全文获取类型
收费全文 | 843篇 |
免费 | 26篇 |
国内免费 | 3篇 |
专业分类
化学 | 543篇 |
晶体学 | 4篇 |
力学 | 19篇 |
数学 | 177篇 |
物理学 | 129篇 |
出版年
2023年 | 8篇 |
2022年 | 16篇 |
2021年 | 30篇 |
2020年 | 21篇 |
2019年 | 16篇 |
2018年 | 16篇 |
2017年 | 18篇 |
2016年 | 22篇 |
2015年 | 40篇 |
2014年 | 26篇 |
2013年 | 50篇 |
2012年 | 50篇 |
2011年 | 62篇 |
2010年 | 30篇 |
2009年 | 27篇 |
2008年 | 45篇 |
2007年 | 54篇 |
2006年 | 46篇 |
2005年 | 45篇 |
2004年 | 40篇 |
2003年 | 39篇 |
2002年 | 27篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 11篇 |
1998年 | 6篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1991年 | 12篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 2篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1962年 | 1篇 |
1961年 | 1篇 |
1906年 | 1篇 |
排序方式: 共有872条查询结果,搜索用时 312 毫秒
51.
Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as 15N and 13C. This report explores certain features arising in solution‐state 1H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both 13C and 1H, solution‐phase 1H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring 13C nuclei appeared larger than the typically dominant 12C‐bonded 1H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from 13C→1H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the 13C‐bound 1H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity 1H NMR traces was explored. 相似文献
52.
Carlos Eduardo Barão Leandro Daniel de Paris João Henrique Dantas Matheus Mendonça Pereira Lucio Cardozo Filho Heizir Ferreira de Castro Gisella Maria Zanin Flavio Faria de Moraes Cleide Mara Faria Soares 《Applied biochemistry and biotechnology》2014,172(1):263-274
The use of lipases in industrial processes can result in products with high levels of purity and at the same time reduce pollutant generation and improve both selectivity and yields. In this work, lipase from Thermomyces lanuginosus was immobilized using two different techniques. The first involves the hydrolysis/polycondensation of a silica precursor (tetramethoxysilane (TMOS)) at neutral pH and ambient temperature, and the second one uses tetraethoxysilane (TEOS) as the silica precursor, involving the hydrolysis and polycondensation of the alkoxide in appropriate solvents. After immobilization, the enzymatic preparations were dried using the aerogel and xerogel techniques and then characterized in terms of their hydrolytic activities using a titrimetric method with olive oil and by the formation of 2-phenylethyl acetate in a transesterification reaction. The morphological properties of the materials were characterized using scanning electron microscopy, measurements of the surface area and pore size and volume, thermogravimetric analysis, and exploratory differential calorimetry. The results of the work indicate that the use of different silica precursors (TEOS or TMOS) and different drying techniques (aerogel or xerogel) can significantly affect the properties of the resulting biocatalyst. Drying with supercritical CO2 provided higher enzymatic activities and pore sizes and was therefore preferable to drying, using the xerogel technique. Thermogravimetric analysis and differential scanning calorimetry analyses revealed differences in behavior between the two biocatalyst preparations due to the compounds present. 相似文献
53.
Liliane Majed Salem Hayar Rawan Zeitoun Britt Marianna Maestroni Sylvie Dousset 《Molecules (Basel, Switzerland)》2022,27(1)
In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg−1), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns. 相似文献
54.
55.
Cucinotta V Giuffrida A Grasso G Maccarrone G Messina M 《Journal of chromatography. A》2002,979(1-2):137-145
Six different racemates of the profen family were used as analytes in order to test the chiral selector properties of three members of a new class of cyclodextrin derivatives, hemispherodextrins (HMs), in capillary electrophoresis. In addition to experiments carried out to separate each enantiomeric pair one by one, other experiments were carried out on samples containing all six enantiomeric pairs. Electropherograms were obtained either by adding a single HM to the background electrolyte (BGE), or a binary mixture of HMs. The results obtained confirm the excellent chiral selector properties of the HMs, and furthermore show that these compounds can also be used for achiral selection. When mixing different HMs, a complementary effect in chiral selectivity is observed, which, in our opinion, deserves further study. 相似文献
56.
The static dielectric properties of (001)(GaAs)(p)/(AlAs)(p) superlattices have been calculated as a function of their period p for 1< or = p < or =12, starting from density-functional theory. The interplay between quantum confinement and local field effects is shown to be crucial. For light polarized in the growth direction it leads to the otherwise surprising justification of the use of a classical effective medium theory, even for the smallest periods. Only the inclusion of both contributions allows in ab initio and in semiempirical calculations to reproduce the experimentally observed birefringence. 相似文献
57.
Marina Quartu Maria Pina Serra Marianna Boi Viviana Ibba Tiziana Melis Marina Del Fiacco 《BMC neuroscience》2008,9(1):108
Background
The polysialylated neuronal cell adhesion molecule (PSA-NCAM) is considered a marker of developing and migrating neurons and of synaptogenesis in the immature vertebrate nervous system. However, it persists in the mature normal brain in some regions which retain a capability for morphofunctional reorganization throughout life. With the aim of providing information relevant to the potential for dynamic changes of specific neuronal populations in man, this study analyses the immunohistochemical occurrence of PSA-NCAM in the human trigeminal ganglion (TG) and brainstem neuronal populations at prenatal and adult age. 相似文献58.
Alberto Andreussi Lucio Bianco Salvatore Ricciardelli 《European Journal of Operational Research》1981,8(4):345-354
The objective of this study is the development of a simulation model to assist in aircraft sequencing operations in the terminal area. After the definition of the main characteristics of the model, a general structure of a terminal area is considered with a variable number of feeder fixes and alternative paths from the fixes to the runways. The model is designed so as to evaluate different operating policies. A discrete events simulation philosophy, using Fortran as simulation language, is employed. Finally a model application to the Rome terminal area is illustrated. The results obtained show that the model, here presented, is general enough to simulate the terminal area behaviour of any airport. 相似文献
59.
60.
Mishkovsky M Frydman L 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,173(2):344-350
A new protocol for processing the data arising in ultrafast 2D NMR is discussed and exemplified, based on the interlaced Fourier transformation. This approach is capable of dealing in a single, combined fashion, with the two mirror-imaged interferograms arising in this kind of experiment as a result of the acquisition of a train of magnetic field gradient echoes. By combining all the acquired data points into a common Fourier processing procedure the spectral width along the direct-acquisition domain becomes effectively doubled, giving the opportunity of employing acquisition gradients that are approximately half as strong as hitherto required. This in turn should lead to an overall enhancement in the signal-to-noise ratio of the experiment of ca. 2, as well as to improvements in the achievable digital resolution. These expectations were tested by carrying out a series of homo- and heteronuclear ultrafast 2D NMR acquisitions, and found systematically fulfilled. The robustness and conditions that allow the interlaced numerical procedure to be implemented in routine analytical applications were explored and are briefly discussed. 相似文献