全文获取类型
收费全文 | 322篇 |
免费 | 30篇 |
国内免费 | 2篇 |
专业分类
化学 | 267篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 33篇 |
物理学 | 39篇 |
出版年
2024年 | 2篇 |
2023年 | 12篇 |
2022年 | 14篇 |
2021年 | 20篇 |
2020年 | 11篇 |
2019年 | 15篇 |
2018年 | 15篇 |
2017年 | 4篇 |
2016年 | 27篇 |
2015年 | 17篇 |
2014年 | 14篇 |
2013年 | 31篇 |
2012年 | 22篇 |
2011年 | 36篇 |
2010年 | 15篇 |
2009年 | 8篇 |
2008年 | 24篇 |
2007年 | 12篇 |
2006年 | 12篇 |
2005年 | 11篇 |
2004年 | 5篇 |
2003年 | 4篇 |
2002年 | 7篇 |
2001年 | 5篇 |
2000年 | 2篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1987年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1926年 | 1篇 |
1896年 | 1篇 |
排序方式: 共有354条查询结果,搜索用时 46 毫秒
21.
Maxime Balestrat Abhijeet Lale Andr Vinícius Andrade Bezerra Vanessa Proust Eranezhuth Wasan Awin Ricardo Antonio Francisco Machado Pierre Carles Ravi Kumar Christel Gervais Samuel Bernard 《Molecules (Basel, Switzerland)》2020,25(22)
The pyrolysis (1000 °C) of a liquid poly(vinylmethyl-co-methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000–1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere. Then, the structural evolution of the amorphous network of ammonia-, nitrogen- and argon-treated ceramics has been studied above 1000 °C under nitrogen and argon by X-ray diffraction and electron microscopy. HRTEM images coupled with XRD confirm the formation of nanocomposites after annealing at 1400 °C. Their unique nanostructural feature appears to be the result of both the molecular origin of the materials and the nature of the atmosphere used during pyrolysis. Samples are composed of an amorphous Si-based ceramic matrix in which TiNxCy nanocrystals (x + y = 1) are homogeneously formed “in situ” in the matrix during the process and evolve toward fully crystallized compounds as TiN/Si3N4, TiNxCy (x + y = 1)/SiC and TiC/SiC nanocomposites after annealing to 1800 °C as a function of the atmosphere. 相似文献
22.
Peterson RL Himes RA Kotani H Suenobu T Tian L Siegler MA Solomon EI Fukuzumi S Karlin KD 《Journal of the American Chemical Society》2011,133(6):1702-1705
The new cupric superoxo complex [LCu(II)(O(2)(?-))](+), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases. 相似文献
23.
K. R. Jayaprakash Yuli Starosvetsky Alexander F. Vakakis Maxime Peeters Gaetan Kerschen 《Nonlinear dynamics》2011,63(3):359-385
We study standing waves (nonlinear normal modes—NNMs) and band zones in finite granular chains composed of spherical granular
beads in Hertzian contact, with fixed boundary conditions. Although these are homogeneous dynamical systems in the notation
of Rosenberg (Adv. Appl. Mech. 9:155–242, 1966), we show that the discontinuous nature of the dynamics leads to interesting effects such as separation between beads, NNMs
that appear as traveling waves (these are characterized as pseudo-waves), and localization phenomena. In the limit of infinite
extent, we study band zones, i.e., pass and stop bands in the frequency–energy plane of these dynamical systems, and classify
the essentially nonlinear responses that occur in these bands. Moreover, we show how the topologies of these bands significantly
affect the forced dynamics of these granular media subject to narrowband excitations. This work provides a classification
of the coherent (regular) intrinsic dynamics of one-dimensional homogeneous granular chains with no pre-compression, and provides
a rigorous theoretical foundation for further systematic study of the dynamics of granular systems, e.g., the effects of disorders
or clearances, discrete breathers, nonlinear localized modes, and high-frequency scattering by local disorders. Moreover,
it contributes toward the design of granular media as shock protectors, and in the passive mitigation of transmission of unwanted
disturbances. 相似文献
24.
