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51.
52.
Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study 下载免费PDF全文
Dr. Jean‐Yves Salpin Violette Haldys Dr. Sébastien Guillaumont Prof. Jeanine Tortajada Marcela Hurtado Prof. Al Mokhtar Lamsabhi 《Chemphyschem》2014,15(14):2959-2971
Gas‐phase interactions between Pb2+ ions and cytosine (C) were studied by combining tandem mass spectrometry, infrared multiple photon dissociation spectroscopy, and density functional theory (DFT) calculations. Both singly and doubly charged complexes were generated by electrospray. The [Pb(C)?H]+ complex was extensively studied, and this study shows that two structures, involving the interaction of the metal with the deprotonated canonical keto‐amino tautomer of cytosine, are generated in the gas phase; the prominent structure is the bidentate form involving both the N1 and O2 electronegative centers. The DFT study also points out a significant charge transfer from the nucleobase to the low‐lying p orbitals of the metal and a strong polarization of the base upon complexation. The various potential energy surfaces explored to account for the fragmentation observed are consistent with the high abundance of the [PbNH2]+ fragment ion. 相似文献
53.
A general model is introduced to study pressure-induced reactivity on unsaturated systems in the condensed state. The model is applied here to dimethylacetylene (DMA) in the solid phase II (C/2m) because it has been proposed that two DMA molecules can react to form tetramethyl-cyclobutadiene (TMCBD). The proposed reaction process has been modeled by studying the structural and electronic changes undergone by two DMA molecules as they approach each other preserving the crystal symmetry of phase II. Both monodeterminantal (MP2 and DFT) and multideterminantal (CASSCF and MRMP2) methodologies were used to check the reliability of our model in predicting the reactivity of the system under compression. In all cases, structural results are in agreement with low-temperature diffraction experiments for the solid phase II. Our model indicates that DMA is expected to form the TMCBD dimer at intermolecular distances close to 2 A. This value is in excellent agreement with previous calculations on the existence of long carbon-carbon bonds. 相似文献
54.
Iron topochemistry and surface reactivity of amphibole asbestos: relations with in vitro toxicity 总被引:1,自引:0,他引:1
Pacella A Andreozzi GB Fournier J Stievano L Giantomassi F Lucarini G Rippo MR Pugnaloni A 《Analytical and bioanalytical chemistry》2012,402(2):871-881
Chemical reactivity of asbestos tremolite from Italy and USA localities and Union Internationale Contre le Cancer (UICC) crocidolite
was studied in relation to Fe content, oxidation state, and structural coordination. Direct correlation between amount of
Fe2+ at the exposed M(1) and M(2) sites of the amphibole structure and fiber chemical reactivity was established. The in vitro
toxicity of the same samples was investigated on human alveolar A549 cell line. Relationship between crystal-chemical features
and cell toxicity is not straightforward. UICC crocidolite has Fe content and chemical reactivity largely higher than that
of tremolite samples, but all show comparable in vitro toxic potential. Results obtained evidenced that Fe topochemistry is
not a primary factor for induced cell toxicity, though it accounts for asbestos chemical reactivity (and possibly genotoxicity). 相似文献
55.
Larisa Dunai Guillermo Peris-Fajarnes Ismael Lengua Lengua Ignacio Tortajada Monta?a 《Acoustical Physics》2012,58(5):610-617
In the present paper a study of sound localization is carried out, considering two different sounds emitted from different hit materials (wood and bongo) as well as a Delta sound. The motivation of this research is to study how humans localize sounds coming from different materials, with the purpose of a future implementation of the acoustic sounds with better localization features in navigation aid systems or training audio-games suited for blind people. Wood and bongo sounds are recorded after hitting two objects made of these materials. Afterwards, they are analysed and processed. On the other hand, the Delta sound (click) is generated by using the Adobe Audition software, considering a frequency of 44.1 kHz. All sounds are analysed and convolved with previously measured non-individual Head-Related Transfer Functions both for an anechoic environment and for an environment with reverberation. The First Choice method is used in this experiment. Subjects are asked to localize the source position of the sound listened through the headphones, by using a graphic user interface. The analyses of the recorded data reveal that no significant differences are obtained either when considering the nature of the sounds (wood, bongo, Delta) or their environmental context (with or without reverberation). The localization accuracies for the anechoic sounds are: wood 90.19%, bongo 92.96% and Delta sound 89.59%, whereas for the sounds with reverberation the results are: wood 90.59%, bongo 92.63% and Delta sound 90.91%. According to these data, we can conclude that even when considering the reverberation effect, the localization accuracy does not significantly increase. 相似文献
56.
57.
