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1.
M. Di Valentin A. Bisol G. Agostini G. Giacometti D. Carbonera 《Applied magnetic resonance》2006,30(3-4):555-576
A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C60, TTF-P-C60 and C-P-PF, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C60, versus fluorinated free-base porphyrin, PF), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C60 triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C60: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge. 相似文献
2.
不完全信息群体决策专家权重的集结 总被引:8,自引:5,他引:3
本文对于属性权重信息和属性效用信息都不完全的群体多属性决策问题,通过构造属性值区间和运用系统聚类分析法,对群体决策中的专家进行分类,并确定每位专家的权重. 相似文献
3.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
4.
R. Pizzoferrato L. Lagonigro T. Ziller A. Di Carlo R. Paolesse F. Mandoj A. Ricci C. Lo Sterzo 《Chemical physics》2004,300(1-3):217-225
We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φIR=4×10−4 is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er3+. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R0, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials. 相似文献
5.
Qi Wang Huaxiang Yang Zhiqiang Fan Hong Xu 《Journal of polymer science. Part A, Polymer chemistry》2004,42(5):1093-1099
Ethylisobutylaluminoxane (EBAO) and its analogues were synthesized by a reaction between an triethylaluminum (Et3Al)/triisobutylaluminum (i‐Bu3Al) mixture and 4‐fluorobenzeneboronic acid, phenylboronic acid, or n‐butaneboronic acid and subsequent hydrolysis with water. They were used as cocatalysts in ethylene polymerization catalyzed by an iron complex {[(ArN?C(Me))2C5H3N]FeCl2, where Ar is 2,6‐diisopropylphenyl}. Polyethylene with a high molecular weight and a narrow molecular weight distribution was prepared with modified EBAOs, and the performance of the iron complex at high polymerization temperatures was greatly improved. The activators for the iron complex also affected the polymerization activity and the molecular weight of the resultant polyethylene. It was suggested that the stereo and electronic effects of the substitute groups of aluminoxane contributed to the improved performance of the new activators. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1093–1099, 2004 相似文献
6.
Based on the complexation between proteins and Cu(II) coupled with the time-resolved chemiluminescence (CL) technique, a highly sensitive and quantitative assay for measuring proteins in solution is described. The complexes of proteins with Cu(II) have a strongly catalytic effect on the luminol-H2O2 CL reaction. Because the CL emission produced by the complexes is much more long-lived than that by Cu(II), the CL signals originating from proteins can be easily identified and measured with a time-resolved technique. On this basis, bovine albumin fraction V (BAF V) can be quantitatively determined in the range of 0.01 - 5.0 microg/ml with a detection limit of 5.8 ng/ml. The results show that the proposed assay exhibits a small variation in the response values for the same amount of different proteins, as compared to the Lowry as well as Bradford assays. The CL assay has also been studied for the detection of immobilized proteins. 相似文献
7.
8.
A. Di Maio A. Rocco P. Ferraro M. De Rosa P. De Natale S. De Nicola A. Finizio G. Pierattini G. Coppola M. Iodice V. Striano 《Optics and Lasers in Engineering》2007,45(3):385
In view of the growing interest for non-destructive tests of materials, geodynamical monitoring and in general remote sensing, there is a great effort to bring practical optical sensors from research labs to industrial and environmental applications. In this paper, we employ digital holographic technique as an efficient tool for evaluating the strain measurement capability of fiber Bragg gratings (FBG). A cantilever beam has been employed as a test structure under loading test. The strain measurements results obtained by fiber-based sensors have been compared to those obtained by using full-field digital holographic technique and point-wise strain gauge sensors glued on the same cantilever beam. A simple theoretical model is also presented to interpret and compare the experimental results coming from different techniques. 相似文献
9.
B. Savo P. Romano A. Nigro R. Di Leo 《Physica C: Superconductivity and its Applications》2002,370(4):275-280
The flat voltage noise component of current biased, high-transparency Nb/AlOx/Nb superconducting tunnel junctions has been investigated at frequencies up to 70 kHz. Several aspects of the analyzed phenomena suggest the presence of current noise effects induced by the discreteness of the charge carriers. At subgap voltages, where excess currents occur, a behavior coherent with a multiple Andreev reflection-assisted transport through the tunnel barrier has been found. However, the measured charge values exceed any theoretical prediction. 相似文献
10.
Onofrio Mario Di Vincenzo Plamen Koshlukov Roberto La Scala 《Advances in Applied Mathematics》2006,37(4):541
In this paper we describe completely the involutions of the first kind of the algebra UTn(F) of n×n upper triangular matrices. Every such involution can be extended uniquely to an involution on the full matrix algebra. We describe the equivalence classes of involutions on the upper triangular matrices. There are two distinct classes for UTn(F) when n is even and a single class in the odd case.Furthermore we consider the algebra UT2(F) of the 2×2 upper triangular matrices over an infinite field F of characteristic different from 2. For every involution *, we describe the *-polynomial identities for this algebra. We exhibit bases of the corresponding ideals of identities with involution, and compute the Hilbert (or Poincaré) series and the codimension sequences of the respective relatively free algebras.Then we consider the *-polynomial identities for the algebra UT3(F) over a field of characteristic zero. We describe a finite generating set of the ideal of *-identities for this algebra. These generators are quite a few, and their degrees are relatively large. It seems to us that the problem of describing the *-identities for the algebra UTn(F) of the n×n upper triangular matrices may be much more complicated than in the case of ordinary polynomial identities. 相似文献