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171.
Elena Perju Simon J. Dünki Dorina M. Opris 《Journal of polymer science. Part A, Polymer chemistry》2016,54(18):2940-2948
A synthetic strategy to polydimethylsiloxanes and polymethylsiloxanes containing thiol functions as end‐ or side‐groups, respectively, is presented. Such polymers are important starting materials for elastomeric networks and postpolymerization modifications. The synthesis starts either with vinyl end‐functionalized polydimethylsiloxanes or with polymethylvinylsiloxanes. The vinyl groups are reacted either with thioacetic acid or with a thioacetic acid/butanethiol mixture via a UV‐initiated thiol‐ene reaction to form the respective thioester quantitatively within few minutes. The thioesters are subsequently deprotected to the respective thiols by reduction with LiAlH4. The resulting thiol containing polysiloxanes can be used for the formation of networks or another functionalization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2940–2948 相似文献
172.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling
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Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
173.
Andreiy A. Gushchin Vladimir I. Grinevich Valeriy Ya. Shulyk Elena Yu. Kvitkova Vladimir V. Rybkin 《Plasma Chemistry and Plasma Processing》2018,38(1):123-134
The processes of degradation of 2,4-dichlorophenol (2,4-DCP) aqueous solutions under the action of atmospheric pressure of DBD in oxygen were studied. The degradation of 2,4-DCP proceeds efficiently, the degree of decomposition reaching 100%. The degradation kinetics of 2,4-DCP obeys a formal first-order kinetic law on concentration of 2,4-DCP. The effective rate constants depend weakly on the experimental conditions and are equal to ~ 2 s?1. Based on experimental data, the energy efficiency of 2,4-DCP decomposition was determined to be in the range of 0.039–0.173 molecules per 100 eV depending on the experimental conditions. The composition of the products was studied by gas chromatography, chromatography-mass spectrometry, UV/visible spectroscopy, fluorescent methods and some chemical methods. The main decomposition products present in the solution were found to be carboxylic acids, aldehydes and chloride ions, whereas carbon dioxide and molecular chlorine appear in the gas. The results obtained are compared with similar data from other advanced oxidation processes (AOP’s) methods. 相似文献
174.
175.
Elena V. Khoroshilova 《Optimization Letters》2013,7(6):1193-1214
The paper presents a method for solving optimal control problem with free right end and linear differential equations constraints. The proposed iterative process of extragradient-type is formulated in the functional subspace of piecewise continuous controls of L 2. The convergence of the method is proved. 相似文献
176.
Elena Akhmatskaya José M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1383-1393
Modification of the polymer–polymer interfacial tension is a way to tailor‐make particle morphology of waterborne polymer–polymer hybrids. This allows achieving a broader spectrum of application properties and maximizing the synergy of the positive properties of both polymers, avoiding their drawbacks. In situ formation of graft copolymer during polymerization is an efficient way to modify the polymer–polymer interfacial tension. Currently, no dynamic model is available for polymer–polymer hybrids in which a graft copolymer is generated during polymerization. In this article, a novel model based on stochastic dynamics is developed for predicting the dynamics of the development of particle morphology for composite waterborne systems in which a graft copolymer is produced in situ during the process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
177.
State-of-the-art compact recirculating electron accelerators operating at intermediate energies (tens of MeV) are reviewed. The acceleration schemes implemented in the rhodotron, ridgetron, fantron, and cylindertron machines are discussed. Major accelerator components such as the electron guns, accelerating cavities, and bending magnets are described. The parameters of currently operating recirculating accelerators are tabulated, and applications of these accelerators in different processes of irradiation are exemplified. 相似文献
178.
179.
Jessica Cid Dr. Jorge J. Carbó Dr. Elena Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12794-12802
Most trivalent boron reagents are electrophiles owing to the vacancy for two electrons to fill the outer orbital of boron; however, interestingly, trivalent boron compounds can change their electrophilic character to a nucleophilic character by only changing the nature of the substituents on the boron atoms. With the help of computational tools, we have analyzed the structural‐ and electronic properties of boryl fragments that were either bonded to main‐group metals or coordinated to transition‐metals/rare‐earth‐metals and we have designed a map that might help to identify certain trends. This trend map will be useful for selecting an appropriate trivalent boron compound, depending on the sought reactivity. 相似文献
180.