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31.
The effect of the dynamic molecular rearrangements leading to compositional segregation is revealed in coarse-grained molecular dynamics simulations of short pulse laser interaction with a polymer solution in a volatile matrix. An internal release of matrix vapor at the onset of the explosive boiling of the overheated liquid is capable of pushing polymer molecules to the outskirts of a transient bubble, forming a polymer-rich surface layer enclosing the volatile matrix material. The results explain unexpected "deflated balloon" structures observed in films deposited by the matrix-assisted pulsed laser evaporation technique. 相似文献
32.
Nida Sheibat‐Othman Ana‐Maria Cenacchi‐Pereira Amilton Martins Dos Santos Elodie Bourgeat‐Lami 《Journal of polymer science. Part A, Polymer chemistry》2011,49(22):4771-4784
We report the kinetics and mechanism of soap‐free emulsion polymerization of styrene using laponite platelets as stabilizers. The polymerization was initiated by potassium persulfate and the latex particles were stabilized by laponite platelets dispersed in water. Laponite adsorption on the polymer particles was enhanced by the addition of poly(ethylene glycol) monomethylether methacrylate (PEGMA). Particle nucleation can be described using the classical homogeneous nucleation mechanism followed by coagulation of unstable precursors. Oligomeric radicals formed in the water phase become insoluble and precipitate on the laponite surface leading to primary precursor particles composed of a few polymer chains and one or several clay platelets. Mature latex particles are then generated by coagulation and growth of the previously formed precursor particles. Both the nucleation and initial aggregation rates increased in the presence of PEGMA. Calorimetric monitoring of the polymerization allowed estimating the heat produced by the reaction and the monomer conversion. Hence, using the monomer material balance, the number of radicals in the polymer particles could be estimated precisely. The average number of radicals per particle, $ \bar n $ , was found to be high in the range 3–6. This result was attributed to strong attractive interactions between the growing radicals and the clay surface. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
33.
Bilé EG Sassine R Denicourt-Nowicki A Launay F Roucoux A 《Dalton transactions (Cambridge, England : 2003)》2011,40(24):6524-6531
Novel anionic species, such as hydrogen carbonate (HCO(3)(?)), fluoride (F(?)), triflate (CF(3)SO(3)(?)), tetrafluoroborate (BF(4)(?)) and chloride (Cl(?)) were investigated as new partners of water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium salts, used as a protective agent of rhodium colloids. The effect of the surfactant polar head on the micellar behavior, size and morphology of the nanospecies was studied by adapted physico-chemical experiments (surface tension measurements, dynamic light scattering, thermogravimetric and TEM analyses) and discussed in terms of strong or weak stabilization of the growing nanoparticles surface. Finally, the influence of the nanoenvironment generated by the surfactant with various counter-anions was evaluated via the hydrogenation of aromatics. 相似文献
34.
Scaglia E Sockalingum GD Schmitt J Gobinet C Schneider N Manfait M Thiéfin G 《Analytical and bioanalytical chemistry》2011,401(9):2919-2925
Assessment of liver fibrosis is of paramount importance to guide the therapeutic strategy in patients with chronic hepatitis
C (CHC). In this pilot study, we investigated the potential of serum Fourier transform infrared (FTIR) spectroscopy for differentiating
CHC patients with extensive hepatic fibrosis from those without fibrosis. Twenty-three serum samples from CHC patients were
selected according to the degree of hepatic fibrosis as evaluated by the FibroTest: 12 from patients with no hepatic fibrosis
(F0) and 11 from patients with extensive fibrosis (F3–F4). The FTIR spectra (ten per sample) were acquired in the transmission
mode and data homogeneity was tested by cluster analysis to exclude outliers. After selection of the most discriminant wavelengths
using an ANOVA-based algorithm, the support vector machine (SVM) method was used as a supervised classification model to classify
the spectra into two classes of hepatic fibrosis, F0 and F3–F4. Given the small number of samples, a leave-one-out cross-validation
algorithm was used. When SVM was applied to all spectra (n = 230), the sensitivity and specificity of the classifier were 90.1% and 100%, respectively. When SVM was applied to the
subset of 219 spectra, i.e., excluding the outliers, the sensitivity and specificity of the classifier were 95.2% and 100%,
respectively. This pilot study strongly suggests that the serum from CHC patients exhibits infrared spectral characteristics,
allowing patients with extensive fibrosis to be differentiated from those with no hepatic fibrosis. 相似文献
35.
Capriotti AL Caracciolo G Cavaliere C Crescenzi C Pozzi D Laganà A 《Analytical and bioanalytical chemistry》2011,401(4):1195-1202
The knowledge about the interaction between plasma proteins and nanocarriers employed for in vivo delivery is fundamental
to understand their biodistribution. Protein adsorption onto nanoparticle surface (protein corona) is strongly affected by
vector surface characteristics. In general, the primary interaction is thought to be electrostatic, thus surface charge of
carrier is supposed to play a central role in protein adsorption. Because protein corona composition can be critical in modifying
the interactive surface that is recognized by cells, characterizing its formation onto lipid particles may serve as a fundamental
predictive model for the in vivo efficiency of a lipidic vector. In the present work, protein coronas adsorbed onto three
differently charged cationic liposome formulations were compared by a shotgun proteomic approach based on nano-liquid chromatography–high-resolution
mass spectrometry. About 130 proteins were identified in each corona, with only small differences between the different cationic
liposome formulations. However, this study could be useful for the future controlled design of colloidal drug carriers and
possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins into body
fluids. 相似文献
36.
