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101.
Bianchi I Forlani R Minetto G Peretto I Regalia N Taddei M Raveglia LF 《Journal of combinatorial chemistry》2006,8(4):491-499
An efficient strategy for the solution-phase parallel synthesis of a library of pyrrole-amides is described. Key reactions include functional homologation of beta-ketoesters with a set of aldehydes followed by oxidation to produce a series of differently substituted 1,4-dicarbonyl compounds. Rapid cyclization using a microwave-assisted Paal-Knorr reaction provided a set of 24 pyrrole esters that were further functionalized through a trimethylaluminum-mediated aminolysis to obtain a larger library of 288 diverse pyrrole-3-amides. The tetrasubstitution allows a good exploration of the chemical space around the central pyrrole core. The last step was entirely automated with a Bohdan Myriad personal synthesizer. 相似文献
102.
Direct current voltammetry and differential pulse voltammetry have been used to investigate the electrochemical behaviour of two phytochelatins: heptapeptide (gamma-Glu-Cys)3-Gly and pentapeptide (gamma-Glu-Cys)2-Gly, tripeptide glutathione gamma-Glu-Cys-Gly and its fragments: dipeptides Cys-Gly and gamma-Glu-Cys at the hanging mercury drop electrode in the presence of cobalt(II) ions. Most interesting results were obtained with direct current voltammetry in the potential region of -0.80 V up to -1.80 V. Differential pulse voltammetry of the same solutions of Co(II) with peptides gives more complicated voltammograms with overlapping peaks, probably in connection with the influence of adsorption at slow scan rates necessarily used in this method. However, in using Brdicka catalytic currents for analytical purposes, differential pulse voltammograms seem to be more helpful. Presented investigations have shown that particularly the prewave of cobalt(II) allows distinguishing among phytochelatins, glutathione, and its fragments. 相似文献
103.
The formation process of methanol-water mixtures, (MeOH/H2O)n, n = 2, 3,..., 8 is studied at the molecular level using the general effective fragment potential (EFP2) method and second-order perturbation theory (MP2). Extensive Monte Carlo/simulated annealing global optimizations were used to locate global minimum structures for each n, for both homo and hetero clusters. Mixing at the microscopic level was investigated, and some general conclusions about the microsolvation behavior of these mixtures are presented. For all of these clusters, incomplete mixing is observed at the molecular level. Low-energy (MeOH/H2O)n clusters retain much of their initial structure in the global minima of the mixed clusters. 相似文献
104.
The mechanism of the degenerate 1,5-hydride shift in 2,6-dimethyl-2-heptyl cations has been investigated using ab initio MP2 and density functional theory (DFT) hybrid (B3LYP) calculations. The potential-energy profile for the 1,5-hydride shift consists of three minima corresponding to two equivalent acyclic carbocations and one symmetrically mu-hydrido-bridged carbocation, while two equivalent unsymmetrically hydrido-bridged carbocations were located as transition-state structures. The calculated relative energy differences between acyclic carbocations and symmetrically mu-hydrido-bridged structure are significantly affected by introduction of alkyl and (CH2)n-substituents at the C4 position of the 2,6-dimethyl-2-heptyl cation structure. DFT self-consistent isodensity polarizable continuum method (SCI-PCM) and MP2 PCM continuum methods have been used to calculate the effect of solvation on geometries and relative energies of the species involved in the 1,5-hydride shift. It is found that relative energies of acyclic and mu-hydrido-bridged carbocation structures as well as the energy barriers for 1,5-hydride shifts are in accord with experimental data if solvation effects are taken into account. 相似文献
105.
Igor Dolinka Ivana Đurđev James East Preeyanuch Honyam Kritsada Sangkhanan Jintana Sanwong Worachead Sommanee 《Algebra Universalis》2018,79(3):75
Fix (not necessarily distinct) objects i and j of a locally small category S, and write \(S_{ij}\) for the set of all morphisms \(i\rightarrow j\). Fix a morphism \(a\in S_{ji}\), and define an operation \(\star _a\) on \(S_{ij}\) by \(x\star _ay=xay\) for all \(x,y\in S_{ij}\). Then \((S_{ij},\star _a)\) is a semigroup, known as a sandwich semigroup, and denoted by \(S_{ij}^a\). This article develops a general theory of sandwich semigroups in locally small categories. We begin with structural issues such as regularity, Green’s relations and stability, focusing on the relationships between these properties on \(S_{ij}^a\) and the whole category S. We then identify a natural condition on a, called sandwich regularity, under which the set \({\text {Reg}}(S_{ij}^a)\) of all regular elements of \(S_{ij}^a\) is a subsemigroup of \(S_{ij}^a\). Under this condition, we carefully analyse the structure of the semigroup \({\text {Reg}}(S_{ij}^a)\), relating it via pullback products to certain regular subsemigroups of \(S_{ii}\) and \(S_{jj}\), and to a certain regular sandwich monoid defined on a subset of \(S_{ji}\); among other things, this allows us to also describe the idempotent-generated subsemigroup \(\mathbb E(S_{ij}^a)\) of \(S_{ij}^a\). We also study combinatorial invariants such as the rank (minimal size of a generating set) of the semigroups \(S_{ij}^a\), \({\text {Reg}}(S_{ij}^a)\) and \(\mathbb E(S_{ij}^a)\); we give lower bounds for these ranks, and in the case of \({\text {Reg}}(S_{ij}^a)\) and \(\mathbb E(S_{ij}^a)\) show that the bounds are sharp under a certain condition we call MI-domination. Applications to concrete categories of transformations and partial transformations are given in Part II. 相似文献
106.
