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31.
A. Gallegos Saliner I. Tsakovska M. Pavan G. Patlewicz A. P. Worth 《SAR and QSAR in environmental research》2013,24(3-4):331-342
The German Federal Institute for Risk Assessment (BfR) has developed a Decision Support System (DSS) to assess certain hazardous properties of pure chemicals, including skin and eye irritation/corrosion. The BfR–DSS is a rule-based system that could be used for the regulatory classification of chemicals in the European Union. The system is based on the combined use of two predictive approaches: exclusion rules based on physicochemical cut-off values to identify chemicals that do not exhibit a certain hazard (e.g., skin irritation/corrosion), and inclusion rules based on structural alerts to identify chemicals that do show a particular toxic potential. The aim of the present study was to evaluate the structural inclusion rules implemented in the BfR–DSS for the prediction of skin irritation and corrosion. The following assessments were performed: (a) a confirmation of the structural rules by rederiving them from the original training set (1358 substances), and (b) an external validation by using a test set of 200 chemicals not used in the derivation of the rules. It was found as a result that the test data set did not match the training set relative to the inclusion of structural alerts associated with skin irritation/corrosion, albeit some skin irritants were in the test set. 相似文献
32.
Flávio A. Pavan Sheila Leal Tania M.H. Costa Edilson V. Benvenutti Yoshitaka Gushikem 《Journal of Sol-Gel Science and Technology》2002,23(2):129-133
Aniline/silica sol-gel material was obtained. The aniline was immobilized on the silica surface using chloropropyltrimethoxysilane as bridge reagent. The base activator NaH was used to produce a fast SN2 reaction between the base and the alkylorganosilane. The resulting modified silica was characterized by elemental analysis and infrared spectroscopy using an oven cell. The organic coverage on the surface was proportional to the organic precursor concentration. The aniline/silica materials are thermally stable up to 300°C, in high vacuum. 相似文献
33.
Teresa M. V. D. Pinho e Melo Clara S. B. Gomes Maria I. L. Soares Antanio M. d'A Rocha Gonsalves Jos A. Paixo Ana M. Beja Manuela Ramos Silva 《Journal of heterocyclic chemistry》2004,41(4):493-497
3‐Carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate was generated from (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid and its reactivity studied. This münchnone showed low reactivity as dipole although from the reaction with dimethyl acetylenedicarboxylate the corresponding (3R)‐3‐phenyl‐17H,3H‐pyrrolo[1,2‐c]thiazole‐5,6,7‐tricarboxylate could be isolated. The thermolysis of (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid in refluxing acetic anhydride led to the synthesis of N‐(1‐ethoxycarbonyl‐2‐phenylvinyl)‐2‐phenyl‐4‐thioxo‐1,3‐thiazolidine. The structure of methyl (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazoliddine‐4‐carboxylate was determined by X‐ray crystallography. 相似文献
34.
Frutos LM Castano O Andres JL Merchan M Acuna AU 《The Journal of chemical physics》2004,120(3):1208-1216
Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter gamma=(2g(2)/kappa(1))(1/2) in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and kappa(1) is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of pi,pi(*) triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of C=C bond stretchings and C-C bond torsions, which collectively change the ground-state COT bent conformation (D(2d)) toward a planar triplet state (D(8h)). 相似文献
35.
Togapur Pavan Kumar Mohammad Abdul Sattar Vanka Uma Maheshwara Sarma 《Tetrahedron: Asymmetry》2013,24(24):1615-1619
An efficient protocol for the enantioselective Michael additions of ketones to chalcones catalyzed by a hydroxyphthalimide linked triazole–pyrrolidine derivative has been developed. The corresponding products, 1,5-dicarbonyl compounds, were obtained in good yields with high levels of stereoselectivities under mild reaction conditions employing benzoic acid as an additive. 相似文献
36.
High-level quantum-chemical ab initio coupled-cluster and multiconfigurational perturbation methods have been used to compute the vertical and adiabatic ionization potentials of several water clusters: dimer, trimer, tetramer, pentamer, hexamer book, hexamer ring, hexamer cage, and hexamer prism. The present results establish reference values at a level not reported before for these systems, calibrating different computational strategies and helping to discard less reliable theoretical and experimental data. The systematic study with the increasing size of the water cluster allows obtaining some clues on the structure and reductive properties of liquid water. 相似文献
37.
38.
Kaaki K Hervé-Aubert K Chiper M Shkilnyy A Soucé M Benoit R Paillard A Dubois P Saboungi ML Chourpa I 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1496-1505
We report the efficient one-step synthesis and detailed physicochemical evaluation of novel biocompatible nanosystems useful for cancer therapeutics and diagnostics (theranostics). These systems are the superparamagnetic iron oxide nanoparticles (SPIONs) carrying the anticancer drug doxorubicin and coated with the covalently bonded biocompatible polymer poly(ethylene glycol) (PEG), native and modified with the biological cancer targeting ligand folic acid (PEG-FA). These multifunctional nanoparticles (SPION-DOX-PEG-FA) are designed to rationally combine multilevel mechanisms of cancer cell targeting (magnetic and biological), bimodal cancer cell imaging (by means of MRI and fluorescence), and bimodal cancer treatment (by targeted drug delivery and by hyperthermia effect). Nevertheless, for these concepts to work together, the choice of ingredients and particle structure are critically important. Therefore, in the present work, a detailed physicochemical characterization of the organic coating of the hybrid nanoparticles is performed by several surface-specific instrumental methods, including surface-enhanced Raman scattering (SERS) spectroscopy, X-ray photoelectron spectrometry (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). We demonstrate that the anticancer drug doxorubicin is attached to the iron oxide surface and buried under the polymer layers, while folic acid is located on the extreme surface of the organic coating. Interestingly, the moderate presence of folic acid on the particle surface does not increase the particle surface potential, while it is sufficient to increase the particle uptake by MCF-7 cancer cells. All of these original results contribute to the better understanding of the structure-activity relationship for hybrid biocompatible nanosystems and are encouraging for the applications in cancer theranostics. 相似文献
39.
Summary The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the 0-0 transition for the valence1A1( *) state is calculated to appear near 7.9 eV, close to the (n
y
3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition. 相似文献
40.
Summary FeIII complexes of a tetradentate ligand with pendant benzimidazolyl groups have been synthesized and characterized. Room temperature Mössbauer spectra depict a quadruple split doublet in the case of NO
inf3
p–
as co-ligand, while a nearly symmetrical one line spectrum is obtained for complexes with Cl–as co-ligand. The isomer shift values are towards the lower end of the range found for other high spin FeIII complexes. 1H-n.m.r. spectra of the complexes reveal relatively broad linewidths with large isotropic shifts. Paramagnetically shifted resonances are observed in the range of –10.0–+70.0 p.p.m.Author to whom all correspondence should be directed. 相似文献