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951.
    
Cyanosilylation, aldol coupling and asymmetric Henry reactions were carried out with L- and D-valmet ligands in different configurations: i) coordinated to sodium ions, as organocatalysts, with week base properties, ii) complexes with copper(II), as homogeneous catalysts, and iii) immobilized copper(II) complexes onto graphene oxide (GO) as heterogeneous catalysts. For the reaction of benzaldehyde and nitromethane in water these afforded an asymmetric Henry reaction, with a spectacular increase of the conversion and ee (92.5 and 95.8 %, respectively) after the deposition on GO. Ligand complexed copper was also effective for cyanosilylation and Aldol coupling reaction.  相似文献   
952.
    
An irreversible Carnot cycle engine operating as a closed system is modeled using the Direct Method and the First Law of Thermodynamics for processes with Finite Speed. Several models considering the effect on the engine performance of external and internal irreversibilities expressed as a function of the piston speed are presented. External irreversibilities are due to heat transfer at temperature gradient between the cycle and heat reservoirs, while internal ones are represented by pressure losses due to the finite speed of the piston and friction. Moreover, a method for optimizing the temperature of the cycle fluid with respect to the temperature of source and sink and the piston speed is provided. The optimization results predict distinct maximums for the thermal efficiency and power output, as well as different behavior of the entropy generation per cycle and per time. The results obtained in this optimization, which is based on piston speed, and the Curzon–Ahlborn optimization, which is based on time duration, are compared and are found to differ significantly. Correction have been proposed in order to include internal irreversibility in the externally irreversible Carnot cycle from Curzon–Ahlborn optimization, which would be equivalent to a unification attempt of the two optimization analyses.  相似文献   
953.
    
