全文获取类型
收费全文 | 2082篇 |
免费 | 59篇 |
国内免费 | 7篇 |
专业分类
化学 | 1184篇 |
晶体学 | 7篇 |
力学 | 38篇 |
数学 | 380篇 |
物理学 | 539篇 |
出版年
2020年 | 17篇 |
2019年 | 32篇 |
2018年 | 15篇 |
2016年 | 45篇 |
2015年 | 42篇 |
2014年 | 24篇 |
2013年 | 72篇 |
2012年 | 100篇 |
2011年 | 91篇 |
2010年 | 67篇 |
2009年 | 71篇 |
2008年 | 83篇 |
2007年 | 86篇 |
2006年 | 82篇 |
2005年 | 65篇 |
2004年 | 63篇 |
2003年 | 50篇 |
2002年 | 48篇 |
2001年 | 51篇 |
2000年 | 42篇 |
1999年 | 21篇 |
1998年 | 37篇 |
1997年 | 26篇 |
1996年 | 29篇 |
1995年 | 21篇 |
1994年 | 27篇 |
1993年 | 42篇 |
1992年 | 36篇 |
1991年 | 27篇 |
1990年 | 27篇 |
1989年 | 19篇 |
1988年 | 21篇 |
1987年 | 23篇 |
1986年 | 14篇 |
1985年 | 22篇 |
1984年 | 27篇 |
1983年 | 26篇 |
1982年 | 31篇 |
1981年 | 20篇 |
1980年 | 17篇 |
1979年 | 31篇 |
1978年 | 32篇 |
1977年 | 25篇 |
1976年 | 17篇 |
1975年 | 30篇 |
1974年 | 14篇 |
1973年 | 19篇 |
1971年 | 19篇 |
1970年 | 16篇 |
1969年 | 19篇 |
排序方式: 共有2148条查询结果,搜索用时 15 毫秒
81.
82.
83.
84.
In the last years, the number of new psychoactive substances, so‐called ‘legal highs’, has enormously increased. They are sold via online shops often with inaccurate and false information about the content. The aim of this work was to study the metabolism and the detectability of the drug of abuse diphenyl‐2‐pyrrolidinemethanol (D2PM) in rat urine using gas chromatography‐mass spectrometry and liquid chromatography‐high resolution‐tandem mass spectrometry. Five phase I and two phase II metabolites were identified suggesting hydroxylation at the pyrrolidine and diphenyl part as the main metabolic steps. Assuming similar kinetics, an intake of D2PM should be detectable in human urine mainly via its metabolites. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
85.
Dipl.‐Chem. Steffen Styra Dr. Sandra González‐Gallardo Dr. Felix Armbruster Dr. Pascual Oña‐Burgos Dipl.‐Chem. Eric Moos Dr. Matthias Vonderach Priv.‐Doz. Dr. Patrick Weis Priv.‐Doz. Dr. Oliver Hampe Dipl.‐Chem. Anneken Grün Dipl.‐Chem. Yvonne Schmitt Prof. Dr. Markus Gerhards Dipl.‐Chem. Fabian Menges Dipl.‐Chem. Maximilian Gaffga Prof. Dr. Gereon Niedner‐Schatteburg Prof. Dr. Frank Breher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8436-8446
A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ3N‐Si(3,5‐Me2pz)3Mo(CO)3]? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me2pz)3}?) with [Mo(CO)3(η6‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ1Si:κ3N‐Si(3,5‐Me2pz)3Mo(CO)3}]? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc+)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo0/MoI redox couple. 相似文献
86.
