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81.
Wang Y Fernández I Duvall M Wu JI Li Q Frenking G Schleyer PR 《The Journal of organic chemistry》2010,75(23):8252-8257
Quantitative evaluations of the aromaticity (antiaromaticity) of neutral exocyclic substituted cyclopropenes (HC)(2)C=X (X = BH to InH (group 13), CH(2) to SnH(2) (group 14), NH to SbH (group 15), O to Te (group 16)) by their computed extra cyclic resonance energies (ECRE, via the block-localized wave function method) and by their aromatic stabilization energies (ASEs, via energy decomposition analyses) correlate satisfactorily (R(2) = 0.974). Electronegative X-based substituents increase the aromaticity of the cyclopropene rings, whereas electropositive substituents have the opposite effect. For example, (HC)(2)C=O is the most aromatic (ECRE = 10.3 kcal/mol), and (HC)(2)C=InH is the most antiaromatic (ECRE = -15.0 kcal/mol). The most refined dissected nucleus-independent chemical shift magnetic aromaticity index, NICS(0)(πzz), also agrees with both energetic indexes (R(2) = 0.968, for ECRE; R(2) = 0.974, for ASE), as do anisotropy of the induced current density plots. 相似文献
82.
Israel Vainsencher 《Bulletin of the Brazilian Mathematical Society》2001,32(1):37-44
We consider the smooth compactification constructed in [12] for a space of varieties like twisted cubics. We show this compactification embeds naturally in a product of flag varieties.Partially supported by CNPq, Pronex (ALGA) 相似文献
83.
The degree of diastereoselectivity in the wrapping of four new chiral Salan ligands to form chiral-at-metal titanium complexes ranged from mild to perfect as a function of the ligands' N substituents; the enantiomerically pure complexes catalyzed the addition of diethyl zinc to benzaldehyde in 73-76% enantiomeric excess. 相似文献
84.
Jian Liu Zhen Zhao ChunMing Xu AiJun Duan GuiYuan Jiang JinSen Gao WenYong Lin Israel E. Wachs 《中国科学B辑(英文版)》2008,51(6):551-561
UV-Raman spectroscopy was used to study the molecular structures of TiO2 or ZrO2-supported vanadium oxide catalysts. The real time reaction status of soot combustion over these catalysts was detected by
in-situ UV-Raman spectroscopy. The results indicate that TiO2 undergoes a crystalline phase transformation from anatase to rutile phase with the increasing of reaction temperature. However,
no obvious phase transformation process is observed for ZrO2 support. The structures of supported vanadium oxides also depend on the V loading. The vanadium oxide species supported on
TiO2 or ZrO2 attain monolayer saturation when V loading is equal to 4 (4 is the number of V atoms per 100 support metal ions). Interestingly,
this loading ratio (V4/TiO2 and V4/ZrO2) gave the best catalytic activities for soot combustion reaction on both supports (TiO2 and ZrO2). The formation of surface oxygen complexes (SOC) is verified by in-situ UV Raman spectroscopy and the SOC mainly exist as carboxyl groups during soot combustion. The presence of NO in the reaction
gas stream can promote the production of SOC.
Supported by the National Natural Science Foundation of China (Grant Nos. 20473053, 20773163 and 20525621), the Beijing Natural
Science Foundation (Grant No. 2062020), and the 863 Program of China (Grant No. 2006AA06Z346) 相似文献
85.
Lera Israel Leka Khasnabis Sutripto Wangatia Lodrick Makokha Femi Olu Emmanuel Ramamurthy Praveen C 《Journal of Solid State Electrochemistry》2022,26(1):195-209
Journal of Solid State Electrochemistry - Highly efficient, abundant, and low-cost materials are highly demanded for energy conversion applications to address the rising consumption of energy. In... 相似文献
86.
Mechanistic Insight into the Stereochemical Control of Lactide Polymerization by Salan–Aluminum Catalysts 下载免费PDF全文
Konstantin Press Prof. Israel Goldberg Prof. Moshe Kol 《Angewandte Chemie (International ed. in English)》2015,54(49):14858-14861
Alkyl aluminum complexes of chiral salan ligands assembled around the 2,2′‐bipyrrolidine core form as single diastereomers that have identical configurations of the N donors. Active catalysts for the polymerization of lactide were formed upon the addition of benzyl alcohol. Polymeryl exchange between enantiomorphous aluminum species had a dramatic effect on the tacticity of the poly(lactic acid) (PLA) in the polymerization of racemic lactide (rac‐LA): The enantiomerically pure catalyst of the nonsubstituted salan ligand led to isotactic PLA, and the racemic catalyst exhibited lower stereocontrol. The enantiomerically pure catalyst of the chloro‐substituted salan ligand led to PLA with a slight tendency toward heterotacticity, whereas the racemic catalyst led to PLA of almost perfect heterotacticity following an insertion/auto‐inhibition/exchange mechanism. 相似文献
87.
