全文获取类型
收费全文 | 826篇 |
免费 | 38篇 |
国内免费 | 4篇 |
专业分类
化学 | 655篇 |
晶体学 | 7篇 |
力学 | 11篇 |
数学 | 102篇 |
物理学 | 93篇 |
出版年
2023年 | 4篇 |
2022年 | 12篇 |
2021年 | 23篇 |
2020年 | 27篇 |
2019年 | 17篇 |
2018年 | 13篇 |
2017年 | 10篇 |
2016年 | 35篇 |
2015年 | 38篇 |
2014年 | 22篇 |
2013年 | 42篇 |
2012年 | 51篇 |
2011年 | 65篇 |
2010年 | 41篇 |
2009年 | 29篇 |
2008年 | 42篇 |
2007年 | 56篇 |
2006年 | 42篇 |
2005年 | 37篇 |
2004年 | 33篇 |
2003年 | 29篇 |
2002年 | 18篇 |
2001年 | 9篇 |
2000年 | 19篇 |
1999年 | 16篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 13篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1967年 | 3篇 |
排序方式: 共有868条查询结果,搜索用时 31 毫秒
81.
Synthesis of Novel Ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐Carboxylates as Potential Anticancer Agents 下载免费PDF全文
Victor Facchinetti Felipe A. Guimarães Marcus Vinícius N. de Souza Claudia Regina B. Gomes Maria Cecília B. V. de Souza James L. Wardell Solange M. S. V. Wardell Thatyana R. A. Vasconcelos 《Journal of heterocyclic chemistry》2015,52(4):1245-1252
A series of ethyl (substituted)phenyl‐4‐oxothiazolidin‐3‐yl)‐1‐ethyl‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylates ( 7a , 7b , 7c , 7d , 7e , 7f , 7g ) has been prepared from reactions between aminoquinolones 6 with arenealdehydes and mercaptoacetic acid. The critical intermediates, 6 a and 6b , were obtained from appropriate amines by a sequence of steps involving (i) reaction with diethylethoxymethylenemalonate, (ii) thermal cyclization in diphenyl ether, (iii) ethylation and (iv) Pd/C catalyzed reduction. New compounds 7a , 7b , 7c , 7d , 7e , 7f , 7g were fully identified and characterized by NMR (1H and 13C) and specifically for 7d by X‐ray crystallography. Compounds 7b , 7c , 7d , 7e , 7f were found not to exhibit activity at 10 uM concentrations against gastric ascitis (AGP‐01), gastric adenocarcinoma kind intestinal (ACP‐02), colon (HCT‐116) and murine melanome (B16F10) cancer cells. However, none exhibited cytotoxicity against normal cells human fibroblast (MRC‐5), murine fibroblast (NIH3T3) and normal human melanocyte (Melan‐A). 相似文献
82.
83.
84.
Frontispiece: Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH4][M(HCOO)3] by Solid‐State NMR Spectroscopy 下载免费PDF全文
85.
Daniel Kogelnig Anna Regelsberger Anja Stojanovic Franz Jirsa Regina Krachler Bernhard K. Keppler 《Monatshefte für Chemie / Chemical Monthly》2011,253(3):769-772
Abstract
Extraction of Zn(II) from aqueous solution using polymer inclusion membranes based on poly(vinyl chloride) containing the phosphonium-based ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos? IL 101) is described. Zn(II) could efficiently be extracted from 5 M hydrochloric acid solution with membranes containing 30 wt% Cyphos IL 101, whereas back-extraction was successfully achieved with 1 M sulfuric acid. Prepared membranes were evaluated in terms of stability in air as well as in terms of leaching of the ionic liquid from the membranes in aqueous solution. 相似文献86.
Rio-Echevarria IM Tavano R Causin V Papini E Mancin F Moretto A 《Journal of the American Chemical Society》2011,133(1):8-11
The stabilizing action of C(α)-tetrasubstituted α-amino acids inserted into a sequence of short peptides allowed for the first time the preparation of water-soluble nanoparticles of different materials coated with a helix-structured undecapeptide. This peptide coating strongly favors nanoparticle uptake by human immune system cells. 相似文献
87.
