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111.
Three test series of single-edge-notched beams in three-point bending are conducted to evaluate the fracture energy of concrete.
The fracture energy is determined from the area under the complete load: load-point deflection diagram. The nonlinear fictitious
crack model is implemented in a finite-element analysis showing good agreement with the experimental data.
By varying the notch depth and the beam depth it is shown that the fracture energy, traditionally presented as a material
property, depends upon the specimen size and configuration. This is atributed to the energy dissipation in the process zone
which is not accounted for in the analytical model. 相似文献
112.
Warren C. Young 《Experimental Mechanics》1969,9(6):275-280
The use of two monochromatic light sources to obtain two isochromatic patterns permits a fully automated shear-difference analysis of the stress distribution in a three-dimensional photoelastic model. A development is given of the logic necessary to process the data taken from an automated polariscope as well as the design details of the polariscope. 相似文献
113.
Micah T. Nelp Vahe Bandarian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(36):10773-10775
The biosynthesis of nitriles is known to occur through specialized pathways involving multiple enzymes; however, in bacterial and archeal biosynthesis of 7‐deazapurines, a single enzyme, ToyM, catalyzes the conversion of the carboxylic acid containing 7‐carboxy‐7‐deazaguanine (CDG) into its corresponding nitrile, 7‐cyano‐7‐deazaguanine (preQ0). The mechanism of this unusual direct transformation was shown to proceed via the adenylation of CDG, which activates it to form the newly discovered amide intermediate 7‐amido‐7‐deazaguanine (ADG). This is subsequently dehydrated to form the nitrile in a process that consumes a second equivalent of ATP. The authentic amide intermediate is shown to be chemically and kinetically competent. The ability of ToyM to activate two different substrates, an acid and an amide, accounts for this unprecedented one‐enzyme catalysis of nitrile synthesis, and the differential rates of these two half reactions suggest that this catalytic ability is derived from an amide synthetase that gained a new function. 相似文献
114.
Fuchs called a partially-ordered integral domain, say D, division closed if it has the property that whenever a > 0 and ab > 0, then b > 0. He showed that if D is a lattice-ordered division closed field, then D is totally ordered. In fact, it is known that for a lattice-ordered division ring, the following three conditions are equivalent: a) squares are positive, b) the order is total, and c) the ring is division closed. In the present article, our aim is to study \({\ell}\)-rings that possibly possess zerodivisors and focus on a natural generalization of the property of being division closed, what we call regular division closed. Our investigations lead us to the concept of a positive separating element in an \({\ell}\)-ring, which is related to the well-known concept of a positive d-element. 相似文献
115.
116.
Boehner CM Frye EC O'Connell KM Galloway WR Sore HF Dominguez PG Norton D Hulcoop DG Owen M Turner G Crawford C Horsley H Spring DR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(47):13230-13239
The prevalence of the biaryl structural motif in biologically interesting and synthetically important molecules has inspired considerable interest in the development of methods for aryl-aryl bond formation. Herein we describe a novel strategy for this process involving the fluoride-free, palladium-catalysed cross-coupling of readily accessible aryldisiloxanes and aryl bromides. Using a statistical-based optimisation process, preparatively useful reaction conditions were formulated to allow the cross-coupling of a wide range of different substrates. This methodology represents an attractive, cost-efficient, flexible and robust alternative to the traditional transition-metal-catalysed routes typically used to generate molecules containing the privileged biaryl scaffold. 相似文献
117.
Brayshaw SK Schiffers S Stevenson AJ Teat SJ Warren MR Bennett RD Sazanovich IV Buckley AR Weinstein JA Raithby PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4385-4395
We introduce a new highly efficient photochromic organometallic dithienylethene (DTE) complex, the first instance of a DTE core symmetrically modified by two Pt(II) chromophores [Pt(PEt(3))(2)(C≡C)(DTE)(C≡C)Pt(PEt(3))(2)Ph] (1), which undergoes ring-closure when activated by visible light in solvents of different polarity, in thin films and even in the solid state. Complex 1 has been synthesised and fully photophysically characterised by (resonance) Raman and transient absorption spectroscopy complemented by calculations. The ring-closing photoconversion in a single crystal of 1 has been followed by X-ray crystallography. This process occurs with the extremely high yield of 80%--considerably outperforming the other DTE derivatives. Remarkably, the photocyclisation of 1 occurs even under visible light (>400 nm), which is not absorbed by the non-metallated DTE core HC≡C(DTE)C≡CH (2) itself. This unusual behaviour and the high photocyclisation yields in solution are attributed to the presence of a heavy atom in 1 that enables a triplet-sensitised photocyclisation pathway, elucidated by transient absorption spectroscopy and DFT calculations. The results of resonance Raman investigation confirm the involvement of the alkynyl unit in the frontier orbitals of both closed and open forms of 1 in the photocyclisation process. The changes in the Raman spectra upon cyclisation have permitted the identification of Raman marker bands, which include the acetylide stretching vibration. Importantly, these bands occur in the spectral region unobstructed by other vibrations and can be used for non-destructive monitoring of photocyclisation/photoreversion processes and for optical readout in this type of efficiently photochromic thermally stable systems. This study indicates a strategy for generating efficient solid-state photoswitches in which modification of the Pt(II) units has the potential to tune absorption properties and hence operational wavelength across the visible range. 相似文献
118.
