全文获取类型
收费全文 | 468篇 |
免费 | 14篇 |
国内免费 | 3篇 |
专业分类
化学 | 409篇 |
晶体学 | 1篇 |
力学 | 7篇 |
数学 | 12篇 |
物理学 | 56篇 |
出版年
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 21篇 |
2020年 | 22篇 |
2019年 | 16篇 |
2018年 | 6篇 |
2017年 | 11篇 |
2016年 | 29篇 |
2015年 | 14篇 |
2014年 | 13篇 |
2013年 | 42篇 |
2012年 | 42篇 |
2011年 | 54篇 |
2010年 | 27篇 |
2009年 | 15篇 |
2008年 | 32篇 |
2007年 | 27篇 |
2006年 | 27篇 |
2005年 | 21篇 |
2004年 | 16篇 |
2003年 | 9篇 |
2002年 | 8篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1960年 | 1篇 |
1935年 | 1篇 |
1923年 | 1篇 |
排序方式: 共有485条查询结果,搜索用时 10 毫秒
51.
Lucie Appy Anaïs Depaix Xavier Bantreil Frédéric Lamaty Suzanne Peyrottes 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):930-931
AbstractWe have developed original one-pot and protecting group-free approaches, which are also user-friendly and reliable, to synthesize nucleotides and derivatives starting from nucleoside 5’-monophosphates. Both methods present convenient set-up, i.e., non-dry solvents and reagents, substrates in their sodium or acid form, and commercially available and cheap phosphorus reagents as sodium and potassium salts. 相似文献
52.
Ferdinand H. Lutter Lucie Grokenberger Philipp Spieß Jeffrey M. Hammann Konstantin Karaghiosoff Paul Knochel 《Angewandte Chemie (International ed. in English)》2020,59(14):5546-5550
A combination of 10 % CoCl2 and 20 % 2,2′‐bipyridine ligands enables cross‐coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3‐ and 1,4‐substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with primary and secondary alkylzinc reagents providing the alkylated alkynes. 相似文献
53.
54.
Dr. Mégane Muschi Anusha Lalitha Dr. Saad Sene Dr. Damien Aureau Dr. Mathieu Fregnaux Dr. Imène Esteve Dr. Lucie Rivier Dr. Naseem Ramsahye Dr. Sabine Devautour-Vinot Dr. Clémence Sicard Prof. Nicolas Menguy Dr. Christian Serre Prof. Guillaume Maurin Prof. Nathalie Steunou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10439-10444
An innovative strategy is proposed to synthesize single-crystal nanowires (NWs) of the Al3+ dicarboxylate MIL-69(Al) MOF by using graphene oxide nanoscrolls as structure-directing agents. MIL-69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM-HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL-69(Al) NWs involving size-confinement and templating effects. The formation of MIL-69(Al) seeds and the self-scroll of GO sheets followed by the anisotropic growth of MIL-69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures. 相似文献
55.
Lucie Strnadlová Petra Šulcová Mario Llusar 《Journal of Thermal Analysis and Calorimetry》2010,100(2):661-665
The inorganic ceramic compounds based on the CeO2 belong into the group of high-temperature pigments. The pigments have been prepared by the classical dry process (i.e. solid-state
reaction) in the temperature range from 1,300 to 1,600 °C and by the coprecipitation at the three different temperatures:
400, 600 and 1,100 °C. The principal of these pigments makes the host lattice of the CeO2, which is doped by terbium ions. This incorporation of the doped ions leads to obtaining of the interesting dark orange colour
after application into ceramic glaze. The aim of our research was to improve and optimize the synthesis conditions of these
pigments. The samples were submitted to thermal analysis (TG–DTA) for determination of the temperature interval of the pigment
formation and the thermal stability of pigments. The compounds were also measured from the point of view of their colouring,
structure and particle size distribution. 相似文献
56.
Twenty nine phenolic compounds comprising nine phenolic acids, sixteen flavonoids (including eight tea catechins, glycosides and aglycones), four coumarins plus caffeine were analysed within 20 min using ultra high performance liquid chromatography (UHPLC) with PDA detection. UHPLC system was equipped with C18 analytical column (100 mm × 2.1 mm, 1.7 μm), utilising 0.1% formic acid and methanol mobile phase in the gradient elution mode. The developed method was tested for the system suitability: resolution, asymmetry factor, peak capacity, retention time repeatability and peak area repeatability. The method was fully validated in the terms of linearity (r2 > 0.9990 for all 30 compounds), range (typically 1-100 mg L−1), LOD, LOQ, inter/intra-day precision (<3% and <9% respectively) and inter/intra-day accuracy (typically 100 ± 10%). Subsequently the method was applied to the identification (spectral information and peak purity calculations were profited) and quantification of phenolic compounds and caffeine present in tea infusions and extracts. 相似文献
57.
Khemtémourian L Doménech E Doux JP Koorengevel MC Killian JA 《Journal of the American Chemical Society》2011,133(39):15598-15604
Human islet amyloid polypeptide (IAPP) is the major component of the amyloid deposits found in the pancreatic islets of patients with type 2 diabetes mellitus. After synthesis, IAPP is stored in the β-cell granules of the pancreas at a pH of approximately 5.5 and released into the extracellular compartment at a pH of 7.4. To gain insight into the possible consequences of pH differences for properties and membrane interaction of IAPP, we here compared the aggregational and conformational behavior of IAPP as well as IAPP-membrane interactions at pH 5.5 and pH 7.4. Our data reveal that a low pH decreases the rate of fibril formation both in solution and in the presence of membranes. We observed by CD spectroscopy that these differences in kinetics are directly linked to changes in the conformational behavior of the peptide. Mechanistically, the processes that occur at pH 5.5 and pH 7.4 appear to be similar. At both pH values, we found that the kinetic profile of IAPP fibril growth matches the kinetic profile of IAPP-induced membrane damage, and that both are characterized by a lag phase and a sigmoidal transition. Furthermore, monolayer studies as well as solid-state NMR experiments indicate that the differences in kinetics and conformational behavior as function of pH are not due to a different mode of membrane insertion. Our study suggests that a low pH prevents aggregation and membrane damage of IAPP in the secretory granules, most likely by affecting the ionization properties of the peptide. 相似文献
58.
59.
In theory, with identical stationary phase chemistry, the transfer of an HPLC method to UHPLC conditions is straightforward and necessitates the calculation of new conditions based on column and instrument geometries. Occasionally, undesirable changes in selectivity, retention or efficiency have been reported and have been attributed to a frictional heating phenomenon that is due to the elevated generated pressure drop. In the present study, the frictional heating in a UHPLC system was evaluated experimentally under gradient elution conditions (acetonitrile/buffer at pH 3 and 9) with generated pressure drops in the range of 100-1000 bar on both 1.0mm and 2.1mm I.D. columns using a mixture of 10 representative basic, acidic and neutral pharmaceutical compounds. Under adiabatic conditions (i.e., still-air oven), the longitudinal temperature gradient was estimated at +4 °C, +8 °C and +16 °C at 300, 600 and 1000 bar, respectively, on a 2.1mm I.D. column using an empirical measurement procedure. With the 1.0mm I.D. column, these values were reduced to +3 °C, +6 °C and +12 °C, respectively. Finally, various approaches to eliminate or at least to reduce the effect of frictional heating are briefly discussed. 相似文献
60.