Mtei RP Lyashenko G Stein B Rubie N Hille R Kirk ML 《Journal of the American Chemical Society》2011,133(25):9762-9774
The electronic structure of a genuine paramagnetic des-oxo Mo(V) catalytic intermediate in the reaction of dimethyl sulfoxide reductase (DMSOR) with (CH(3))(3)NO has been probed by electron paramagnetic resonance (EPR), electronic absorption, and magnetic circular dichroism (MCD) spectroscopies. EPR spectroscopy reveals rhombic g- and A-tensors that indicate a low-symmetry geometry for this intermediate and a singly occupied molecular orbital that is dominantly metal centered. The excited-state spectroscopic data were interpreted in the context of electronic structure calculations, and this has resulted in a full assignment of the observed MCD and electronic absorption bands, a detailed understanding of the metal-ligand bonding scheme, and an evaluation of the Mo(V) coordination geometry and Mo(V)-S(dithiolene) covalency as it pertains to the stability of the intermediate and electron-transfer regeneration. Finally, the relationship between des-oxo Mo(V) and des-oxo Mo(IV) geometric and electronic structures is discussed relative to the reaction coordinate in members of the DMSOR enzyme family. 相似文献
88.
Peixoto L Min B Martins G Brito AG Kroff P Parpot P Angelidaki I Nogueira R 《Bioelectrochemistry (Amsterdam, Netherlands)》2011,81(2):99-103
The biological oxygen demand (BOD) may be the most used test to assess the amount of pollutant organic matter in water; however, it is time and labor consuming, and is done ex-situ. A BOD biosensor based on the microbial fuel cell principle was tested for online and in situ monitoring of biodegradable organic content of domestic wastewater. A stable current density of 282±23mA/m(2) was obtained with domestic wastewater containing a BOD(5) of 317±15mg O(2)/L at 22±2°C, 1.53±0.04mS/cm and pH 6.9±0.1. The current density showed a linear relationship with BOD(5) concentration ranging from 17±0.5mg O(2)/L to 78±7.6mg O(2)/L. The current generation from the BOD biosensor was dependent on the measurement conditions such as temperature, conductivity, and pH. Thus, a correction factor should be applied to measurements done under different environmental conditions from the ones used in the calibration. These results provide useful information for the development of a biosensor for real-time in situ monitoring of wastewater quality. 相似文献
89.
Regina Rotman 《Mathematische Zeitschrift》2011,269(1-2):543-554
In this paper, we will present two upper bounds for the length of a smallest “flower-shaped” geodesic net in terms of the volume and the diameter of a manifold. Minimal geodesic nets are critical points of the length functional on the space of graphs immersed into a Riemannian manifold. Let M n be a closed Riemannian manifold of dimension n. We prove that there exists a minimal geodesic net that consists of one vertex and at most 2n ? 1 geodesic loops based at that vertex of total length ≤ 2n!d, where d is the diameter of M n . We also show that there exists a minimal geodesic net that consists of one vertex and at most ${3^{(n+1)^2}}$ loops of total length ${\leq2 (n+1)!^2 3^{(n+1)^3}\,Fill\,Rad\,M^n \leq2(n+1)!^{\frac{5}{2}}3^{(n+1)^3}(n+1)n^n vol(M^n)^{\frac{1}{n}}}$ , where Fill Rad M n denotes the filling radius and vol(M n ) denotes the volume of M n . 相似文献
90.
Broeckhoven K Verstraeten M Choikhet K Dittmann M Witt K Desmet G 《Journal of chromatography. A》2011,1218(8):1153-1169
We report on a general theoretical assessment of the potential kinetic advantages of running LC gradient elution separations in the constant-pressure mode instead of in the customarily used constant-flow rate mode. Analytical calculations as well as numerical simulation results are presented. It is shown that, provided both modes are run with the same volume-based gradient program, the constant-pressure mode can potentially offer an identical separation selectivity (except from some small differences induced by the difference in pressure and viscous heating trajectory), but in a significantly shorter time. For a gradient running between 5 and 95% of organic modifier, the decrease in analysis time can be expected to be of the order of some 20% for both water–methanol and water–acetonitrile gradients, and only weakly depending on the value of VG/V0 (or equivalently tG/t0). Obviously, the gain will be smaller when the start and end composition lie closer to the viscosity maximum of the considered water-organic modifier system. The assumptions underlying the obtained results (no effects of pressure and temperature on the viscosity or retention coefficient) are critically reviewed, and can be inferred to only have a small effect on the general conclusions. It is also shown that, under the adopted assumptions, the kinetic plot theory also holds for operations where the flow rate varies with the time, as is the case for constant-pressure operation. Comparing both operation modes in a kinetic plot representing the maximal peak capacity versus time, it is theoretically predicted here that both modes can be expected to perform equally well in the fully C-term dominated regime (where H varies linearly with the flow rate), while the constant pressure mode is advantageous for all lower flow rates. Near the optimal flow rate, and for linear gradients running from 5 to 95% organic modifier, time gains of the order of some 20% can be expected (or 25–30% when accounting for the fact that the constant pressure mode can be run without having to leave a pressure safety margin of 5–10% as is needed in the constant flow rate mode). 相似文献