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11.
Of ammonium, lithium and sodium salts of dodecyl sulfate studied as surfactants in the separation of iridoid glycosides by micellar electrokinetic capillary chromatography (MECC), the last one gave the best results. Eleven neutral iridoid glycosides were separated by MECC with sodium dodecyl sulfate as surfactant, and the water–micelle partition coefficients of the compounds were calculated. The separation system was coupled via a coaxial sheath flow electrospray interface to a mass spectrometer, and the partial filling technique was used in the on-line analysis. Seven plant species belonging to five genera (Plantago, Veronica, Melampyrum, Succisa and Valeriana) were screened for the iridoid glycosides by the new method that was developed. The findings confirmed those of an earlier study on five of the iridoid glycosides. Some new iridoid glycosides were found in Plantago lanceolata, Veronica spicata and V. chamaedrys. 相似文献
12.
Photochemical switching has been studied of double-tailed phosphate amphiphiles containing azobenzene units in both tails in aqueous vesicular dispersions and in mixed vesicular systems with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). Since the ease of switching depends on the strength of the bilayer packing, particular emphasis has been placed on the occurrence of H-aggregation in the hydrophobic core of the vesicles. UV-vis spectrometry was employed to monitor H-aggregation and showed how this process depends on the ionic strength and on the mode of preparation of the vesicles. Two types of H-aggregates were observed in mixed DOPC vesicles with 5 mol % of azobenzene phosphate: one with lambda(max) at around 300 nm and one with lambda(max) at 305-320 nm. Those with lambda(max) at 300 nm could not be trans-cis photoisomerized, whereas those with lambda(max) at 305-320 nm are more loosely packed and can be photochemically switched. The permeability of the vesicular bilayers, as probed with leakage experiments using calcein as a fluorescent probe, was examined as another measure for the strength of bilayer packing. Leakage occurred only for DOPC vesicles containing more than 20 mol % of azobenzenephosphate, irradiated with UV light to induce trans-cis photoisomerization. We contend that detailed information on bilayer packing will be of crucial importance for fine-tuning the lateral pressure in vesicular membranes with the ultimate aim to steer the opening and closing of mechanosensitive protein channels of large conductance. 相似文献
13.
Markus Håkansson Johanna Suomi Mauri Nauma Jouko Kankare Jarkko U. Eskola 《Analytica chimica acta》2006,556(2):450-454
Double insulating barrier tunnel emission electrodes were fabricated by adding a new pure aluminum layer upon oxidized aluminum electrodes by vacuum evaporation and thermally oxidizing the new aluminum layer in air at room temperature. Resulting Al/Al2O3/Al/Al2O3 electrodes allow the use of various aluminum alloys in the electrode body necessary for hardness or shaping ability of the electrode while obtaining the luminescence properties of pure aluminum oxide. During electrical excitation of luminescent labels by cathodic hot electron injection into aqueous electrolyte solution, the background noise is mainly based on high-field-induced solid-state electroluminescence and F-center luminescence of the outer aluminum oxide film. The more defect states and/or impurity centers the outer oxide film contains, the higher is the background emission intensity. The present electrode fabrication method provides a considerable improvement in signal-to-noise ratio for time-resolved electrochemiluminescence (TR-ECL) measurements when the original native oxide film of the electrode body contains luminescence centers displaying long-lived luminescence. The excellent performance of the present electrodes is demonstrated by extremely low-level detection of Tb(III) chelates, luminol, Pt(II) coproporphyrin and Tb(III) labels in an immunometric immunoassay by time-resolved electrochemiluminescence. 相似文献
14.