Nicole Rolland Georges Vass Jeanine Cleophax Anne-Marie Sepulchre Stephan D. Gero Andr Cier 《Helvetica chimica acta》1982,65(5):1627-1636
Total synthesis of α-disaccharidyl-2,5,6-trideoxy-streptamines related to aminoglycoside antibiotics derived from maltose and lactose The synthesis of the hitherto unknown 4-O-substituted α-linked pseudo-tri-saccharides 1,2 and 3 is described. The key intermediates required in the reaction sequence are the glycals 12, 13 and 14 , prepared from maltose, lactose and the chiral ditosyloxy-cyclohexanol 15 , readily accessible from quinic acid. The pivotal step in the reaction's scheme - a stereospecific α-glycosylution procedure -, is an acid-catalyzed addition of the alcohol 15 to the glycals 12, 13 and 14 leading to the corresponding 2,3-unsaturated trisaccharides. The latter compounds were transformed to the target α-glycosides of 2,5,6-trideoxystreptamine 1, 2 and 3 which were devoid of significant antibacterial activity. These results indicate that the presence of an ether linkage at the position 4′ is probably critical for antibacterial activity. 相似文献
58.
Buchmann W Spezia R Tournois G Cartailler T Tortajada J 《Journal of mass spectrometry : JMS》2007,42(4):517-526
The electronebulization of a cobalt(II)/cysteine(Cys) mixture in water/methanol (50/50) produced mainly cobalt-cationized species. Three main groups of the Co-cationized species can be distinguished in the ESI-MS spectrum: (1) the cobalt complexes including the cysteine amino acid only (they can be singly charged, for example, [Co(Cys)n- H]+ with n = 1-3 or doubly charged such as [Co + (Cys)2]2+); (2) the cobalt complexes with methanol: [Co(CH3OH)n- H]+ with n = 1-3, [Co(CH3OH)4]2+; and (3) the complexes with the two different types of ligands: [Co(Cys)(CH3OH) - H]+. Only the singly charged complexes were observed. Collision-induced dissociation (CID) products of the [Co(Cys)2]2+, [Co(Cys)2 - H]+ and [Co(Cys) - H]+ complexes were studied as a function of the collision energy, and mechanisms for the dissociation reactions are proposed. These were supported by the results of deuterium labelling experiments and by density functional theory calculations. Since [Co(Cys) - H]+ was one of the main product ions obtained upon the CID of [Co(Cys)2]2+ and of [Co(Cys)2 - H]+ under low-energy conditions, the fragmentation pathways of [Co(Cys) - H]+ and the resulting product ion structures were studied in detail. The resulting product ion structures confirmed the high affinity of cobalt(II) for the sulfur atom of cysteine. 相似文献
59.
Terrier P Tortajada J Zin G Buchmann W 《Journal of the American Society for Mass Spectrometry》2007,18(11):1977-1989
MALDI-MS was evaluated as a method for the study of noncovalent complexes involving DNA oligonucleotides and various polybasic compounds (basic polypeptides and polyamines). Complexes involving single-stranded DNA were successfully detected using DHAP matrix in the presence of an ammonium salt. Control experiments confirmed that the interactions involved basic sites of the polybasic compounds and that the complexes were not formed in the gas phase but were pre-existing in the matrix crystals. Moreover, the pre-existence in solution was probed by isothermal titration calorimetry at concentration and ionic strength similar to those used for mass spectrometry. Spectra showed no important difference between negative and positive ion modes. The influence of nature and size of DNA and polybasic compound on the relative intensities and stoichiometries of the complexes was investigated. Despite the fact that relative intensities can be affected by ionization yields and the gas-phase stabilities of the different species, numerous trends observed in the MALDI study were consistent with the expected in-solution behaviors. Experimental conditions related to sample preparation were investigated also. Complex abundance generally decreased when increasing the ammonium acetate concentration. It was dramatically decreased when using ATT instead of DHAP. Penta-L-arginine is an exception to these observations. Lastly, in the case of complexes involving DNA duplex, the ATT matrix was shown to favor the observation of specific DNA duplex but not that of its complex with polybasic compounds. Inversely, DHAP was appropriate for the conservation of DNA-polybasic compound interaction but not for the transfer of intact duplex. 相似文献
60.
Robert Finsy Lue Deriemaeker Nicolas De Jaeger Rik Sneyers Jan Vanderdeelen Paul Van der Meeren Hugo Demeyere Jeanine Stone-Masui Anne Haestier Julius Clauwaert Walter De Wispelaere Pascal Gillioen Sabine Steyfkens Erik Gelad 《Particle & Particle Systems Characterization》1993,10(3):118-128
The practical performances of single and multi-angle photon correlation spectroscopy (PCS) for resolving bimodal distributions of industrial poly (methyl methacrylate) samples was investigated in a comparative study by several users affiliated to academic and industrial groups and by two suppliers of commercial equipment. The results for the harmonic intensity averaged diameters obtained by cumulants analysis reported by the different laboratories are in agreement, in addition to the results for the normalized second cumulants. The uncertainty on the latter quantities is large, however. For the bimodal samples with two populations with average diameters in a ratio of about 2.5 : 1, not all users were able to resolve the distribution in its components by single-angle PCS. Some slight improvement was obtained by multi-angle PCS. Other indirect techniques (polarization intensity differential scattering, static light scattering data and disc photosedimentometer) appeared to be superior for resolving the bimodal distributions. 相似文献