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991.
The dinuclear ytterbium pyridyl diamido complexes [Cp(2)Yb(THF)](2)[mu-eta(1):eta(2)-(NH)(2)(C(5)H(3)N-2,6)] (1a) and [Cp(2)Yb(THF)](2)[mu-eta(1):eta(2)-(NH)(2)(C(5)H(3)N-2,3)] (1b) are easily prepared by protonolysis of Cp(3)Yb with 0.5 equiv of the corresponding diaminopyridine in accepted yields, respectively. Treatment of 1a with 2 equiv of dicyclohexylcarbodiimide (CyN=C=NCy) in THF at low temperature leads to the isolation of the formal double N-H addition product (Cp(2)Yb)(2)[mu-eta(2):eta(2)-(CyN(CyNH)CN)(2)(C(5)H(3)N-2,6)] (2) in 42% yield. Compound 2 is unstable to heat and slowly isomerized to the mixed neutral/dianionic diguanidinate complex (Cp(2)Yb)(2)[mu-eta(2):eta(2)-(CyNH)(2)CN(C(5)H(3)N-2,6)NC(NCy)(2)](THF) (3) at room temperature. Similarly, treatment of 1b with 2 equiv of CyN=C=NCy gives the addition/ isomerization product (Cp(2)Yb)(2)[mu-eta(2):eta(2):eta(1)-(CyNH)(2)CN(C(5)H(3)N-2,3)NC(NCy)(2)] (4). Moreover, the reaction of various ytterbium aryl diamido complexes (prepared in situ from [Cp(2)YbMe](2) and aryldiamine, respectively) with CyN=C=NCy affords the corresponding addition products (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(6)H(4)-1,4)] (5), (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(6)H(4)-1,3)](6), and (Cp(2)Yb)(2)[mu-eta(2):eta(2)-{CyN(CyNH)CN}(2)(C(13)H(8)-2,7)] (7), respectively. In contrast to pyridyl-bridged bis(guanidinate monoanion) complexes, aryl-bridged bis(guanidinate monoanion) complexes 5-7 are stable even with prolonged heating at 110 degrees C. All the results not only demonstrate that the presence of the pyridyl bridge can impart the diamido complexes with a unique reactivity and initiate the unexpected reaction sequence but also indicate evidently that the number and distribution of negative charges of the diguanidinate ligand is tunable from double monoanionic units to mixed neutral/dianionic isomers. All the complexes are characterized by elemental analysis and IR spectroscopies. The structures of complexes 1a, 3, 5, 6, and 7 are also determined through X-ray single-crystal diffraction analysis. 相似文献
992.
Antonio Alonso-Ayuso Felipe Carvallo Laureano F. Escudero Monique Guignard Jiaxing Pi Raghav Puranmalka Andrés Weintraub 《European Journal of Operational Research》2014
Deterministic mine planning models along a time horizon have proved to be very effective in supporting decisions on sequencing the extraction of material in copper mines. Some of these models have been developed for, and used successfully by CODELCO, the Chilean state copper company. In this paper, we wish to consider the uncertainty in a very volatile parameter of the problem, namely, the copper price along a given time horizon. We represent the uncertainty by a multistage scenario tree. The resulting stochastic model is then converted into a mixed 0–1 Deterministic Equivalent Model using a compact representation. We first introduce the stochastic model that maximizes the expected profit along the time horizon over all scenarios (i.e., as in a risk neutral environment). We then present several approaches for risk management in a risk averse environment. Specifically, we consider the maximization of the Value-at-Risk and several variants of the Conditional Value-at-Risk (one of them is new), the maximization of the expected profit minus the weighted probability of having an undesirable scenario in the solution provided by the model, and the maximization of the expected profit subject to stochastic dominance constraints recourse-integer for a set of profiles given by the pairs of target profits and bounds on either the probability of failure or the expected profit shortfall. We present an extensive computational experience on the actual problem, by comparing the risk neutral approach, the tested risk averse strategies and the performance of the traditional deterministic approach that uses the expected value of the uncertain parameters. The results clearly show the advantage of using the risk neutral strategy over the traditional deterministic approach, as well as the advantage of using any risk averse strategy over the risk neutral one. 相似文献
993.
994.
The magnetic properties of the ferrimagnetic cobaltite CaBaCo4O7 are systematically investigated. We find that the susceptibility exhibits a downward deviation below ∼360 K, suggesting the occurrence of short-range magnetic correlations at a temperature well above TC. The effective moment is determined to be ., which is consistent with that expected for the Co2+/Co3+ high spin species. Using a criterion given by Banerjee [Phys. Lett. 12 (1964) 16], we demonstrate that the paramagnetic to ferrimagnetic transition in CaBaCo4O7 has a first order character. 相似文献
995.
