全文获取类型
收费全文 | 553篇 |
免费 | 11篇 |
国内免费 | 1篇 |
专业分类
化学 | 426篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 69篇 |
物理学 | 61篇 |
出版年
2021年 | 6篇 |
2020年 | 11篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2017年 | 4篇 |
2016年 | 14篇 |
2015年 | 13篇 |
2014年 | 15篇 |
2013年 | 23篇 |
2012年 | 27篇 |
2011年 | 25篇 |
2010年 | 10篇 |
2009年 | 10篇 |
2008年 | 22篇 |
2007年 | 13篇 |
2006年 | 18篇 |
2005年 | 13篇 |
2004年 | 15篇 |
2003年 | 11篇 |
2002年 | 9篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1992年 | 6篇 |
1991年 | 13篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 11篇 |
1987年 | 11篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1979年 | 8篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 12篇 |
1974年 | 23篇 |
1973年 | 16篇 |
1972年 | 5篇 |
1969年 | 3篇 |
1956年 | 4篇 |
1902年 | 3篇 |
1901年 | 3篇 |
1888年 | 3篇 |
排序方式: 共有565条查询结果,搜索用时 328 毫秒
21.
Martin Pisárčik Mája Polakovičová Ferdinand Devínsky 《Central European Journal of Chemistry》2013,11(4):619-628
The solubilisation of poorly soluble antineoplastic drug camptothecin by nonionic surfactants (polysorbates and octylphenol ethoxylates) and alkyldimethylamine oxide surfactants with the alkyl chain length 8 to 16 carbon atoms was investigated. The hydrophobicity of the solubilising agent turned out to be the primary structural parameter controlling the solubility efficiency of camptothecin in an aqueous solution. The quantitative parameter of solubilisation (drug loading coefficient) provided values in the range of 0.1–1.2% and 0.1–1.0% for alkyldimethylamine oxides and nonionic surfactants, respectively. The decreasing number of oxyethylene units and the extension of the hydrophobic part of nonionic surfactant molecule resulted in the increase of camptothecin solubility. From the dynamic light scattering measurements, the hydrodynamic diameter values of camptothecin-loaded alkyldimethylamine oxide and nonionic micelles were found in the range of 4–42 nm and 5–120 nm, respectively. The experimental values confirmed the increase in micellar size with the increasing alkyl chain length. The values of the packing parameter of camptothecin-loaded dodecyldimethylamine oxide micelles indicate their spherical shape at all the investigated surfactant concentrations. A simple computer model of camptothecin-loaded dodecyldimethylamine oxide micelle provided the diameter of the structure cross section which is consistent with the experimental values. 相似文献
22.
Jan Kameník Henrieta Dulaiova Ferdinand Šebesta Kamila Šťastná 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(2):841-846
The method developed for cesium concentration from large freshwater samples was tested and adapted for analysis of cesium radionuclides in seawater. Concentration of dissolved forms of cesium in large seawater samples (about 100 L) was performed using composite absorbers AMP-PAN and KNiFC-PAN with ammonium molybdophosphate and potassium–nickel hexacyanoferrate(II) as active components, respectively, and polyacrylonitrile as a binding polymer. A specially designed chromatography column with bed volume (BV) 25 mL allowed fast flow rates of seawater (up to 1,200 BV h?1). The recovery yields were determined by ICP-MS analysis of stable cesium added to seawater sample. Both absorbers proved usability for cesium concentration from large seawater samples. KNiFC-PAN material was slightly more effective in cesium concentration from acidified seawater (recovery yield around 93 % for 700 BV h?1). This material showed similar efficiency in cesium concentration also from natural seawater. The activity concentrations of 137Cs determined in seawater from the central Pacific Ocean were 1.5 ± 0.1 and 1.4 ± 0.1 Bq m?3 for an offshore (January 2012) and a coastal (February 2012) locality, respectively, 134Cs activities were below detection limit (<0.2 Bq m?3). 相似文献
23.
24.
