全文获取类型
收费全文 | 601篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 408篇 |
晶体学 | 4篇 |
力学 | 17篇 |
数学 | 72篇 |
物理学 | 121篇 |
出版年
2024年 | 3篇 |
2023年 | 6篇 |
2022年 | 19篇 |
2021年 | 18篇 |
2020年 | 18篇 |
2019年 | 11篇 |
2018年 | 18篇 |
2017年 | 12篇 |
2016年 | 26篇 |
2015年 | 14篇 |
2014年 | 16篇 |
2013年 | 32篇 |
2012年 | 33篇 |
2011年 | 42篇 |
2010年 | 25篇 |
2009年 | 21篇 |
2008年 | 39篇 |
2007年 | 45篇 |
2006年 | 27篇 |
2005年 | 24篇 |
2004年 | 39篇 |
2003年 | 15篇 |
2002年 | 18篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 10篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1974年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有622条查询结果,搜索用时 15 毫秒
41.
Ramon Subiros-Funosas Gerardo A. Acosta Ayman El-Faham Fernando Albericio 《Tetrahedron letters》2009,50(45):6200-1844
Here we demonstrate the compatibility of Oxyma-based uronium-type coupling reagent COMU with microwave-assisted peptide synthesizers. Consistent with previous reports, COMU displayed higher efficiency than benzotriazole classical immonium salts HATU and HBTU in the demanding synthesis of the Aib derivative of Leu-Enkephalin pentapeptide and did not yield Oxyma-based byproducts. Thus, the combination of microwave irradiation and COMU resulted in a similar performance in considerably shorter time to that achieved by manual synthesis. 相似文献
42.
Miguel A. Vzquez Segura Josefa Donoso Francisco Muoz INS Fernandez
de
Pirola Francisco Garcia Blanco Gerardo R. Echevarria 《Photochemistry and photobiology》1993,57(Z1):923-928
Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (fN, fz) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (QN), fluorescence ratio of the neutral to the zwitterionic form (øN/øZ) and the rate constant of tautomerization (k1) from Z to N in the excited state. Some of these parameters (fN, Δv, QN, k1) were found to depend on the proton donor character of the solvent, whereas others (øN/øZ) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment. 相似文献
43.
44.
Karla-Alejandra Lpez-Gastlum Enrique F. Velzquez-Contreras Juventino J. García Marcos Flores-Alamo Gerardo Aguirre Daniel Chvez-Velasco Jayanthi Narayanan Fernando Rocha-Alonzo 《Molecules (Basel, Switzerland)》2021,26(23)
Two new glycine-Schiff base copper(II) complexes were synthesized. Single crystal X-ray diffraction (SCXRD) allowed us to establish the structure of both complexes in the solid state. The glycine-Schiff base copper(II) complex derived from 2′-hydroxy-5′-nitroacetophenone showed a mononuclear hydrated structure, in which the Schiff base acted as a tridentate ligand, and the glycine-Schiff base copper(II) complex derived from 2′-hydroxy-5′-methylacetophenone showed a less common tetranuclear anhydrous metallocyclic structure, in which the Schiff base acted as a tetradentate ligand. In both compounds, copper(II) had a tetracoordinated square planar geometry. The results of vibrational, electronic, and paramagnetic spectroscopies, as well as thermal analysis, were consistent with the crystal structures. Both complexes were evaluated as catalysts in the olefin cyclopropanation by carbene transference, and both led to very high diastereoselectivity (greater than 98%). 相似文献
45.
