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61.
M. A. Carpenter 《Phase Transitions》2013,86(1-3):189-199
Experimental and observational evidence is reviewed for the mechanisms and kinetics of antiphase domain coarsening in silicate minerals. The expected rate law has the form (domain size)n ≈ annealing time, but the ideal value of n=2 has been observed in only one of three cases. Values of n≈8 or 10 are interpreted as implying adsorption of impurity atoms onto the antiphase boundaries. Diffusion of these impurities can then provide the rate determining step for boundary migration. Local ordering at the boundaries can also provide some stabilising influence, though this does not appear to affect the coarsening rate law. If the stabilisation is sufficient it might result in the development of an incommensurate superstructure, either as a stable phase or as a metastable phase under non-equilibrium conditions. The effective width of these boundaries appears to be ~ 25°, or approximately two unit cells, and their maximum effective interaction length appears to be ~ 4 times this width. 相似文献
62.
Acyl nitrile oxides are readily generated and trapped in a nitrating mixture with N-methylmaleimide. 相似文献
63.
64.
L. E. Carpenter Ii R. A. Jacobson J. G. Verkade 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):475-479
Abstract The crystal and molecular structure of the strainless phosphite ester MeOP(OCH2)2C(CH2O)2POMe determined by x-ray means is reported. The methoxy groups are in axial positions on the chair-form-six-membered rings. 相似文献
65.
The predominant degradation reaction in the γ-irradiation of nine poly(olefin sulfone)s was found to be C-S bond scission with elimination of SO2 and olefin. The extent of depolymerization, measured by the yields of the two comonomers, increased over five irradiation temperatures from 0 to 150° C and could be correlated with the ceiling temperature. Thus G (total volatile products) increased from 10 to 10,000 over this temperature range. Minor radiolysis products included the alkanes corresponding to (1) loss of the side chain group and (2) scavenging of the side chain radical by monomer olefin. There was a deficiency of olefin relative to SO2, except at high temperatures, and isomerization of the product olefin in some cases. These observations are attributed to reactions of radiation-induced polymeric cations. 相似文献
66.
Dr. Thomas Hansen Dr. Alba Nin-Hill Prof. Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Prof. Dr. Carme Rovira 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201649
The development of small-molecule covalent inhibitors and probes continuously pushes the rapidly evolving field of chemical biology forward. A key element in these molecular tool compounds is the “electrophilic trap” that allows a covalent linkage with the target enzyme. The reactivity of this entity needs to be well balanced to effectively trap the desired enzyme, while not being attacked by off-target nucleophiles. Here we investigate the intrinsic reactivity of substrates containing a class of widely used electrophilic traps, the three-membered heterocycles with a nitrogen (aziridine), phosphorus (phosphirane), oxygen (epoxide) or sulfur atom (thiirane) as heteroatom. Using quantum chemical approaches, we studied the conformational flexibility and nucleophilic ring opening of a series of model substrates, in which these electrophilic traps are mounted on a cyclohexene scaffold (C6H10Y with Y=NH, PH, O, S). It was revealed that the activation energy of the ring opening does not necessarily follow the trend that is expected from C−Y leaving-group bond strength, but steeply decreases from Y=NH, to PH, to O, to S. We illustrate that the HOMONu–LUMOSubstrate interaction is an all-important factor for the observed reactivity. In addition, we show that the activation energy of aziridines and phosphiranes can be tuned far below that of the corresponding epoxides and thiiranes by the addition of proper electron-withdrawing ring substituents. Our results provide mechanistic insights to rationally tune the reactivity of this class of popular electrophilic traps and can guide the experimental design of covalent inhibitors and probes for enzymatic activity. 相似文献
67.
Brønsted acid-catalyzed inverse-electron demand (IED) aza-Diels-Alder reactions between 2-aza-dienes and ethylene were studied using quantum chemical calculations. The computed activation energy systematically decreases as the basic sites of the diene progressively become protonated. Our activation strain and Kohn-Sham molecular orbital analyses traced the origin of this enhanced reactivity to i) “Pauli-lowering catalysis” for mono-protonated 2-aza-dienes due to the induction of an asynchronous, but still concerted, reaction pathway that reduces the Pauli repulsion between the reactants; and ii) “LUMO-lowering catalysis” for multi-protonated 2-aza-dienes due to their highly stabilized LUMO(s) and more concerted synchronous reaction path that facilitates more efficient orbital overlaps in IED interactions. In all, we illustrate how the novel concept of “Pauli-lowering catalysis” can be overruled by the traditional concept of “LUMO-lowering catalysis” when the degree of LUMO stabilization is extreme as in the case of multi-protonated 2-aza-dienes. 相似文献
68.
69.
Eva Blokker Dr. Xiaobo Sun Prof. Dr. Jordi Poater Dr. Ir. J. Martijn van der Schuur Dr. Trevor A. Hamlin Prof. Dr. F. Matthias Bickelhaupt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(63):15616-15622
We have quantum chemically analyzed element−element bonds of archetypal HnX−YHn molecules (X, Y=C, N, O, F, Si, P, S, Cl, Br, I), using density functional theory. One purpose is to obtain a set of consistent homolytic bond dissociation energies (BDE) for establishing accurate trends across the periodic table. The main objective is to elucidate the underlying physical factors behind these chemical bonding trends. On one hand, we confirm that, along a period (e. g., from C−C to C−F), bonds strengthen because the electronegativity difference across the bond increases. But, down a period, our findings constitute a paradigm shift. From C−F to C−I, for example, bonds do become weaker, however, not because of the decreasing electronegativity difference. Instead, we show that the effective atom size (via steric Pauli repulsion) is the causal factor behind bond weakening in this series, and behind the weakening in orbital interactions at the equilibrium distance. We discuss the actual bonding mechanism and the importance of analyzing this mechanism as a function of the bond distance. 相似文献
70.
Dr. Zheng Deng Dr. Chang-Jong Kang Prof. Dr. Mark Croft Dr. Wenmin Li Dr. Xi Shen Dr. Jianfa Zhao Prof. Dr. Richeng Yu Prof. Dr. Changqing Jin Prof. Dr. Gabriel Kotliar Dr. Sizhan Liu Prof. Dr. Trevor A. Tyson Dr. Ryan Tappero Prof. Dr. Martha Greenblatt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(21):8317-8323
Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order–disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y2CoIrO6 and Y2CoRuO6 polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6 and Y2CoRuO6. 相似文献