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81.
Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials. These interactions may strongly influence the electronic behavior of microporous materials that confine ions and charges to length scales comparable to proton-coupled electron transfer. Yet despite mounting evidence that both solvent and electrolyte influence charge transport through ion–charge interactions in metal–organic frameworks, fundamental microscopic insights are only just beginning to emerge. Here, through electrochemical analysis of two open-framework chalcogenides TMA2FeGe4S10 and TMA2ZnGe4S10, we outline the key signatures of ion-coupled charge transport in band-type and hopping-type microporous conductors. Pressed-pellet direct-current and impedance techniques reveal that solvent enhances the conductivity of both materials, but for distinct mechanistic reasons. This analysis required the development of a fitting method that provides a novel quantitative metric of concerted ion–charge motion. Taken together, these results provide chemical parameters for a general understanding of electrochemistry in nanoconfined spaces and for designing microporous conductors and electrochemical methods used to evaluate them.Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials. 相似文献
82.
Nanoparticle modified LNA probes have been used for colorimetric identification of double stranded DNA via parallel triplex formation, eliminating the need for prior denaturation of the target duplex. 相似文献
83.
Protein immobilization capacity and covalent binding coverage of pulsed plasma polymer surfaces 总被引:1,自引:0,他引:1
Yongbai Yin Daniel Bax David R. McKenzie Marcela M.M. Bilek 《Applied Surface Science》2010,256(16):4984-3733
Three carbon surfaces were deposited using pulsed plasma enhanced chemical vapour deposition method: a low and a high nitrogen-containing plasma polymer surfaces and a diamond-like carbon surface. The surfaces were analysed using both X-ray photoelectron spectroscopy (XPS) technique and the enzyme-linked immunosorbent assay (ELISA) method combining with sodium dodecyl sulphate (SDS) cleaning to investigate the capacity and covalent binding of the immobilized proteins. A good correlation was found on quantification of remaining protein after SDS cleaning using the ELISA method and the XPS technique. All surfaces had similar initial capacity of protein attachment but with large different resistance to SDS cleaning. The analysis showed that the high nitrogen-containing plasma polymer was the best biocompatible material due to its highest resistance to SDS cleaning, i.e. with the highest quantity (∼80%) of proteins bound covalently. 相似文献
84.
Let \({{\uppercase {\mathcal{p}}}} \) be the ordered set of isomorphism types of finite ordered sets (posets), where the ordering is by embeddability. We study first-order definability in this ordered set. We prove among other things that for every finite poset P, the set \(\{p,p^{\partial}\}\) is definable, where p and \(p^{\partial}\) are the isomorphism types of P and its dual poset. We prove that the only non-identity automorphism of \({{\uppercase {\mathcal{p}}}}\) is the duality map. Then we apply these results to investigate definability in the closely related lattice of universal classes of posets. We prove that this lattice has only one non-identity automorphism, the duality map; that the set of finitely generated and also the set of finitely axiomatizable universal classes are definable subsets of the lattice; and that for each member K of either of these two definable subsets, \(\{K,K^{\partial}\}\) is a definable subset of the lattice. Next, making fuller use of the techniques developed to establish these results, we go on to show that every isomorphism-invariant relation between finite posets that is definable in a certain strongly enriched second-order language \(\textup{\emph L}_2\) is, after factoring by isomorphism, first-order definable up to duality in the ordered set \({{\uppercase {\mathcal{p}}}}\). The language \(\textup{\emph L}_2\) has different types of quantifiable variables that range, respectively, over finite posets, their elements and order-relation, and over arbitrary subsets of posets, functions between two posets, subsets of products of finitely many posets (heteregenous relations), and can make reference to order relations between elements, the application of a function to an element, and the membership of a tuple of elements in a relation. 相似文献
85.
McKenzie I 《The journal of physical chemistry. A》2010,114(48):12759-12763
Radicals formed by the addition of hydrogen (H) or muonium (Mu) to tris(8-hydroxyquinoline)aluminum(III) (Alq(3)) have been studied using density functional theory (DFT) calculations. Drew et al. (Phys. Rev. Lett. 2008, 100, 116601) studied Alq(3) using the longitudinal field muon spin relaxation technique and assumed the formation of muoniated radicals and rapid intermolecular electron hopping with a rate of (1.4 ± 0.2) × 10(12) s(-1). In this work, the results of DFT calculations on Alq(3), the H/Mu adducts of Alq(3), and the corresponding anions and cations are reported. The energy required to transfer an electron to or from the H/Mu adducts of Alq(3) is prohibitively large, ranging from 4.09 to 5.68 eV, which suggests that the unpaired electron does not hop onto neighboring molecules and that there is no long-range diffusion of the unpaired electron. The hyperfine coupling constants for the muoniated radicals were calculated and used to predict avoided level crossing resonance fields, which will allow experimenters to confirm that the unpaired electron is localized in close proximity to the muon. 相似文献
86.
