全文获取类型
收费全文 | 393篇 |
免费 | 7篇 |
国内免费 | 4篇 |
专业分类
化学 | 244篇 |
晶体学 | 7篇 |
力学 | 19篇 |
数学 | 64篇 |
物理学 | 70篇 |
出版年
2023年 | 7篇 |
2022年 | 2篇 |
2021年 | 11篇 |
2020年 | 8篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2016年 | 7篇 |
2015年 | 2篇 |
2014年 | 11篇 |
2013年 | 15篇 |
2012年 | 32篇 |
2011年 | 23篇 |
2010年 | 10篇 |
2009年 | 13篇 |
2008年 | 26篇 |
2007年 | 24篇 |
2006年 | 23篇 |
2005年 | 19篇 |
2004年 | 13篇 |
2003年 | 11篇 |
2002年 | 14篇 |
2001年 | 8篇 |
2000年 | 10篇 |
1999年 | 9篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1968年 | 4篇 |
1941年 | 2篇 |
1940年 | 1篇 |
1913年 | 1篇 |
1897年 | 1篇 |
1891年 | 1篇 |
排序方式: 共有404条查询结果,搜索用时 125 毫秒
21.
Clarissa A. Olivati Rodrigo F. Bianchi Osvaldo N. Oliveira Jr. 《Polymer Degradation and Stability》2006,91(10):2342-2346
Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process. 相似文献
22.
Jorge Ferreira Raquel Zilz Igor S. Boeira Sabrina M. da Silva Adriana C.A. Casagrande Osvaldo L. Casagrande 《应用有机金属化学》2019,33(3)
A new set of Cr(III) complexes, {L}CrCl3(THF), based on thiophene–imine ( 2a , L = PhOC6H4(N═CH)‐2‐SC4H3; 2b , L = PhOC2H4(N═CH)‐2‐SC4H3; 2c , L = Ph(NH)C2H4(N═CH)‐2‐SC4H3; 2d , L = PhOC6H4(N═CH)‐2‐SC4H2‐5‐Ph; 2e , L = Ph(NH)C2H4(N═CH)‐2‐SC4H2‐5‐Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α‐olefins with turnover frequencies in the range 9500–93 500 (mol ethylene) (mol Cr)?1 h?1, and producing mostly oligomers (95.0–99.3 wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2 wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined. 相似文献
23.
A simple and high‐resolution HPLC‐PDA method for simultaneous quantification of local anesthetics in in vitro buccal permeation enhancement studies 下载免费PDF全文
Renê O. Couto Camila Cubayachi Renata F. V. Lopez Cristiane M. de Gaitani Vinícius Pedrazzi Osvaldo de Freitas 《Biomedical chromatography : BMC》2016,30(6):857-866
A simple, isocratic, high‐resolution and prompt HPLC‐PDA method was developed and validated for the simultaneous quantification of prilocaine (PCL) and lidocaine (LCL) hydrochlorides in in vitro buccal iontophoresis‐driven permeation studies. A reversed‐phase C18 column (250 mm x 4.6 mm, 3μm, 110Å) was used for the chromatographic separation. The mobile phase contained acetonitrile: 0.1M sodium phosphate buffer, pH 7.0 (1:1, v/v), plus 0.05% (v/v) diethylamine. The isocratic flow rate was set at 1 mL/min and the detection wavelength was 203 nm. PCL and LCL eluted in 8.9 min and 13 min, respectively, and the system suitability parameters varied within an acceptable range. The method was selective, sensitive, precise, accurate and robust, producing a linear plot at the concentration range of 0.25 to 10 µg/mL. The application of this method was demonstrated by a significant enhancement of the permeation of PCL and LCL with the application of iontophoresis (1 mA/cm2 per 1 h) through isolated porcine esophageal epithelium. The amount of the drug retained in the epithelium also increased with the application of an electrical current. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
24.
Olimpo García-Beltrán Bruce K. Cassels Natalia Mena Marco T. Nuñez Osvaldo Yañez Julio Caballero 《Tetrahedron letters》2014
In this Letter we present a new probe, (E)-7-(diethylamino)-2-oxo-2H-chromene-3-carbaldehyde oxime (JB), which can detect Cu2+ ions in HEPES buffer under physiological conditions. Benesi–Hildebrand and Job plots demonstrate that the stoichiometry of the Cu2+ complex formed is 2:1. Possible interference with other analytes was examined, and the decrease of the fluorescence of JB at 510 nm when it reacts with Cu2+ was shown to be highly selective. This probe accumulates in the plasmalemma of human neuroblastoma SH-SY5Y cells. Molecular dynamics (MD) simulations revealed that JB interacts with the lipid bilayer at the level of the glycerol moieties. 相似文献
25.
