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1.
Alexopoulos T Allen C Anderson EW Areti H Banerjee S Beery PD Biswas NN Bujak A Carmony DD Carter T Cole P Choi Y De Bonte RJ Erwin AR Findeisen C Goshaw AT Gutay LJ Hirsch AS Hojvat C Kenney VP Lindsey CS LoSecco JM McMahon T McManus AP Morgan N Nelson KS Oh SH Piekarz J Porile NT Reeves D Scharenberg RP Stampke SR Stringfellow BC Thompson MA Turkot F Walker WD Wang CH Wesson DK 《Physical review letters》1990,64(9):991-994
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Summary Various modifications of a thin-layer chromatography fluorimetric method for the determination of 7 H-benz(de)anthracen-7-one (BO) and phenalen-1-one (PO) in complex mixtures have been compared. The best modifications consisted of one-dimensional thin-layer chromatography followed by elution, evaporation, solution in trifluoroacetic acid, followed by either spectrophotofluorimetric or fluorimetric assay. In some cases a quenching agent was necessary to quench the fluorescence of the interferences. Urban atmospheres and air pollution source effluents can be analyzed by these micromethods. These methods with slight modification could be applied to the determination of the aza heterocyclic and the other ring-carbonyl compounds found in urban atmospheres and air pollution source effluents.
Zusammenfassung Verschiedene Modifikationen einer dünnschichtchromatographischen, fluorimetrischen Methode zur Bestimmung von 7 H-Benz(de)-anthracen-7-on (BO) und Phenalen-1-on (PO) in komplexen Gemischen wurden verglichen. Am besten bewährte sich eindimensionale Dünnschichtchromatographie, nachfolgende Elution, Abdampfen, Aufnehmen in Trifluoressigsäure und schließlich Bestimmung durch Spektralfluoreszenz-oder Fluoreszenzmessung. In manchen Fällen war es nötig, die Fluoreszenz störender Substanzen mit einem geeigneten Reagens zu löschen. Stadtatmosphäre oder Quellen der Luftverunreinigung können mit diesen Mikromethoden analysiert werden. Sie eignen sich nach geringfügiger Modifikation auch zur Bestimmung von azaheterocyklischen und anderen Ring-Carbonylverbindungen in der Atmosphäre.
Résumé On a comparé entre elles différentes modifications d'une méthode de fluorimétrie avec chromatographie en couche mince pour le dosage de la benzo-7 H anthracène-one-7 (BO) et de la phénalène-one-1 (PO) en mélanges complexes. Les modifications les meilleures ont consisté en une Chromatographie en couche mince unidimensionnelle suivie d'élution, évaporation, mise en solution dans l'acide trifluoroacétique, opérations suivies d'une recherche spectrophotofluorimétrique ou fluorimétrique. Dans certains cas, un agent d'extinction s'est montré nécessaire pour éteindre la fluorescence due aux interférences. On peut analyser par ces microméthodes les atmosphères urbaines et les écoulements sources de pollution de l'air. Ces méthodes ont pu être appliquées après légère modification au dosage des composés aza hétérocycliques et autres composés carbonyles cycliques trouvés dans les atmosphères urbaines et dans les écoulements sources de pollution de l'air.相似文献
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Alfred Fischer Michael W. Morgan Colin Eaborn 《Journal of organometallic chemistry》1977,136(3):323-332
Rates of cleavage of some picoyl- and (quinolylmethyl)-trimethylsilanes (RSiMe3, where R = PyCH2 or QnCH2SiMe3) have been measured in “90%” aqueous methanolic sodium methoxide at 50°C. Relative reactivities are: 2-PyCH2, 1.0; 3-PyCH2, 0.030; 4-PyCH2, 8.9; 2-QnCH2, 41; 3-QnCH2, 0.161; 4-QnCH2, 37. The rates correlate well with those for base-catalysed hydrogen-exchange in the parent carbon acids RH. Approximate pKa's (based on the scale of ion-pair acidities in CsNHC6H11H2NC6H11, with pKa of 9-phenylfluorene = 18.6) for the carbon acids, RH, can be derived as follows: 2-PyCH3, 29.5; 3-PyCH3, 34; 4-PyCH3, 27; 2-QnCH3, 25; 3-QnCH3, 32; 4-QnCH3, 25.Rates of cleavage of pyridyl- and quinolyl-trimethylsilanes (PySiMe3 and QnSiMe3) by sodium hydroxide in 4 : 1 v/v Me2SO/H2O at 50°C have also been measured; and the relative reactivities are: 2-Py, 1.0; 3-Py, 2.9; 4-Py, 8.4; 2-Qn, 15.9; 3-Qn, 12.7; 4-Qn, 184. The sequence of reactivity differes from that for base-catalysed hydrogen-exchange at the relevant positions of pyridine and quinoline, indicating that the reactivities are not determined in both cases (if in either) solely by the stabilities of the corresponding carbanions. 相似文献
