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101.
[reaction: see text] The photochemistry of N-acyl-5,7-dinitroindoline (1) was studied in acetonitrile using nanosecond time-resolved infrared (TRIR) spectroscopy. Upon photolysis, two nearly but not completely overlapping sets of transient IR bands are observed that are assigned to two non-interconvertible conformers of mixed acetic nitronic anhydride 7. While syn-7 reverts rapidly to 1, anti-7 is long-lived and is able to acylate amines. Results of density functional theory calculations support conclusions based on experimental TRIR data. 相似文献
102.
Michael Schaefer Christian N?ther Wolfgang Bensch 《Monatshefte für Chemie / Chemical Monthly》2004,27(7):461-470
Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P21/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]2Sb4S8·0.75 H2O two [Zn(tren)]2+ cations are bound to the [Sb4S8]4– anion via S atoms. The Zn2+ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb4S8]4– anion. The anion is formed by SbS3 and SbS4 units which share common corners and edges. The interconnection mode yields three different non-planar Sb2S2 heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb2S3 by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]2Sb4S8·0.75 H2O are reported. 相似文献
103.
Formation and Crystal Structure of an Oxygen Bridged Titanium Amino Bisphenoxide Di‐(μ‐oxo)‐titan‐bis[aminobisphenoxide] ( 3 ) was obtained by reaction of (i‐Prop)2TiL* ( 2 ) {L* = O‐4, 6‐(t‐Bu)2C6H2‐2‐CH2‐[1, 4‐N2C5H10]‐2'‐CH2‐4', 6'‐(t‐Bu)2C6H2O] with water in a molar ratio 1:1 in diethylether. Both i‐Propyl moieties are substituted yielding the dimeric oxygen bridged amino bisphenoxide complex. The six coordinate Ti atoms are a result of Ti—N and Ti—O interactions of the corresponding atoms of the amino bisphenoxide ligand and the bridging O atoms. The central planar Ti2O2 ring may be considered as the general structural feature of the title compound: Space group P1¯, Z = 1, lattice dimensions at —60°C: a = 11.6899(4), b = 11.7873(4), c = 12.6462(4) Å, α = 98.070(1), β = 99.660(1), γ = 95.343(1)°, R1 = 0.0469, wR2 = 0.1049, GooF = 0.939. 相似文献
104.
105.
We have chemically prepared a sample of antiferromagnetic alpha-Fe2O3 nanoparticles by a gel-sol technique. M?ssbauer spectra of the as-prepared sample showed that superparamagnetic relaxation was suppressed due to strong magnetic interparticle interactions even at room temperature. However, subsequent grinding of the sample by hand in a mortar for some minutes resulted in fast superparamagnetic relaxation of some of the particles. The effect was even more dramatic if the alpha-Fe2O3 powder was ground for a longer time or together with nonmagnetic eta-Al2O3 nanoparticles. Similar effects were found after low-energy ball milling. Thus it is found that the agglomeration of the nanoparticles during preparation under wet conditions results in strong magnetic interparticle interaction, but a relatively gentle mechanical treatment is sufficient to break up the agglomerates, resulting in much weaker interactions. We show that these effects can also be seen when a soil sample containing magnetic nanoparticles is ground. 相似文献
106.
107.
108.
Christian Huber Christian Krause Tobias Werner Otto S. Wolfbeis 《Mikrochimica acta》2003,142(4):245-253
This article describes the preparation and performance of an optical sensor for continuous measurement of chloride at extracellular (serum) levels (20–200mM). The sensor is based on dynamic quenching of the fluorescence of lucigenin which was photo-immobilized on a hydrogel. Quenching occurs via a collisional mechanism, and the decrease in fluorescence intensity on exposure to 100mM chloride typically is –60%. It allows the determination of chloride in the 1 to 200mM concentration range, with a precision of ±3mM at 120mM. Bromide, iodide and salicylate act as interferents, while the effect of pH and oxygen is negligibly small. The sensor displays strong fluorescence intensity, excellent reproducibility, long-term stability, response times in the order of 2–5min, and is used in a commercial serum and blood chloride analyzer.Received January 21, 2003; accepted April 6, 2003
Published online July 28, 2003 相似文献
109.
VladimirA. Azov Franois Diederich Yoriko Lill Bert Hecht 《Helvetica chimica acta》2003,86(6):2149-2155
We report the synthesis of modified Cram‐type cavitands bearing one or two fluorescent labels for single‐molecule spectroscopic studies of vase? kite conformational switching (Scheme 3). Syntheses were performed by stepwise bridging of the four couples of neighboring H‐bonded OH groups of resorcin[4]arene bowls (Schemes 2 and 3). The new substitution patterns enable the construction of a large variety of future functional architectures. 1H‐NMR Investigations showed that the new partially and differentially bridged cavitands feature temperature‐ and pH‐triggered vase? kite conformational isomerism similar to symmetrical cavitands with four identical quinoxaline bridges (Table). It was discovered that vase? kite switching of cavitands is strongly solvent‐dependent. 相似文献
110.
Henri Brunner Christian Zettler Manfred Zabel 《Monatshefte für Chemie / Chemical Monthly》2003,134(9):1253-1269
Summary. The synthesis of new chiral tridentate ligands is reported which coordinate transition metals in a meridional way. The ligands contain a pyridine ring, an oxazoline ring, and a strongly coordinating diphenylphosphanyl group. The methionine-derived ligand forms a copper complex, which has been studied by X-ray crystallography. The new ligands were tested in models of enantioselective catalyses, such as hydrogenation of ketopantolactone, hydrosilylation of acetophenone, and transfer hydrogenation of acetophenone.X-ray structure analysesReceived March 4, 2003; accepted March 4, 2003
Published online August 18, 2003 相似文献