Wackerbarth H Larsen FB Hansen AG McKenzie CJ Ulstrup J 《Dalton transactions (Cambridge, England : 2003)》2006,(28):3438-3444
Densely packed Self-Assembled Monolayers (SAMs) of a peroxide-bridged dicobalt complex, [Co2(O2)(bpbp)(O2CCH2CH2S)]2+, 3, (bpbp- = 2,6-bis((N,N-bis-(2-picolyl)amino)-methyl)-4-tert-butylphenolato) have been prepared on atomically planar Au(111) surfaces. Surface voltammetric and interfacial capacitance data, along with electrochemical scanning tunnelling microscopy (in situ STM) imaging, support the formation of a densely packed adlayer of 3 attached via a gold-thiolate bond. In solution, the disulfide linked precursor for 3 reversibly binds dioxygen with high affinity. Electrochemical measurements show that the redox potential of the O22-/O2*- couple of the monolayer of 3 is cathodically shifted by nearly 500 mV compared to the precursor in solution. This is attributed to the close proximity of the O2 binding site to the gold surface. Since the redox potential of the O22-/O2*- couple reflects tentatively the binding affinity of O2 to the deoxygenated CoII2 binding site, the potential of the O22-/O2*- couple of the SAM of 3 suggests a much higher affinity towards O2 compared to the solution precursor. 相似文献
87.
88.
Mads Sondrup Møller Dr. Victor Petrunin Prof. Susanne Mossin Prof. Vickie McKee Prof. Christine J. McKenzie 《欧洲无机化学杂志》2023,26(27):e202300235
Reactions of chemisorbed reagents inside the crystalline molecular solid state are rare but offer unexploited methods for selective solvent-free chemical synthesis. Here we show that the greenhouse gas precursor, nitric oxide (NO) is chemisorbed by crystals of the hexafluorophosphate salts of complexes containing dicobalt sites. On NO sorption a cascade of reactions results in the in-crystal synthesis of nitrite and other gaseous NOx. Recrystallization enabled structural elucidation of the mixed valent {[(bpbp)Co2(μ-(η1-O : η1-N)-ONO)]2(bdc)}4+ (bpbp=2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato, bdc=1,4-benzenedicarboxylato) cation. Overlapping signals in the solid-state EPR spectra confirm the CoIICoIII oxidation state and the presence of NO2 trapped inside the unrecrystallised solid products (br. g=4, triplet g=2 (340 mT), A(N)=73 MHz), despite three cycles of vacuum and N2 flushing. Consistently, νN−O bands appear in the Raman and IR spectra that are due to the coordinated nitrate and the trapped NO2 that were synthesized in-crystal. The latter is expelled by heating the solid to 160 °C or by recrystallization. Dimetallic cooperativity is proposed for the NO transformations in these rare examples of selective, chemisorptive substrate reactions in the solid-state. 相似文献
89.
Optimal strong Mal’cev conditions for congruence meet-semidistributivity in locally finite varieties
Jelena Jovanović Petar Marković Ralph McKenzie Matthew Moore 《Algebra Universalis》2016,76(3):305-325
Locally finite, congruence meet-semidistributive varieties have been characterized by numerous Mal’cev conditions and, recently, by two strong Mal’cev conditions. We provide three new strong Mal’cev characterizations and a new Mal’cev characterization each of which improves the known ones in some way. 相似文献
90.
Abstract Since the circulation, in 1974, of the first draft of “The construction D + XD S [X], J. Algebra 53 (1978), 423–439” a number of variations of this construction have appeared. Some of these are: The generalized D + M construction, the A + (X)B[X] construction, with X a single variable or a set of variables, and the D + I construction (with I not necessarily prime). These constructions have proved their worth not only in providing numerous examples and counter examples in commutative ring theory, but also in providing statements that often turn out to be forerunners of results on general pullbacks. The aim of this paper will be to discuss these constructions and the remarkable uses they have been put to. I will concentrate more on the A + XB[X] construction, its basic properties and examples arising from it. 相似文献