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41.
42.
We introduce a general and versatile MS Windows application for solving the spherically symmetric diffusion problem, involving up to two coupled spherically symmetric Smoluchowski equations. The application is based on a modular, configurable, user-friendly graphical interface, in which input parameters are introduced through a graphical representation of the system of partial differential equations and output attributes can be obtained graphically during propagation. The numerical algorithm consists of finite differencing in space and Chebyshev propagation in time; it includes an implementation of virtual gridding, which enhances the accuracy of calculating boundary conditions and steep potentials. The program has b een checked against a wide collection of analytical solutions and applied to an experimentally open problem in excited-state proton-transfer to solvent. © 1996 by John Wiley & Sons, Inc. 相似文献
43.
Henry Feugeas MC De Marco G Peretti II Godon-Hardy S Fredy D Claeys ES 《Magnetic resonance imaging》2005,23(9):929-937
Our purpose was to investigate leukoaraïosis (LA) using three-dimensional MR imaging combined with advanced image-processing technology to attempt to group signal abnormalities according to their etiology. Coronal T2-weighted fast fluid-attenuated inversion-recovery (FLAIR) sequences and three-dimensional T1-weighted fast spoiled gradient recalled echo sequences were used to examine cerebral white matter changes in 75 elderly people with memory complaint but no dementia. They were otherwise healthy, community-dwelling subjects. Three subtypes of LA were defined on the basis of their shape, geography and extent: the so-called subependymal/subpial LA, perivascular LA and “bands” along long white matter tracts. Subependymal changes were directly contiguous with ventricular spaces. They showed features of “water hammer” lesions with ventricular systematisation and a more frequent location around the frontal horns than around the bodies (P=.0008). The use of cerebrospinal fluid (CSF) contiguity criterion allowed a classification of splenial changes in the subpial group. Conversely, posterior periventricular lesions in the centrum ovale as well as irregular and extensive periventricular lesions were not directly contiguous with CSF spaces. The so-called perivascular changes showed features of small-vessel-associated disease; they surrounded linear CSF-like signals that followed the direction of perforating vessels. Distribution of these perivascular changes appeared heterogeneous (P ranging from .04 to 5·10−16). These findings suggest that subependymal/subpial LA and subcortical LA may be separate manifestations of a single underlying pulse-wave encephalopathy. 相似文献
44.
N. Agmon 《国际化学动力学杂志》1981,13(4):333-365
Models for the energy profile along the reaction coordinate are utilized to determine the barrier's height and location as a function of ΔG. These form the basis for structure–reactivity correlations and afford a unified formulation for various postulates in the field of physical organic chemistry. Current experimental evidence is examined for the resulting correlations, and some of their applications as an aid to the chemical kineticist are presented. 相似文献
45.
Noam Agmon 《Chemical physics》1980,45(2):249-260
A variant of a new empirical method, enables one to express a collinear triatomic potential energy surface as a family of Morse curves along “natural” bond order coordinates orthogonal to the reaction coordinate. The procedure depends on a single adjustable parameter which is related to the barrier's height. Because an analytical expression for the number of vibrational states of a Morse oscillator is available, one has an analytical approximation for the number of states along the reaction coordinate. The extrema in the number of states are utilized in various versions of classical microcanonical variational transition state theory (among which is a new version, which is in better agreement with dynamical results), to estimate the probability of a collinear reactions, as a function of the total energy. The analytical expressions are also used to analyze the origins of the maximum and minima in the number of states. 相似文献
46.
47.
Glow-discharge-initiated polymerization of acrylic acid incorporated in poly(ethylene terephthalate) (PET) films was investigated. An increase in polymerization yield with plasma treatment duration and power was found. Polymerization was not confined to the film surface. At high power and long treatment time, polymerization in the bulk of the PET also took place. Water regain and contact angle of the PET-treated films were affected by the presence of poly(acrylic acid) (PAA). The carboxyl groups of the PAA chains incorporated in the PET matrix were utilized for further chemical modification of the PET film. Poly(ethylene glycol) (PEG) was grafted onto PAA by esterification. DSC studies showed the presence of both PAA and PEG in the PET matrix and shed light on the morphology of the multicomponent polymeric system. Free isocyanate groups were introduced into the PET matrix by reacting PAA carboxyl groups with hexamethylene diisocyanate. 相似文献
48.
Uri Stoin Dr. Alexander I. Shames Itamar Malka Prof. Ilana Bar Prof. Yoel Sasson 《Chemphyschem》2013,14(18):4158-4164
In the recent decades superoxide [O2?.] has become the subject of considerable interest. Nonetheless, generation of superoxide compounds is still a substantial challenge. The standard methods for synthesis of superoxide derivatives are either through the oxidation of molten alkali metals with hot air or by using electrolytic reduction of oxygen in aprotic solvent such as dimethylformamide. No methodology is available for the generation of superoxides in protic solutions and particularly not in water. We propose a new in situ method for alkali superoxide preparation by using sodium hydroxide and hydrogen peroxide at room temperature and in aqueous solution. 相似文献
49.
When a resting enzyme is activated, substrate concentration profile evolves in its vicinity, ultimately tending to steady state. We use modern theories for many-body effects on diffusion-influenced reactions to derive approximate analytical expressions for the steady-state profile and the Laplace transform of the transient concentration profiles. These show excellent agreement with accurate many-particle Brownian-dynamics simulations for the Michaelis-Menten kinetics. The steady-state profile has a hyperbolic dependence on the distance of the substrate from the enzyme, albeit with a prefactor containing the complexity of the many-body effects. These are most conspicuous for the substrate concentration at the surface of the enzyme. It shows an interesting transition as a function of the enzyme turnover rate. When it is high, the contact concentration decays monotonically to steady state. However, for slow turnover it is nonmonotonic, showing a minimum due to reversible substrate binding, then a maximum due to diffusion of new substrate toward the enzyme, and finally decay to steady state. Under certain conditions one can obtain a good estimate for the critical value of the turnover rate constant at the transition. 相似文献
50.
Nadal Desbarats L Herlidou S de Marco G Gondry-Jouet C Le Gars D Deramond H Idy-Peretti I 《Magnetic resonance imaging》2003,21(6):645-650
Magnetic Resonance Diffusion-Weighted Imaging (DWI) has been reported to be helpful for the differential diagnosis between abscesses and cystic/necrotic brain tumors. However the number of patients is still limited, and the sensitivity and specificity of the method remain to be confirmed. The primary purpose of this study was to investigate a larger sample of patients, all investigated under the same experimental conditions, in order to obtain statistically significant data. Moreover, there is no consensus about the appropriate values of b required to use to make an accurate diagnosis from DWI. The secondary purpose of this study was to determine the discriminating threshold b values for raw diffusion-weighted images and for normalized diffusion-weighted images. On the basis of 14 abscesses, 10 high-grade gliomas and 2 metastases, we show that the calculation of accurate Apparent Diffusion Coefficient (ADC) values gives a specificity rate of 100%. Without ADC calculation, we show that image normalization is required to make an accurate differential diagnosis, and we highlight the ability of DWI to discriminate between brain abscesses and cystic/necrotic brain tumors using normalized signal intensity at lower b values (503 s/mm(2)) than usual. 相似文献