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21.
D. Maric J.P. Burrows R. Meller G.K. Moortgat 《Journal of photochemistry and photobiology. A, Chemistry》1993,70(3):205-214
The UV—visible absorption spectrum of molecular chlorine at 298 K was investigated in the wavelength range 200–550 nm with a spectral resolution of 0.2 nm. Except for minor discrepancies, the absorption cross-sections are in agreement with those found in the literature. In the region 250λ-550 nm, the Cl2 spectrum can be adequately described by a semi-empirical function of the wavelength A (in vacuum) and temperature T where TANH=tanh(hcx559.751 cm−1/2kT). The absorption of solar radiation by the weak continuum around λmax=406.5 nm contributes 9% or more of the photodissociation of molecular chlorine in the atmosphere, but the banded Cl2 features (λ 479 nm) are of negligible atmospheric significance. 相似文献
22.
23.
M. J. Tiera V. A. De Oliveira H. D. Burrows M. Graça Miguel M. G. Neumann 《Colloid and polymer science》1998,276(3):206-212
The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate– methacrylic acid copolymers
with different fractions of acid groups (x) has been studied in aqueous solution at various pH values using the fluorescence of covalently bonded 9-vinyl anthracene
as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing
fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations. With Tl(I),
quenching of the anthracene group fluorescence is observed, indicating that the thallium(I) approaches the probe and suggesting
that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene
quenching data and from studies with the fluo-rescent-probe sodium pyrenetetra-sulfonate. Good agreement is obtained between
the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye–Hückel effects
and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases
in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably
as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined
from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide
as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)–carboxylate interactions contribute to the
binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it
is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in
the polymer. It is proposed that the terbium(III) interacts with six carboxylic groups on the polymer chain, with three being
coordinated and three attracted by electrostatic interactions.
Received: 10 June 1997 Accepted: 24 October 1997 相似文献
24.
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
25.
A. M. Amorim Da Costa H. D. Burrows C. F. G. C. Geraldes J. J. C. Teixeira-dias C. G. Bazuin D. Guillon 《Liquid crystals》2013,40(3):215-226
Abstract Structures of the thermotropic mesophases of lead(II) decanoate are reassigned following optical and X-ray diffraction studies. These results, and those of D.S.C., Raman and 207Pb N.M.R. spectroscopy, indicate formation of a lower temperature mesophase involving mainly increased lateral disorder, and a higher temperature Lα (smectic A) phase resulting from chain disordering and decreased lead-carboxylate interaction. Comparison of experimental thermodynamic data for the phase transitions with theoretical data in the literature indicates that the entropy change for the lower to higher mesophase transition is dominated by the increase in chain disorder. 相似文献
26.
27.
Carlos?M.?Matias Jo?o?M.?Sousa M.?Emília?Quinta-Ferreira Mona?Arif Hugh?D.?Burrows 《Journal of fluorescence》2010,20(1):377-380
Fura-2 is widely used as a fluorescent probe to monitor dynamic changes in cytosolic free calcium in cells, where Ca2+ can enter through several types of voltage-operated or ligand-gated channels. However, Fura-2 is also sensitive to other
metal ions, such as zinc, which may be involved in ionic channels and receptors. There is interest, in particular, in studying
the synapses between mossy fibers and CA3 pyramidal cells which contain both calcium and high quantities of free or loosely
bound zinc. We have found, through fluorescence probing, that endogenous zinc inhibits mossy fiber calcium transients. However,
since these results might be explained by an effect of the zinc chelator N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine
(TPEN) on the spectral properties of Fura-2, we have carried out a validation of the method through fluorescence excitation
spectra of the complex Fura-2/calcium, and show that TPEN does not affect these spectra. This supports the idea that the observed
calcium enhancement is related to a zinc inhibition of presynaptic calcium mechanisms, and confirms the use of the chelator
TPEN as a general procedure for the biophysical study of Ca(II) in the presence of Zn(II) using Fura-2. 相似文献
28.
The UV absorption spectrum of acetylperoxy radicals, produced in several photochemical systems, has been investigated using the molecular modulation technique. Rate coefficients were determined at 28 and 715 Torr for the reaction CH3COO2 + NO2(+M) → CH3COO2NO2(+M), which exhibits a pressure dependence. 相似文献
29.
Diode laser spectroscopy has been employed to monitor the formation of chlorine nitrate (ClONO2) in the association reaction of ClO with NO2. Chlorine nitrate is the only stable end-product of this reaction at room temperature. Time-resolved measurements of ClONO2 formation using molecular modulation showed no evidence for any involvement of unstable isomers of ClNO3 in the reaction. These measurements gave a value of k1 = (1.8 ± 0.4) × 10?31 cm6/molecule2 · s for the reaction at 295 K and an upper limit of 5 ms for the lifetime of any isomeric products at this temperature. 相似文献
30.
Oxidation of single- or double-stranded DNA containing a 7,8-dihydro-8-oxoguanosine lesion with the one-electron oxidant Na2IrCl6 in the presence of spermine led to formation of a covalent adduct that was analyzed by gel electrophoresis, HPLC, ESI-MS, and UV-vis. The adduct was labile to heat, exhibiting a t1/2 of 12 h at 37 degrees C, and the ultimate hydrolysis product was characterized as a deoxyribosylurea lesion. Data from model studies with 1,3-diaminopropane vs 1,4-diaminobutane are consistent with initial formation of a C5 spermine adduct from a dehydro-8-oxoguanosine intermediate, followed by rearrangement to a spiroaminal subject to slow hydrolysis at C4 of the purine. Spermine adducts could also be formed from oxidation of the analogous G-containing oligomer from reaction with singlet oxygen, albeit in lower yield. These results are surprising in light of the traditional view that spermine is radioprotective against DNA oxidation. 相似文献