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In situ soft X-ray studies of ethylene oxidation mechanisms and intermediates on the Pt(111) surface
Burnett DJ Gabelnick AM Fischer DA Marsh AL Gland JL 《The journal of physical chemistry. B》2005,109(12):5659-5666
In situ studies of ethylene oxidation on Pt(111) have been performed using a powerful combination of fluorescence yield soft X-ray methods for temperatures up to 600 K and oxygen pressures up to 0.01 Torr. Absolute carbon coverages have been determined both in steady-state and dynamic catalytic conditions on the Pt(111) surface. Fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) experiments above the carbon K edge were used to identify the structure and bonding of the dominant surface species during oxidation. TP-FYNES experiments of preadsorbed ethylene coverages in oxygen pressures up to 0.01 Torr indicate a stable intermediate is formed over the 215-300 K temperature range. By comparing the intensity of the C-H sigma resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate has been determined explicitly. Based on calibration with known C-H stoichiometries, the intermediate has a C(2)H(3) stoichiometry for oxygen pressures up to 0.01 Torr, indicating oxydehydrogenation occurs before skeletal oxidation. FYNES spectra at normal and glancing incidences were performed to characterize the structure and bonding of this intermediate. Using FYNES spectra of ethylene, ethylidyne, and acetylene as reference standard, this procedure indicates the oxidation intermediate is tri-sigma vinyl. Thus, oxidation of ethylene proceeds through a vinyl intermediate, with oxydehydrogenation preceding skeletal oxidation. 相似文献
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The apperrance of peaks at non-integral masses in linked scans, where the ratio B/E is kept constant, is shown to be caused by fragmentations of metastable ions occuring in the region between the magnetic and electric sectors. A formula is given for calculating the mass of the parent metastable ion and that of its daughter ion. 相似文献
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The mass spectral properties under medium and high resolution of a new protecting group for sterols is described and its ability to direct fragmentation is compared with established derivatives. The mass spectra obtained are characterised by strong molecular ions which fragment to produce a more even ion distribution than the familiar TMS ethers. This results in enhanced abundance of hydrocarbon fragments, with molecular structural details given greater prominence than is found with other derivatives. 相似文献
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Vinyl-containing poly(acrylic acid-co-itaconic acid) copolymers were synthesized and used to formulate light-curable cements containing reactive glass fillers (Fuji II LC). The conditions for light curing were studied and optimized. Effects of molecular weight (MW), grafting ratio, comonomer, liquid composition, powder/liquid (P/L) ratio, glass powder and aging were evaluated. The results show that the vinyl-containing glass-ionomer cements (GICs) prepared in this study exhibit higher compressive strength (CS, 225.6 MPa), diametral tensile strength (DTS, 28.4 MPa) and much higher flexural strength (FS, 116.4 MPa), as compared to commercial Fuji II LC GIC (186.6 in CS, 19.1 in DTS and 57.1 in FS). The optimal light-exposure time was found to be around 10 min, and concentrations of CQ and DC were 0.5% (by weight) and 1.0%, respectively. Effects of MW, grafting ratio, P/L ratio and content of polymer in the liquid formulation were significant. The highest strengths were found for the optimal formulations where the MW was 15,000 (weight average), grafting ratio 25 mol%, P/L ratio 2.7 and liquid composition 50:20:30. During aging, the cement showed an increase of strength over the first week and then no change for a month. SEM analysis suggests that more integrated microstructures and smaller glass particles can lead to higher FS and higher polymer content in GICs leads to tough fracture surface and plastic deformation. 相似文献