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991.
Lucas H. Martorano Jordana T. Brito Ana Carolina F. de Albuquerque Carlos Magno Rocha Ribeiro Rodolfo Goetze Fiorot José Walkimar de Mesquita Carneiro Fabio Luiz Paranhos Costa Alessandra L. Valverde Fernando Martins dos Santos Junior 《Magnetic resonance in chemistry : MRC》2022,60(4):434-441
Recently, structural elucidation of natural products has undergone a revolution. The combined use of different modern spectroscopic methods has allowed obtaining a complete structural assignment of natural products using small amounts of sample. However, despite the extraordinary ongoing advances in spectroscopy, the mischaracterization of natural products has been and remains a recurrent problem, especially when the substance presents several stereogenic centers. The misinterpretation of nuclear magnetic resonance (NMR) data has resulted in frequent reports addressing structural reassignment. In this context, a great effort has been devoted to developing quantum chemical calculations that simulate NMR parameters accurately, allowing to achieve a more precise spectral interpretation. In this work, we employed a protocol for theoretical calculations of 1H NMR chemical shifts and coupling constants using density functional theory (DFT), followed by the application of the DP4+ method to revisit the structure of Heliannuol L, a member of the Heliannuol class, isolated from Helianthus annuus. Our results indicate that the originally proposed structure of Heliannuol L needs a stereochemical reassignment, placing the hydroxyl bonded to C10 in the opposite side of the methyl and hydroxyl groups bonded to C7 and C8, respectively. 相似文献
992.
María Galiana-Cameo Marina Borraz Yaroslava Zelenkova Dr. Vincenzo Passarelli Prof. Fernando J. Lahoz Prof. Jesús J. Pérez-Torrente Prof. Luis A. Oro Dr. Andrea Di Giuseppe Dr. Ricardo Castarlenas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9598-9608
A series of Rh(κ2-BHetA)(η2-coe)(IPr) complexes bearing 1,3-bis-hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reaction of the dinuclear precursor [Rh(μ-Cl)(IPr)(η2-coe)]2 with the corresponding anionic BHetA species. The RhI-NHC-BHetA compounds catalyze the dimerization of aryl alkynes, showing excellent selectivity for the head-to-tail enynes. Among them, the acetanilidato-based catalyst has shown an outstanding catalytic performance reaching unprecedented TOF levels of 2500 h−1 with complete selectivity for the gem-isomer. Investigation of the reaction mechanism supports a non-oxidative pathway in which the BHetA ligand behaves as proton shuttle through intermediate κ1-HBHetA species. However, in the presence of pyridine as additive, the identification of the common RhIIIH(C≡CPh)2(IPr)(py)2 intermediate gives support for an alternative oxidative route. 相似文献
993.
Dr. Francisco Javier Ortiz-López M. Sc. Daniel Carretero-Molina Dr. Marina Sánchez-Hidalgo M. Sc. Jesús Martín Dr. Ignacio González M. Sc. Fernando Román-Hurtado Dr. Mercedes de la Cruz Dr. Sergio García-Fernández Dr. Fernando Reyes M. Sc. Julia Patricia Deisinger Dr. Anna Müller Dr. Tanja Schneider Dr. Olga Genilloud 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12754-12758
Lantibiotics are ribosomally synthesized and post-translationally modified peptides (RiPPs) characterized by the presence of lanthionine or methyllanthionine rings and their antimicrobial activity. Cacaoidin, a novel glycosylated lantibiotic, was isolated from a Streptomyces cacaoi strain and fully characterized by NMR, mass spectrometry, chemical derivatization approaches and genome analysis. The new molecule combines outstanding structural features, such as a high number of d -amino acids, an uncommon glycosylated tyrosine residue and an unprecedented N,N-dimethyl lanthionine. This latter feature places cacaoidin within a new RiPP family located between lanthipeptides and linaridins, here termed lanthidins. Cacaoidin displayed potent antibacterial activity against Gram-positive pathogens including Clostridium difficile. The biosynthetic gene cluster showed low homology with those of other known lanthipeptides or linaridins, suggesting a new RiPP biosynthetic pathway. 相似文献
994.
Katherine Paredes-Gil Dayán Páez-Hernández Ramiro Arratia-Pérez Fernando Mendizábal 《International journal of quantum chemistry》2020,120(5):e26108
Time-dependent density functional theory (TD-DFT)/periodic DFT calculations were performed to determine the role of pro-aromatic organic D-A -π -A type dyes (the NL1-NL17 family) with Thieno[3,4-b]pyrazine (Tpy) as A acceptor group into dye-sensitized solar-cells (DSSC). This work presents a discussion of the ground and excited states of these dyes along with the aromaticity analysis and the electron injection step using a dye@(TiO2)72 model. The results suggest that the pro-aromatic behavior increases from the thiophene ring to the pyrazine when an acceptor π-bridge such as phenyl is used. This strong pro-aromaticity is also reflected in the electron injection step, studied using a 3x2 3 layer (TiO2)72 slab model. The resulting adsorption energies (ΔEads and ΔGads) and the electron injection (ΔGinject) in the stablest coordination mode, Bid_CN_COOH, indicate that the redox reaction (Dye* ➔ Dye+ + e−) is stronger and more spon than the adsorption reaction (Dye+ + TiO2 [+e−] ➔ Dye@TiO2) in the electron injection. In this way, the highest efficiency of NL6 and NL12 is a consequence of the more significant pro-aromatic characteristics and the more spontaneous redox process. Finally, these NL dyes are promising in the molecular engineering of D-A -π -A metal-free types dyes. 相似文献
995.
Akari Narayama Sosa Israel González Alejandro Trejo Álvaro Miranda Fernando Salazar Miguel Cruz-Irisson 《Journal of computational chemistry》2020,41(31):2653-2662
Recently, the need of improvement of energy storage has led to the development of Lithium batteries with porous materials as electrodes. Porous Germanium (pGe) has shown promise for the development of new generation Li-ion batteries due to its excellent electronic, and chemical properties, however, the effect of lithium in its properties has not been studied extensively. In this contribution, the effect of surface and interstitial Li on the electronic properties of pGe was studied using a first-principles density functional theory scheme. The porous structures were modeled by removing columns of atoms in the [001] direction and the surface dangling bonds were passivated with H atoms, and then replaced with Li atoms. Also, the effect of a single interstitial Li in the Ge was analyzed. The transition state and the diffusion barrier of the Li in the Ge structure were studied using a quadratic synchronous transit scheme. 相似文献
996.
Sotiles Anne Raquel Gomez Neffer Arvey Gomez Wypych Fernando 《Journal of Thermal Analysis and Calorimetry》2020,140(4):1715-1723
Journal of Thermal Analysis and Calorimetry - The synthesized phases with chemical composition $$left[ {{text{M}}^{2 + }_{6} {text{Al}}_{3} left( {text{OH}} right)_{18} } right]left[... 相似文献
997.
We present low-order functional observer existence conditions; the proposed existence conditions always lead to a design of functional observers of order less than or equal to that of a Luenberger observer. The proposed low-order observer always exists if a Luenberger observer exists. 相似文献
998.
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