Couturier M Ménard F Ragan JA Riou M Dauphin E Andresen BM Ghosh A Dupont-Gaudet K Girardin M 《Organic letters》2004,6(11):1857-1860
Lewis-base-catalyzed cycloisomerization of bis(enones) to decalins has been demonstrated as an alternative to the traditional Lewis acid catalyzed Diels-Alder cycloaddition. In this process, a trialkylphosphine mediates both bond formation steps in two distinct catalytic cycles. The single-pot operation generates two carbon-carbon bonds and up to five contiguous stereocenters in one step, starting from achiral, aliphatic substrates; eight examples are provided. [reaction: see text] 相似文献
25.
ortho‐, meta‐, and para‐Dihydroindenofluorene Derivatives as Host Materials for Phosphorescent OLEDs 下载免费PDF全文
Maxime Romain Sébastien Thiery Anna Shirinskaya Dr. Céline Declairieux Dr. Denis Tondelier Bernard Geffroy Dr. Olivier Jeannin Dr. Joëlle Rault‐Berthelot Dr. Rémi Métivier Dr. Cyril Poriel 《Angewandte Chemie (International ed. in English)》2015,54(4):1176-1180
This work reports the first structure–properties relationship study of ortho [2,1‐c]‐, meta [1,2‐a]‐, and para [1,2‐b]dihydroindenofluorenes, highlighting the influence of bridge rigidification on the electronic properties. This study has made it possible to devise an extended π‐conjugated molecule with both a high triplet state energy level and excellent thermal and morphological stability. As a proof of concept, dihydroindenofluorenes were used as the host in sky‐blue phosphorescent organic light‐emitting diodes (PhOLEDs) w ith high performance. 相似文献
26.
A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing. 相似文献
27.
Boulet-Audet M Vollrath F Holland C 《Physical chemistry chemical physics : PCCP》2011,13(9):3979-3984
Whilst rheology is the reference technique to study the mechanical properties of unspun silk, we know little of the structure and the dynamics that generate them. By coupling infrared spectroscopy and shearing forces to study silk fibroin conversion, we are introducing a novel tool to address this gap in our knowledge. Here the silk conversion process has been studied dynamically using polarized attenuated total reflectance Fourier transform infrared spectroscopy whilst applying shear, thus revealing silk protein conformation and molecular orientation in situ. Our results show that the silk conversion process starts with a pre-alignment of the proteins followed by a rapid growth of the β-sheet formation and then a subsequent deceleration of the growth. We propose that this tool will provide further insight into not only silk but any biopolymer solution, opening a new window into biological materials. 相似文献
28.
It is shown that, when a Monte Carlo algorithm is used for estimation of any physical quantity A, a simple and fast additional procedure can be implemented that simultaneously estimates the sensitivity of A to any problem parameter. The proposed approach is general and systematic in the sense that: (i) it includes domain-deformation sensitivities, i.e., cases where a change in the parameter modifies the domain over which the sampled random variables are defined and (ii) a simple generic procedure is presented to address all remaining free choices in terms of variance minimization. 相似文献
29.
Gilles Casano Maxime Robin Pascale Barbier Vincent Peyrot Robert Faure 《Magnetic resonance in chemistry : MRC》2010,48(9):738-744
The complete 1H and 13C NMR assignment of 9 acetamidochalcones, 18 acetamidoflavones, 18 aminoflavones, 9 acetamidoflavonols and 9 aminoflavonols has been performed using one‐ and two‐dimensional NMR techniques including COSY, HMQC and HMBC experiments. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
30.
Stefan Warsink Peter Hauwert Maxime A. Siegler Anthony L. Spek Cornelis J. Elsevier 《应用有机金属化学》2009,23(6):225-228
The synthesis of an air‐stable series of Pd0 complexes with dissymmetric bidentate N‐heterocyclic carbene–amine ligands has been performed. The key step is an unprecedented carbene transfer from AgI to obtain electron‐rich zero‐valent palladium precatalysts. The coordination behavior of the ligands was determined with X‐ray crystallography. Surprising results were obtained in the catalysis of transfer semi‐hydrogenation, where the addition of base appeared not to be necessary to obtain the desired product stereoselectively. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献