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71.
R. A. Cruz R. C. Castillo F. J. Garcia R. I. Reed 《Journal of mass spectrometry : JMS》1977,12(1):21-23
The mass spectra of [17-13C]phyllocladene and [3-13C]methylenecholestane have been examined. It is shown that there are some rearrangements at 70 e V as in the case of [17-13C]kaurene. However, no extensive randomization is evident at the molecular ion level. The results are interesting because very little is known about 13C randomization in polycyclic aliphatic hydrocarbons. The percentage retention of label was calculated for each ion. 相似文献
72.
J. M. Campelo A. Garcia D. Luna J. M. Marinas 《Reaction Kinetics and Catalysis Letters》1984,26(1-2):73-77
Electron donor and acceptor properties of AlPO4 and AlPO4–SiO2 (2080 wt. %) supported rhodium catalysts have been studied. It was observed that the effect of metal deposition on both electron acceptor and donor properties depend on the support and precipitation agent. AlPO4 supported rhodium showed better acoeptor than donor properties, while for Rh/AlPO4–SiO2, the acceptor properties were superior. However, the effect of metal on the redox properties is slight.
AlPO4 QlPO4 SiO2 (2080 .%). ]ye . AlPO4 , , Rh/AlPO4–SiO2 . , - .相似文献
73.
Tricyclic basic dyes (proflavine, acridine orange, pyronine, pyronine Y, oxonine, thionine and methylene blue) often form one‐to‐one or two‐to‐one complexes with CB[7] and CB[8], respectively. In the case of pyronine Y, the complexes with CB[7] and CB[8] have a one‐to‐one and three‐to‐one stoichiometry, respectively. The binding constants for CB[7] complexes range from 3.07×106 to 1.70×107 m ?1. In the case of CB[8], the association constant varies between 3.24×1013 and 2.50×1016 m ?2. Overall, these binding constants are four orders of magnitude higher than those reported for the same dyes in β and γ‐cyclodextrins. Formation of the host–guest complexes leads to an increase in the fluorescence quantum yields in the case of CB[7], while the dimeric or trimeric dye encapsulated in CB[8] are remarkably less fluorescent than the same dye in diluted solutions. 相似文献
74.
Amanda C. Garcia Thomas Touzalin Celine Nieuwland Nickson Perini Marc T. M. Koper 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(37):13133-13137
Herein, the effect of the alkali cation (Li+, Na+, K+, and Cs+) in alkaline electrolytes with and without Fe impurities is investigated for enhancing the activity of nickel oxyhydroxide (NiOOH) for the oxygen evolution reaction (OER). Cyclic voltammograms show that Fe impurities have a significant catalytic effect on OER activity; however, both under purified and unpurified conditions, the trend in OER activity is Cs+ > Na+ > K+ > Li+, suggesting an intrinsic cation effect of the OER activity on Fe‐free Ni oxyhydroxide. In situ surface enhanced Raman spectroscopy (SERS), shows this cation dependence is related to the formation of superoxo OER intermediate (NiOO?). The electrochemically active surface area, evaluated by electrochemical impedance spectroscopy (EIS), is not influenced significantly by the cation. We postulate that the cations interact with the Ni?OO? species leading to the formation of NiOO??M+ species that is stabilized better by bigger cations (Cs+). This species would then act as the precursor to O2 evolution, explaining the higher activity. 相似文献
75.
Alberto Palazzolo Sophie Feuillastre Viktor Pfeifer Sbastien Garcia‐Argote Donia Bouzouita Simon Tricard Cline Chollet Elodie Marcon David‐Alexandre Buisson Sophie Cholet Franois Fenaille Guy Lippens Bruno Chaudret Grgory Pieters 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):4945-4949
A general approach for the efficient hydrogen‐isotope exchange of nucleobase derivatives is described. Catalyzed by ruthenium nanoparticles, using mild reaction conditions, and involving either D2 or T2 as isotopic sources, this reaction possesses a wide substrate scope and a high solvent tolerability. This novel method facilitates the access to essential diagnostic tools in drug discovery and development: tritiated pharmaceuticals with high specific activities and deuterated oligonucleotides suitable for use as internal standards during LC‐MS quantification. 相似文献
76.
