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61.
Dr. Hadas Shalit Peleg Prof. Dr. Anat Milo 《Angewandte Chemie (International ed. in English)》2023,62(26):e202219070
The chemistry community is currently witnessing a surge of scientific discoveries in organic chemistry supported by machine learning (ML) techniques. Whereas many of these techniques were developed for big data applications, the nature of experimental organic chemistry often confines practitioners to small datasets. Herein, we touch upon the limitations associated with small data in ML and emphasize the impact of bias and variance on constructing reliable predictive models. We aim to raise awareness to these possible pitfalls, and thus, provide an introductory guideline for good practice. Ultimately, we stress the great value associated with statistical analysis of small data, which can be further boosted by adopting a holistic data-centric approach in chemistry. 相似文献
62.
Ladislav Androvič Jan Bartáček Miloš Sedlák 《Research on Chemical Intermediates》2016,42(6):5133-5145
This mini-review describes recent developments and trends in the area of syntheses and applications of azo compounds, which are planned to act as initiators of radical reactions, particularly polymerizations. The paper reports chemical modifications of well-known initiators (AIBN, etc.) or variants of syntheses of new types of these compounds. The chemical modifications of basic skeletons of azo initiators are discussed in the context with their properties and applications. Also discussed are the contemporary trends in the development of these initiators, particularly in preparation of microparticles and nanoparticles of polymers or hybrid inorganic–organic microparticles and nanoparticles prepared for intentional studies and applications. 相似文献
63.
Menner A Ikem V Salgueiro M Shaffer MS Bismarck A 《Chemical communications (Cambridge, England)》2007,(41):4274-4276
Porous polymer foams (poly-Pickering-HIPEs) have been synthesised from stable high internal phase emulsion templates solely stabilised by low concentrations of functionalised titania nanoparticles. 相似文献
64.
Oriented arrays of both rutile and anatase nanorods have been synthesised in a two-stage process, employing multi-walled carbon nanotubes as the initial structural template. 相似文献
65.
Vlastimil Matějec Miroslav Chomát Miloš Hayer Ivan Kašík Daniela Berková Fethi Abdelmalek Nicole Jaffrezic-Renault 《Czechoslovak Journal of Physics》1999,49(5):883-888
The paper summarizes results achieved in the Institute of Radio Engineering and Electronics in the field of investigation
and fabrication of novel fiber-optic structures for evanescent-wave chemical sensing. Several approaches for increasing the
evanescent-wave sensitivity of multimode silica optical fibers to gaseous and liquid chemicals are shown. These approaches
make use of the decrease of the core diameter in sectorial and capillary sectorial fibers, modification of trajectories of
optical rays in the cores of inverted-graded-index fibers, tailoring of the refractive index of porous layers applied on silica
cores, an output mode filter preventing the detection of rays propagating at low axial angles or fibers bent in single or
multiple turns.
Presented at the 1st Czech-Chinese Workshop “Advanced Materials for Optoelectronics”, Prague, Czech Republic, June 13–17,
1998.
This work was supported by the Grant Agency of the Czech Republic (projects No. 102/96/0939 and No. 102/98/1358) and by joint
project No. 4104 of AS CR and CNRS, France. 相似文献
66.
Ludmila Hejtmánková Josef Jirman Miloš Sedlák 《Research on Chemical Intermediates》2009,35(5):615-623
The paper deals with a simple and sufficient synthesis of key precursor of Lasofoxifene. The 1-(4-benzyloxyphenyl)-6-methoxy-2-phenyl-3,4-dihydronaphthalene was prepared by a sequence of five reactions steps: first 1-(4-benzyloxyphenyl)-6-methoxy-3,4-dihydronaphthalene
was prepared (70%), and this was quantitatively epoxidized to 7b-[4-(benzyloxy)phenyl]-5-methoxy-1a,2,3,7b-tetrahydronaphtho[1,2-b]oxirene. Catalytic (ZnI2) isomerization of the epoxide gave 1-(4-benzyloxyphenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalen-2-one (75%). Its subsequent
reaction with phenylmagnesium bromide gave 1-(4-benzyloxyphenyl)-6-methoxy-2-phenyl-1,2,3,4-tetrahydro-2-naphthol (87%). Acid-catalysed
dehydration of this alcohol by polyphosphoric acid (25°C) provides 1-(4-benzyloxyphenyl)-6-methoxy-2-phenyl-1,4-dihydronaphthalene (80%). Dehydration in the system of acetic anhydride/polyphosphoric acid gives 1-(4-benzyloxyphenyl)-6-methoxy-2-phenyl-3,4-dihydronaphthalene (66%). 相似文献
67.