Purpose
To propose a simple and accurate quantitative method based on the linear relationship between magnetic resonance (MR) signal enhancement (ΔSI=SIpostcontrast−SIprecontrast) and gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA) concentration (C) by using T1-weighted three-dimensional magnetization-prepared rapid acquisition gradient-echo (T1 3D MP-RAGE) sequence for the in vivo measurement of Gd-DTPA concentration in real-time neuroimaging at 3.0 T.Methods
Phantom experiment was carried out to study the linear fitting of signal intensity change vs. Gd-DTPA concentration (ΔSI-C) curve. A goodness-of-fit test was performed to compare the accuracy between the proposed method and the conventional method based on longitudinal relaxation rate (R1=1/T1) measurement. The influences on the goodness of fit (R2) and the signal-to-noise ratio (SNR) by sequence parameters were explored. Six human subjects with different brain tumors, who underwent a Gd-DTPA-enhanced MRI, were enrolled for in vivo application of the novel method.Results
A good linear relationship between ΔSI and Gd-DTPA concentration existed over the concentration range of 0-1 mM (R2=0.985). The linearity of the ΔSI-C curve was as good as that of the 1/T1-C curve (R2=0.988). Concentrations calculated by both methods had a strong correlation (R2=0.920). An improved linearity of the ΔSI-C curve and an increased SNR can be achieved using sequences with a shorter inversion time (TI) and a higher flip angle. The concentration range of Gd-DTPA in human brain tumors was within the quantitative scope of 0-1 mM.Conclusions
The proposed quantitative method based on ΔSI measurement is accurate and applicable for real-time neuroimaging at 3.0 T. 相似文献996.
In this paper we explore the influence of adaptive memory in the performance of heuristic methods when solving a hard combinatorial
optimization problem. Specifically, we tackle the adaptation of tabu search and scatter search to the bandwidth minimization
problem. It consists of finding a permutation of the rows and columns of a given matrix which keeps the non-zero elements
in a band that is as close as possible to the main diagonal. This is a classic problem, introduced in the late sixties, that
also has a well-known formulation in terms of graphs. Different exact and heuristic approaches have been proposed for the
bandwidth problem. Our contribution consists of two new algorithms, one based on the tabu search methodology and the other
based on the scatter search framework. We also present a hybrid method combining both for improved outcomes. Extensive computational
testing shows the influence of the different elements in heuristic search, such as neighborhood definition, local search,
combination methods and the use of memory. We compare our proposals with the most recent and advanced methods for this problem,
concluding that our new methods can compete with them in speed and running time. 相似文献
997.
This paper presents a theoretical analysis for the long-term non-linear elastic in-plane behaviour and buckling of shallow concrete-filled steel tubular (CFST) arches. It is known that an elastic shallow arch does not buckle under a load that is lower than the critical loads for its bifurcation or limit point buckling because its buckling equilibrium configuration cannot be achieved, and the arch is in a stable equilibrium state although its structural response may be quite non-linear under the load. However, for a CFST arch under a sustained load, the visco-elastic effects of creep and shrinkage of the concrete core produce significant long-term increases in the deformations and bending moments and subsequently lead to a time-dependent change of its equilibrium configuration. Accordingly, the bifurcation point and limit point of the time-dependent equilibrium path and the corresponding buckling loads of CFST arches also change with time. When the changing time-dependent bifurcation or limit point buckling load of a CFST arch becomes equal to the sustained load, the arch may buckle in a bifurcation mode or in a limit point mode in the time domain. A virtual work method is used in the paper to investigate bifurcation and limit point buckling of shallow circular CFST arches that are subjected to a sustained uniform radial load. The algebraically tractable age-adjusted effective modulus method is used to model the time-dependent behaviour of the concrete core, based on which solutions for the prebuckling structural life time corresponding to non-linear bifurcation and limit point buckling are derived. 相似文献
998.
Liu Y Sun Y Du J Lv X Zhao Y Chen M Wang P Guo W 《Organic & biomolecular chemistry》2011,9(2):432-437
A new rhodamine B-based dual-function chromo- and fluorogenic probe for Cu(2+) and ClO(-) has been designed, synthesized, and characterized. The probe comprises a spectroscopic unit of rhodamine B and a Cu(2+)-specific chelating unit of pyridinecarboxamide as well as a ClO(-)-specific reactive moiety of diacylhydrazine, and is a highly selective and extremely sensitive fluorescent and colorimetric sensor for Cu(2+) and ClO(-) in different pH conditions. Compared with the reported probes for Cu(2+) or ClO(-), this is the first chemosensor based on a small molecule that can detect both Cu(2+) and ClO(-), respectively, at 1 nM level. 相似文献
999.
A finite-temperature density functional approach to describe the properties of parahydrogen in the liquid-vapor coexistence region is presented. The first proposed functional is zero-range, where the density-gradient term is adjusted so as to reproduce the surface tension of the liquid-vapor interface at low temperature. The second functional is finite-range and, while it is fitted to reproduce bulk pH(2) properties only, it is shown to yield surface properties in good agreement with experiments. These functionals are used to study the surface thickness of the liquid-vapor interface, the wetting transition of parahydrogen on a planar Rb model surface, and homogeneous cavitation in bulk liquid pH(2). 相似文献
1000.
A supramolecular assembly for visible light responsive release of cargo molecules is presented. Sulforhodamine 101 was loaded inside the mesopores of mercaptopropyl-functionalized mesoporous silica nanoparticles (MP-MSN) and entrapped by mercaptopropyl-coordinated Ru(bpy)(2)(PPh(3))-moieties. Irradiation with visible light triggers the release of capping species and loaded molecules. 相似文献