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11.
Magali A. Rodrigues Sérgio Brochsztain Teresa C. Barros Mauricio S. Baptista Mario J. Politi 《Photochemistry and photobiology》1999,70(1):35-39
Abstract— The effect of the protonation state of a novel aqueous soluble N,N'-di(2-phosphonoethyl)-l,4,5,8-naphthalene-diimide (DPN) on its spectroscopic properties is studied. In aqueous solution DPN depicts linear Lambert-Beer plots up to the solubility limits at pH 1.0, 7.1 and 10.1, in accordance with its solubilization as a monomer. A small increase in the extinction coefficients with pH is observed. Conversely a strong decrease in the fluorescence emission yields are observed with the increase in pH. These results are shown to originate from the distinct efficiencies of the intersystem crossing of DPN as a function of the net charge on the phosphono moieties. Accordingly, from the decrease in fluorescence emission, titration curves were obtained resulting in two pKa of –1.5 and 6.7 in agreement with the potentiometric analysis. In parallel monitoring the amount of heat deposited in the system shows an inverse pattern, that is, increase in the thermal tensing time-resolved signal with pH. Laser flash photolysis and thermal Iensing data in the absence and presence of oxygen show the interplay of an intersystem crossing process with the protonation state of the dye. The changes in protonation from neutral to two- and four-fold charged species are accompanied by an enhancing effect on the naphthalenediimide ring toward spin inversion (triplet formation) and consequently in different fluorescence yields 相似文献
12.
Hacer Guzlek Ines I.R. Baptista Philip L. Wood Andrew Livingston 《Journal of chromatography. A》2010,1217(40):6230-6240
Literature lists a number of counter-current chromatography (CCC) models that can predict the retention time and to a certain extent the peak width of a solute eluting from a CCC column. The approach described in this paper distinguishes itself from previous reports by relating all model parameters directly to column dimensions and experimental settings. Most importantly, this model can predict a chromatogram from scratch without resorting to traditional calibration using empirical values. The model validation with experimental results obtained across a range of CCC instruments demonstrated that the solute retention time, peak width, and peak resolution could be predicted within reasonable accuracy. Additionally, the effect of several process parameters, such as mobile phase flow rate, rotational speed of the column or β-value, showed that the model is robust and applicable to a wide range of CCC instruments. Overall, this model proved to be a useful tool for parameter estimation and, most significantly, separation optimisation. 相似文献
13.
Leonardo T Baptista L da Silva EC Arbilla G 《The journal of physical chemistry. A》2011,115(26):7709-7721
A density functional theory (DFT) study of the mechanisms of carbonyl oxide reactions from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis is presented. The geometries, energies, and harmonic vibrational frequencies of each stationary point were determined by B3LYP/6-31(d,p) and BH&HLYP/cc-pVDZ methods. According to the calculations, the ozonolysis reactions are initiated by the formation of van der Waals (VDW) complexes to yield primary ozonides, which rapidly open to carbonyl oxide compounds. These carbonyl oxide compounds react to form dioxanes and hydroperoxides. The hydroperoxides react by isomerization to form stable products. Glyoxal and methyl-glyoxal have been identified as the final product from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis. Our results are in good agreement with the experimental studies. 相似文献
14.
We study iteration of polynomials on symmetric stochastic matrices. In particular, we focus on a certain one-parameter family
of quadratic maps which exhibits chaotic behavior for a wide range of the parameters. The well-known dynamical behavior of
the quadratic family on the interval, and its dependence on the parameter, is reproduced on the spectrum of the stochastic
matrices. For certain subclasses of stochastic matrices the referred dynamical behavior is also obtained in the matrix entries.
Since a stochastic matrix characterizes a Markov chain, we obtain a discrete dynamical system on the space of reversible Markov
chains. Therefore, depending on the parameter, there are initial conditions for which the corresponding reversible Markov
chains will lead under iteration to a fixed point, to a periodic point, or to an aperiodic point. Moreover, there are sensitivity
to initial conditions and the coexistence of infinite repulsive periodic orbits, both features of chaos. 相似文献
15.
Anselmo Rodrigues Iberê L. Caldas Murilo S. Baptista Jos Roberto C. Piqueira 《Chaos, solitons, and fractals》2004,21(5):1271-1280
In this work we propose the use of a targeting method applied to chaotic systems in order to reach special trajectories that encode arbitrary sources of messages. One advantage of this procedure is to overcome dynamical constraints which impose limits in the amount of information that the chaotic trajectories can encode. Another advantage is the message decoding, practically instantaneous and independent of any special technique or algorithm. Furthermore, with this procedure, information can be transmitted with no errors due to bounded noise. 相似文献
16.
