全文获取类型
收费全文 | 367篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 278篇 |
晶体学 | 2篇 |
力学 | 2篇 |
数学 | 51篇 |
物理学 | 60篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 13篇 |
2015年 | 10篇 |
2014年 | 14篇 |
2013年 | 19篇 |
2012年 | 23篇 |
2011年 | 25篇 |
2010年 | 23篇 |
2009年 | 13篇 |
2008年 | 16篇 |
2007年 | 21篇 |
2006年 | 27篇 |
2005年 | 22篇 |
2004年 | 12篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 14篇 |
2000年 | 13篇 |
1999年 | 11篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1963年 | 1篇 |
1962年 | 1篇 |
1960年 | 1篇 |
1938年 | 1篇 |
1932年 | 2篇 |
排序方式: 共有393条查询结果,搜索用时 15 毫秒
61.
El Gabaly F Gallego S Muñoz C Szunyogh L Weinberger P Klein C Schmid AK McCarty KF de la Figuera J 《Physical review letters》2006,96(14):147202
By means of spin-polarized low-energy electron microscopy, we show that the magnetic easy axis of one to three atomic-layer thick cobalt films on Ru(0001) changes its orientation twice during deposition: One-monolayer and three-monolayer thick films are magnetized in plane, while two-monolayer films are magnetized out of plane. The Curie temperatures of films thicker than one monolayer are well above room temperature. Fully relativistic calculations based on the screened Korringa-Kohn-Rostoker method demonstrate that only for two-monolayer cobalt films does the interplay between strain, surface, and interface effects lead to perpendicular magnetization. 相似文献
62.
Fernández Julio R. Gallego Inés Jiménez-Losada Andrés Ordóñez Manuel 《Fuzzy Optimization and Decision Making》2022,21(4):531-551
Fuzzy Optimization and Decision Making - Cost-allocation problems in a fixed network are concerned with distributing the costs for use by a group of clients who cooperate in order to reduce such... 相似文献
63.
Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Silvia Alonso‐de Castro Prof. Aitziber L. Cortajarena Prof. Fernando López‐Gallego Prof. Luca Salassa 《Angewandte Chemie (International ed. in English)》2018,57(12):3143-3147
Recent advances in bioorthogonal catalysis promise to deliver new chemical tools for performing chemoselective transformations in complex biological environments. Herein, we report how FAD (flavin adenine dinucleotide), FMN (flavin mononucleotide), and four flavoproteins act as unconventional photocatalysts capable of converting PtIV and RuII complexes into potentially toxic PtII or RuII?OH2 species. In the presence of electron donors and low doses of visible light, the flavoproteins mini singlet oxygen generator (miniSOG) and NADH oxidase (NOX) catalytically activate PtIV prodrugs with bioorthogonal selectivity. In the presence of NADH, NOX catalyzes PtIV activation in the dark as well, indicating for the first time that flavoenzymes may contribute to initiating the activity of PtIV chemotherapeutic agents. 相似文献
64.
Francisco Javier Gallego B. P. Purnaprajna 《Transactions of the American Mathematical Society》1997,349(6):2477-2492
The purpose of this article is to study a certain kind of numerical K3 surfaces, the so-called K3 carpets. These are double structures on rational normal scrolls with trivial dualizing sheaf and irregularity . As is deduced from our study, K3 carpets can be obtained as degenerations of smooth K3 surfaces. We also study the Hilbert scheme near the locus parametrizing K3 carpets, characterizing those K3 carpets whose corresponding Hilbert point is smooth. Contrary to the case of canonical ribbons, not all K3 carpets are smooth points of the Hilbert scheme.
65.
González-Alvarez A Alfonso I Díaz P García-España E Gotor-Fernández V Gotor V 《The Journal of organic chemistry》2008,73(2):374-382
The interaction of a synthetic enantiopure azamacrocyclic receptor (L) with biologically important chiral dicarboxylates (A, 1-7) has been studied by means of potentiometric titrations in 0.15 M NaCl aqueous solution in a wide pH range. This macrocycle forms strong complexes of the type [HnLA](n-2) (with n = 0-5). As a general trend, the binding is much tighter at basic or neutral pH than in acidic medium. Interestingly, nonprotected excitatory amino acids (Asp and Glu) are strongly bound even at acidic pH. Regarding selectivity, the receptor showed stereoselective binding toward those substrates bearing an H-bonding donor at Calpha, being S-selective in most of the cases, except for glutamic acid. Thus, L displayed an excellent enantioselectivity for (S)-malate dianion (KS/KR = 11.50 at pH 10.0 and KS/KR = 6.86 at pH 7.0) and exhibited moderate enantiopreference for (S,S)-tartrate (KSS/KRR = 3.01 at pH 10 and KSS/KRR = 1.70 at pH 7.0). For this last anion, a very good diastereopreference was also observed (KSS/KRS = 8.46 at pH 10 and KSS/KRS = 4.99 at pH 7.0). On the contrary, L is smoothly R-selective toward (R)-Glu (KR/KS = 3.22 at pH 10 and KR/KS = 2.05 at pH 7.0) due to its longer and more flexible molecular structure. The stereoselectivity of the corresponding complexes decreased when decreasing pH values. For the hydroxy derivatives, mass spectrometry also reflected the trends observed by potentiometry and confirmed the receptor:dicarboxylate 1:1 stoichiometry of the supramolecular complexes. Additional experimental techniques were used to study the most stereoselective example. Solution studies by NMR suggested a good geometrical complementarity between the malate dianion and the receptor, which showed a predominant helical conformation in solution. Besides, self-diffusion rates (PGSE) of the diastereomeric complexes with malate also agree with binding data. Circular dichroism was also used in this case at different pH values, showing a very good correlation between the helical content of the receptor and the stereoselectivity of the molecular recognition process. 相似文献
66.