Israel Scheinfeld James C. Parham George Bosworth Brown 《Journal of heterocyclic chemistry》1982,19(5):1231-1233
N-Oxidation of 2-amino-6-chloropurine to the 3-oxide provided a convenient intermediate for the synthesis of 2-amino-6-substituted purine 3-oxides, including the previously unavailable 2,6-diaminopurine 3-oxide. Thiation of the 6-halogen was accompanied by reduction of the N-oxide. The properties of the 1- and 3-oxides of 2,6-diaminopurine are compared. 相似文献
88.
Volker Bach Jürg Fröhlich Israel Michael Sigal 《Communications in Mathematical Physics》1999,201(2):249-290
We consider systems of static nuclei and electrons – atoms and molecules – coupled to the quantized radiation field. The interactions
between electrons and the soft modes of the quantized electromagnetic field are described by minimal coupling, p→p−e
A (x), where A(x) is the electromagnetic vector potential with an ultraviolet cutoff. If the interactions between the electrons and the quantized
radiation field are turned off, the atom or molecule is assumed to have at least one bound state. We prove that, for sufficiently
small values of the fine structure constant α, the interacting system has a ground state corresponding to the bottom of its
energy spectrum. For an atom, we prove that its excited states above the ground state turn into metastable states whose life-times
we estimate. Furthermore the energy spectrum is absolutely continuous, except, perhaps,
in a small interval above the ground state energy and around the threshold energies of the atom or molecule.
Received: 3 September 1998 / Accepted: 17 March 1999 相似文献
89.
Mössbauer and magnetic susceptibility measurements were used to study the magnetic properties of Ln1.9Sr1.1Cu2O6 (Ln=Pr,Nd) and La2SrCu2O6 materials. These compounds were prepared by solid-state reaction and crystallize in a tetragonal structure, space group I4/mmm with two formula units per unit cell. There is only one crystallographic site for Cu atoms, which form a double layer of CuO5 pyramids. These compounds are not superconducting, but we show, using Mössbauer spectroscopy (MS) on iron doped samples and susceptibility measurements, that the Cu planes order antiferromagnetically. The hyperfine fields on iron nuclei at 4.2 K extend from 472 kOe for La2SrCu2O6 to 501 kOe for Nd1.9Sr1.1Cu2O6. The ordering temperaturesT
N are: R20, 190, and 250 K for Ln=La, Pr and Nd, respectively. 相似文献
90.
The coordination chemistry of amine tris(phenolate) ligands around V(III) and V(V) is described for the first time. Three amine tris(phenolate) ligands were employed featuring different steric and electronic influence exerted by the phenolate substituents in the ortho and para positions being either t-Bu, Me, or Cl. V(III) complexes of all ligands (1-3) were readily obtained by reaction between the ligand precursors and VCl3(THF)3 in the presence of triethylamine. The complexes obtained were pentacoordinate, a THF ligand completing the coordination sphere of the metal, which was found to be of almost perfect TBP geometry, as revealed by crystallography. V(V) oxo complexes of all the ligands (4-6) were readily obtained by a reaction between the ligand precursors and VO(OPr)3. The oxo complexes of the alkyl-bearing ligands (4 and 5) could also be synthesized by the air oxidation of the corresponding V(III) complexes (1 and 2); however, the attempted air oxidation of the V(III) complex bound to the electron-poor ligand (3) did not yield the corresponding oxo complex 6. 1H NMR and crystallographic analysis of complexes 4 and 5 supported their TBP structures. Complex 6, on the other hand, was found to be composed of a TBP complex (6a) and an octahedral complex (6b) in equilibrium, the octahedral complex being more stable at lower temperatures. An X-ray structure of 6b revealed a mononuclear oxo complex, the sixth coordination site being occupied by an aqua ligand to which two THF molecules are H-bonded. Complexes 4-6 catalyze the epoxidation of olefins by t-BuOOH, albeit slowly. These complexes may thus be considered as structural and functional models of vanadium-dependent haloperoxidase enzymes. 相似文献