A. M. G. Pacheco M. C. Freitas M. S. Baptista M. T. S. D. Vasconcelos J. P. Cabral 《Journal of Radioanalytical and Nuclear Chemistry》2008,276(1):135-141
This study deals with the influence of the exposure conditions on biological uptake, by looking into concentrations of Ni
and V in lichen thalli and tree bark after continuous and discontinuous field trials at littoral sites impacted by anthropogenic
emissions. Biomonitors were assessed by k
0-INAA and AAS. Correlations at Sines are more apparent than at Viana or Lisboa. When data from all sites are pooled, V shows
correlations for practically every situation while Ni shows none, which may indicate a dissimilar uptake mechanism for each
element. At Sines, V/Ni ratios reach values that comply with emissions from oil-related industries. 相似文献
17.
G. B. Baptista E. C. Montenegro C. V. Barros Leite A. S. Paschoa 《Journal of Radioanalytical and Nuclear Chemistry》1980,60(1):227-235
The accuracy of the quantitative analysis of thick targets by XRF is impaired by effects due to the absorption of X-rays in
the matrix associated with the non-uniformity of the X-ray beam and the lack of knowledge of the actual distribution of trace
elements in the target. The uncertainty in the elemental mass associated to a definite number X-rays detected is discussed
in the paper. A correction factor is derived to account specifically for the effect of the absorption of X-rays and the non-uniformity
of the X-ray beam.
Work partially supported by Conselho Nacional de Desenvolvimento Científico e Tecnológico, Financiadora de Estudos e Projetos
and International Atomic Energy Agency. 相似文献
18.
Lopes SC Soares CM Baptista AM Goormaghtigh E Cabral BJ Castanho MA 《The journal of physical chemistry. B》2006,110(7):3385-3394
The analgesic dipeptide kyotorphin (L-Tyr-L-Arg) and an acylated kyotorphin derivative were studied by a combination of theoretical (molecular dynamics simulation and quantum mechanics methods) and experimental (fluorescence and infrared spectroscopies) approaches both in solution and in model systems of membranes. At biological pH the peptides have a neutral net charge. Nevertheless, their phenolic rings interact with phospholipid molecules (partition coefficient varies from 6 x 10(2) to 2 x 10(4), depending on the lipid and pH used) despite being exposed to the aqueous bulk medium. The lowest energy transition dipole moment is displaced from the normal to the lipid bilayer by 20 degrees on average. The observed extensive interaction, pK(a), precise location, and well-defined orientation in membranes combined with the ability to discriminate rigid raftlike membrane domains suggest that kyotorphin meets the structural constraints needed for receptor-ligand interaction. The acylated kyotorphin derivative mimics kyotorphin properties and represents a promising way for entrapment in a drug carrier and transport across the blood-brain barrier. 相似文献
19.
R.M. Szmoski F.A.S. Ferrari S.E. de S. Pinto M.S. Baptista R.L. Viana 《Physics letters. A》2013,377(10-11):760-765
There is a broad area of research to ensure that information is transmitted securely. Within this scope, chaos-based cryptography takes a prominent role due to its nonlinear properties. Using these properties, we propose a secure mechanism for transmitting data that relies on chaotic networks. We use a nonlinear on–off device to cipher the message, and the transfer entropy to retrieve it. We analyze the system capability for sending messages, and we obtain expressions for the operating time. We demonstrate the system efficiency for a wide range of parameters. We find similarities between our method and the reservoir computing. 相似文献
20.
C. Jesus P. Caldas O. Frazão J. L. Santos P. A. S. Jorge J. M. Baptista 《Fiber and Integrated Optics》2013,32(6):440-449
Abstract A fiber optic sensing system for simultaneous measurement of refractive index and temperature, based on a hybrid fiber Bragg grating/long-period grating arrangement is described. The experimental results show that this setup has a good performance in terms of linearity and sensitivity, the ratiometric output changes 4%/0.001 RIU and 3.6%/°C, respectively. The sensor resolution for the refractive index is ≈2 × 10?5 RIU. The simultaneous measurement of the refractive index and temperature was demonstrated. The sensing configuration has the ability to be read-out in reflection and works in the telecommunications window. 相似文献