Angela Milinkovic Dr. Antoine Dupé Ao. Univ.-Prof. Dr. Ferdinand Belaj Univ.-Prof. Dr. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(55):e202201867
Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2(LR)2] (R=H 1 a ; R=CF3 1 b ) combined with B(C6F5)3 ( 1 a /B(C6F5)3, 1 b /B(C6F5)3) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H2 and Et3SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR)2][HB(C6F5)3] (R=H 2 a ; R=CF3 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2O leads to [Mo(NtBu)(NHtBu)(LR)2][(HO)B(C6F5)3] (R=H 3 a ; R=CF3 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C6F5)3]−. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR)2][{PhCH2O}B(C6F5)3] (R=H 4 a ; R=CF3 4 b ). Catalysis occurs at [HB(C6F5)3]− while [Mo(NtBu)(NHtBu)(LR)2]+ (R=H or CF3) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC). 相似文献
25.
Tuan-Anh Nguyen Øyvind Weiby Gregersen Ferdinand Männle Philippe Brachet 《Journal of Sol-Gel Science and Technology》2014,69(2):237-249
The substitution of fossil based packaging materials with materials from renewable sources is a topic of current interest. Polyhedral oligomeric silsesquioxanes with fatty acid moieties can have a renewable content of more than 90 % and are therefore called bio-POSS. In this study the bio-POSS octa-(ethyl erucamide) silsesquioxane was coated on a paperboard substrate as a liquid coating. The water resistance and the water vapour barrier properties of the paperboard were improved. Samples on which the bio-POSS coating layer was dried at 80 °C had a slightly higher water resistance and water vapour barrier than samples dried at room temperature. UV treatment of the coating layer had little effect. Solid state 1H-NMR of UV treated coatings showed no reaction of double bonds of bio-POSS in the coating layer. Multiple coating considerably enhanced the water resistance and water vapour barrier properties of the paperboard, due to an increase in the coating thickness and a reduction in number of pores on top coated surfaces. 相似文献
26.
Kleiton da Cruz Cunha Leonardo da Silva Pardellas Fabiano Barbieri Gonzaga 《Journal of solution chemistry》2020,49(3):306-315
This work presents the results from stability studies for several electrolytic conductivity (EC) reference materials submitted to repeated use conditions, as required by the last version of the ISO 17034 standard. Eight batches of reference materials, composed of water or water/n-propanol and HCl or KCl (at different concentrations), were studied, with nominal EC values ranging from 5 to 12,825 µS·cm−1. The materials were submitted to a simulation of repeated use, with the manipulation of bottles once a week and their storage under refrigeration with air gaps inside them. They were then analyzed once a month by the EC primary measurement method. The measurement results were evaluated to check for deviations from conventional long-term stability monitoring and for variation trends using normalized error and linear regression statistical tests. The results indicated that the repeated use simulation caused deviations in the EC for the 100 and 500 µS·cm−1 reference materials and variation trends in the EC for the 5000 and 12,825 µS·cm−1 reference materials. From the results, the uncertainty related to stability monitoring under repeated use conditions was calculated for each reference material. 相似文献
27.
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
28.
ζ-Oxo-α, β-enones react with lithium dimethylcuprate to give cyclic aldols such as hydroxydecalone 1 and hydroxyspiro[4.5]decanone 2 in a regio- and stereospecific manner. This new reaction, a combination of conjugate methyl addition to α, β-enones with directed intramolecular aldolisation, is suggested to proceed via either enoate anions, such as 8 and 11 , or radical anions, such as 9 → 10 and 12 → 13 , as intermediates. 相似文献
29.
A 980-nm pump-induced nonlinear refractive-index (n2) change in erbium-doped (20-m) and ytterbium-doped (20-m) fibers has been measured at 1064 nm by time-delayed photorefractive beam coupling in a co-propagating and counterpropagating geometry. It was found that n2 decreases at the wavelength of the probe beam when the pump beam is present. We present a semiclassical theory based on a four-state system that accounts for the pump-induced change of n2. Both theoretical and experimental results show that a significant index change, of the order of 10%, can be obtained for cw pump powers as small as 10 mW. 相似文献
30.
Bushev P Wilson A Eschner J Raab C Schmidt-Kaler F Becher C Blatt R 《Physical review letters》2004,92(22):223602
An excited-state atom whose emitted light is backreflected by a distant mirror can experience trapping forces, because the presence of the mirror modifies both the electromagnetic vacuum field and the atom's own radiation reaction field. We demonstrate this mechanical action using a single trapped barium ion. We observe the trapping conditions to be notably altered when the distant mirror is translated across an optical wavelength. The well-localized barium ion enables the spatial dependence of the forces to be measured explicitly. The experiment has implications for quantum information processing and may be regarded as the most elementary optical tweezers. 相似文献