Basic Physicochemical Properties of Polyethylene Glycol Coated Gold Nanoparticles that Determine Their Interaction with Cells
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Pablo del Pino Fang Yang Dr. Beatriz Pelaz Dr. Qian Zhang Karsten Kantner Raimo Hartmann Dr. Natalia Martinez de Baroja Marta Gallego Marco Möller Dr. Bella B. Manshian Dr. Stefaan J. Soenen René Riedel Prof. Dr. Norbert Hampp Prof. Dr. Wolfgang J. Parak 《Angewandte Chemie (International ed. in English)》2016,55(18):5483-5487
A homologous nanoparticle library was synthesized in which gold nanoparticles were coated with polyethylene glycol, whereby the diameter of the gold cores, as well as the thickness of the shell of polyethylene glycol, was varied. Basic physicochemical parameters of this two‐dimensional nanoparticle library, such as size, ζ‐potential, hydrophilicity, elasticity, and catalytic activity ,were determined. Cell uptake of selected nanoparticles with equal size yet varying thickness of the polymer shell and their effect on basic structural and functional cell parameters was determined. Data indicates that thinner, more hydrophilic coatings, combined with the partial functionalization with quaternary ammonium cations, result in a more efficient uptake, which relates to significant effects on structural and functional cell parameters. 相似文献
67.
A simple, expeditious procedure for confirming the presence of N-nitrosamines in previously screened positive water samples was proposed. Water samples were continuously aspirated into a photometric flow system for screening. Positive samples were then confirmed and N-nitrosamines were identified by gas chromatography using different detectors (mass spectrometry, flame ionization and nitrogen-phosphorus). The system for the screening purpose was based on the preconcentration of the analytes onto a sorbent column, elution, and derivatization to form nitrite, then formation of a coloured product (Griess reaction) and photometric detection. The detection limits of the gas chromatographic method for 100 ml of sample were 2.0-3.5 microg/l, 20-80 and 3-13 ng/l for flame ionization, nitrogen-phosphorus and mass spectrometric detectors, respectively. The precision as RSD was similar for all detectors (3.0-6.5%). The screening of different types of water showed that wastewaters contain levels of N-nitrosamines that can be detected only using MS as a detector. 相似文献
68.
Carola Dittfurth Evaristo Ballesteros Mercedes Gallego Miguel Valcárcel 《Spectrochimica Acta Part B: Atomic Spectroscopy》1996,51(14):1935-1941
Flame atomic absorption spectrometry was used for the determination of Mn in biological material following preconcentration by precipitation. The proposed preconcentration method is based on the continuous precipitation of Mn(II) as hydrated Mn(IV) oxide in ammonia buffer and dissolution of the precipitate with hydrogen oxalate or dilute nitric acid. The sensitivity of the Mn determination is increased by the presence of hydrogen peroxide, which raises the rate of oxidation of Mn(II) to Mn(IV). By using a time-based technique (at a sample loading rate of 4 ml min−1) a concentration factor of up to 55 was obtained using 24 ml of sample. The effect of concurrent cations was investigated; the most adverse effect was exerted by Fe(III), which interfered at concentrations 50 times higher than that of Mn(II). 相似文献
69.
Micael Gallego Abraham Duarte Manuel Laguna Rafael Martí 《Computational Optimization and Applications》2009,44(3):411-426
The maximum diversity problem presents a challenge to solution methods based on heuristic optimization. We undertake the development
of hybrid procedures within the scatter search framework with the goal of uncovering the most effective designs to tackle
this difficult but important problem. Our research revealed the effectiveness of adding simple memory structures (based on
recency and frequency) to key scatter search mechanisms. Our extensive experiments and related statistical tests show that
the most effective scatter search variant outperforms state-of-the-art methods. 相似文献
70.
A sorption study of 25 volatile organic compounds (VOCs) in different agricultural soils was carried out by using headspace-gas chromatography-mass spectrometry. The extraction of the VOCs from soil samples was carried out following the EPA method with some differences such as addition of potassium chloride and different instrumental conditions which provide higher sample throughput. In addition, a complementary study on several procedures for soil fortification with VOCs was also assayed, fortification with minimal sample handling was selected in order to minimise evaporation losses of the VOCs. The effect of clay minerals (7.0-69.7%) and organic carbon (0.2-3.5%) contents on acid and alkaline (pH 5.3-8.8) soils were evaluated. Based on the results, all compounds assayed were more sorbed in alkaline soils than acid ones; chlorobenzenes interact more strongly with agricultural soils than do alkylbenzenes. The organic carbon content affects the sorption of 25 VOCs in alkaline soils (the highest sorption was found for the most organic soil), while in acid soils VOC sorption increases as the organic carbon content decreases. The clay mineral fraction plays an important role in the sorption of VOCs in acid soil owing to pi-/n-electron interactions, this effect being more marked for chlorobenzenes. 相似文献