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81.
We consider repulsive potential energies $\mathcal {E}_{q}(\Sigma)$ , whose integrand measures tangent-point interactions, on a large class of non-smooth m-dimensional sets Σ in ? n . Finiteness of the energy $\mathcal {E}_{q}(\Sigma)$ has three sorts of effects for the set Σ: topological effects excluding all kinds of (a priori admissible) self-intersections, geometric and measure-theoretic effects, providing large projections of Σ onto suitable m-planes and therefore large m-dimensional Hausdorff measure of Σ within small balls up to a uniformly controlled scale, and finally, regularizing effects culminating in a geometric variant of the Morrey–Sobolev embedding theorem: Any admissible set Σ with finite $\mathcal {E}_{q}$ -energy, for any exponent q>2m, is, in fact, a C 1-manifold whose tangent planes vary in a Hölder continuous manner with the optimal Hölder exponent μ=1?(2m)/q. Moreover, the patch size of the local C 1,μ -graph representations is uniformly controlled from below only in terms of the energy value $\mathcal {E}_{q}(\Sigma)$ . 相似文献
82.
Darbandi Masih Laurent Sophie Busch Martin Li Zi-An Yuan Ying Krüger Michael Farle Michael Winterer Markus Vander Elst Luce Muller Robert N. Wende Heiko 《Journal of nanoparticle research》2013,15(5):1-9
Quasi-critical fluctuations occur close to critical points or close to continuous phase transitions. In three-dimensional systems, precision tuning is required to access the fluctuation regime. Lowering the dimensionality enhances the parameter space for quasi-critical fluctuations considerably. This enables one to make use of novel properties emerging in fluctuating systems, such as giant susceptibilities, Casimir forces or novel quasi-particle interactions. Examples are discussed ranging from simple metal–adsorbate systems to unconventional superconductivity in iron-based superconductors. 相似文献
83.
Phil M. Pithan Christopher Kuhlmann Prof. Dr. Carsten Engelhard Prof. Dr. Heiko Ihmels 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16088-16098
A series of new 5-mono- and 5,5′-bisamino-substituted azothiazole derivatives was synthesized from the readily available diethyl azothiazole-4,4′-dicarboxylate. This reaction most likely comprises an initial Michael-type addition by the respective primary alkyl and aromatic amines at the carbon atom C5 of the substrate. Subsequently, the resulting intermediates are readily oxidized by molecular oxygen to afford the amino-substituted azothiazole derivatives. The latter exhibit remarkably red-shifted absorption bands (λabs=507–661 nm) with high molar extinction coefficients and show a strong positive solvatochromism. As revealed by spectrometric titrations and circular and linear dichroism studies, the water-soluble, bis-(dimethylaminopropylamino)-substituted azo dye associates with duplex DNA by formation of aggregates along the phosphate backbone at high ligand–DNA ratios (LDR) and by intercalation at low LDR, which also leads to a significant increase of the otherwise low emission intensity at 671 nm. 相似文献
84.
Uta Albold Heiko Bamberger Philipp P. Hallmen Joris vanSlageren Biprajit Sarkar 《Angewandte Chemie (International ed. in English)》2019,58(29):9802-9806
The energy barrier leading to magnetic bistability in molecular clusters is determined by the magnetic anisotropy of the cluster constituents. By incorporating a highly anisotropic four‐coordinate cobalt(II) building block into a strongly coupled fully air‐ and moisture‐stable three‐spin system, it proved possible to suppress under‐barrier Raman processes leading to 350‐fold increase of magnetization relaxation time and pronounced hysteresis. Relaxation times of up to 9 hours at low temperatures were found. 相似文献
85.
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87.
Heiko Lange Klaus Bergander Dr. Roland Fröhlich Dr. Seda Kehr Dr. Shuichi Nakamura Prof. Dr. Norio Shibata Prof. Dr. Takeshi Toru Prof. Dr. Dieter Hoppe Prof. Dr. 《化学:亚洲杂志》2008,3(1):88-101
Substitution reactions that employ primary‐carbamoyl‐protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post‐deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature‐dependent epimerization process was monitored by 1H and 6Li NMR spectroscopy. 相似文献
88.
Allard S Forster M Souharce B Thiem H Scherf U 《Angewandte Chemie (International ed. in English)》2008,47(22):4070-4098
The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing. 相似文献
89.
Jiang H Li Y Pelzer M Cannon MJ Randlett C Junga H Jiang X Ji QC 《Journal of chromatography. A》2008,1192(2):230-238
A sensitive and selective bioanalytical assay was developed and validated for the determination of enantiomeric molindone in human plasma using high-performance liquid chromatography-tandem mass spectrometry along with supported liquid extraction procedures. The chiral separation was evaluated and optimized on macrocyclic antibiotic type chiral stationary phases (CSPs) based on teicoplanin aglycone (Chirobiotic TAG) in polar organic, polar ionic, and reversed-phase mode chromatography, respectively. Complete baseline separation was achieved on a Chirobiotic TAG column under isocratic condition in reversed-phase chromatography. The method validation was conducted using a Chirobiotic TAG column (100 mm x 2.1 mm) over the curve range 0.100-100 ng/ml for each molindone enantiomer using 0.0500 ml of plasma sample. The flow rate was 0.8 ml/min and the total run time was 9 min. Supported liquid extraction in a 96-well plate format was used for sample preparation. Parameters including recovery, matrix effect, linearity, sensitivity, specificity, carryover, precision, accuracy, dilution integrity, and stability were evaluated. The intra- and inter-day precision and accuracy of the quality control samples at low, medium, and high concentration levels were RSD 相似文献
90.
Intermolecular interactions between a prototypical transition metal hydride WH(CO)2NO(PH3)2 and a small proton donor H2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20–30% of the bond energy and to 30–40% of the bond enthalpy. An energy decomposition analysis reveals that the H?H bond of transition metal hydrides contains both covalent and electrostatic contributions. 相似文献