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71.
A novel 4-[4-(pentafluoro-λ⁶-sulfanyl)phenyl]-1,2,4-triazole-3,5-dione (5a) was synthesised as a potential [18F]radio-prosthetic group for radiolabelling peptides and proteins via selective bioconjugation with the phenolic side chains of tyrosine residues. Preliminary conjugation tests revealed the rapid hydrolysis of 5a under semi-aqueous conditions; these results led to further investigation into the electronic substituent effects of PTAD derivatives and corresponding hydrolytic stabilities. Five derivatives of 5a with para substituents of varying electron donating and withdrawing effects were synthesised for the investigation. The bioconjugation of these derivatives with model tyrosine was monitored in both aqueous and organic media in the presence of a variety of catalysts. From these investigations, we have found HFIP to be an effective catalyst when used in tandem with DCM as a solvent to give PTAD-tyrosine conjugate products (6a–f) in satisfactory to good yields (54–79%), whereas analogous reactions performed in acetonitrile were unsuccessful. The discovery of this system has allowed for the successful conjugation of electron-deficient PTAD derivatives to tyrosine, which would otherwise be unachievable under aqueous reaction conditions. The inclusion of these electron-deficient, fluorinated PTAD derivatives for use in the PTAD-tyrosine conjugation will hopefully broaden their applicability within fields such as 19F-MRI and PET imaging. 相似文献
72.
D. Hugh Powell Andr E. Merbach Gabriel Gonzlez Ern Brücher Kroly Micskei M. Francesca Ottaviani Klaus Khler Alex Von Zelewsky Oleg Ya. Grinberg Yakob S. Lebedev 《Helvetica chimica acta》1993,76(5):2129-2146
EPR Spectra have been measured for aqueous solutions of a series of Gd3+ complexes at variable temperature and a range of magnetic fields; S-band (0.14 T), X-band (0.34 T), Q-band (1.2 T), and 2-mm-band (5.0 T). The major contribution to the observed line widths is magnetic-field-dependent and is interpreted as being due to the modulation of the zero-field splitting produced by distortion of the complexes from perfect symmetry. The transverse and longitudinal relaxation matrices for an 8S ion with such an interaction have been calculated using Redfield theory with vector-coupling methods, and diagonalised numerically to obtain relaxation rates and intensities for the degenerate transitions which contribute to the multiplet. The observed line width, which is inversely proportional to the magnetic field at low temperatures, is best described by the intensity-weighted mean transverse relaxation time for the four transitions with non-zero intensity. A least-squares fit of the data yields the square of the zero-field splitting tensor, Δ2, and a correlation time, τv, with activation energy, Ev. The physical significance of these parameters and the extent of validity of the theoretical approach are considered. The parameters are used to predict the magnetic-field dependence of the longitudinal and transverse electronic relaxation times, which are discussed in the context of their relevance to 1H-NMR relaxivity. 相似文献
73.
Denise Baudry Michel Ephritikhine Hugh Felkin Yves Dromzee Yves Jeannin 《Journal of organometallic chemistry》1984,272(3):403-409
Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph3P)2(η-C6H8)ReH3 (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph3P)2(η-1,3-diene)ReH3 are discussed. 相似文献
74.
Burrows HD Fernandes M Seixas de Melo J Monkman AP Navaratnam S 《Journal of the American Chemical Society》2003,125(50):15310-15311
The lowest triplet state of tris(8-hydroxyquinoline)aluminium(III) (Alq3) has been prepared by pulse radiolysis/energy transfer from appropriate donors in benzene solutions and has an absorption maximum around 510 nm with a lifetime of about 50 mus. It is quenched by molecular oxygen, leading to singlet oxygen formation. From flash photolysis and singlet oxygen formation measurements, a quantum yield of triplet formation of 0.24 was determined for direct photolysis of the complex. A value of 2.10 +/- 0.10 eV was determined for the energy of the lowest triplet state by energy transfer studies and was confirmed by phosphorescence measurements on Alq3, either in the heavy atom solvent ethyl iodide or photosensitized by benzophenone in benzene. Dexter (exchange) energy transfer was observed from triplet Alq3 to platinum(II) octaethylporphyrin. 相似文献
75.
The Necessary Maximality Principle for c. c. c. forcing with real parameters is equiconsistent with the existence of a weakly compact cardinal. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
76.
Hugh J. Barclay 《Natural Resource Modeling》1987,2(2):299-323
Four sets of models are examined which represent various pairwise combinations of several methods of pest control. These methods involve the release of sterile male pests, the inundative release of parasitoids, insecticide application, pheromone trapping and food-baited trapping with either insecticides or sterilants. It was observed that two pest control methods will combine synergistically, and thus be complimentary, if their optimal action is at different pest densities and varies differently with pest density. The synergism thus generated by differing dependence on density, can however, be obscured if the two control methods interfere with each other in some other way, as occurs for example with the use of both insecticides and inundative release of parasitoids. 相似文献
77.
Hugh Rieley Daniel J. Colby Darren P. McMurray Stuart M. Reeman 《Surface science》1997,390(1-3):243-249
The effects of physisorption and two-dimensional ordering on the photochemistry of N2O4 were investigated. Ordered monolayers were prepared by adsorption of NO2 at 100 K on a water-ice surface. Irradiation with a continuous light source in the wavelength region 300–400 nm or with pulsed laser radiation at 355 nm resulted in exclusive desorption of NO2. This desorption was induced by electronic absorption directly in the adsorbate via a transition corresponding to the (
)1B2u←(
)1Ag transition in N2O4, as in the gas phase. However, the subsequent dynamics in the excited state were markedly different from the gas-phase counterpart. Time-of-flight mass spectrometry of NO2 photodesorbed at 355 nm revealed a most probable fragment translational energy of ca. 17 meV; and the angular distribution of the nascent NO2 was peaked sharply in a direction around 10° from the normal. It is apparent that, despite the weak interaction with the substrate, significant energy transfer occurs in the ordered physisorbed monolayer to yield nascent NO2 with very low translational energy and a constrained angle of escape which is consistent with a high degree of adsorbate order and alignment. 相似文献
78.
Conclusion Might there be a chance of proving in a simple way thatx/π(x) is asymptotic to an increasing function, thus getting another proof of PNT? This is probably wishful thinking. However,
there is a natural candidate for the increasing function. LetL(x) be the upper convex hull of the full graph ofxπ(x) (precise definition to follow). The piecewise linear functionL(x) is increasing becausex/π(x) → ∞ asx → ∞. Moreover, using PNT, we can give a proof thatL(x) is indeed asymptotic tox/π(x). But the point of our work in this article is that for someone who wishes to understand why the growth of primes is governed
by natural logarithms, a reasonable approach is to convince oneself via computation that the convex hull just mentioned satisfies
the hypothesis of our theorem, and then use the relatively simple proof to show that this hypothesis rigorously implies the
prime number theorem. 相似文献
79.
Hugh Felkin Peter W. Lednor Jean-Michael Normant Robin A.J. Smith 《Journal of organometallic chemistry》1978,157(4):C64-C66
Fe(cot)2 (cot = cyclooctatetraene) reacts with certain phosphines and phosphites to give Fe(cot)L3 compounds in good yield. Reaction of Fe(cot)2 with Ph2PCH2CH2PPh2 under N2 gives a complex containing coordinated dinitrogen, which is converted into Fe(cot)(Ph2PCH2CH2PPh2)(CO) on reaction with CO or formate esters. 相似文献
80.