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131.
[reaction: see text] Treatment of 1,4-dilithio-1,3-butadiyne (1) with dichalcogenides RSSR or RSeSeR affords dithio- and diseleno-1,3-butadiynes (2, 3), perthio- and perseleno-[3]-cumulenes (4, 5), perthio- and perseleno-1,3-butadienes (6, 7), and/or perthio- and perseleno-but-1-ene-3-ynes (8, 9). The products can be controlled by stoichiometry and temperature, by the presence or absence of oxygen, and by choice of the "R" group. By X-ray crystallography, hexa(methylthio)-1,3-butadiene is highly twisted, with a torsion angle [Phi(CCCC)] of 84.7 degrees and an elongated C(2)-C(3) distance of 1.484(3) A. 相似文献
132.
Frank R. Fronczek Richard D. Gandour Laura M. B. Gehrig Lyman R. Caswell Karen A. McDowell I. Alam 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(3):379-383
The first crystal structure of a potassium cation complex with dicyclohexano-18-crown-6 is reported. The potassium 2-nitrophenoxide complex ofsyn-cis-syn dicyclohexano-18-crown-6 crystallizes in the triclinic space group P
with cell constantsa=8.604(2),b=10.772(4),C=16.123(5)Å, =73.86(3)°,=77.61(3)°, =82.68(3)° andZ=2 forD
c
=1.31 g cm–3. Least-squares refinement based on 2742 observed reflections led to a final conventionalR value of 0.040. Dicyclohexano-18-crown-6 has the shape of a saddle with the potassium cation sitting at the saddlepoint. The structure of the 2-nitrophenoxide anion is dominanted by the quinoid resonance contributor. Because the complex is devoid of significant intercomplex interactions, it is a prototypical 1:1:1 complex.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82043 (26 pages).Now Mrs. K. M. Balo. 相似文献
133.
In a series of methyl substituted 1-(2′,6′-dichlorobenzyl)-1,4-dihydronicotinamides those compounds with the methyl α to the pyridine nitrogen are at least one order of magnitude more reactive than the analogues without methyl or methyl on the 5-position. 相似文献
134.
Diorganogallium Fluorides. The Crystal Structure of the Mixed Crystal [B(CH2Ph)3]0.92[Ga(CH2Ph)3]0.08 · NCMe The reaction of GaR3 with BF3 · OEt2 in diethylether leads to the diorganogallium fluorides R2GaF [R = i-Pr ( 1 ), CH2Ph ( 2 ), Mes ( 3 )]. Compound 1 is also available by the reaction of i-Pr2GaBr ( 6 ) with KF at ?20°C in acetonitrile. The by-product B(CH2Ph)3, formed together with 2 during the first reaction, crystallizes with ca. 8% Ga(CH2Ph)3 in acetonitrile as [B(CH2Ph)3]0.92[Ga(CH2Ph)3]0.08 · NCMe ( 4 ) in the space group P21/n with a = 1050.32(7) pm, b = 1159.5(2) pm, c = 1591.6(1) pm and β = 96.931(6)°. 相似文献
135.
Classifying wine according to geographical origin via quadrupole-based ICP–mass spectrometry measurements of boron isotope ratios 总被引:1,自引:0,他引:1
The potential of quadrupole-based ICP–MS as a tool for B-isotopic analysis of wines and its usefulness in provenance determinations
were assessed. A precision of 0.1–0.25% RSD (corresponding to a relative standard deviation of the mean of three replicate
measurements of 0.06–0.12%) was sufficient to establish small differences in the B isotope ratios in wines from different
geographical origins. Each sample measurement was bracketed by measurements of a standard and mass bias drift correction made
by interpolation. Sample preparation was kept to a minimum to avoid possible fractionation. Dilution of the wine samples by
a factor of 100 with 0.65% HNO3 was found to reduce matrix-induced mass discrimination substantially. Wines from three wine-producing regions, Stellenbosch,
Robertson, and Swartland, in the Western Cape Province of South Africa, and wines from specific regions in France (Bergerac)
and Italy (Valpolicella) were analyzed by ICP–QMS for their B-isotopic compositions. It was concluded that the 11B/10B ratios can be used to characterize wines from different geographical origins. Average 11B/10B ratios in red wines from South Africa (Stellenbosch), France (Bergerac), and Italy (Valpolicella) were found to differ by
between 0.5 and 1.5%. 相似文献
136.