68.
Mariusz P. Mitoraj Goran V. Janjić Vesna B. Medaković Dušan Ž. Veljković Artur Michalak Snežana D. Zarić Miloš K. Milčić 《Journal of computational chemistry》2015,36(3):171-180
The water/aromatic parallel alignment interactions are interactions where the water molecule or one of its O? H bonds is parallel to the aromatic ring plane. The calculated energies of the interactions are significant, up to ΔECCSD(T)(limit) = ?2.45 kcal mol?1 at large horizontal displacement, out of benzene ring and CH bond region. These interactions are stronger than CH···O water/benzene interactions, but weaker than OH···π interactions. To investigate the nature of water/aromatic parallel alignment interactions, energy decomposition methods, symmetry‐adapted perturbation theory, and extended transition state‐natural orbitals for chemical valence (NOCV), were used. The calculations have shown that, for the complexes at large horizontal displacements, major contribution to interaction energy comes from electrostatic interactions between monomers, and for the complexes at small horizontal displacements, dispersion interactions are dominant binding force. The NOCV‐based analysis has shown that in structures with strong interaction energies charge transfer of the type π → σ*(O? H) between the monomers also exists. © 2014 Wiley Periodicals, Inc. 相似文献
69.
Jana Hudecová Jan Horníček Dr. Miloš Buděšínský Dr. Jaroslav Šebestík Martin Šafařík Ge Zhang Dr. Timothy A. Keiderling Dr. Petr Bouř 《Chemphyschem》2012,13(11):2748-2760
The tryptophan (Trp) aromatic residue in chiral matrices often exhibits a large optical activity and thus provides valuable structural information. However, it can also obscure spectral contributions from other peptide parts. To better understand the induced chirality, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) spectra of Trp‐containing cyclic dipeptides c‐(Trp‐X) (where X=Gly, Ala, Trp, Leu, nLeu, and Pro) are analyzed on the basis of experimental spectra and density functional theory (DFT) computations. The results provide valuable insight into the molecular conformational and spectroscopic behavior of Trp. Whereas the ECD is dominated by Trp π–π* transitions, VCD is dominated by the amide modes, well separated from minor Trp contributions. The ROA signal is the most complex. However, an ROA marker band at 1554 cm?1 indicates the local χ2 angle value in this residue, in accordance with previous theoretical predictions. The spectra and computations also indicate that the peptide ring is nonplanar, with a shallow potential so that the nonplanarity is primarily induced by the side chains. Dispersion‐corrected DFT calculations provide better results than plain DFT, but comparison with experiment suggests that they overestimate the stability of the folded conformers. Molecular dynamics simulations and NMR results also confirm a limited accuracy of the dispersion‐DFT model in nonaqueous solvents. Combination of chiral spectroscopies with theoretical analysis thus significantly enhances the information that can be obtained from the induced chirality of the Trp aromatic residue. 相似文献
70.
This paper explores different phenomena that cause distortions of infrared absorption spectra by mixing of reflective and absorptive band shape components of infrared spectra, and the resulting distortion of observed band shapes. In the context of this paper, we refer to the line shape of the variations of the refractive index in spectral regions of an absorption maximum (i.e., in regions of "anomalous dispersion") as "dispersive" or "reflective" line shape contributions, in analogy to previous spectroscopic literature. These distortions usually result in asymmetric bands with a negative intensity contribution at the high wavenumber of the band, accompanied by a shift toward lower wavenumber, and confounded band intensities. In extreme cases of band distortions caused by the "resonance Mie" (RMie) mechanism, spectral peaks may be split into doublets of peaks, change from positive to negative peaks, or appear as derivative-shaped features. 相似文献