Jorge A. Vila Yelena A. Arnautova Osvaldo A. Martin Harold A. Scheraga 《Journal of computational chemistry》2014,35(4):309-312
The goal of this study is twofold. First, to investigate the relative influence of the main structural factors affecting the computation of the 13C′ shielding, namely, the conformation of the residue itself and the next nearest‐neighbor effects. Second, to determine whether calculation of the 13C′ shielding at the density functional level of theory (DFT), with an accuracy similar to that of the 13Cα shielding, is feasible with the existing computational resources. The DFT calculations, carried out for a large number of possible conformations of the tripeptide Ac‐G XY ‐NMe, with different combinations of X and Y residues, enable us to conclude that the accurate computation of the 13C′ shielding for a given residue X depends on the: (i) (?,ψ) backbone torsional angles of X ; (ii) side‐chain conformation of X ; (iii) (?,ψ) torsional angles of Y ; and (iv) identity of residue Y . Consequently, DFT‐based quantum mechanical calculations of the 13C′ shielding, with all these factors taken into account, are two orders of magnitude more CPU demanding than the computation, with similar accuracy, of the 13Cα shielding. Despite not considering the effect of the possible hydrogen bond interaction of the carbonyl oxygen, this work contributes to our general understanding of the main structural factors affecting the accurate computation of the 13C′ shielding in proteins and may spur significant progress in effort to develop new validation methods for protein structures. © 2013 Wiley Periodicals, Inc. 相似文献
26.
Bovine lactoferrin purification from whey using Yellow HE‐4R as the chromatographic affinity ligand 下载免费PDF全文
María Fernanda Baieli Nicolás Urtasun María Victoria Miranda Osvaldo Cascone Federico Javier Wolman 《Journal of separation science》2014,37(5):484-487
The worldwide production of whey increases by around 186 million tons each year and it is generally considered as a waste, even when several whey proteins have important economic relevance. For its valorization, inexpensive ligands and integrated chromatography methods need to be developed for specific and low‐cost protein purification. Here, we describe a novel affinity process with the dye Yellow HE‐4R immobilized on Sepharose for bovine lactoferrin purification. This approach based on a low‐cost ligand showed an efficient performance for the recovery and purification of bovine lactoferrin directly from whey, with a yield of 71% and a purification factor of 61. 相似文献
27.
María Fernanda Manrique-de-la-Cuba Luis Leyva-Parra Diego Inostroza Prof. Badhin Gomez Dr. Alejandro Vásquez-Espinal Prof. Jorge Garza Dr. Osvaldo Yañez Prof. William Tiznado 《Chemphyschem》2021,22(10):906-910
We report the global minima structures of Li8Si8, Li10Si9, and Li12Si10 systems, in which silicon moieties maintain structural and chemical bonding characteristics similar to those of their building blocks: the aromatic clusters Td−Li4Si4 and C2v−Li6Si5. Electron counting rules, chemical bonding analysis, and magnetic response properties verify the silicon unit‘s aromaticity persistence. This study demonstrates the feasibility of assembling silicon-based nanostructures from aromatics clusters as building blocks. 相似文献
28.
Giorgio Olivo Giorgio Capocasa Barbara Ticconi Osvaldo Lanzalunga Stefano Di Stefano Miquel Costas 《Angewandte Chemie (International ed. in English)》2020,59(31):12703-12708
Predictability is a key requirement to encompass late‐stage C?H functionalization in synthetic routes. However, prediction (and control) of reaction selectivity is usually challenging, especially for complex substrate structures and elusive transformations such as remote C(sp3)?H oxidation, as it requires distinguishing a specific C?H bond from many others with similar reactivity. Developed here is a strategy for predictable, remote C?H oxidation that entails substrate binding to a supramolecular Mn or Fe catalyst followed by elucidation of the conformation of the host‐guest adduct by NMR analysis. These analyses indicate which remote C?H bonds are suitably oriented for the oxidation before carrying out the reaction, enabling prediction of site selectivity. This strategy was applied to late‐stage C(sp3)?H oxidation of amino‐steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal. 相似文献
29.
Laura C. Carpi Osvaldo A. Rosso Patricia M. Saco Martín Gómez Ravetti 《Physics letters. A》2011,375(4):801-804
A methodology to analyze dynamical changes in complex networks based on Information Theory quantifiers is proposed. The square root of the Jensen-Shannon divergence, a measure of dissimilarity between two probability distributions, and the MPR Statistical Complexity are used to quantify states in the network evolution process. Three cases are analyzed, the Watts-Strogatz model, a gene network during the progression of Alzheimer's disease and a climate network for the Tropical Pacific region to study the El Niño/Southern Oscillation (ENSO) dynamic. We find that the proposed quantifiers are able not only to capture changes in the dynamics of the processes but also to quantify and compare states in their evolution. 相似文献
30.