This work is driven by a practical question: corrections of Artificial Intelligence (AI) errors. These corrections should be quick and non-iterative. To solve this problem without modification of a legacy AI system, we propose special ‘external’ devices, correctors. Elementary correctors consist of two parts, a classifier that separates the situations with high risk of error from the situations in which the legacy AI system works well and a new decision that should be recommended for situations with potential errors. Input signals for the correctors can be the inputs of the legacy AI system, its internal signals, and outputs. If the intrinsic dimensionality of data is high enough then the classifiers for correction of small number of errors can be very simple. According to the blessing of dimensionality effects, even simple and robust Fisher’s discriminants can be used for one-shot learning of AI correctors. Stochastic separation theorems provide the mathematical basis for this one-short learning. However, as the number of correctors needed grows, the cluster structure of data becomes important and a new family of stochastic separation theorems is required. We refuse the classical hypothesis of the regularity of the data distribution and assume that the data can have a rich fine-grained structure with many clusters and corresponding peaks in the probability density. New stochastic separation theorems for data with fine-grained structure are formulated and proved. On the basis of these theorems, the multi-correctors for granular data are proposed. The advantages of the multi-corrector technology were demonstrated by examples of correcting errors and learning new classes of objects by a deep convolutional neural network on the CIFAR-10 dataset. The key problems of the non-classical high-dimensional data analysis are reviewed together with the basic preprocessing steps including the correlation transformation, supervised Principal Component Analysis (PCA), semi-supervised PCA, transfer component analysis, and new domain adaptation PCA.  相似文献   
954.
We show that the parameter space of the Minimal Supersymmetric Standard Model includes a region where the down-type fermion masses are generated by the loop-induced couplings to the up-type Higgs doublet. In this region the down-type Higgs doublet does not acquire a vacuum expectation value at tree level, and has sizable couplings in the superpotential to the tau leptons and bottom quarks. Besides a light standard-like Higgs boson, the Higgs spectrum includes the nearly degenerate states of a heavy spin-0 doublet which can be produced through their couplings to the b quark and decay predominantly into τ + τ ? or τν.  相似文献   
955.
We give new necessary and sufficient integral conditions for the existence of exponential dichotomy of skew-product flows. Our methods are based on the structure of the associated stable subspace and unstable subspace. We propose a nonlinear approach, extending the study of exponential stability in terms of integral conditions to the case of uniform exponential dichotomy. We apply the main results to the study of uniform exponential dichotomy of non-autonomous systems.  相似文献   
956.
In the paper the results of 241Pu activity concentration determination in the biggest Polish rivers are presented. The analysis of more than 100 river water samples showed the Vistula and the Odra as well as three Pomeranian Rivers are important sources of 241Pu in the southern Baltic Sea. There were differences in 241Pu activities depending on season and sampling site and the plutonium contamination came mainly from the global atmospheric fallout as well as the Chernobyl accident, which is confirmed by plutonium activity ratios of 241Pu/239+240Pu and 238Pu/239+240Pu.  相似文献   
957.
The Michael cyanoethylation of 1-(2-aminoethyl)piperazine, 4,4′-methylenebis(cyclohexylamine) and bis(3-aminopropylamine)amine, leading to acrylonitrile free (<100 ppm) polyamino nitriles, as a key step in the synthesis of higher polyamines useful in the synthesis of acylpolyamine neurotoxins, was carried out regioselectively on a multigram scale by careful tuning of reaction conditions, without a necessity to protect nitrogen atoms. The higher reactivity of primary amino groups in aliphatic diamines and triamines [as in bis(3-aminopropylamine)amine] was also observed in the cyclic amine, 4,4′-methylenebis(cyclohexylamine), but reversed in 1-(2-aminoethyl)piperazine. The compounds with a dicyanoethylated nitrogen atom were thermally less stable than the monocyanoethylated ones.  相似文献   
958.
Nanocrystalline Ho-doped BaTiO3, with average nanocrystals size of 20 nm, have been prepared using a sol–gel combustion technique. The structural and morphological properties of the powders have been investigated by X-ray powder diffraction and high resolution transmission electron microscopy. Chemical states of the holmium on the Ba0.97Ho0.03TiO3 ceramic surface were analyzed using X-ray photoelectron spectroscopy. Furthermore, their photoluminescence properties were analyzed.  相似文献   
959.
Proteasomes degrade the majority of proteins in mammalian cells, are involved in the regulation of multiple physiological functions, and are established targets of anticancer drugs. The proteasome has three types of active sites. Chymotrypsin-like sites are the most important for protein breakdown and have long been considered the only suitable targets for antineoplastic drugs; however, our recent work demonstrated that inhibitors of caspase-like sites sensitize malignant cells to inhibitors of the chymotrypsin-like sites. Here, we describe the development of specific cell-permeable inhibitors and an activity-based probe of the trypsin-like sites. These compounds selectively sensitize multiple myeloma cells to inhibitors of the chymotrypsin-like sites, including antimyeloma agents bortezomib and carfilzomib. Thus, trypsin-like sites are cotargets for anticancers drugs. Together with inhibitors of chymotrypsin- and caspase-like sites developed earlier, we provide the scientific community with a complete set of tools to separately modulate proteasome active sites in living cells.  相似文献   
960.
Nanosized metal aluminates, MAl2O4 (M = Ni, Co), have been prepared following a nonpolluting, low temperature, and self-sustaining starch single-fuel combustion synthesis. The mixed fuel-coordinating actions of starch have given rise to an intermediary precursor which afforded monodisperse metal aluminate nanoparticles. The thermal analysis of the [M(II), Al(III)]-starch precursors indicates a similar thermochemical reactivity for the two compounds, displaying a sequence of well-defined decomposition stages associated with three endothermic effects and three/four (nickel/cobalt) exothermic ones. The XRD data confirm the formation of spinelic phase and a continuous growth of particle sizes with the increase of calcination temperatures. The mechanisms proposed for the formation of metal aluminates essentially consist in a combination of solid-state reactions of amorphous NiO/Co3O4 and Al2O3 simple oxides. The evaluation criterion of Ni(II) cations into the spinelic lattice is original and is based on the distinct occupancy degree of tetrahedral and octahedral sites in NiAl2O4 and γ-Al2O3. TEM/HRTEM investigations performed on the cobalt(II) and nickel(II) aluminate oxide powders resulted after calcination at 800 and 900 °C, respectively, for 1 h show the formation of irregular and isolated plate-like particles for Co(II)-based spinelic oxides (the average particle size is 16.6 nm) and submicron aggregates of small, bimodal, and almost uniform (as shape and size) of NiAl2O4 mixed oxide (the mean particle size is 33.6 nm). The NIR–UV–Vis spectra for the resulted MAl2O4 (M = Co, Ni) mixed oxides reveal a massive presence of tetrahedral divalent cations both for short- and long-time calcined samples. NiO impurities are detected using FTIR and electronic spectra for all NiAl2O4 samples.  相似文献   
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