Douglas A. Livingston Andreas Pfaltz Jakob Schreiber Albert Eschnmoser Dorothe Ankel-Fuchs Johanna Moll Rolf Jaenchen Rudolf K. Thauer 《Helvetica chimica acta》1984,67(1):334-351
Factor F430 from Methanogenic Bacteria: Structure of the Protein-free Factor Factor F430, the porphinoid nickel-containing coenzyme of the methylcoenzyme-M reductase of metanogenic bacteria is shown to be the 33,83,122,133,182-pentaacid derivative of the pentamethylester F430M, the structure of which had been determined previously (see structural formulae 1 and 2 ). The structure assignment rests on chromatographic, UV/VIS-, CD-, IR-, and 13C-NMR-spectroscopic as well as FAB-mass spectral comparision of F430 with F430M and the pentaacid prepared by acid-catalyzed hydrolysis of F430M. In the cells of Methanobacterium thermoautotrophicum, factor F430 is present in a ‘bound’ and also, depending on the growth conditions, in ‘free’ form, the latter being defined as the part of total F430 that can be extracted from the cells under extremely mild conditions (80% EtOH at 0–4°). From the (protein)-‘bound’ form, F430 is extracted by subsequently treating the cells at 0–4° with 80% EtOH containing (e.g.), 2m LiCi. From both sources, the extracted factor is the same pentaacid, and there is no indication for the existence of a protein-free F430 species that would contain additional (covalently bound) structural elements. 相似文献
15.
Tae-Kyu Ha Urs P. Wild Ren O. Kühne Charles Loesch Thierry Schaffhauser Johanna Stachel Alexander Wokaun 《Helvetica chimica acta》1978,61(3):1193-1199
Ab initio SCF and CI calculations on the cationic and neutral complexes of formaldehyde and lithium are reported. For the cationic complex CH2O/Li+, the stabilization energy of 41.7 kcal/mol obtained from the SCF calculation increases to 51.6 kcal/mol if a configuration interaction is introduced. For the neutral complex CH2O?/Li+, the C2v-conformer of the 2A1-state with the equilibrium bond distances of d(C? O) = 1.23 Å and d (O? Li) = 1.90 Å is calculated to be more stable than the 2B1-state with d (C? O) = 1.34 Å, and d (O? Li) = 1.65 Å. Charge transfer and polarization effects upon complex formation are discussed. 相似文献
16.
Christian Roussel Alexandru T. Balaban Ulf Berg Michel Chanon Roger Gallo Gerd Klatte Joseph A. Memiaghe Jacques Metzger Daniela Oniciu Johanna Pierrot-Sanders 《Tetrahedron》1983,39(24):4209-4219
The effect of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical substituent with the appropriate van der Waals radius, was considered in kinetics of alkylalion of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework. The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group. 相似文献
17.
Jiao J Kanellopoulos J Wang W Ray SS Foerster H Freude D Hunger M 《Physical chemistry chemical physics : PCCP》2005,7(17):3221-3226
27Al spin-echo, high-speed MAS (nu(rot) = 30 kHz), and MQMAS NMR spectroscopy in magnetic fields of B0 = 9.4, 14.1, and 17.6 T were applied for the study of aluminum species at framework and extra-framework positions in non-hydrated zeolites Y. Non-hydrated gamma-Al2O3 and non-hydrated aluminum-exchanged zeolite Y (Al,Na-Y) and zeolite H,Na-Y were utilized as reference materials. The solid-state 27Al NMR spectra of steamed zeolite deH,Na-Y/81.5 were found to consist of four signals. The broad low-field signal is caused by a superposition of the signals of framework aluminum atoms in the vicinity of bridging hydroxyl protons and framework aluminum atoms compensated in their negative charge by aluminum cations (delta(iso) = 70 +/- 10 ppm, C(QCC) = 15.0 +/- 1.0 MHz). The second signal is due to a superposition of the signals of framework aluminum atoms compensated by sodium cations and tetrahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 65 +/- 5 ppm, C(QCC) = 8.0 +/- 0.5 MHz). The residual two signals were attributed to aluminum cations (delta(iso) = 35 +/- 5 ppm, C(QCC) = 7.5 +/- 0.5 MHz) and octahedrally coordinated aluminum atoms in neutral extra-framework aluminum oxide clusters (delta(iso) = 10 +/- 5 ppm, C(QCC) = 5.0 +/- 0.5 MHz). By chemical analysis and evaluating the relative solid-state 27Al NMR intensities of the different signals of aluminum species occurring in zeolite deH,Na-Y/81.5 in the non-hydrated state, the aluminum distribution in this material was determined. 相似文献
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20.
Dr. Johanna Scheck Lisa M. Fuhrer Dr. Baohu Wu Dr. Markus Drechsler Prof. Dr. Denis Gebauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):13002-13007
Hematite (α-Fe2O3) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room-temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase-separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism. 相似文献