Apparent two-dimensional behavior of TiO2 nanotubes revealed by light absorption and luminescence 总被引:1,自引:0,他引:1
Bavykin DV Gordeev SN Moskalenko AV Lapkin AA Walsh FC 《The journal of physical chemistry. B》2005,109(18):8565-8569
Optical absorption and photoluminescence (PL) properties of colloidal TiO(2) nanotubes, produced by the alkali hydrothermal method, were studied at room temperature in the range 300-700 nm. Nanotubes having an internal diameter in the range 2.5-5 nm have very similar optical properties, in contrast to the expected behavior for quasi-1-D systems. This is explained by the complete thermal smearing of all 1-D effects, due to the large effective mass of charge carriers in TiO(2), resulting in an apparent 2-D behavior of TiO(2) nanotubes. 相似文献
137.
Schönherr H Johnson JM Lenz P Frank CW Boxer SG 《Langmuir : the ACS journal of surfaces and colloids》2004,20(26):11600-11606
The adsorption of phosphatidylcholine (PC) vesicles (30, 50, and 100 nm nominal diameters) and of dye-labeled PC vesicles (labeled with 6% Texas Red fluorophore (TR) and encapsulated carboxy fluorescein (CF)) to glass surfaces was studied by contact mode atomic force microscopy in aqueous buffer. These studies were performed in part to unravel details of the previously observed isolated rupture of dye-labeled PC vesicles on glass (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), specifically to differentiate partial rupture, that is, pore formation and leakage of entrapped dye, from full rupture to form bilayer disks. In addition, the adhesion potential of PC vesicles on glass was calculated based upon the adhesion-driven flattening of adsorbed vesicles and a newly developed theoretical model. The vesicles were found to flatten considerably upon adsorption to glass (width-to-height ratio of approximately 5), which leads to an estimate for the adhesion potential and for the critical rupture radius of 1.5 x 10(-4) J/m2 and 250 nm, respectively. Independent of vesicle size and loading with dye molecules, the adsorption of intact vesicles was observed at all concentrations below a threshold concentration, above which the formation of smooth lipid bilayers occurred. In conjunction with previous work (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), these data show that 6% TR 20 mM CF vesicles adsorb to the surface intact but undergo partial rupture in which they exchange content with the external buffer. 相似文献
138.
Immo Weber Frank W. Heinemann Panagiotis Bakatselos Ulrich Zenneck 《Helvetica chimica acta》2007,90(4):834-845
A pressure‐controlled procedure for the SN1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd0‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ). 相似文献
139.
Frank Sobott Andreas Wattenberg Wolfgang Kleinekofort Anja Pfenninger Bernhard Brutschy 《Analytical and bioanalytical chemistry》1998,360(7-8):745-749
A recently developed soft desorption method for mass spectrometry is presented, which is called Laser Induced Liquid Beam
Ionization/Desorption (LILBID). Analyte ions are desorbed from a thin jet of analyte solution directly into vacuum by means
of an IR laser pulse, which has been tuned to a vibrational resonance of the solvent. A comparative experiment with ammonium
chloride and aniline hydrochloride shows that ion formation via proton transfer takes place in the solution. Thermally unstable
compounds, as well as supra- and biomolecular complexes, can be detected intact and mass analyzed in a reflectron time-of-flight
(Re-TOF) mass spectrometer. During the desorption process, noncovalent interactions and some solvation characteristics are
preserved. Three examples for the capacity of LILBID are given in this short overview: (a) ion-solvent interactions with the formation of a clathrate structure Cs+(H2O)20, (b) host-guest interactions with the K+ selectivity of valinomycin, and (c) noncovalent interactions with the dimerization of gramicidin.
Received: 29 July 1997 / Revised: 4 September 1997 / Accepted: 12 September 1997 相似文献
140.
Thermolysis of η2-benzoyl(phenyl)zirconocene yields the η2-benzophenonzirconocene complex 2, isolated as a dimer. 2 exhibits an ambivalent reactivity pattern. The formation of five-membered metallacycles from 2 and olefinic hydrocarbons possibly proceeds analogous to reactions of “normal” metalolefin π-complexes. However, both reactions with the electron-deficient olefins dimethylfumarate and -maleate and the behavior towards electrophilic and protic reagents as well as aromatic hydrocarbons might be interpreted in terms of a metallaoxirane-character of 2. 相似文献