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131.
María del Pilar Godoy-Caballero María Julia Culzoni Teresa Galeano-Díaz María Isabel Acedo-Valenzuela 《Analytica chimica acta》2013
This paper presents the development of a non-aqueous capillary electrophoresis method coupled to UV detection combined with multivariate curve resolution-alternating least-squares (MCR-ALS) to carry out the resolution and quantitation of a mixture of six phenolic acids in virgin olive oil samples. p-Coumaric, caffeic, ferulic, 3,4-dihydroxyphenylacetic, vanillic and 4-hydroxyphenilacetic acids have been the analytes under study. All of them present different absorption spectra and overlapped time profiles with the olive oil matrix interferences and between them. The modeling strategy involves the building of a single MCR-ALS model composed of matrices augmented in the temporal mode, namely spectra remain invariant while time profiles may change from sample to sample. So MCR-ALS was used to cope with the coeluting interferences, on accounting the second order advantage inherent to this algorithm which, in addition, is able to handle data sets deviating from trilinearity, like the data herein analyzed. The method was firstly applied to resolve standard mixtures of the analytes randomly prepared in 1-propanol and, secondly, in real virgin olive oil samples, getting recovery values near to 100% in all cases. The importance and novelty of this methodology relies on the combination of non-aqueous capillary electrophoresis second-order data and MCR-ALS algorithm which allows performing the resolution of these compounds simplifying the previous sample pretreatment stages. 相似文献
132.
Chunmei Zhang Zhijia Liu Yongming Li Qi Li Chaojun Song Zhuwei Xu Yun Zhang Yusi Zhang Ying Ma Yuanjie Sun Lihua Chen Liang Fang Angang Yang Kun Yang Boquan Jin 《Analytica chimica acta》2013
In this study, detection of staphylococcal enterotoxin A (SEA) in multi-matrices using a highly sensitive and specific microplate chemiluminescence enzyme immunoassay (CLEIA) has been established. A pair of monoclonal antibodies (mAbs) was selected from 37 anti-SEA mAbs by pairwise analysis, and the experimental conditions of the CLEIA were optimized. This CLEIA exhibited high performance with a wide dynamic range from 6.4 pg mL−1 to 1600 pg mL−1, and the measured low limit of detection (LOD) was 3.2 pg mL−1. No cross-reactivity was observed when this method was applied to test SEB, SEC1, and SED. It has also been successfully applied for analyzing SEA in a variety of environmental, biological, and clinical matrices, such as sewage, tap water, river water, roast beef, peanut butter, cured ham, 10% nonfat dry milk, milk, orange juice, human urine, and serum. Thus, the highly sensitive and SEA-specific CLEIA should make it attractive for quantifying SEA in public health and diagnosis in near future. 相似文献
133.
A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L−1, 1.0 mg L−1, 1.3 mg L−1 and 0.2 mg L−1 were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments. 相似文献
134.
Yongqing Li Jiuchuang Yuan Maodu Chen Fengcai Ma Mengtao Sun 《Journal of computational chemistry》2013,34(19):1686-1696
An accurate single‐sheeted double many‐body expansion potential energy surface is reported for the title system. A switching function formalism has been used to warrant the correct behavior at the and dissociation channels involving nitrogen in the ground and first excited states. The topographical features of the novel global potential energy surface are examined in detail, and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel surface can be using to treat well the Renner–Teller degeneracy of the and states of . Such a work can both be recommended for dynamics studies of the reaction and as building blocks for constructing the double many‐body expansion potential energy surface of larger nitrogen/hydrogen‐containing systems. In turn, a test theoretical study of the reaction has been carried out with the method of quantum wave packet on the new potential energy surface. Reaction probabilities, integral cross sections, and differential cross sections have been calculated. Threshold exists because of the energy barrier (68.5 meV) along the minimum energy path. On the curve of reaction probability for total angular momentum J = 0, there are two sharp peaks just above threshold. The value of integral cross section increases quickly from zero to maximum with the increase of collision energy, and then stays stable with small oscillations. The differential cross section result shows that the reaction is a typical forward and backward scatter in agreement with experimental measurement result. © 2013 Wiley Periodicals, Inc. 相似文献
135.
We consider sequences of random variables whose probability generating functions have only roots on the unit circle, which has only been sporadically studied in the literature. We show that the random variables are asymptotically normally distributed if and only if the fourth central and normalized (by the standard deviation) moment tends to 3, in contrast to the common scenario for polynomials with only real roots for which a central limit theorem holds if and only if the variance is unbounded. We also derive a representation theorem for all possible limit laws and apply our results to many concrete examples in the literature, ranging from combinatorial structures to numerical analysis, and from probability to analysis of algorithms. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46,707–738, 2015 相似文献
136.
