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101.
The chemical reactions involved in the antioxidant behaviour of the thiodipropionate esters have been investigated and three distinct mechanisms have been identified. The first is a radical trapping process involving the sulphenic acid formed by breakdown of the sulphinyldipropionate ester which is an oxidation product of the thiodipropionate. The second is a radical generating reaction resulting from a redox reaction between hydroperoxides and the sulphenic acid. The third is a Lewis acid catalysed destruction of hydroperoxide by a further oxidation product of the sulphenic acid. Sulphur dioxide satisfies some of the requirements of this catalytic species but it seems likely that other products are also involved. Hydroperoxide deactivation by complexing with sulphoxide does not appear to be involved. 相似文献
102.
Molecular dynamics simulations were performed in order to obtain a detailed understanding of the self-diffusion mechanisms of methanol in the zeolite NaY system. We derived a new force-field term to describe the interactions between the methanol molecules and the extraframework cations. From the simulations, we show that diffusive behavior in the high-temperature range consists of a combination of both short- and long-range motions at low and intermediate loadings. This type of motion is characterized by an activation energy that decreases as the loading increases. At low loadings, we also observe short-range diffusive behavior based on a surface-mediated mechanism. The short-range behavior corresponds to motion only on the length scale of an FAU supercage, whereas the long-range behavior involves intercage diffusion. For the saturation loading corresponding to 96 methanol molecules per unit cell, only short-range motions within the same supercage predominate. Finally, the preferential arrangement of the adsorbate molecules around the extraframework cations are examined and compared with those previously deduced from experimental data. 相似文献
103.
104.
Swarnavo Sarkar Joseph B. Hubbard Michael Halter Anne L. Plant 《Entropy (Basel, Switzerland)》2021,23(1)
Gene regulatory networks (GRNs) control biological processes like pluripotency, differentiation, and apoptosis. Omics methods can identify a large number of putative network components (on the order of hundreds or thousands) but it is possible that in many cases a small subset of genes control the state of GRNs. Here, we explore how the topology of the interactions between network components may indicate whether the effective state of a GRN can be represented by a small subset of genes. We use methods from information theory to model the regulatory interactions in GRNs as cascading and superposing information channels. We propose an information loss function that enables identification of the conditions by which a small set of genes can represent the state of all the other genes in the network. This information-theoretic analysis extends to a measure of free energy change due to communication within the network, which provides a new perspective on the reducibility of GRNs. Both the information loss and relative free energy depend on the density of interactions and edge communication error in a network. Therefore, this work indicates that a loss in mutual information between genes in a GRN is directly coupled to a thermodynamic cost, i.e., a reduction of relative free energy, of the system. 相似文献
105.
The heterogeneous graphical Granger model (HGGM) for causal inference among processes with distributions from an exponential family is efficient in scenarios when the number of time observations is much greater than the number of time series, normally by several orders of magnitude. However, in the case of “short” time series, the inference in HGGM often suffers from overestimation. To remedy this, we use the minimum message length principle (MML) to determinate the causal connections in the HGGM. The minimum message length as a Bayesian information-theoretic method for statistical model selection applies Occam’s razor in the following way: even when models are equal in their measure of fit-accuracy to the observed data, the one generating the most concise explanation of data is more likely to be correct. Based on the dispersion coefficient of the target time series and on the initial maximum likelihood estimates of the regression coefficients, we propose a minimum message length criterion to select the subset of causally connected time series with each target time series and derive its form for various exponential distributions. We propose two algorithms—the genetic-type algorithm (HMMLGA) and exHMML to find the subset. We demonstrated the superiority of both algorithms in synthetic experiments with respect to the comparison methods Lingam, HGGM and statistical framework Granger causality (SFGC). In the real data experiments, we used the methods to discriminate between pregnancy and labor phase using electrohysterogram data of Islandic mothers from Physionet databasis. We further analysed the Austrian climatological time measurements and their temporal interactions in rain and sunny days scenarios. In both experiments, the results of HMMLGA had the most realistic interpretation with respect to the comparison methods. We provide our code in Matlab. To our best knowledge, this is the first work using the MML principle for causal inference in HGGM. 相似文献
106.
King AK Plant DF Golding P Lawson MA Davies PB 《The journal of physical chemistry. A》2012,116(9):2080-2088
The cyclic phosphazene trimer P(3)N(3)(OCH(2)CF(3))(6)and the related cyclic tetramer P(4)N(4)(OCH(2)CF(3))(8) have been synthesized, isolated and their vapor-phase absorption spectra recorded at moderate resolution using an FTIR spectrometer. The interpretation of these spectra is achieved primarily by comparison with the results of high-precision density functional calculations, which enable the principal absorption features to be assigned and conclusions to be drawn regarding the geometries and conformations adopted by both molecules. These in turn allow interesting comparisons to be made with analogous cyclic halo-phosphazenes (such as P(3)N(3)Cl(6)) and other related ring compounds. The highly flexible nature of the two cyclic phosphazenes precludes a complete theoretical study of their potential energy hypersurfaces and a novel alternative approach involving the analysis of a carefully selected subset of the possible molecular conformations has been shown to produce satisfactory results. The two cyclic phosphazene oligomers have been proposed as the major low-to-medium temperature pyrolysis products of the parent polyphosphazene (PN(OCH(2)CF(3))(2))(n), and the identification of vibrational absorption features characteristic of each molecule will enable future studies to test the validity of this proposition. 相似文献
107.
针对深水钻井中水基钻井液易形成天然气水合物从而导致钻井作业无法正常进行的问题,利用自行设计研制的气体水合物反应装置,模拟深水钻井温度压力条件,对水基钻井液添加剂进行了天然气水合物形成的实验研究。分析了各实验体系形成水合物的过冷度。以过冷度为评价指标,评价了各种钻井液添加剂在深水钻井水合物形成过程中的作用。结果表明,在钻井液使用的加量范围内,阳离子聚丙烯酰胺CPAM、两性离子聚合物FA367等对天然气水合物的形成有抑制作用,且随着加量的增加抑制作用增强;磺甲基丹宁SMT、木质素磺酸盐FCLS对天然气水合物的形成有微弱的促进作用,但影响不大。聚合物添加剂的离子类型对天然气水合物的形成影响不大。 相似文献
108.
109.
We report on an optical fiber Mach-Zehnder interferometer made by offset splicing a dual-mode fiber with two single-mode fibers. The extinction ratio can be tuned from less than 1 dB to greater than 28 dB by rotating the dual-mode fiber along its axial direction. The interferometer is utilized as a pulse shaper to convert a 2.5 ps Gaussian pulse to a 5.2 ps flat-top pulse. 相似文献
110.
Three New C21 Steroidal Glycosides from the Roots of Cynanchum komarovii Al.Iljinski 总被引:3,自引:0,他引:3
LiQinWANG YueMaoSHEN YuQingWEI XingXU JunZHOU 《中国化学快报》2004,15(2):200-203
Three new C21 steroidal glycosides named komaroside A, komaroside B, komaroside C were isolated from the ethanolic extract of the roots of Cynanchum komarovii Al.Iljinski(Asclepiadaceae), their structures were determined by physiochemical and spectroscopic analysis. 相似文献