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201.
Winnewisser G Lewen F Thorwirth S Behnke M Hahn J Gauss J Herbst E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(22):5501-5510
Gas-phase oxadisulfane (HSOH), the missing link between the well-known molecules hydrogen peroxide (HOOH) and disulfane (HSSH), was synthesized by flash vacuum pyrolysis of di-tert-butyl sulfoxide. Using mass spectrometry, the pyrolysis conditions have been optimized towards formation of HSOH. Microwave spectroscopic investigation of the pyrolysis products allowed-assisted by high-level quantum-chemical calculations--the first measurement of the rotational-torsional spectrum of HSOH. In total, we have measured approximately 600 lines of the rotational-torsional spectrum in the frequency range from 64 GHz to 1.9 THz and assigned some 470 of these to the rotational-torsional spectrum of HSOH in its ground torsional state. Some 120 out of the 600 lines arise from the isotopomer H(34)SOH. The HSOH molecule displays strong c-type and somewhat weaker b-type transitions, indicating a nonplanar skew chain structure, similar to the analogous molecules HOOH and HSSH. The rotational constants (MHz) of the main isotopomer (A=202 069, B=15 282, C=14 840), determined by applying a least-squares analysis to the presently available data set, are in excellent agreement with those predicted by quantum-chemical calculations (A=202 136, B=15 279, C=14 840). Our theoretical treatment also derived the following barrier heights against internal rotation in HSOH (when in the cis and trans configurations) to be V(cis) approximately equal to 2216 cm(-1) and V(trans) approximately equal to 1579 cm(-1). The internal rotational motion results in detectable torsional splittings that are dependent on the angular momentum quantum numbers J and K(a). 相似文献
202.
N-Acylimines (2) possess the characteristics of both hetero-1,3-dienes and dienophiles. They react with the kinetically stabilised cyclobutadienes 1 to form 4-aza-2-oxabicyclo[4.2.0]octa-3,7-dienes (3) and/or 2-azabicyclo[2.2.0]hex-5-enes (4). Compounds of the type 3 undergo acid-catalysed isomerisation to give compounds 4. Homocyclopropenylium intermediates of the type 5 are supposed to be involved in both processes (1 + 2 → 3 + 4 and 3 → 4). 相似文献
203.
204.
Winnewisser G 《Analytical and bioanalytical chemistry》1996,355(5-6):571-575
The space between the stars is not void, but filled with interstellar matter, mainly composed of dust and gas, which gather in large interstellar clouds. In our Galaxy these interstellar clouds are distributed along a thin, but extended layer which basically traces out the spiral distribution of matter: the stars, the gas, and the dust component. Up to the present time more than 100 different molecules have been identified in interstellar molecular clouds. The majority of the interstellar molecules constitute carbon containing organic substances. During the past years, overwhelming evidence has been gathered, mainly through spectroscopic observations, that interstellar molecular clouds provide the birthplaces for stars. In fact detailed high spectral and spatial resolution spectroscopic measurements reveal physical and chemical processes of the intricate star formation process. 相似文献
205.
Gisbert Tuchalski Franziska Emmerling Karsten Grger Andr Hnsicke Thomas Nagel Günter Reck 《Journal of Molecular Structure》2006,800(1-3):28-44
The molecular and crystal structures of the hydrochlorides of d-nebivolol, dl-nebivolol, and seven nebivolol isomers have been determined by X-ray structure analysis. The absolute configuration of all the compounds could be determined unambiguously using anomal dispersion effects. Two compounds, dl-nebivolol (NEB-1d,l) and the (S,R,S,R) nebivolol isomer (NEB-6), crystallize as racemic mixtures in the centrosymmetric space group P-1. d-Nebivolol and six nebivolol isomers crystallize in space group P212121. The d- and l-nebivolol molecules in NEB-1d and NEB-1d,l adopt a conformation which is significantly different compared with that of all nebivolol isomers. With the exception of dl-nebivolol (NEB-1d,l) numerous intermolecular hydrogen bonds connect the molecules forming molecular layers. 相似文献
206.
The rotational spectra of formaldehyde, H212C16O and its isotopic species H213C16O, H212C18O, and H213C18O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H212C16O and H213C16O a large number of ΔKa = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:
H212C16O | H213C16O | H212C18O | H213C18O | |
A/MHz | 281 970.572 (24) | 281 993.258(135) | 281 961.94 (39) | 281 985.00 (93) |
B/MHz | 38 836.0456(13) | 37 811.0887(25) | 36 904.1693(66) | 35 859.256(10) |
C/MHz | 34 002.2034(12) | 33 213.9790(25) | 32 511.5311(63) | 31 697.868(10) |