讨论了一类两种群具有二次相关性收获率的捕食与被捕食系统,利用常微分定性方法和分支理论,得到了系统平衡点处的性态和极限环的存在性条件,并用Matlab软件对其进行数值模拟,推广了相关文献中两种群捕食模型定性分析的相应结论. 相似文献
137.
The initial value problem for creeping flow of the upper convected Maxwell fluid at high Weissenberg number
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Michael Renardy 《Mathematical Methods in the Applied Sciences》2015,38(5):959-965
We consider the equations for time dependent creeping flow of an upper convected Maxwell fluid. For finite Weissenberg number, these equations can be reformulated as a coupled system of a hyperbolic equation for the stresses and an elliptic equation for the velocity. In the high Weissenberg number limit, however, the elliptic equation becomes degenerate. As a consequence, the initial value problem is no longer uniquely solvable if we just naively let the Weissenberg number go to infinity in the equations. In this paper, we make an a priori assumption on the stresses, which is motivated by the behavior in shear flow. We formulate a systematic perturbation procedure to solve the resulting initial value problem. Copyright © 2014 JohnWiley & Sons, Ltd. 相似文献
138.
Eduardo González‐Olivares Lina M. Gallego‐Berrío Betsabé González‐Yañez Alejandro Rojas‐Palma 《Mathematical Methods in the Applied Sciences》2015,38(18):5183-5196
In this work, a modified Holling–Tanner predator–prey model is analyzed, considering important aspects describing the interaction such as the predator growth function is of a logistic type; a weak Allee effect acting in the prey growth function, and the functional response is of hyperbolic type. Making a change of variables and time rescaling, we obtain a polynomial differential equations system topologically equivalent to the original one in which the non‐hyperbolic equilibrium point (0,0) is an attractor for all parameter values. An important consequence of this property is the existence of a separatrix curve dividing the behavior of trajectories in the phase plane, and the system exhibits the bistability phenomenon, because the trajectories can have different ω ? limit sets; as example, the origin (0,0) or a stable limit cycle surrounding an unstable positive equilibrium point. We show that, under certain parameter conditions, a positive equilibrium may undergo saddle‐node, Hopf, and Bogdanov–Takens bifurcations; the existence of a homoclinic curve on the phase plane is also proved, which breaks in an unstable limit cycle. Some simulations to reinforce our results are also shown. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
139.
Existence of global weak solutions for Navier‐Stokes‐Poisson equations with quantum effect and convergence to incompressible Navier‐Stokes equations
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In this paper, we consider a three dimensional quantum Navier‐Stokes‐Poisson equations. Existence of global weak solutions is obtained, and convergence toward the classical solution of the incompressible Navier‐Stokes equation is rigorously proven for well prepared initial data. Furthermore, the associated convergence rates are also obtained. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
140.
Characterization of the potential energy surfaces of two small but challenging noncovalent dimers: (P2)2 and (PCCP)2
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This work characterizes eight stationary points of the P2 dimer and six stationary points of the PCCP dimer, including a newly identified minimum on both potential energy surfaces. Full geometry optimizations and corresponding harmonic vibrational frequencies were computed with the second‐order Møller–Plesset (MP2) electronic structure method and six different basis sets: aug‐cc‐pVXZ, aug‐cc‐pV(X+d)Z, and aug‐cc‐pCVXZ where X = T, Q. A new L‐shaped structure with C2 symmetry is the only minimum for the P2 dimer at the MP2 level of theory with these basis sets. The previously reported parallel‐slipped structure with C2h symmetry and a newly identified cross configuration with D2 symmetry are the only minima for the PCCP dimer. Single point energies were also computed using the canonical MP2 and CCSD(T) methods as well as the explicitly correlated MP2‐F12 and CCSD(T)‐F12 methods and the aug‐cc‐pVXZ (X = D, T, Q, 5) basis sets. The energetics obtained with the explicitly correlated methods were very similar to the canonical results for the larger basis sets. Extrapolations were performed to estimate the complete basis set (CBS) limit MP2 and CCSD(T) binding energies. MP2 and MP2‐F12 significantly overbind the P2 and PCCP dimers relative to the CCSD(T) and CCSD(T)‐F12 binding energies by as much as 1.5 kcal mol?1 for the former and 5.0 kcal mol?1 for the latter at the CBS limit. The dominant attractive component of the interaction energy for each dimer configuration was dispersion according to several symmetry‐adapted perturbation theory analyses. © 2014 Wiley Periodicals, Inc. 相似文献