全文获取类型
收费全文 | 3464篇 |
免费 | 202篇 |
国内免费 | 10篇 |
专业分类
化学 | 2350篇 |
晶体学 | 7篇 |
力学 | 122篇 |
数学 | 616篇 |
物理学 | 581篇 |
出版年
2024年 | 5篇 |
2023年 | 44篇 |
2022年 | 74篇 |
2021年 | 82篇 |
2020年 | 72篇 |
2019年 | 102篇 |
2018年 | 73篇 |
2017年 | 50篇 |
2016年 | 148篇 |
2015年 | 126篇 |
2014年 | 129篇 |
2013年 | 202篇 |
2012年 | 304篇 |
2011年 | 332篇 |
2010年 | 187篇 |
2009年 | 161篇 |
2008年 | 259篇 |
2007年 | 233篇 |
2006年 | 221篇 |
2005年 | 188篇 |
2004年 | 160篇 |
2003年 | 115篇 |
2002年 | 98篇 |
2001年 | 43篇 |
2000年 | 40篇 |
1999年 | 26篇 |
1998年 | 17篇 |
1997年 | 15篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 12篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1929年 | 4篇 |
排序方式: 共有3676条查询结果,搜索用时 15 毫秒
71.
Polfer NC Haselmann KF Zubarev RA Langridge-Smith PR 《Rapid communications in mass spectrometry : RCM》2002,16(10):936-943
Electron capture dissociation (ECD) of polypeptides has been demonstrated using a commercially available 3 Tesla Fourier transform ion cyclotron resonance (FTICR) instrument. A conventional rhenium filament, designed for high-energy electron impact ionisation, was used to effect ECD of substance P, bee venom melittin and bovine insulin, oxidised B chain. A retarding field analysis of the effective electron kinetic energy distribution entering the ICR cell suggests that one of the most important parameters governing ECD for this particular instrument is the need to employ low trapping plate voltages. This is shown to maximise the abundance of low-energy electrons. The demonstration of ECD at this relatively low magnetic field strength could offer the prospect of more routine ECD analysis for the wider research community, given the reduced cost of such magnets and (at least theoretically) the greater ease of electron/ion cloud overlap at lower field. 相似文献
72.
73.
Heck vinylation of 2-bromo-6-methyl-3-substituted pyridines using η3-allylpalladium chloride dimer/P(o-Tol)3 complex/toluene and dimethylacetamide (DMA) as co-solvent with methyl acrylate is reported. Electronic and steric effects were investigated engaging diversely 2-bromo-3,6-disubstituted pyridines. As application, a new synthesis of the 6-methyl cyclopenta[b]pyridinone building-block connecting Heck vinylation, alkene reduction and Dieckmann condensation is described. 相似文献
74.
The IDCP-promoted intramolecular C-glycosylation of pentenyl α-mannopyranosides carrying, at O-2, an activated benzyl group gave, unexpectedly, the 1,2-trans-fused bicyclic product which corresponds to an α-C-aryl mannopyranose derivative. This remarkable, strained C-glycosyl compound was rapidly epimerized to the more stable 1,2-cis product on treatment with BF3·Et2O. The IDCP-reaction product could be elaborated into a 2-(α-C-mannopyranosyl)-3,4,5-trimethoxybenzyl alcohol derivative. 相似文献
75.
Herv Bouchard Jean-Pierre Pulicani Marc Vuilhorgne Jean-Dominique Bourzat Alain Commer on 《Tetrahedron letters》1994,35(52):9713-9716
A new route to semisynthetic 19-nor-7β, 8β-methylene taxoids, such as compound 8, from the 7-O-trifluoromethanesulfonyl derivative 6 is reported. Evidence for a dissociation of the triflate to form a carbocation at C-7 under the reaction conditions is presented. Electrochemical reduction of the cyclopropane taxoid 8 gives, besides the expected 10-dehydroxy-cyclopropane analog 10, the 7-membered C-ring derivative 11. 相似文献
76.
Secondary structure motifs in nucleic acid probes generally impair intended hybridization reactions and so efforts to predict and avoid such structures are commonly employed in probe design schemes. Another key facet of probe design that has received much less attention, however, is that secondary structure at targeted probe binding site regions may also impair hybridization. Thus, evaluation of both probe and target site secondary structures together should improve hybridization prediction and design effectiveness. Several challenges confound this goal, including imperfect empirical rules and parameters underlying predictions and the fact that folding algorithms scale poorly with respect to sequence length. Here, we attempt to quantify the consequences of target site structure on predicted hybridization using sequences sampled from the human genome. We also provide a methodology for choosing a reasonable “window size” around target sites that is as small as possible without compromising folding algorithm prediction accuracy. 相似文献
77.
Hexanethiolate monolayer-protected gold nanoclusters (MPCs) were used as redox quenchers at the polarizable water/1,2-dichloroethane (DCE) interface. Photocurrent responses originating from the heterogeneous quenching of photoexcited water soluble porphyrin complexes by MPCs dissolved in the DCE phase were observed. As MPCs can function as both electron acceptors and donors, the photocurrent results from the superposition of two simultaneous processes, which correspond to the oxidation and reduction of MPCs. The magnitude of the net photocurrent is essentially determined by the balance of the kinetics of these two processes, which can be controlled by tuning the Galvani potential difference between the two phases. We show that, within the available potential window, the apparent electron-transfer rate constants follow classical Butler-Volmer dependence on the applied potential difference. 相似文献
78.
Collot J Gradinaru J Humbert N Skander M Zocchi A Ward TR 《Journal of the American Chemical Society》2003,125(30):9030-9031
Homogeneous and enzymatic catalysis offer complementary means to generate enantiomerically pure compounds. Incorporation of achiral biotinylated rhodium-diphosphine complexes into (strept)avidin yields artificial metalloenzymes for the hydrogenation of N-protected dehydroamino acids. A chemogenetic optimization procedure allows one to produce (R)-acetamidoalanine with 96% enantioselectivity. These hybrid catalysts display features reminiscent both of enzymatic and of homogeneous systems. 相似文献
79.
Skander M Humbert N Collot J Gradinaru J Klein G Loosli A Sauser J Zocchi A Gilardoni F Ward TR 《Journal of the American Chemical Society》2004,126(44):14411-14418
We report on the generation of artificial metalloenzymes based on the noncovalent incorporation of biotinylated rhodium-diphosphine complexes in (strept)avidin as host proteins. A chemogenetic optimization procedure allows one to optimize the enantioselectivity for the reduction of acetamidoacrylic acid (up to 96% ee (R) in streptavidin S112G and up to 80% ee (S) in WT avidin). The association constant between a prototypical cationic biotinylated rhodium-diphosphine catalyst precursor and the host proteins was determined at neutral pH: log K(a) = 7.7 for avidin (pI = 10.4) and log K(a) = 7.1 for streptavidin (pI = 6.4). It is shown that the optimal operating conditions for the enantioselective reduction are 5 bar at 30 degrees C with a 1% catalyst loading. 相似文献
80.
Paul Kirren Lucile Barka Saher Rahmani Nicolas Bondon Nicolas Donzel Philippe Trens Aurlie Bessire Laurence Raehm Clarence Charnay Jean-Olivier Durand 《Molecules (Basel, Switzerland)》2022,27(13)
(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO2) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth’s temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO2 present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO2 adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO2 adsorption were obtained with 6% bipyridine: 1.045 mmol·g−1 at 298 K and 2.26 mmol·g−1 at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application. 相似文献