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121.
Stacey M. Frumm Zi Peng Fan Kenneth N. Ross Jeremy R. Duvall Supriya Gupta Lynn VerPlank Byung-Chul Suh Edward Holson Florence F. Wagner William B. Smith Ronald M. Paranal Christopher F. Bassil Jun Qi Giovanni Roti Andrew L. Kung James E. Bradner Nicola Tolliday Kimberly Stegmaier 《Chemistry & biology》2013,20(5):713-725
122.
The development of a general catalytic asymmetric aldehyde alpha-alkylation reaction constitutes a major challenge in organic synthesis. Here, we report the first and successful approach toward its solution: (S)-alpha-methyl proline catalyzes the intramolecular alkylation of various halo aldehydes to the corresponding formyl cyclopentanes, -cyclopropanes, or -pyrrolidines in excellent yields and enantioselectivities. Most remarkably, racemization, aldolization, or catalyst alkylation do not occur to any significant extend, further illustrating the power, mildness, and profound selectivity of enamine catalysis. 相似文献
123.
Costa M Cà ND Gabriele B Massera C Salerno G Soliani M 《The Journal of organic chemistry》2004,69(7):2469-2477
An effective and straightforward approach to the synthesis of 4H-3,1-benzoxazines 3 and 4, quinazolin-2-ones 5, and quinoline-4-one derivatives 6 and 7 is provided by palladium-catalyzed cyclization-alkoxycarbonylation of variously substituted 2-(trimethylsilanyl)ethynylaniline amide or urea derivatives 2. Reactions are carried out in 7:1 MeCN/MeOH at 65 or 75 degrees C in the presence of catalytic amounts of 10% Pd/C in conjunction with Bu(4)NI and KF and under 2.4 MPa of a 3:1 mixture of CO and air. Anti and syn 6-exo-dig cyclization modes account for the formation of the two stereoisomers. Isomerization of the vinylpalladium intermediate may occur as well. Formation of a double carbonylation product 7r and of a gem-dimethoxycarbonylation product 6s, whose structures have been determined by X-ray diffraction analysis, is justified through an unusual type of rearrangement. 相似文献
124.
Giorgia Oliviero Nicola Borbone Vincenzo Piccialli Gennaro Piccialli Luciano Mayol 《Tetrahedron》2010,66(10):1931-6144
We report here an efficient solid-phase synthesis of N-1-alkyl-substituted analogues of cyclic inosine-diphosphate-ribose (cIDPR), a mimic of cyclic ADP-ribose (cADPR). Our synthetic strategy makes use of a polystyrene support to which inosine was bonded through a 2′,3′-acetal linkage. Insertion of a ω-hydroxy-polymethylene chain of variable length on N-1, followed by conversion into N-1-alkylinosine-bis-phosphate derivatives and cyclization, allowed to obtain analogues of cIDPR of various ring size. The cyclization step was carried out both in solid-phase and in solution by pyrophosphate bond formation. The effect of the N-1-polymethylene chain length on the cyclization yields as well as the reaction conditions, which led to the solid-phase pyrophosphate bond formation, were thoroughly investigated. 相似文献
125.
Jocelyn S. Y. Chen Tijmen G. Euser Dr. Nicola J. Farrer Dr. Peter J. Sadler Prof. Michael Scharrer Dr. Philip St. J. Russell Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5607-5612
We report the use of a liquid‐filled hollow‐core photonic crystal fiber (PCF) as a highly controlled photochemical reactor. Hollow‐core PCFs have several major advantages over conventional sample cells: the sample volume per optical path length is very small (2.8 nL cm?1 in the fiber used), long optical path lengths are possible as a result of very low intrinsic waveguide loss, and furthermore the light travels in a diffractionless single mode with a constant transverse intensity profile. As a proof of principle, the (very low) quantum yield of the photochemical conversion of vitamin B12, cyanocobalamin (CNCbl) to hydroxocobalamin ([H2OCbl]+) in aqueous solution was measured for several pH values from 2.5 to 7.5. The dynamics of the actively induced reaction were monitored in real‐time by broadband absorption spectroscopy. The PCF nanoreactor required ten thousand times less sample volume compared to conventional techniques. Furthermore, the enhanced sensitivity and optical pump intensity implied that even systems with very small quantum yields can be measured very quickly—in our experiments one thousand times faster than in a conventional cuvette. 相似文献
126.
127.
EC Tam NA Maynard DC Apperley JD Smith MP Coles JR Fulton 《Inorganic chemistry》2012,51(17):9403-9415
A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR(2)) (M = Ge, Sn, Pb; BDI = CH{(CH(3))CN-2,6-iPr(2)C(6)H(3)}(2); R = Ph, Cy, SiMe(3)) have been synthesized. Two different conformations (endo and exo) are observed in the solid-state; the complexes with an endo conformation have a planar coordination geometry at phosphorus (M = Ge, Sn; R = SiMe(3)) whereas the complexes possessing an exo conformation have a pyramidal geometry at phosphorus. Solution-state NMR studies reveal through-space scalar coupling between the tin and the isopropyl groups on the N-aryl moiety of the BDI ligand, with endo and exo exhibiting different J(SnC) values. The magnitudes of the tin-phosphorus and lead-phosphorus coupling constants, |J(SnP)| and |J(PbP)|, differ significantly depending upon the hybridization of the phosphorus atom. For Sn(BDI)(P{SiMe(3)}(2)), |J(SnP)| is the largest reported in the literature, surpassing values attributed to compounds with tin-phosphorus multiple-bonds. Low temperature NMR studies of Pb(BDI)(P{SiMe(3)}(2)) show two species with vastly different |J(PbP)| values, interpreted as belonging to the endo and exo conformations, with sp(2)- and sp(3)-hybridized phosphorus, respectively. 相似文献
128.
Gotterbarm K Luckas N Höfert O Lorenz MP Streber R Papp C Viñes F Steinrück HP Görling A 《The Journal of chemical physics》2012,136(9):094702
We studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (~0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO(4), with SO(2) and SO(3) being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO(2), SO(3), and eventually SO(4), also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From the experiments we determined the activation energy of the rate limiting step to be 85 ± 6 kJ mol(-1) by Arrhenius analysis, matching the calculated endothermicity of the SO formation. 相似文献
129.
Biosensors are desired for the detection of a wide range of analytes in various scenarios, for example environmental monitoring for biological threats, from toxins to viruses and bacteria. Ideally a single sensor will be capable of simultaneous multianalyte detection. The varying nature, and in particular disparate size, of such a variety of analytes poses a significant challenge in the development of effective high-confidence instruments. Many existing biosensors employ functionalized flow cells in which spatially defined arrays of surface-immobilized recognition elements, such as antibodies, specifically capture their analyte of interest. To function optimally, arrays should provide equivalent responses for equivalent events across their active area. Experimental data obtained using a grating coupled surface plasmon resonance (GC-SPR) instrument, the BIAcore Flexchip, have revealed differences in response behaviors between proteinaceous and particulate analytes. In particular, the magnitude of responses seen with Bacillus anthracis spores appears to be influenced by shear and gravitational effects while those from soluble proteins are more uniform. We have explored this dependence to understand its fundamental impact on the successful implementation of multianalyte environmental biological detection systems. 相似文献