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121.
Lam WW Yiu SM Lee JM Yau SK Kwong HK Lau TC Liu D Lin Z 《Journal of the American Chemical Society》2006,128(9):2851-2858
The oxidation of alkanes and arylalkanes by KMnO(4) in CH(3)CN is greatly accelerated by the presence of just a few equivalents of BF(3), the reaction occurring readily at room temperature. Carbonyl compounds are the predominant products in the oxidation of secondary C-H bonds. Spectrophotometric and kinetics studies show that BF(3) forms an adduct with KMnO(4) in CH(3)CN, [BF(3).MnO(4)](-), which is the active species responsible for the oxidation of C-H bonds. The rate constant for the oxidation of toluene by [BF(3).MnO(4)](-) is over 7 orders of magnitude faster than by MnO(4)(-) alone. The kinetic isotope effects for the oxidation of cyclohexane, toluene, and ethylbenzene at 25.0 degrees C are as follows: k(C6H12)/k(C6D12) = 5.3 +/- 0.6, k(C7H8)/k(C7D8) = 6.8 +/- 0.5, k(C8H10)/k(C8D10) = 7.1 +/- 0.5. The rate-limiting step for all of these reactions is most likely hydrogen-atom transfer from the substrate to an oxo group of the adduct. A good linear correlation between log(rate constant) and C-H bond energies of the hydrocarbons is found. The accelerating effect of BF(3) on the oxidation of methane by MnO(4)(-) has been studied computationally by the Density Functional Theory (DFT) method. A significant decrease in the reaction barrier results from BF(3) coordination to MnO(4)(-). The BF(3) coordination increases the ability of the Mn metal center to achieve a d(1) Mn(VI) electron configuration in the transition state. Calculations also indicate that the species [2BF(3).MnO(4)](-) is more reactive than [BF(3).MnO(4)](-). 相似文献
122.
Alexander Elgart László Erdős Benjamin Schlein Horng-Tzer Yau 《Archive for Rational Mechanics and Analysis》2006,179(2):265-283
We consider the dynamics of N boson systems interacting through a pair potential N ?1 V a (x i ?x j ) where V a (x)=a ?3 V(x/a). We denote the solution to the N-particle Schrödinger equation by Ψ N, t . Recall that the Gross-Pitaevskii (GP) equation is a nonlinear Schrödinger equation and the GP hierarchy is an infinite BBGKY hierarchy of equations so that if u t solves the GP equation, then the family of k-particle density matrices solves the GP hierarchy. Under the assumption that a=N ?? for 0<3/5, we prove that as N→∞ the limit points of the k-particle density matrices of Ψ N, t are solutions of the GP hierarchy with the coupling constant in the nonlinear term of the GP equation given by ∫V(x)dx. The uniqueness of the solutions of this hierarchy remains an open question. 相似文献
123.
For any arrangement of hyperplanes in ??3, we introduce the soul of this arrangement. The soul, which is a pseudo-complex, is determined by the combinatorics of the arrangement of hyperplanes. In this paper, we give a sufficient combinatoric condition for two arrangements of hyperplanes to be diffeomorphic to each other. In particular we have found sufficient conditions on combinatorics for the arrangement of hyperplanes whose moduli space is connected. This generalizes our previous result on hyperplane point arrangements in ??3. 相似文献
124.
Shinobu Hosono Bong H. Lian Keiji Oguiso Shing-Tung Yau 《Communications in Mathematical Physics》2003,241(2-3):245-286
We find a concise relation between the moduli , of a rational Narain lattice (,) and the corresponding momentum lattices of left and right chiral algebras via the Gauss product. As a byproduct, we find an identity which counts the cardinality of a certain double coset space defined for isometries between the discriminant forms of rank two lattices. 相似文献
125.
Strauss E Thomas B Yau ST 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8768-8772
The redox reaction of cytochrome c immobilized on the bare surfaces of microelectrodes and macroscopic electrodes (macroelectrodes) composed of different planes of highly oriented pyrolytic graphite has been investigated using cyclic voltammetry. The protein-immobilized microelectrodes were fabricated using a simple masking method. For both macroelectrodes and microelectrodes, the redox reaction of immobilized cytochrome c needs to be activated by increasing the electrochemical potential maximum of cyclic voltammetry to a high positive value. The redox currents of this protein-electrode system can be enhanced using two approaches. The oxidation and reduction currents of cytochrome c adsorbed on microelectrodes that are composed of the edge plane show an anomalous enhancement compared to those for macroelectrodes composed of the basal plane. The difference in the surface chemical properties of the two kinds of electrodes results in the current anomaly. The oxidation current of the macroelectrode can be selectively enhanced by decreasing the potential minimum. 相似文献
126.
