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1.
Gas-phase proton affinities of cyclophanes containing intra-annular amino groups were calculated using density functional theory (DFT) at the B3LYP/6-31+G∗∗//B3LYP/6-31G∗ level. They are higher in magnitude as those for proton sponges such as 1,8-bisaminonaphthalene, however, they are slightly weaker bases than 1,8-bis(dimethylamino)naphthalene. The high basicity of the cyclophane diamines is attributed mainly to their structural flexibility, which allows them to maximize the hydrogen bond strength in the cations by achieving N-H?N linearity, while strain relief upon protonation is less important. Another contributing factor is the stabilizing interaction of the added proton with adjacent phenyl π systems of the cyclophanes. Barriers for proton transfer between the nitrogen atoms of the diamine cations are also reported. 相似文献
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Arylazoimidazoles (2) are N,N-chelating ligands. The polymerization trend of the azolate system is restricted via N(1)-benzylation. The parent molecules (2), N(1)-benzylated products (3) and palladium complexes (4) were made by standard methods. The ligands (3) and complexes (4) are new. They have been characterized by elemental analysis, i.r., u.v.-vis. and high resolution 1H-n.m.r. spectral data. Redox studies were carried out by cyclic voltammetry. On complexation, azo reduction is shifted anodically. 相似文献
3.
Aryl bromides (3 equiv) were coupled efficiently with triarylbismuths (1 equiv) in an atom-efficient way using the Pd(OAc)2/PPh3 catalytic system in the presence of K3PO4 as base in DMF at 90 °C, providing excellent yields of the cross-coupled biaryls in short reaction times. 相似文献
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An extremely short synthesis of 2,2-dimethyl-3-hydroxymethyl cyclopentanone 2 (R1 = R2 = Me), an advanced intermediate in the synthesis of the pheromone planococcyl acetate 3, is described. 相似文献
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Rahul S. Patil Dr. Debasis Banerjee Cory M. Simon Prof. Jerry L. Atwood Dr. Praveen K. Thallapally 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12618-12623
Separation of xenon and krypton is of industrial and environmental concern; the existing technologies use cryogenic distillation. Thus, a cost‐effective, alternative technology for the separation of Xe and Kr and their capture from air is of significant importance. Herein, we report the selective Xe uptake in a crystalline porous organic oligomeric molecule, noria, and its structural analogue, PgC‐noria, under ambient conditions. The selectivity of noria towards Xe arises from its tailored pore size and small cavities, which allows a directed non‐bonding interaction of Xe atoms with a large number of carbon atoms of the noria molecular wheel in a confined space. 相似文献
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Critical current (I c) characteristics of 2G YBCO superconducting tape under the influence of twisting moment was experimentally investigated at varying current ramp rates in the self-field. Under a uniform twist, the degradation in the current-carrying capacity of YBCO tape up to 30% was observed at 77 K. The degradation is largely attributed to the shear stress and torsional shear strain resulting from the twisting. The superconductor to resistive transition index, n, is also found to behave in an identical manner with increase in the twisting. Finite element analysis (FEA) of the tape in the experimental configuration with twisting moment being applied on to it has been carried out in COMSOL. The torsional strain calculated analytically as per the experimental configuration matches closely with that of FEA results, which shows that the critical current degradation is a function of strain. 相似文献
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