Laura Seoane Pablo Martínez-Landeira Lina Besada Juan M. Ruso Félix Sarmiento Gerardo Prieto 《Colloid and polymer science》2002,280(7):624-629
The aggregation characteristics of oxacillin in aqueous solutions have been examined by means of conductivity measurements over the temperature range 288.15-313.15 K and by static light scattering measurements at 298.15 K. Two critical concentrations were detected in conductivity and light scattering over the concentration range 0-0.35 mol kg-1. Light scattering measurements indicate the formation of dimers at the first critical concentration (0.024 mol kg-1) and the subsequent formation of aggregates with an aggregation number of 8 at the second critical concentration (0.104 molkg-1). The thermodynamic parameters of aggregation were derived from the critical concentration data using a mass-action model that has been modified for application to systems of low aggregation number. Values for the enthalpy of aggregate formation calculated by this method showed that the aggregation became increasingly exothermic with increasing temperature. The values of the two critical concentrations show that this penicillin, oxacillin, is more hydrophobic than other molecules of similar structure. 相似文献
46.
Manuel Snchez-Chaves Gerardo Martínez Enrique Lpez Madruga 《Journal of polymer science. Part A, Polymer chemistry》1999,37(15):2941-2948
2-Hydroxyethyl methacrylate (HEMA) and styrene (S) have been copolymerized in a 3 mol · L−1N,N′-dimethylformamide (DMF) solution using 2,2′azobis (isobutyronitrile) (AIBN) as an initiator over a wide composition and conversion range. From low-conversion experiments and 1H-NMR analysis, the monomer reactivity ratios were determined according to the Mayo–Lewis terminal model. The comparison of the obtained results with those previously reported for copolymerization in bulk and in toluene reveals a relatively small but noticeable solvent effect that can be qualitatively explained by the bootstrap model. Cumulative copolymer composition as a function of conversion is satisfactorily described by the integrated Mayo–Lewis equation; overall copolymerization rate increases with increasing the HEMA/S ratio, and individual monomer conversion is closely related to the monomer molar fraction in the feed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2941–2948, 1999 相似文献
47.
Manuel Snchez‐Chaves Gerardo Martínez Enrique Lpez Madruga Carmen Fernndez‐Monreal 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1192-1199
Free‐radical copolymerization of glycidyl methacrylate (GMA) with N‐vinylpyrrolidone (VPD) was carried out at 50 °C using 3.0 mol · L?1 of N,N′‐dimethylformamide solution and 9.0 · 10?3 mol · L?1 of 2,2′‐azobisisobutyronitrile as an initiator. The modification reaction of GMA‐VPD copolymers with a model bioactive carboxylic acid, 6‐methoxy‐α‐methyl‐2‐naphthaleneacetic acid (naproxen), was studied in the homogeneous phase using basic catalysts. The influence of the type of catalyst and the GMA content was evaluated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1192–1199, 2002 相似文献
48.
49.
Gerardo G. Naumis A. Bazán M. Torres R. Quintero-Torres 《Physica B: Condensed Matter》2008,403(18):3179-3184
One of the few examples in which the physical properties of an incommensurable system reflect an underlying higher dimensionality is presented. Specifically, we show that the reflectivity distribution of an incommensurable one-dimensional cavity is given by the density of states of a tight-binding Hamiltonian in a two-dimensional triangular lattice. Such effect is due to an independent phase decoupling of the scattered waves, produced by the incommensurable nature of the system, which mimics a random noise generator. This principle can be applied to design a cavity that avoids resonant reflections for almost any incident wave. An optical analogy, by using three mirrors with incommensurable distances between them, is also presented. Such array produces a countable infinite fractal set of reflections, a phenomena which is opposite to the effect of optical invisibility. 相似文献
50.
Huanwen Chen Gerardo Gamez Renato Zenobi 《Journal of the American Society for Mass Spectrometry》2009,20(11):1947-1963
Ambient mass spectrometry—mass spectrometric analysis with no or minimal effort for sample preparation—has experienced a very
rapid development during the last 5 years, with many different methods now available for ionization. Here, we review its range
of applications, the hurdles encountered for its quantitative use, and the proposed mechanisms for ion formation. Clearly,
more effort needs to be put into investigation of matrix effects, into defining representative sampling of heterogeneous materials,
and into understanding and controlling the underlying ionization mechanisms. Finally, we propose a concept to reduce the number
of different acronyms describing very similar embodiments of ambient mass spectrometry. 相似文献