A capillary zone electrophoresis (CZE)-potential gradient detection (PGD) method coupled with field-amplified sample injection was developed to determine alkali metal, alkaline-earth metal, nickel, lead and ammonium ions. The capillary surface was coated with dialkylimidazolium-based ionic liquid and thus the electroosmotic flow (EOF) of the capillary was reversed. The buffer composed of 7.5 mM lactic acid, 0.6 mM 18-crown-6, 12 mM alpha-cyclodextrin (alpha-CD); it was adjusted to pH 4.0 by 1-hexyl-3-methylimidazolium hydroxide. The 11 cations were baseline separated within 14 min with 5.1-18.9 x 10(4) plates (for 40-cm-long capillary) in separation efficiency, and the detection limits were in the range of 0.27-7.3 ng/ml. The method showed good reproducibility in terms of migration time with RSD < or = 0.90% for run-to-run and < or = 1.65 for day-to-day assessment. 相似文献
127.
In situ scanning tunneling microscopy (STM) combined with linear sweep voltammetry was used to examine spatial structures of sulfur adatoms (SA) and benzenethiol (BT) molecules adsorbed on an ordered Ru(0001) electrode in 0.1 M HClO4. The Ru(0001) surface, prepared by mechanical polishing and electrochemical reduction at -1.5 V (vs RHE) in 0.1 M HClO4, contained atomically flat terraces with an average width of 20 nm. Cyclic voltammograms obtained with an as-prepared Ru(0001) electrode in 0.1 M HClO4 showed characteristics nearly identical to those of Ru(0001) treated in high vacuum. High-quality STM images were obtained for SA and BT to determine their spatial structures as a function of potential. The structure of the SA adlayer changed from (2 x mean square root of 3)rect to domain walls to (mean square root of 7 x mean square root of 7)R19.1 degrees and then to disordered as the potential was scanned from 0.3 to 0.6 V. In contrast, molecules of BT were arranged in (2 x mean square root of 3)rect between 0.1 and 0.4 V, while they were disordered at all other potentials. Adsorption of BT molecules was predominantly through the sulfur headgroup. Sulfur adatoms and adsorbed BT molecules were stable against anodic polarization up to 1.0 V (vs RHE). These two species were adsorbed so strongly that their desorption did not occur even at the onset potential for the reduction of water in 0.1 M KOH. 相似文献
128.
Wei‐Yu Lin Hsian‐Wen Wang Zhi‐Chang Liu Jun Xu Chih‐Wei Chen Yun‐Chin Yang Shou‐Ling Huang Hsiao‐Ching Yang Prof. Tien‐Yau Luh Prof. 《化学:亚洲杂志》2007,2(6):764-774
Two dimers and a series of polymers with 5,6‐endo pendant aryl groups that contain different substituents at the para positions were synthesized. The conformation and stereochemistry of the dimers and polymers were determined by nonlinear optical analysis (EFISH) as well as UV/Vis and 13C NMR spectroscopy. The chemical shifts of C7 for the polymers appeared as two peaks in the 13C NMR spectra when the substituents are electron‐withdrawing groups. The percentage decrease in the relative extinction coefficient of the polymers, εd, was linearly related to the Hammett constant σ. Polynorbornenes with electron‐withdrawing substituents may adopt isotactic stereochemistry with all pendant groups aligned in one direction. The nature of the interactions between neighboring chromophores may be one of the most important factors in directing the stereoregularity and conformation of these polymers. The corresponding polymers derived from the exo isomers appeared to be less stereoregular. 相似文献
129.
130.
Invariance principles are proved under diffusive scaling for the centered position of a tagged particle in the simple exclusion process with asymmetric nonzero drift jump probabilities in dimensions d ≥ 3. The method of proof is by martin‐gale techniques which rely on the fact that symmetric random walks are transient in high dimensions. © 2000 John Wiley & Sons, Inc. 相似文献