Cooper BF Hamaed H Friedl WW Stinchcombe MR Schurko RW Macdonald CL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(22):6148-6161
The use of the univalent indium reagent [In([18]crown-6)][OTf] as a donor is investigated by its reactions with acceptors including InX(3) (X=Cl, Br, I). The donor-acceptor complexes of the form [X([18]crown-6)In-InX(3)] obtained in this manner represent the first new isomeric form of indium(II) halides identified for at least five decades. The formation of such complexes appears to be particularly favorable and they are isolated as products in many reactions involving low-valent indium, a halide source, and [18]crown-6. A convenient solution-phase synthesis of In[ECl(4)] salts is reported. This facile and direct syntheses of In[ECl(4)] (E=Al, Ga, In) salts allows for the in situ preparation and isolation of crown-ether complexes of the form [In([18]crown-6)][ECl(4)], whose existence had been postulated but never confirmed. Solution-phase and solid-state NMR experiments reveal that these compounds can exist as either donor-acceptor complexes or ionic salts, depending on the phase of the system, the nature of the solvent employed, and the identity of the metalate anion involved. Similar investigations into the effect of a smaller crown ether allow for the isolations of salts containing the cation [In([15]crown-5)](+). Computational investigations into the nature of the crowned univalent indium donor fragments, and on the donor-acceptor complexes produced, demonstrate the influence of anionic substituents on the reactivity of lone pair of electrons of the In(I) center. Natural bond orbital (NBO) analysis of donor-acceptor models shows that the composition of the E-E bond MO should provide the ability to predict which models should form stable complexes. 相似文献
119.
Kenwright JL Galloway WR Blackwell DT Isidro-Llobet A Hodgkinson J Wortmann L Bowden SD Welch M Spring DR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(10):2981-2986
Herein, a new copper-catalysed strategy for the synthesis of rare nitrogen-linked seven-, eight- and nine-membered biaryl ring systems is described. It is proposed that the reaction proceeds through a highly activated intramolecularly co-ordinated copper catalyst. The process is technically simple, proceeds under relatively mild conditions, displays a broad substrate scope and forms biologically valuable products that are difficult to synthesise by other methods. We envisage that this methodology will prove useful in a wide synthetic context, with possible applications in both target-oriented and diversity-oriented synthesis. 相似文献
120.
A heme model system has been developed in which the heme-propionate is the only proton donating/accepting site, using protoporphyrin IX-monomethyl esters (PPIX(MME)) and N-methylimidazole (MeIm). Proton-coupled electron transfer (PCET) reactions of these model compounds have been examined in acetonitrile solvent. (PPIX(MME))Fe(III)(MeIm)(2)-propionate (Fe(III)~CO(2)) is readily reduced by the ascorbate derivative 5,6-isopropylidine ascorbate to give (PPIX(MME))Fe(II)(MeIm)(2)-propionic acid (Fe(II)~CO(2)H). An excess of the hydroxylamine TEMPOH or of hydroquinone similarly reduces Fe(III)~CO(2), and TEMPO and benzoquinone oxidize Fe(II)~CO(2)H to return to Fe(III)~CO(2). The measured equilibrium constants, and the determined pK(a) and E(1/2) values, indicate that Fe(II)~CO(2)H has an effective bond dissociation free energy (BDFE) of 67.8 ± 0.6 kcal mol(-1). In these PPIX models, electron transfer occurs at the iron center and proton transfer occurs at the remote heme propionate. According to thermochemical and other arguments, the TEMPOH reaction occurs by concerted proton-electron transfer (CPET), and a similar pathway is indicated for the ascorbate derivative. Based on these results, heme propionates should be considered as potential key components of PCET/CPET active sites in heme proteins. 相似文献