全文获取类型
收费全文 | 852篇 |
免费 | 2篇 |
国内免费 | 4篇 |
专业分类
化学 | 627篇 |
晶体学 | 6篇 |
力学 | 29篇 |
数学 | 91篇 |
物理学 | 105篇 |
出版年
2023年 | 7篇 |
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 7篇 |
2019年 | 4篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 31篇 |
2012年 | 36篇 |
2011年 | 53篇 |
2010年 | 22篇 |
2009年 | 16篇 |
2008年 | 49篇 |
2007年 | 61篇 |
2006年 | 51篇 |
2005年 | 49篇 |
2004年 | 63篇 |
2003年 | 44篇 |
2002年 | 36篇 |
2001年 | 8篇 |
2000年 | 5篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 12篇 |
1996年 | 12篇 |
1995年 | 11篇 |
1994年 | 10篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 16篇 |
1989年 | 10篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 21篇 |
1983年 | 10篇 |
1982年 | 17篇 |
1981年 | 5篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 18篇 |
1977年 | 13篇 |
1976年 | 13篇 |
1975年 | 8篇 |
1974年 | 8篇 |
1973年 | 5篇 |
1968年 | 3篇 |
排序方式: 共有858条查询结果,搜索用时 46 毫秒
61.
Botek E d'Antuono P Jacques A Carion R Champagne B Maton L Taziaux D Habib-Jiwan JL 《Physical chemistry chemical physics : PCCP》2010,12(42):14172-14187
A joint theoretical-experimental investigation has been carried out to unravel the details of the complexation of cations by fluoroionophores based on coumarin 343 and to interpret the modifications in the ligand and also in the coumarin structural, electronic, magnetic, and vibrational properties. It is confirmed that C343-dea (1) complexes the cations by both the lactone and the amide oxygen atoms whereas for C343-crown (2) and C343-dibenzocrown (3), the cations are complexed by the oxygen atoms of the lactone as well as those of the crown ligand. These complexations induce geometric modifications, which are delocalized over the coumarin backbone and are related to electronic reorganizations that modify the spectroscopic signatures. This paper analyzes these signatures and shows how they are related as well as how they can be used to monitor the complexation process. Upon complexation, the UV-visible absorption spectra display a bathochromic shift of the most intense electronic transition; this shift is generally larger for the most flexible compound 1 as well as when complexing divalent cations. NMR spectra bear many signatures of the complexation, of which the most remarkable ones are the large shielding of C(1) and the large deshieldings of C(9) and C(16). Additional makers of complexation are highlighted in the IR vibrational spectra, in particular the bands associated with the lactone and amide CO vibrations, which are downshifted when the corresponding CO is involved in the complexation mode and, otherwise, upshifted. A high degree of consistency characterizes the different geometrical, electronic, magnetic, and vibrational signatures, which substantiates the assignment of the modes of complexation in 1-3. In addition, the agreement between the experimental data and the theoretical values is rather satisfactory, in that it at least enables us to interpret the spectral signatures. 相似文献
62.
The ground state, oxidized ground state, (3)MLCT and (3)MC excited states have been studied by DFT and TDDFT for two Ru(II) complexes bearing an N(6) or N(5)C coordination sphere. The effect of replacing one Ru-N dative bond by one Ru-C covalent bond have been studied and quantified on their ground state by the means of geometry optimization, NBO analysis and calculation of their IR vibrations. IR fingerprints of the Ru-C bond have been found at 945 and 1113 cm(-1). In addition, this study confirmed and quantified the effects of N→C(-) substitution on the spectroscopic properties of the [RuN(5)C](+) complex: a broader and bathochromically-shifted absorption spectrum, a smaller ground-(3)MLCT energy gap and a highly energetic (3)MC state are the major characteristics of the carbon-containing monocationic complex. 相似文献
63.
Clementine Cailleteau Ludovic Micallef Clemence Lepage Philippe Jean-Paul Cardot Jean-Louis Beneytout Bertrand Liagre Serge Battu 《Analytical and bioanalytical chemistry》2010,398(3):1273-1283
Differentiation therapy could be one strategy for stopping cancer cell proliferation. A plant steroid, diosgenin, is known
to induce megakaryocytic differentiation in human erythroleukemia (HEL) cells. In recent studies, the use of sedimentation
field-flow fractionation (SdFFF) allowed the preparation of subpopulations that may differ in regard to sensitivity to differentiation
induction. The specific goal of this study was to determine the relationship between cell cycle stage and sensitivity to megakaryocytic
differentiation induction of HEL cells. After first confirming the capacity of diosgenin to specifically select targets, hyperlayer
SdFFF cell sorting was used to prepare fractions according to cell cycle position from crude HEL cells. The sensitivities
of these fractions to diosgenin-induced differentiation were then tested. The coupling of SdFFF cell separation to imaging
flow cytometry showed that G1-phase cells were more sensitive to differentiation induction than S/G2M-phase cells, confirming
the relationship between cell status at the start of induction, the extent of the biological event, and the potential of SdFFF
in cancer research. 相似文献
64.
Biswas R Maillard N Kofoed J Reymond JL 《Chemical communications (Cambridge, England)》2010,46(46):8746-8748
Fluorescence screening of a 96-membered SPOT library of histidine containing dendritic and linear peptides revealed the remarkable esterolytic activity of short histidine oligomers that show catalytic proficiencies within one order of magnitude of histidine-containing esterase peptide dendrimers. 相似文献
65.
Candice Grivel Jean-Louis Rocca Davy Guillarme Jean-Luc Veuthey Sabine Heinisch 《Journal of chromatography. A》2010,1217(4):459-472
Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested. 相似文献
66.
67.
Zhao Z Bouchoule S Song J Galopin E Harmand JC Decobert J Aubin G Oudar JL 《Optics letters》2011,36(22):4377-4379
Near-transform-limited subpicosecond pulses at 1.56 μm were generated from an optically pumped InP-based vertical-external-cavity surface-emitting laser (VECSEL) passively mode-locked at 2 GHz repetition rate with a fast InGaAsNSb/GaAs semiconductor saturable absorber mirror (SESAM). The SESAM microcavity resonance was adjusted via a selective etching of phase layers specifically designed to control the magnitude of both the modulation depth and the intracavity group delay dispersion of the SESAM. Using the same VECSEL chip, we observed that the mode-locked pulse duration could be reduced from several picoseconds to less than 1 ps with a detuned resonant SESAM. 相似文献
68.
Jean-Louis Luche 《Ultrasonics sonochemistry》1994,1(2):S111-S118
Examples of sonochemical reactions occuring under heterogeneous conditions are discussed with respect to their mechanism. The activation of a metal surface involves complex phenomena, in which parameters of importance seem to be the hardness and the adhesion of the passivating layer. Some considerations are given on the probable link between sonochemistry and tribochemistry. 相似文献
69.
In this paper we define multisections of intervals that yield sharp lower bounds in branch-and-bound type methods for interval global optimization. A so called 'generalized kite', defined for differentiable univariate functions, is built simultaneously with linear boundary forms and suitably chosen centered forms. Proofs for existence and uniqueness of optimal cuts are given. The method described may be used either as an accelerating device or in a global optimization algorithm with an efficient pruning effect. A more general principle for decomposition of boxes is suggested. 相似文献
70.