David Gode Christian Schmitt Matthias Engel Dietrich A. Volmer 《Analytical and bioanalytical chemistry》2014,406(12):2841-2852
Enzyme-catalyzed reactions play key roles in disease pathology, thus making them relevant subjects of therapeutic inhibitor screening experiments. Matrix-assisted laser desorption/ionization (MALDI) assays have been demonstrated to be able to replace established screening approaches. They offer increased sample throughput, but care must be taken to avoid instrumental bias from differences in ionization efficiencies. We compared a MALDI-triple-quadrupole (QqQ) method for the Dyrk1A peptide substrate woodtide to LC–MS, liquid chromatography with ultraviolet detection (LC–UV), luminescence, and radiometric assays. MALDI measurements were performed on a MALDI-QqQ instrument in the multiple-reaction monitoring mode. Different MALDI conditions were investigated to address whether matrix type, sample support, and MRM- or SIM-based detection conditions can be used to accommodate the molar responses of substrate peptide and its phosphorylated form. UV detection served as a reference method. The impact of MALDI matrix on IC50 values was small, even considering that matrix preparations were used that are known to alleviate response differences. IC50 values determined by MALDI were ca. 2-fold lower than those determined by LC–UV. Although MALDI generated lower ion yields for the phosphorylated peptide than for the peptide substrate, we found that a correction of compound potencies was readily possible using correction factors based on unbiased LC–UV results. A thorough method development delivered a robust assay with excellent performance (Z′ > 0.91) that was close to that seen for LC–UV. Figure
? 相似文献
87.
David Terrey Jack James Ivan Tankovski Monika Dalim Michel van Spankeren Arpita Chakraborty Eric Schmitt Aman Paul 《Molecules (Basel, Switzerland)》2021,26(6)
Marine feed ingredients derived from cephalopods (e.g., squid) and crustaceans (e.g., krill) are commercially used to improve the palatability of shrimp diets. Increase in global demand for shrimps has resulted in overfishing of these marine organisms and is a matter of concern. Insect protein hydrolysate could be a sustainable alternative for the possible replacement of these marine feed ingredients. During this study, four formulations: diet A (control: not containing any palatability enhancer), diet B (containing squid meal and krill oil), diet C (containing 1% insect protein hydrolysate), and diet D (containing 2% insect protein hydrolysate) were tested for (1) time required by first subject to begin feeding (time to strike) and (2) palatability in Litopenaeus vannamei. Additionally, the chemical composition of all four diet formulations was also analyzed. Results indicate that all diets had similar crude composition. The major essential amino acids in all diets were leucine and lysine, whereas eicosapentaenoic acid was the major omega-3 fatty acid in all diets. There were no significant differences between the mean time to strike for all the tested formulations. Palatability of tested formulations was found in the following order: diet D > diet C > diet B = diet A (p < 0.05), indicating that addition of squid meal and krill oil has no effect on palatability in comparison to control, whereas inclusion of insect protein hydrolysates significantly improves the palatability of formulations. Palatability enhancement potential of insect protein hydrolysate could be attributed to the high free amino acid content and water solubility in comparison to squid meal. 相似文献
88.
89.
Ijiri Y Schulthess TC Borchers JA van der Zaag PJ Erwin RW 《Physical review letters》2007,99(14):147201
In studying well-characterized, exchange-biased Fe(3)O(4)/CoO superlattices, we demonstrate a causal link between the exchange bias effect and the perpendicular coupling of the ferrimagnetic and antiferromagnetic spins. Neutron diffraction studies reveal that for thin CoO layers the onset temperature for exchange biasing T(B) matches the onset of locked-in, preferential perpendicular coupling of the spins, rather than the antiferromagnetic ordering temperature T(N). The results are explained by considering the role of anisotropic exchange first proposed by Dzyaloshinsky and Moriya and developing a model based purely on information on structural defects and exchange for these oxides. The devised mechanism provides a general explanation of biasing in systems with perpendicular coupling. 相似文献
90.
Erwin R. van Rijssel Dr. Pieter van Delft Dr. Gerrit Lodder Prof. Herman S. Overkleeft Prof. Gijsbert A. van der Marel Dr. Dmitri V. Filippov Dr. Jeroen D. C. Codée 《Angewandte Chemie (International ed. in English)》2014,53(39):10381-10385
Lewis acid mediated substitution reactions using [D]triethylsilane as a nucleophile at the anomeric center of the four pentofuranoses, ribose, arabinose, xylose, and lyxose, all proceed with good to excellent stereoselectivity to provide the 1,2‐cis adducts. To unravel the stereoelectronic effects underlying the striking stereoselectivity in these reactions we have mapped the energy landscapes of the complete conformational space of the oxocarbenium ions of the four pentofuranoses. The potential energy surface maps provide a detailed picture of the influence of the differently oriented substituents and their mutual interactions on the stability of the oxocarbenium ions and the maps can be used to account for the observed stereoselectivities of the addition reactions. 相似文献