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331.
332.
Using ultrashort laser pulses of regular (gaussian shaped) time and spectral distribution, theoretically predicted, multiphoton electron emission processes have been observed. On changing this regular form of the ultrashort light pulses, however, the character of the emission process also changes, the explanation of which follows only partly from the evolution of the mode-locking train. 相似文献
333.
DFT computations have been performed on nucleophilic substitutions of phenacyl bromides with pyridines to investigate the mechanism of the reaction. In contrast with earlier suppositions, tetrahedral intermediate is not formed by the addition of pyridine on the C?O group of phenacyl bromide, because the total energy of the reacting species increases continuously, when the distance between the N and C(?O) atoms of reactants is shorter than 2.7 Å. At a greater distance, however, a bridged complex of the reactants is observed, in which the N atom of pyridine is slightly closer to the C atom of the C?O, than to the C atom of the CH2Br group of phenacyl bromide, the distances are 2.87 and 3.05 Å, respectively. The attractive forces between the oppositely polarized N and C(?O) atoms in the complex decrease the free energy of activation of the SN2 attack of pyridine at the CH2Br group. The calculated structural parameters of the SN2 transition states (TS) indicate, that earlier TSs are formed when the pyridine nucleophile bears electron‐donating (e‐d) groups, while electron‐withdrawing (e‐w) groups on phenacyl bromide substrate increase the tightness of the TS. Free energies of activation computed for the SN2 substitution agree well with the data calculated from the results of kinetic experiments and correlate with the σPy substituent constants, derived for pyridines, and with the Hammett σ constants, when the substituents (4‐MeO‐4‐NO2) are varied on the pyridine or on the phenacyl bromide reactants. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
334.
Attila Farkas Balzs Vajna Pter L. Sti Zsombor K. Nagy Hajnalka Pataki Filip Van der Gucht Gyrgy Marosi 《Journal of Raman spectroscopy : JRS》2015,46(6):566-576
Chemical imaging was used in this study as a powerful analytical tool to characterize pharmaceuticals in solid form. The majority of analyses are evaluated with bilinear modelling using only the pure component spectra or just the chemical images themselves to estimate the concentrations in each pixel, which are far from true quantitative determination. Our aim was to create more accurate concentration images using regression methods. For the first time in chemical imaging, variable selections with interval partial least squares (PLS) and with genetic algorithms (PLS‐GA) were applied to increase the efficiency of the models. These were compared to numerous bilinear modelling and multivariate linear regression methods such as univariate regression, classical least squares (CLS), multivariate curve resolution–alternating least squares (MCR‐ALS), principal component regression (PCR) and partial least squares (PLS). Two component spray‐dried pharmaceuticals were used as a model. The paper is shown that, in contrast to the usual way of using either external validation or cross‐validation, both should be performed simultaneously in order to get a clear picture of the prediction errors and to be able to select the appropriate models. Using PLS with variable selection, the root mean square errors were reduced to 3% per pixel by keeping only those peaks that are truly necessary for the estimation of concentrations. It is also shown that interval PLS can point out the best peak for univariate regression, and can thereby be of great help even when regulations allow only univariate models for product quality testing. Variable selection, besides yielding more accurate overall concentrations across a Raman map, also reduces the deviation among pixel concentrations within the images, thereby increasing the sensitivity of homogeneity studies. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
335.
József Z. Farkas 《Journal of Applied Mathematics and Computing》2011,35(1-2):617-633
We consider a class of physiologically structured population models, a first order nonlinear partial differential equation equipped with a nonlocal boundary condition, with a constant external inflow of individuals. We prove that the linearised system is governed by a quasicontraction semigroup. We also establish that linear stability of equilibrium solutions is governed by a generalised net reproduction function. In a special case of the model ingredients we discuss the nonlinear dynamics of the system when the spectral bound of the linearised operator equals zero, i.e. when linearisation does not decide stability. This allows us to demonstrate, through a concrete example, how immigration might be beneficial to the population. In particular, we show that from a nonlinearly unstable positive equilibrium a linearly stable and unstable pair of equilibria bifurcates. In fact, the linearised system exhibits bistability, for a certain range of values of the external inflow, induced potentially by Allée-effect. 相似文献
336.
Papp N Bencsik T Németh K Gyergyák K Sulc A Farkas A 《Natural product communications》2011,6(10):1475-1478
Plants living in different ecological habitats can show significant variability in their histological and phytochemical characters. The main histological features of various populations of three medicinal plants from the Boraginaceae family were studied. Stems, petioles and leaves were investigated by light microscopy in vertical and transverse sections. The outline of the epidermal cells, as well as the shape and cell number of trichomes was studied in leaf surface casts. Differences were measured among the populations of Echium vulgare in the width and height of epidermis cells in the stem, petiole and leaf, as well as in the size of palisade cells in the leaves. Among the populations of Pulmonaria officinalis significant differences were found in the length of trichomes and in the slightly or strongly wavy outline of epidermal radial cell walls. Populations of Symphytum officinale showed variance in the height of epidermal cells in leaves and stems, length of palisade cells and number of intercellular spaces in leaves, and the size of the central cavity in the stem. Boraginaceae bristles were found to be longer in plants in windy/shady habitats as opposed to sunny habitats, both in the leaves and stems ofP. officinalis and S. officinale, which might be connected to varying levels of exposure to wind. Longer epidermal cells were detected in the leaves and stems of both E. vulgare and S. officinale plants living in shady habitats, compared with shorter cells in sunny habitats. Leaf mesophyll cells were shorter in shady habitats as opposed to longer cells in sunny habitats, both in E. vulgare and S. officinale. This combination of histological characters may contribute to the plant's adaptation to various amounts of sunshine. The reported data prove the polymorphism of the studied taxa, as well as their ability to adapt to various ecological circumstances. 相似文献
337.
János Farkas Sándor Békássy Béla Ágai Marianna Hegedüs François Figueras 《合成通讯》2013,43(14):2479-2485
Using a series of clay based catalysts (KSF, KSF/0, KP10, K10, K0, KS), resorcinol is acylated in 1,2-dichloroethane by phenylacetyl chloride with a heterogeneous catalytic procedure. The yield of 1-(2,4-dihydroxyphenyl)-2-phenyl-ethanone is in correlation with the specific surface area of the catalyst. 相似文献
338.
Nitrogen-doped TiO2 thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O2/N2 gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N2 content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO2-xNx layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values. 相似文献
339.