David Vila‐Liarte Maximilian W. Feil Aurora Manzi Juan Luis Garcia‐Pomar He Huang Markus Dblinger Luis M Liz‐Marzn Jochen Feldmann Lakshminarayana Polavarapu Agustín Mihi 《Angewandte Chemie (International ed. in English)》2020,59(40):17750-17756
Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light‐management strategy involving additional processing steps. Herein, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr3 perovskite NC colloids into large area (1 cm2) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This improvement is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal. 相似文献
77.
Morteza Rezaei Talarposhti Tristan Asset Samuel T. Garcia Yechuan Chen Sergio Herrera Sheng Dai Eric J. Peterson Kateryna Artyushkova Iryna Zenyuk Plamen Atanassov 《Chemphyschem》2020,21(12):1331-1339
We investigated the oxygen reduction reaction (ORR) mechanism on Pt nanoparticles (NPs) dispersed on several carbon blacks with various physicochemical properties (i. e. specific surface ranging from 80 to 900 m2 g−1, different graphitization degree, etc.). Using the kinetic isotope effect (KIE) along with various electrochemical characterizations, we determined that the rate determining step (RDS) of the ORR is a proton-independent step when the density of Pt NPs on the surface of the carbon support is high. Upon decrease of the density of Pt NPs on the surface, the RDS of the ORR starts involving a proton, as denoted by an increase of the KIE >1. This underlined the critical role played by the carbon support in the oxygen reduction reaction electrocatalysis by Pt supported on high surface area carbon. 相似文献
78.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
79.
J. M. Garcia de la Vega B. Miguel E. San Fabian 《International journal of quantum chemistry》1997,61(3):533-540
Density functional (DF) calculations of the tetrachloromethane cation and its most important competitive process, the formation of CCl+3, were carried out to explain the possible stability of CCl+4. From results obtained with B-LYP and B-P86 methods, it is possible to produce a slight Jahn-Teller (JT) effect for a Cs planar structure of the cation type CCl2(SINGLE BOND)Cl(SINGLE BOND)Cl+ compatible with the experimental data obtained by electron-spin resonance spectroscopy. A complex of C3v structure CCl+3(SINGLE BOND)Cl which is similar to the previous one found in CF+4 appears when symmetry-broken wave functions are used in HF-LYP and HF-P86 methods. Depending of the DF method employed, either one of the minima [Cs (planar) and C3v] is the most stable and competes with the dissociation of the molecular ion to give CCl+3. The JT stabilization energy is smaller when the JT active coordinates are considered. © 1997 John Wiley & Sons, Inc. 相似文献
80.
Heilemann M Tinnefeld P Sanchez Mosteiro G Garcia Parajo M Van Hulst NF Sauer M 《Journal of the American Chemical Society》2004,126(21):6514-6515
We demonstrate the synthesis and spectroscopic characterization of an unidirectional photonic wire based on four highly efficient fluorescence energy-transfer steps (FRET) between five spectrally different chromophores covalently attached to double-stranded DNA. The DNA-based modular conception enables the introduction of various chromophores at well-defined positions and arbitrary interchromophore distances. While ensemble fluorescence measurements show overall FRET efficiencies between 15 and 30%, single-molecule spectroscopy performed on four spectrally separated detectors easily uncovers subpopulations that exhibit overall FRET efficiencies of up to approximately 90% across a distance of 13.6 nm and a spectral range of approximately 200 nm. Fluorescence trajectories of individual photonic wires show five different fluorescence intensity patterns which can be ascribed to successive photobleaching events. 相似文献