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排序方式: 共有940条查询结果,搜索用时 15 毫秒
1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Mechatronic subsystems have been extensively developed in automotive applications as they increase performance compared to passive components. The Hydractive CRONE suspension based on fractional differentiation is presented as a hybrid system undergoing an infinite sequence of autonomous switchings. The modelling and operation of Hydractive CRONE suspension as a hybrid system are presented. The stability of Hydractive CRONE suspension is demonstrated using the maximum principle extended to hybrid systems. Finally, comfort mode synthesis is proposed using the third generation CRONE control system design. 相似文献
3.
L. Pillier C. Moreau X. Mercier J.F. Pauwels P. Desgroux 《Applied physics. B, Lasers and optics》2002,74(4-5):427-434
Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed
flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding
the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and
spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed
in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the
selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest
influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of
NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption
in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air
flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques.
Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002 相似文献
4.
Ginette Ratovo Jean‐Pierre Souchard Pascale Urizzi Yvon Coulais Franoise Nepveu Etienne Hollande 《应用有机金属化学》2004,18(1):1-8
Pancreatic cancer has an extremely poor prognosis, due, in part, to lack of methods for early diagnosis. The present study was designed to evaluate the potential of labeling low‐density lipoprotein (LDL) with a radionuclide using a lipid chelating agent, bis(stearylamide) of diethylenetriaminepentaacetic acid (L), to detect pancreatic tumors by gamma‐scintigraphy. Previous studies indicated that the difficulty of visualization of pancreatic tumors was due to their poor vascularization. This study compares the ability of two radiotracers, 111In–L–LDL and 153Gd–L–LDL to target highly vascularized rat pancreatic tumors (AR4‐2J) implanted in nude mice. Biodistribution studies showed that the tumor uptake of 111In–L–LDL and 153Gd–L–LDL tracers was twofold and fivefold higher respectively than with the controls (111In citrate and 153Gd citrate respectively). These tracers would thus be suitable for scintigraphic imaging. We show here that LDL could be employed as a delivery system for tracers such as 111In or 153Gd when these two radionuclides are complexed by a lipid‐chelating anchor, and that 111In–L–LDL and 153Gd–L–LDL enabled better visualization of the pancreatic tumor tissues, with a better result with 153Gd–L–LDL. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
5.
The CRONE suspension, French acronym of “suspension à Comportement Robuste d’Ordre Non Entier”, results from a traditional suspension system whose spring and damper are replaced by a mechanical and hydropneumatic system defined by a fractional (so-called non-integer) order force–displacement transfer function. ‘ling, frequency-domain robust control design methodology, optimal approach, stability analysis and performance are presented in this paper. 相似文献
6.
Pascale F Catti M Damin A Orlando R Saunders VR Dovesi R 《The journal of physical chemistry. B》2005,109(39):18522-18527
The vibrational spectrum of Ca3Fe2Si3O12 andradite is calculated at the Gamma point by using the periodic ab initio CRYSTAL program that adopts an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. The full set of frequencies (17 IR active, 25 Raman active, and 55 inactive modes) is calculated. The effect of the basis set on the calculated frequencies is discussed. The modes are characterized by direct inspection of the eigenvectors and isotopic substitution. The present calculations permit us to clarify some of the assignment problems raised by experiments. The mean absolute differences of the various modes with respect to the available experimental IR and Raman data are as small as 9 and 5 cm(-1), respectively. 相似文献
7.
Pascale F Ugliengo P Civalleri B Orlando R D'Arco P Dovesi R 《The Journal of chemical physics》2004,121(2):1005-1013
The structure of the Si-free katoite hydrogarnet (116 atoms in the unit cell) has been investigated at the periodic ab initio quantum mechanical level with the CRYSTAL program, by using a Gaussian type basis set and both the HF and the hybrid B3-LYP Hamiltonians. The structure has been fully optimized at various pressures in the 0-46 GPa range; the modifications of the structure, and in particular of the (OH)4 group, as a function of pressure are analyzed. At the B3-LYP level and P greater than 15 GPa, a O-H...O interaction of increasing strength appears, with important modifications in the local geometry of the tetrahedral site. The calculated omega01(O-H) fundamental vibrational frequency at zero pressure is in excellent agreement with experiment (3674 and 3663 cm(-1), respectively); the omega01(O-H) stretching frequency remains essentially constant in the 0-15 GPa interval, whereas it dramatically decreases at higher pressures with a corresponding anharmonicity increase, as a consequence of the formation of a strong hydrogen bond. The hydration energy of grossular and the formation energy of Si-free katoite have also been computed, and the B3-LYP results are in quite good agreement with experiment. 相似文献
8.
Joël J. E. Moreau Luc Vellutini Catherine Bied Michel Wong Chi Man 《Journal of Sol-Gel Science and Technology》2004,32(1-3):63-67
The acid-hydrolysis of an organo-bridged bisdiethoxysilylated molecular precursor bearing urea groups, (EtO)2MeSi(CH2)3NHCONH(CH2)12NHCONH(CH2)3SiMe(OEt)2, has been performed in pure aqueous medium. Scanning electron microscopy (SEM) analysis of the resulting insoluble solid revealed plate-like forms with a lamellar structure as determined by powder X-ray diffraction (PXRD) studies with a sharp peak at 28.5 Å. The solid state 29Si MAS-NMR spectrum of this bridged siloxane hybrid is consistent with a moderately condensed material with complete preservation of the Si–C bonds throughout the hybrid network. In comparison, the classical sol–gel hydrolysis-condensation of the molecular precursor in ethanol with stoichiometric amount of water and fluoride anion as catalyst produced an amorphous featureless solid. 相似文献
9.
Densities of water+acetonitrile mixture have been measured from 308.15 to 278.15 K over the entire composition range. Partial molal volumes of both components of the mixed system have been calculated and deviations from ideal volumes of mixing have been evaluated. Literature data on viscosity have also been treated by a least square method and activation thermodynamic functions of viscous flow computed. Structural correlations have been made with previous results on acid-base properties; they allow to distinguish several interaction regions between components of binary systems. 相似文献
10.
We study the kinetics of diffusion-limited catalytically activated A+B-->B reactions taking place in three-dimensional systems, in which an annihilation of diffusive A particles by diffusive traps B may happen only if the encounter of an A with any of the Bs happens within a special catalytic subvolumen: these subvolumens being immobile and uniformly distributed within the reaction bath. Suitably extending the classical approach of Wilemski and Fixman [J. Chem. Phys. 58, 4009 (1973)] to such three-molecular diffusion-limited reactions, we calculate analytically an effective reaction constant and show that it comprises several terms associated with the residence and joint residence times of Brownian paths in finite domains. The effective reaction constant exhibits a nontrivial dependence on the reaction radii, the mean density of catalytic subvolumens, and particles' diffusion coefficients. Finally, we discuss the fluctuation-induced kinetic behavior in such systems. 相似文献