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81.
Vogel A Katzka CP Waldmann H Arnold K Brown MF Huster D 《Journal of the American Chemical Society》2005,127(35):12263-12272
The human N-ras protein binds to cellular membranes by insertion of two covalently bound posttranslational lipid modifications, which is crucial for its function in signal transduction and cell proliferation. Mutations in ras may lead to unregulated cell growth and eventually cancer, making it an important therapeutic target. Here we have investigated the molecular details of the membrane binding mechanism. A heptapeptide derived from the C-terminus of the human N-ras protein was synthesized including two hexadecyl modifications. Solid-state 2H NMR was used to determine the packing and molecular dynamics of the ras lipid chains as well as the phospholipid matrix. Separately labeling the chains of the peptide and the phospholipids with 2H enabled us to obtain atomically resolved parameters relevant to their structural dynamics. While the presence of ras only marginally affected the packing of DMPC membranes, dramatically lower order parameters (S(CD)) were observed for the ras acyl chains indicating modified packing properties. Essentially identical projected lengths of the 16:0 ras chains and the 14:0 DMPC chains were found, implying that the polypeptide backbone is located at the lipid-water interface. Dynamical properties of both the ras and phospholipid chains were determined from spin-lattice 2H relaxation (R1Z) measurements. Plots of R1Z rates versus the corresponding squared segmental order parameters revealed striking differences. We propose the ras peptide is confined to microdomains containing DMPC chains which are in exchange with the bulk bilayer on the 2H NMR time scale (approximately 10(-5) s). Compared to the host DMPC matrix, the ras lipid modifications are extremely flexible and undergo relatively large amplitude motions. It is hypothesized that this flexibility is a requirement for the optimal anchoring of lipid-modified proteins to cellular membranes. 相似文献
82.
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85.
The 70 eV mass spectra of a number of 13C- and D-labelled analogs of 1-heptene have been measured, as well as the metastable transitions in the non-labelled compound. Isotopic distributions in the major fragment ions have been calculated from the high and low resolution data. The results show that considerable skeletal rearrangement must take place before formation of most of the fragment ions. Loss of methyl and ethyl radicals occurs mainly from the two ends of the molecule. Ethylene fragments come primarily from the unsaturated end of the molecule, but show evidence of significant prior skeletal rearrangement. The predicted McLafferty rearrangement accounts for only 2/3 of the C4H8+ ions formed, less for the C3H6+ ions. At least 80% of C4H9+ ions appear to be formed by allylic cleavage, as expected, but this mechanism can only account for a maximum of 20% of the formation of the complementary ion C3H5+. Both, this latter ion and C3H6+, are probably generated by loss of hydrogen from C3H7+. Figures obtained for label retention in 1-[13C]- and 1-D-labelled analogs were nearly identical for most fragment ions, probably indicating that the hydrogen atoms in position 1 remain on C(1) even following skeletal rearrangement. A similar result was found for the 7-[13C]- and 7-D-labelled compounds. The main exceptions in the case of the products labelled in position 1 (C4H7+, C3H3+) seem to be due to initial loss of an hydrogen atom from this position followed by further fragmentation. 相似文献
86.