Geiger RA Leto DF Chattopadhyay S Dorlet P Anxolabéhère-Mallart E Jackson TA 《Inorganic chemistry》2011,50(20):10190-10203
Three peroxomanganese(III) complexes [Mn(III)(O(2))(mL(5)(2))](+), [Mn(III)(O(2))(imL(5)(2))](+), and [Mn(III)(O(2))(N4py)](+) supported by pentadentate ligands (mL(5)(2) = N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine, imL(5)(2) = N-methyl-N,N',N'-tris((1-methyl-4-imidazolyl)methyl)ethane-1,2-diamine, and N4py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) were generated by treating Mn(II) precursors with H(2)O(2) or KO(2). Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature, variable-field MCD data demonstrate that these complexes have very similar electronic transition energies and ground-state zero-field splitting parameters, indicative of nearly identical coordination geometries. Because of uncertainty in peroxo (side-on η(2) versus end-on η(1)) and ligand (pentadentate versus tetradentate) binding modes, density functional theory (DFT) computations were used to distinguish between three possible structures: pentadentate ligand binding with (i) a side-on peroxo and (ii) an end-on peroxo, and (iii) tetradentate ligand binding with a side-on peroxo. Regardless of the supporting ligand, isomers with a side-on peroxo and the supporting ligand bound in a tetradentate fashion were identified as most stable by >20 kcal/mol. Spectroscopic parameters computed by time-dependent (TD) DFT and multireference SORCI methods provided validation of these isomers on the basis of experimental data. Hexacoordination is thus strongly preferred for peroxomanganese(III) adducts, and dissociation of a pyridine (mL(5)(2) and N4py) or imidazole (imL(5)(2)) arm is thermodynamically favored. In contrast, DFT computations for models of [Fe(III)(O(2))(mL(5)(2))](+) demonstrate that pyridine dissociation is not favorable; instead a seven-coordinate ferric center is preferred. These different results are attributed to the electronic configurations of the metal centers (high spin d(5) and d(4) for Fe(III) and Mn(III), respectively), which results in population of a metal-peroxo σ-antibonding molecular orbital and, consequently, longer M-O(peroxo) bonds for peroxoiron(III) species. 相似文献
37.
38.
D. Batani A. Conti A. Masini M. Milani M. Costato A. Pozzi E. Turcu R. Allot N. Lisi F. Musumeci A. Triglia 《Il Nuovo Cimento D》1996,18(5):657-662
Summary Soft-X-rays irradiation of yeast cells allows selective interference with different cellular structures. The monitoring of
different physical parameters leads to substantial variations in the response to X-rays showing that monotonicity should not
be taken for granted.
Also at INFM (Istituto Nazionale di Fisica della Materia). 相似文献
39.
T. Di Matteo F. Pozzi T. Aste 《The European Physical Journal B - Condensed Matter and Complex Systems》2010,73(1):3-11
Two kinds of filtered networks: minimum spanning trees (MSTs) and planar maximally filtered graphs (PMFGs) are constructed from dynamical correlations computed over a moving window. We study the evolution over time of both hierarchical and topological properties of these graphs in relation to market fluctuations. We verify that the dynamical PMFG preserves the same hierarchical structure as the dynamical MST, providing in addition a more significant and richer structure, a stronger robustness and dynamical stability. Central and peripheral stocks are differentiated by using a combination of different topological measures. We find stocks well connected and central; stocks well connected but peripheral; stocks poorly connected but central; stocks poorly connected and peripheral. It results that the Financial sector plays a central role in the entire system. The robustness, stability and persistence of these findings are verified by changing the time window and by performing the computations on different time periods. We discuss these results and the economic meaning of this hierarchical positioning. 相似文献
40.
Caracciolo G Pozzi D Caminiti R Amenitsch H 《The journal of physical chemistry. B》2006,110(42):20829-20835
The mechanism of formation of multicomponent lipoplexes was investigated by means of synchrotron Small-Angle X-ray Diffraction (SAXD). Mixed lipid dispersions were prepared by mixing different populations of binary cationic liposomes. When adding DNA to mixed lipid dispersions, multicomponent lipoplexes spontaneously formed exhibiting structural properties, i.e., membrane thickness, surface charge density, and one-dimensional DNA packing density, intermediate between those of binary lipoplexes. These results suggested that DNA lets liposomes come into contact and fuse and that a complete lipid mixing at the molecular level occurs. The equilibrium structure of multicomponent lipoplexes was found to be unique and did not depend on the number and kind of populations composing lipid dispersion but only on the lipid species involved and on their relative molar ratio. According to recent theoretical models we identified two-dimensional lipid mixing entropy as the key factor regulating the existence of only multicomponent lipoplexes with ideally mixed lipid species. 相似文献