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11.
12.
Bahr S Borodin A Höfft O Kempter V Allouche A Borget F Chiavassa T 《The journal of physical chemistry. B》2006,110(17):8649-8656
The interaction of acetic acid (AA, CH(3)COOH), with solid water, deposited on metals, tungsten and gold, at 80 K, was investigated. We have prepared acid/water interfaces at 80 K, namely, acid layers on thin films of solid water and H(2)O adlayers on thin acid films; they were annealed between 80 and 200 K. Metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy UPS(HeII) were utilized to obtain information on the electronic structure of the outermost surface from the study of the electron emission from the weakest bound MOs of the acids, and of the molecular water. Temperature-programmed desorption (TPD) provided information on the desorption kinetics, and Fourier-transformed infrared spectroscopy (FTIR) provided information on the identification of the adsorbed species as well as on the water and acid crystallization. The results are compatible with the finding of ref 1 (preceding paper), made on the basis of DFT calculations, that AA adsorbs on ice as cyclic dimers. Above 120 K, a rearrangement of the AA dimers is suggested by a sharpening of the spectral features in the IR spectra and by spectral changes in MIES and UPS; this is attributed to the glass transition in AA around 130 K. Above 150 K the spectra transform into those characteristic for polycrystalline polymer chains. This structure is stable up to about 180 K; desorption of water takes place from underneath the AA film, and practically all water has desorbed through the AA film before AA desorption starts. There is no indication of water-induced deprotonation of the acid molecules. For the interaction of H(2)O molecules adsorbed on amorphous AA films, the comparison of MIES with the DFT results of ref 1 shows that the initial phase of exposure does not lead to the formation of a top-adsorbed closed water film at 80 K. Rather, the H(2)O molecules become attached to or incorporated into the preexisting AA network by H bonding; no water network is formed in the initial stage of the water adsorption. Also under these conditions no deprotonation of the acid can be detected. 相似文献
13.
Abstract A chiral liquid crystal compound exhibiting the ferroelectric smectic C phase and the recently discovered ferroelectric smectic M phase has been studied by measurements of the Goldstone-mode relaxation frequency and dielectric strength, the spontaneous polarization, the tilt angle and the helical pitch. The data allow the determination of the Goldstone-mode rotational viscosity and the pitch controlling elastic constant. The results indicate that the smectic M phase is characterized by a larger molecular order within the smectic layers compared to the smectic C phase confirming the assumption of a tilted hexatic structure for the smectic M phase. 相似文献
14.
Thevis M Geyer H Bahr D Schänzer W 《European journal of mass spectrometry (Chichester, England)》2005,11(4):419-427
Since January 2005, the list of prohibited substances established by the World Anti-Doping Agency prohibits the opioid agent fentanyl as well as its related drugs in professional and amateur sports. Fast, reliable and robust analytical assays are required that allow the sensitive determination of these compounds or respective metabolites in human urine, and liquid chromatography interfaced to mass spectrometry has proven to be a suitable and powerful tool for drug testing for several years. A screening and confirmation method was developed that enables the identification of fentanyl, alfentanil, remifentanil and sufentanil as well as their N-dealkylated or de-esterified metabolites utilizing solid-phase extraction of a 2 mL urine aliquot followed by LC-electrospray-MS/MS analysis. The procedure was validated in terms of recovery (95.8-104.9%), lower limit of detection (0.5 ng mL-1), specificity and interday precision (3.9-19.8%) for the four opioid drugs and the metabolic product norfentanyl. In addition, the mass spectrometric behavior of fentanyl after electrospray ionization and collision-induced dissociation was studied by synthesis and analysis of structurally related compounds, and dissociation pathways were proposed allowing the characterization of target analytes and corresponding metabolites. 相似文献
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D. Schlauf C. Bahr V.K. Dolganov J.W. Goodby 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(3):461-469
We report a detailed ellipsometric study of freely suspended films of chiral liquid-crystal compounds possessing smectic-A
and smectic-C phases. In the temperature region between the smectic-A - smectic-C bulk and surface transitions, a discontinuous
reconstruction of the tilt profile across the film is observed in the presence of a constant d.c. electric field. Comparison
of the measured ellipsometric quantities with values calculated from model tilt profiles reveals a competition between a structure
possessing a homogeneous tilt direction and large ferroelectric polarization and a structure with opposite tilt direction
in the two film halfs and large flexoelectric polarization.
Received 21 October 1998 相似文献
17.
An isotope dilution technique using enriched stable isotopes is applied to determine the interchangeable heavy-metal fraction
in soils. Metals in two soil samples are extracted at constant pH, with water, NH4NO3, and EDTA. A spike of enriched stable isotopes is added to the suspension of sample and eluant at the beginning of the extraction.
The heavy-metal fraction which exchanges with the added spike during the extraction is called the interchangeable fraction.
The extractable heavy-metal fractions are obtained from the heavy-metal concentrations in the eluates. Isotope ratios and
concentrations are determined by HR-ICP-MS. The isotope dilution technique described enables both the extractable and the
interchangeable heavy-metal fractions to be determined in the same experiment. The combination of both results gives additional
information on elemental availability under different conditions that cannot be obtained by analyzing the extractable heavy-metal
fractions alone. It is demonstrated that in some cases different eluants just shift the distribution of the interchangeable
fraction of an element between the solid and liquid phases (e.g., Pb and Cd in a topsoil sample) while the amount of the interchangeable
fraction itself remains constant. For other elements, as Ni, Zn, and Cr, the use of different eluants (different pH, complexing
agents) sometimes enlarges the interchangeable fraction.
Received: 8 December 1998 / Revised: 30 June 1999 / Accepted: 2 July 1999 相似文献
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J Bahr K Carlsson B Lüning 《Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry》1988,42(7):442-447
An immunological epitope has been located at the well preserved heptade discontinuity in Coil 2B of human cytokeratin 8, with the aid of synthetic peptides, antibodies to these and monoclonal antibodies to cytokeratins. CD revealed 37% alpha-helix in a 31-peptide. 相似文献