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431.
Moreau Y Chen H Derat E Hirao H Bolm C Shaik S 《The journal of physical chemistry. B》2007,111(34):10288-10299
We studied electronic structures and reactivity patterns of azo-compound I species (RN-Cpd I) by comparison to O-Cpd I of, e.g., cytochrome P450. The study shows that the RN-Cpd I species are capable of C=C aziridination and C-H amidation, in a two-state mechanism similar to that of O-Cpd I. However, unlike O-Cpd I, here the nitrogen substituent (R) exerts a major impact on structure and reactivity. Thus, it is demonstrated that Fe=NR bonds of RN-Cpd I will generally be substantially longer than Fe=O bonds; electron-withdrawing R groups will generate a very long Fe=N bond, whereas electron-releasing R groups should have the opposite effect and hence a shorter Fe=N bond. The R substituent controls also the reactivity of RN-Cpd I toward C=C and C-H bonds by exerting steric and electronic effects. Our analysis shows that an electron-releasing substituent will lower the barriers for both bond activation reactions, since the electronic factor makes the reactions highly exothermic, while an electron-withdrawing one should raise both barriers. The steric bulk of the substituent is predicted to inhibit more strongly the aziridination reactions. It is predicted that electron-releasing substituents with small bulk will create powerful aziridination reagents, whereas electron-withdrawing substituents like MeSO(2) will prefer C-H bond activation with preference that increases with steric bulk. Finally, the study predicts (i) that the reactions of RN-Cpd I will be less stereospecific than those of O-Cpd I and (ii) that aziridination will be more stereoselective than amidation. 相似文献
432.
Veeranna Navaneethgowda P. Bodke Yadav D. Basavaraju Manjunatha Pasha Kuntewale Mohiyouddin Mussuvir 《Structural chemistry》2022,33(3):897-906
Structural Chemistry - The present work describes the synthesis of novel 3-[2-(5-phenyl-1,3-thiazol-2-yl)hydrazinyl]-1,3-dihydro-2H-indol-2-one derivatives 4(a-h) and the characterization of... 相似文献
433.
434.
Pasha Zusmanovich 《Journal of Geometry and Physics》2010,60(6-8):1028-1044
We study a certain generalization of Lie algebras where the Jacobian of three elements does not vanish but is equal to an expression depending on a skew-symmetric bilinear form. 相似文献
435.
436.
Synthesis of arylmethylidenes from araldehydes and active methylene compounds catalyzed by catalytic amount of lithium hydroxide (LiOH·H2O) in the absence of a solvent under Grindstone method is reported. The reactions go to completion within 1–5 min and give products in excellent yields at 26 °C. 相似文献
437.
Deyu Wang Sule Erten Ela Shaik M. Zakeeruddin Peter Pechy Ivan Exnar Qing Wang Michael Grätzel 《Electrochemistry communications》2009,11(7):1350-1352
The poor electronic conductivity of LiFePO4 has been one of the major issues impeding it from achieving high power and energy density lithium-ion batteries. In this communication, a novel polymer-wiring concept was proposed to improve the conduction of the insulating electrode material. By using a polymer with tethered “swing” redox active molecules (S) attached on a polymer chain, as the standard redox potential of S matches closely the Fermi level of LiFePO4, electronic communication between the redox molecule and LiFePO4 is established. Upon charging, S is oxidized at the current collector to S+, which then delivers the charge (holes) to the LiFePO4 particles by intermolecular hopping assisted by a “swing” – type motion of the shuttle molecule. And Li+ is extracted. Upon discharging, the above process is just reversed. Preliminary studies with redox polymer consisting of poly (4-vinylpyridine) and phenoxazine moiety tethered with a C12 alkyl chain have shown promising result with carbon-free LiFePO4, where effective electron exchange between the shuttle molecule and LiFePO4 has been observed. In addition, as the redox polymer itself could act as binder, we anticipate that the polymer-wiring concept would provide a viable approach to conducting-additive and binder free electrode for high energy density batteries. 相似文献
438.
This paper, introduces the nearest weighted interval and point approximations of a fuzzy number, and then suggests weighted possibilistic moments about these points of fuzzy numbers. The possibilistic moments play an important role in fuzzy sets and systems, specifically in physics, mathematics and statistics. We provide the definition of the moments of fuzzy numbers as well as the definition of moments in probability theory; some of their applications are mentioned. 相似文献
439.
Marszalek M Fei Z Zhu DR Scopelliti R Dyson PJ Zakeeruddin SM Grätzel M 《Inorganic chemistry》2011,50(22):11561-11567
A series of novel ionic liquids composed of imidazolium, pyridinium, pyrrolidinium, and ammonium cations with tricyanomethanide or tetracyanoborate anions were prepared. The ionic liquids were characterized by NMR and IR spectroscopy and ESI-mass spectrometry, and their physical properties were investigated. Solid state structures of the N-propyl-N-methylpyrrolidinium and triethylpropylammonium tetracyanoborate salts were obtained by single crystal X-ray diffraction. The salts that are liquid at room temperature were evaluated as electrolyte additives in dye-sensitized solar cells, giving rise to efficiencies 7.35 and 7.85% under 100 and 10% Sun, respectively, in combination with the standard Z907 dye. 相似文献
440.
Cheeseman JR Shaik MS Popelier PL Blanch EW 《Journal of the American Chemical Society》2011,133(13):4991-4997
We report calculations of the Raman and Raman optical activity (ROA) spectra of methyl-β-D-glucose utilizing density functional theory combined with molecular dynamics (MD) simulations to provide an explicit hydration environment. This is the first report of such combination of MD simulations with ROA ab initio calculations. We achieve a significant improvement in accuracy over the more commonly used gas phase and polarizable continuum model (PCM) approaches, resulting in an excellent level of agreement with the experimental spectrum. Modeling the ROA spectra of carbohydrates has until now proven a notoriously difficult challenge due to their sensitivity to the effects of hydration on the molecular vibrations involving each of the chiral centers. The details of the ROA spectrum of methyl-β-D-glucose are found to be highly sensitive to solvation effects, and these are correctly predicted for the first time including those originating from the highly sensitive low frequency vibrational modes. This work shows that a thorough consideration of the role of water is pivotal for understanding the vibrational structure of carbohydrates and presents a new and powerful tool for characterizing carbohydrate structure and conformational dynamics in solution. 相似文献