We deal with anomalous diffusions induced by continuous time random walks - CTRW in ?n. A particle moves in ?n in such a way that the probability density function u(·, t) of finding it in region Ω of ?n is given by ∫Ωu(x, t)dx. The dynamics of the diffusion is provided by a space time probability density J(x, t) compactly supported in {t ≥ 0}. For t large enough, u satisfies the equation , where δ is the Dirac delta in space-time. We give a sense to a Cauchy type problem for a given initial density distribution f. We use Banach fixed point method to solve it and prove that under parabolic rescaling of J, the equation tends weakly to the heat equation and that for particular kernels J, the solutions tend to the corresponding temperatures when the scaling parameter approaches 0.
相似文献
$$u\left( {x,t} \right) = \left[ {\left( {J - \delta } \right)*u} \right]\left( {x,t} \right)$$
107.
In this paper, we construct combinatorial bases of Feigin–Stoyanovsky’s type subspaces of standard modules for level k affine Lie algebra \(C_\ell ^{(1)}\). We prove spanning by using annihilating field \(x_\theta (z)^{k+1}\) of standard modules. In the proof of linear independence, we use simple currents and intertwining operators whose existence is given by fusion rules. 相似文献
108.
109.
The development of a fragment–fragment dispersion energy expression, for the general effective fragment potential (EFP2) method is presented. C6 dispersion coefficients, expressed in terms of the dynamic polarizabilties over the imaginary frequency range (α(iν)), were calculated for a set of homo and hetero dimers. Using these coefficients the dispersion energy has been calculated. The dispersion energy is expressed using a simple London series expansion terminated after the n=6 term and implemented using distributed localized molecular orbitals (LMOs). The EFP2 dispersion energy is compared to symmetry adapted perturbation theory (SAPT) values. From this comparison, it is apparent that one needs to include higher order terms in the dispersion energy. Adding an estimated C8 term to the C6 energy greatly improves the agreement with the benchmark SAPT energies. 相似文献
110.
A comprehensive algorithm was recently proposed for calculation of the sonochemical effectiveness factor and wastewater treatment modeling. The presented approach implies that ultrasound is an auxiliary source of free radicals in Fenton type reactions; introduction of ultrasound represents an enhancement of pollutant degradation rates. The sonochemical effectiveness factor was introduced in kinetic models as the eUS factor (Gr?i? et al., 2012 [1]). As a substantial follow-up, this study presents novel considerations. The eUS factor was modeled as a function of employed frequency, actual cavitation-related power intensity of ultrasound and a portion of the cavitationally active zone, i.e. dimensionless active volume. The effect of temperature was disregarded in the present model considerations. Cavitationally active zone in reactors was determined based on the erosion of aluminum foil, resulting in cone-shaped space arising from transducer.In the present study, sonochemical treatment of industrial wastewater containing HCOONa as organic pollutant was performed using different equipment: ultrasonic baths (UB1, UB2 and UB3), cylindrical reactor with homogenizer (HCR) and three-frequency hexagonal cell, i.e. ultrasonic pilot reactor prototype (PP). Explored frequency range was from 20 to 120 kHz. Homogeneous and heterogeneous Fenton-type sonochemical processes, US/Fe(II)(FeSO4,aq.)/H2O2 and US/Fe(II)(steel-plate)/H2O2, respectively, applied to industrial wastewater were investigated in terms of mineralization kinetics. Newly modeled eUS factor was introduced in corresponding kinetic models and the overall model was validated. Kinetic parameters of Fenton process were treated as independent of ultrasound, since eUS factor consists of cavitation-related phenomena responsible for the mineralization rate enhancement. In average, a 21% increase of mineralization efficiency was achieved using a single frequency, while more than 70% increase can be achieved by combining 20, 68 and 120 kHz in PP. 相似文献