 |
1999年 | 9篇 |
1998年 | 4篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 15篇 |
1993年 | 9篇 |
1992年 | 4篇 |
1987年 | 3篇 |
1985年 | 4篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1972年 | 1篇 |
1970年 | 2篇 |
1969年 | 4篇 |
1967年 | 2篇 |
1965年 | 1篇 |
1959年 | 1篇 |
1941年 | 1篇 |
1936年 | 1篇 |
1927年 | 1篇 |
1922年 | 1篇 |
1917年 | 1篇 |
1910年 | 3篇 |
1909年 | 1篇 |
1908年 | 1篇 |
1905年 | 4篇 |
1904年 | 2篇 |
1903年 | 2篇 |
1902年 | 2篇 |
1900年 | 1篇 |
1890年 | 4篇 |
1884年 | 1篇 |
排序方式: 共有243条查询结果,搜索用时 15 毫秒
111.
112.
Detection of perfluorocarbons in blood by headspace solid-phase microextraction combined with gas chromatography/mass spectrometry. 总被引:2,自引:0,他引:2
A new method of detection of perfluorocarbon molecules (PFCs) in blood sample has been established. After an extraction and pre-concentration step performed by headspace solid-phase microextraction (HS-SPME), the PFCs are detected by gas chromatography-mass spectrometry (GC/MS) with an ion trap mass spectrometer in MS and MS/MS modes. The influence of different parameters on the SPME process is discussed. The limit of detection and the linearity of the procedure have been determined for two PFCs. 相似文献
113.
114.
J. Muter L. de Koningh N. J. Lane A. von Asboth F. Wallenstein H. Finck E. von Raumer H. Schlegel F. Voigtländer A. Lidoff E. Twitchell K. Farnsteiner Brunner G. Halphen D. Wesson A. Ssabanejew M. Saytzeff C. Saytzeff A. Saytzeff A. C. Geitel O. Hehner C. A. Mitchell B. Stahmer F. Krafft C. Hell Chr Jordanoff K. Hazura A. Friedreich A. Grüssner R. Benedikt D. Kurbatoff und E. Ljubarsky 《Fresenius' Journal of Analytical Chemistry》1900,39(3):167-183
Ohne Zusammenfassung 相似文献
115.
116.
117.
F Giulieri F Jeanneaux M Goldmann MP Krafft 《Langmuir : the ACS journal of surfaces and colloids》2012,28(33):12022-12029
Langmuir monolayers of double perfluoroalkyl(alkyl) chain amphiphiles fitted with a monomorpholinophosphate polar head, [C(n)F(2n+1)(CH(2))(m)O](2)P(O)[N(CH(2)CH(2))(2)O] (di(FnHm)MP with n = 6, 8, or 9; and m = 1 or 2), were investigated by surface pressure (π)/molecular area (A(0)) compression isotherms for temperatures ranging from 15 to 50 °C, and by grazing-incidence X-ray diffraction (GIXD) at 25 °C. Ultrathin monolayers were obtained for these short surfactants. Though the hydrocarbon spacer is short, it has a remarkable impact on the monolayer's organization. At 25 °C, whereas di(F8H2)MP monolayer presents a liquid expanded (LE)/liquid condensed (LC) transition, simply replacing one CH(2) by a CF(2) in the latter compound's structure at constant chain length, i.e. shortening the spacer from 2 to 1 CH(2) (as in di(F9H1)MP), suppresses the LE phase. At 25°, GIXD established that for both di(F8H2)MP and di(F9H1)MP, the chains form an hexagonal lattice in the LC phase. The collective tilt of the two compounds is close to zero. The lattice of the dense phase can be compressed, as assessed by the continuous linear decrease of the d spacing with increasing pressure. This indicates that the azimuthal distribution of the molecular tilts is progressively reduced upon compression. The d value for di(F9H1)MP is significantly lower than that of di(F8H2)MP, providing evidence for strong condensing effect of the fluorinated chains. Molecular areas were determined directly from the compression curves and also from the X-ray data, the latter allowing reconstruction of the compression isotherms. The calculated lattice compressibilities are ~30% and 50% of the macroscopic compressibilities for di(F9H1)MP and di(F8H2)MP, respectively. Comparison with the experimentally determined isotherms shows that the monolayer of di(F9H1)MP is more stable than that of di(F8H2)MP. The enthalpies and entropies determined for di(F9H1)MP and di(F8H2)MP, derived from the Clausius-Clapeyron equation, confirm that the observed transitions are both of the LE/LC type, although the triple point temperatures are strikingly different (27 °C vs -18 °C); this large difference further illustrates the stabilizing effect of the fluorinated chains. Disorder is hindered by the fluorinated chains and facilitated by a hydrocarbon spacer when larger than 1 CH(2). 相似文献
118.
Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation. 相似文献
119.
Milena Köhler Susanne Machill Reiner Salzer Christoph Krafft 《Analytical and bioanalytical chemistry》2009,393(5):1513-1520
Brain tissue is characterized by high lipid content. The amount of lipids decreases, and its composition changes in the most
frequent primary brain tumor, the glioma. Scope of the current paper was to extract quantitatively lipids from porcine and
human brain tissue as well as from five human gliomas using a modified protocol according to Folch. The lipid extracts were
studied by Raman spectroscopy with 785 nm excitation and by mass spectrometry with electron impact ionization. Porcine and
human brain tissues have similar water and lipid content and show similar Raman and mass spectra. In contrast, gliomas are
characterized by increased water content and decreased lipid content. Elevated phosphatidylcholine to cholesterol ratios in
lipid extracts of gliomas were indicated by Raman bands of the choline group and cholesterol. Due to its higher sensitivity,
mass spectrometry detected increased levels of cholesterol ester relative to cholesterol in lipid extracts of gliomas. For
comparison, thin tissue sections were prepared from the glioma specimens before lipid extraction; infrared spectroscopic images
were recorded and analyzed by a supervised classification model. This study demonstrates how to improve the analysis of brain
tumors and to complement the diagnosis of brain pathologies using a multimodal approach. 相似文献
120.
Sevgi Haman Bayar Christoph Krafft Semra de Jürgen Popp Gunseli Guven Zafer C. Cehreli Elif Hilal Soylu 《Journal of Raman spectroscopy : JRS》2012,43(1):6-15
Human dentin specimens were treated with two different etch‐and‐rinse adhesives, Single Bond 2 (SB2) and Prime & Bond NT (PBNT), and two composite resins, TPH and P60. Cross‐sectional samples, approximately 1 mm thick, were analyzed with Raman line mapping and imaging across the dentin–adhesive–composite interface. The integrated intensities of selected bands associated with adhesive, organic material, composite and hydroxyapatite of dentin were calculated to determine the distribution of adhesive infiltration into demineralized dentin. The results were compared with the enamel‐adhesive composite interface. The demineralized zone was smaller in the enamel‐adhesive interface than in the dentin–adhesive interface. The region of collagen‐adhesive crosslinking was wider in the PBNT adhesive than in the SB2 adhesive. However, a gap at the dentin–PBNT composite interface, which was not observed at the dentin–SB2 composite interface, might compromise the dentin–restoration bond. K‐means cluster analysis of the Raman images confirmed the findings. The ultrastructure of the dentin–resin interface was studied using scanning electron microscopy. Small‐angle X‐ray scattering was also applied to reveal and quantify fine‐scale structural features. SB2 adhesive was found to diffuse more into demineralized dentin along with greater nanosized aggregations in the hybrid layer. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献