全文获取类型
收费全文 | 1049篇 |
免费 | 42篇 |
国内免费 | 1篇 |
专业分类
化学 | 717篇 |
晶体学 | 2篇 |
力学 | 52篇 |
数学 | 152篇 |
物理学 | 169篇 |
出版年
2024年 | 4篇 |
2023年 | 12篇 |
2022年 | 45篇 |
2021年 | 50篇 |
2020年 | 39篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 20篇 |
2016年 | 70篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 69篇 |
2012年 | 82篇 |
2011年 | 112篇 |
2010年 | 53篇 |
2009年 | 34篇 |
2008年 | 50篇 |
2007年 | 57篇 |
2006年 | 53篇 |
2005年 | 55篇 |
2004年 | 30篇 |
2003年 | 33篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1961年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1937年 | 1篇 |
1918年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有1092条查询结果,搜索用时 0 毫秒
91.
Vogliardi S Favretto D Frison G Ferrara SD Seraglia R Traldi P 《Journal of mass spectrometry : JMS》2009,44(1):18-24
Matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry was used for the rapid detection of cocaine, benzoylecgonine and cocaethylene in hair. Different MALDI sample preparation procedures have been tested and the employment of a multi-layer 'graphite-sample-electrosprayed alpha-cyano-4-hydroxycinnamic acid (HCCA)' yielded the best results for standard solutions of the target analytes. The same approach was subsequently applied to hair samples that were known to contain cocaine, benzoylecgonine and cocaethylene, as determined by a classical GC-MS method. It was however necessary to extract hair samples by incubating them in methanol/trifluoroacetic acid for a short time (15 min) at 45 degrees C; 1 microl of the obtained supernatant was deposed on a metal surface treated with graphite, and HCCA was electrosprayed on it. This procedure successfully suppressed matrix peaks and was effective in detecting all the target analytes as their protonated species. The results obtained give further confirmation of the effectiveness of the MALDI for detecting drugs and their metabolites in complex biological matrices. The method can be useful as a fast screening procedure to detect the presence of cocaine and metabolites in hair samples. 相似文献
92.
Marco Dossi Giuseppe Storti Davide Moscatelli 《Macromolecular theory and simulations》2010,19(4):170-178
Initiation kinetics in free radical polymerization is investigated using density functional theory. Thermodynamic and kinetic parameters of the initiation reactions are predicted, and the role of the initiators in the polymerization process is evaluated. Methyl acrylate, methyl methacrylate, acrylonitrile, and styrene homo‐polymerizations with different initiators are studied. Reaction enthalpy and activation energy for each reaction between monomer and the radical fragments arising from the initiators have been determined. The initiation kinetic constants for all of these initiation reactions are evaluated and compared with both computational and experimental propagation kinetic constants of each monomer.
93.
Capozzi G Delogu G Fabbri D Marini M Menichetti S Nativi C 《The Journal of organic chemistry》2002,67(7):2019-2026
Sulfenylation of 6,6'-dimethoxy-2,2'-dihydroxybiphenyl, used as a racemic mixture and single enantiomers, by phthalimidesulfenyl chloride afforded the corresponding 3,3'-N,N'-dithiophthalimide with complete regioselectivity. Simple manipulations of the latter compound allowed access to the corresponding bis-thiol or o-thioquinone as useful intermediates for the synthesis of new sulfur-containing open-chain and macrocyclic C(2) enantiopure ligands. The application of this methodology to the preparation of a biphenyl bearing two cysteine units as potential HIV-1 protease inhibitor is also described. 相似文献
94.
De Riccardis F Di Filippo M Garrisi D Izzo I Mancin F Pasquato L Scrimin P Tecilla P 《Chemical communications (Cambridge, England)》2002,(24):3066-3067
The Na+ transporting properties of the first member of a new class of artificial ionophores, based on a C2-symmetric polyhydroxylated steroid dimer, are described. 相似文献
95.
This paper presents some new data on nitrophenol formation from phenol under illumination, and reviews the studies performed on phenol photonitration, from its discovery in 1988 to the very recent elucidation of its reaction pathway by the authors. Recent experimental results account for the pH effect on phenol photonitration. The nitrogen sources so far investigated are nitrate and nitrite, which undergo photolysis upon absorption of near-UV light. These studies have given a relevant information on the role of both nitrate and nitrite as environmental factors. Such processes can take place both in natural waters and in atmospheric hydrometeors. 相似文献
96.
[reaction: see text] The ring-closing olefin metathesis (RCM) of 2,2'-divinylbiphenyls, using a second-generation RCM ruthenium-based catalyst, leads to differently substituted phenanthrenes in quantitative yield under very mild reaction conditions, independent of both nature and position of the groups present on the biphenyl moiety. 相似文献
97.
Co(II) sulfate reacts with the flexible ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) to yield the coordination network [Co(bix)2(H2O)2](SO4).7H2O, containing polymeric ribbons of rings which penetrate and catenate a 3D single frame of the CdSO4 topology, to produce an open-channel entangled architecture with nanoporous behaviour. 相似文献
98.
Roberta Sanna Davide Sanna Valeria Alzari Daniele Nuvoli Sergio Scognamillo Massimo Piccinini Massimo Lazzari Emilia Gioffredi Giulio Malucelli Alberto Mariani 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4110-4118
Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
99.
This critical review aims at highlighting the prevailing supramolecular approaches employed nowadays in the preparation of luminescent hierarchised materials. Specifically, it has the ambition to illustrate how progresses in the control of the supramolecular interaction toolbox ultimately led to the development of spectacular luminescent nano- and micro-architectures, through a combination of molecular self-assembly and self-organisation processes involving organic π-conjugated molecules. The reader will be guided through a systematic exploration of the most common avenues to prepare and characterise luminescent self-assembled/self-organised materials embedded into one-, two- or three-dimensional networks, accompanied by a critical discussion of their main advantages and limitations. Key representative examples of this research field will be thoroughly described, with a particular focus on those systems displaying potential on the device application scene. Particular attention will be devoted to the design and synthetic approaches aimed at the preparation of the primary π-conjugated molecular modules, the chemical, structural and electronic properties of which dramatically influence the fate and the features of the self-assembled/self-organised material (215 references). 相似文献
100.
Davide Bleiner Alexei Plotnikov Carla Vogt Klaus Wetzig D. Günther 《Analytical and bioanalytical chemistry》2000,368(2-3):221-226
A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-”Time of Flight”-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 μm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 μm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 μm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium μm region. 相似文献