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71.
72.
Zhiyuan Qian Luke Galuska William W. McNutt Michael U. Ocheje Youjun He Zhiqiang Cao Song Zhang Jie Xu Kunlun Hong Rene B. Goodman Simon Rondeau‐Gagn Jianguo Mei Xiaodan Gu 《Journal of Polymer Science.Polymer Physics》2019,57(23):1635-1644
Thermomechanical properties of polymers highly depend on their glass transition temperature (T g). Differential scanning calorimetry (DSC) is commonly used to measure T g of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δc p) at T g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc p from flexible polymer (0.28 J g?1 K?1 for polystyrene) to rigid CPs (10?3 J g?1 K?1 for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc p at T g by a factor of 10, confirming that backbone rigidity reduces the Δc p. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc p. We conclude that the difficulties of determining T g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1635–1644 相似文献
73.
Different methods for the interpretation of linear dichroic spectra of molecules incorporated in uniaxial matrices are discussed. A method based on the combination of both polarized absorption and emission measurements is described for the resolution of absorption and emission spectra into their different polarized components, and for the investigation of molecular distributions in the oriented matrix. The distributions of some planar molecules of different shapes incorporated in stretched polyethylene films are presented. 相似文献
74.
Previous publications2–5 have examined the phenomenon of level crossings as predicted by the semiempirical techniques CNDO/26, IMDO7, and MINDO/38 for certain molecules when the total energy is viewed as a function of some conformational property. The purpose of this article is to examine this same phenomenon using the extended Hückel method(EHM)9, the iterated extended Hückel method(IEHM), and an ab-initio procedure with a minimal STO-3G basis set. The molecule chosen for this study is CO2 due to its structural simplicity and since previous calculations2–5 have demonstrated level crossing with this molecule. 相似文献
75.
76.
Przemysław Koźmiński Ewa Gniazdowska Leon Fuks Agata Oszczak 《Journal of Radioanalytical and Nuclear Chemistry》2012,292(1):67-74
Easy and efficient way to modify of the C-terminus of the peptide using amino acid lysine has been proposed and experimentally
verified. The synthesis yield was high (≥85%) and it was found that reactions can be carried out even with microgram amounts
of the peptide. Using Fmoc-alanine (as the peptide model) with modified C-terminus the procedure of peptide labelling with
monovalent and trivalent 99mTc complexes has been elaborated. 相似文献
77.
This study reveals that Fourier transform infrared is an effective analytical tool in probing the extent of hydrolysis of
cerium and gadolinium acetylacetonates dissolved in methanol. It is found that these acetylacetonates have relatively fast
hydrolysis rates at the early stage of hydrolysis (<6 h). However, their hydrolysis rates become very slow beyond 6-h of hydrolysis
and decrease to near zero after 55-h of hydrolysis. As a result, hydrolysis cannot be completed even after 170 h at room temperature.
These phenomena suggest that the first and second acetylacetone ligands chelated to Ce3+ and Gd3+ ions can actually be hydrolyzed with relative ease at room temperature, similar to alkoxide ligands. It is the last acetylacetone
ligand that is very difficult to be hydrolyzed. 相似文献
78.
Ewa Gniazdowska Przemysław Koźmiński Leon Fuks 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(2):1171-1177
Two types of technetium-99m complexes: (i) with the Hynic ligand linked to Substance P(1–11) and (ii) of the type ‘4 + 1’ consisting of tetradentate tripodal chelator tris(2-mercaptoethyl)-amine and monodentate isocyanide ligand previously coupled with Substance P(1–11), have been prepared on the n.c.a. scale. The obtained conjugates exhibit different lipophilicity and high stability in neutral aqueous solutions, even in the presence of excess concentration of histidine/cysteine competitive standard ligands. The conjugate (99mTc(NS3)(CN))2–SP containing two technetium-99m species in the molecule may be expected to be an extremely good diagnostic radiopharmaceutical. 相似文献
79.
We investigate the phase diagram of the anisotropic spin-1/2 triangular lattice antiferromagnet, with interchain diagonal exchange J' much weaker than the intrachain exchange J. We find that fluctuations lead to a competition between (commensurate) collinear antiferromagnetic and (zigzag) dimer orders. Both states differ in symmetry from the spiral order known to occur for larger J', and are therefore separated by quantum phase transitions from it. The zero-field collinear antiferromagnet is succeeded in a magnetic field by magnetically ordered spin-density-wave and cone phases, before reaching the fully polarized state. Implications for the anisotropic triangular magnet Cs2CuCl4 are discussed. 相似文献
80.
Leon N. Schneider Dr. Eva-Maria Tanzer Krauel Dr. Carl Deutsch Dr. Klaus Urbahns Tobias Bischof Kristina A. M. Maibom Dr. Johannes Landmann Dr. Fabian Keppner Dr. Christoph Kerpen Dr. Michael Hailmann Ludwig Zapf Tanja Knuplez Dr. Rüdiger Bertermann Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10973-10978
Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF3)2 group are rare. One reason is that transfer reagents are scarce and metal-based storable reagents are unknown. Herein, a set of CuI and AgI bis(trifluoromethyl)amido complexes stabilized by N- and P-donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl)amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis(trifluoromethyl)amines, 2-bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N-bis(trifluoromethyl)glycine. 相似文献