Yao M Mantha S Shah VR Vachharajani NN Arnold ME Pursley JM Srinivas NR 《Biomedical chromatography : BMC》2002,16(3):175-182
A high performance liquid chromatographic-mass spectrometric (LC/MS) assay was developed and validated for the determination of BMS-204352 in dog K(3)EDTA plasma. A 0.5 mL aliquot of control plasma was spiked with BMS-204352 and internal standard (IS) and buffered with 1 mL of 5 mM ammonium acetate. The mixture was then extracted with 3 mL of toluene. After separation and evaporation of the organic phase to dryness using nitrogen at 40 degrees C, the residue was reconstituted in the mobile phase and 25 microL of the sample were injected onto a Hypersil C(18) column (2 x 50 mm; 3 microm) at a flow rate of 0.5 mL/min. The mobile phase was consisted of two solvent mixtures (A and B). Solvent A was composed of 5 mM ammonium acetate and 0.1% triethylamine in 75:25 v/v water:methanol, pH adjusted to 5.5 with glacial acetic acid, and solvent B was 5 mM ammonium acetate in methanol. A linear gradient system was used to elute the analytes. The mass spectrometer was programmed to admit the de-protonated molecules at m/z 352.7 (IS) and m/z 357.9 (BMS-204352). Standard curves of BMS-204352 were linear (r(2) > or = 0.998) over the concentration range of 0.5-1000 ng/mL. The mean predicted quality control (QC) concentrations deviated less than 5.1% from the corresponding nominal values (ie 4, 80, 400 and 2000 ng/mL); the within- and between-assay precision of the assay were within 5.5% relative standard deviation. Stability of BMS-204352 was confirmed after at least three freeze/thaw cycles and BMS-204532 was stable in dog plasma when stored frozen at or below -20 degrees C for at least 16 weeks in spiked QC samples and for at least 4 1/2 weeks for in vivo study samples. BMS-204352 and IS were stable in the injection solvent at room temperature for at least 24 h. The assay was applied to delineate the pharmacokinetic disposition of BMS-204352 in dogs following a single intravenous dose administration. In conclusion, the assay is accurate, precise, specific, sensitive and reproducible for the pharmacokinetic analysis of BMS-204532 in dog plasma. 相似文献
87.
Levels of138Ce and140Nd have been studied using the138Ba(α,4nγ)138Ce and140Ce(α, 4nγ)140Nd reactions. Singleγ-ray spectra,γ-γ coincidence spectra, angular and time distributions with respect to the beam bursts have been measured. A number of higher excited states with excitation energies up to about 5 MeV and with spin value up to 12 are populated in both nuclei. The lower states with spins and parities 7?, 5?, 6? and 10+ can be explained by two-quasiparticle neutron configurations of the types (h 11/2 ?1 ,d 3/2 ?1 ) 7? , (h 11/2 ?1 ,S 1/2 ?1 ) 5?, 6? and (h 11/2 ?2 ) 10+. Several high-spin states observed in138Ce and140Nd can be explained qualitatively as four-quasiparticle states with two-proton-two-neutron configurations. The 3? state at an energy of 2,137.4 keV is observed in138Ce. The evidence for the existence of the low-lying 3? states in140Nd at 2,124.0 keV is discussed. Beside the known 9.6 ms (7?) isomeric state in138Ce another state at 3,538.5keV (10+) with a half life of about 200 ns has been observed. The observed levels in the138Ce and140Nd nuclei are compared with theoretical predictions using delta force interaction. 相似文献
88.
Arnold Münster 《Colloid and polymer science》1948,110(3):200-208
Zusammenfassung Die früher entwickelte statistische Theorie der Solvatation gel?ster Fadenmoleküle wird bis zur II. N?herung weitergeführt.
Es werden jetzt auch Dreiergruppen von Fadenmolekülen in die Rechnung einbezogen. Ferner werden der Einflu? des St?rungseffektes
der athermischen L?sung auf die Solvatation und die ?nderung der zwischenmolekularen Schwingungen durch dieselbe berücksichtigt.
Die erhaltenen thermodynamischen Formeln werden für eine Reihe von Spezialf?llen diskutiert. Die Theorie erkl?rt die auffallenden
Versuchsergebnisse an L?sungen der Zellulosederivate. Die Probleme des quantitativen Vergleichs zwischen Theorie und Experiment
werden an Hand des Systems Kautschuk-Benzol diskutiert.
Der Gesellschaft der Freunde der Universit?t Heidelberg danke ich für die Gew?hrung eines Forschungsstipendiums. 相似文献
89.
Arnold Emch 《Commentarii Mathematici Helvetici》1941,14(1):123-133
Ohne Zusammenfassung 相似文献
90.
Arnold Schmidt 《Mathematische Annalen》1938,115(1):485-506
Ohne Zusammenfassung 相似文献