We report Ab Initio studies of the electric dipole polarizability of the linear polyacene series benzene through nonacene. A number of Ab Initio studies were done at different levels of theory for benzene, with all remaining Ab Initio calculations being at the B3LYP/6-311G(2d, 1p)//B3LYP/6-311+G(2d, 1p) level of theory. We find that the NN tensor component
shows a constant increment of 20 atomic units per ring. AM1 and QSAR-quality empirical calculations show poor absolute agreement
with the Ab Initio results but given excellent statistical correlation coefficients with the Ab Initio values. This implies that the results of such cheaper calculations can be suitably scaled for predictive purposes. 相似文献
[Ti[N(Ph)SiMe2]3-tacn]X complexes (X = Cl, 1; I, 2; PF6, 3; BPh4, 4) were studied by NMR and electron absorption and emission methods, which showed that these compounds exist in bromobenzene and dichloromethane solutions as ion pairs. The significant modifications observed in the proton resonances of tacn in C6D5Br, which follow the sequence BPh(4-) > or = PF(6-) > or = I- approximately Cl-, are a qualitative indication of the strength of the interactions that depend on the anion. The reaction of 2 with LiNMe2 led to [Ti(NPh)[NPh(SiMe2)]2-tacn], 5, that forms upon attack of Me2N- at one SiMe2 group. The formation of 5 is discussed on the basis of the interactions identified in solution. 相似文献
In this work, the synthesis of magnetite nanoparticles by two variant chemical coprecipitation methods that involve reflux
and aging conditions was investigated. The influence of the synthesis conditions on particle size, morphology, magnetic properties
and protein adsorption were studied. The synthesized magnetite nanoparticles showed a spherical shape with an average particle
size directly influenced by the synthesis technique. Particles of average size 27 nm and 200 nm were obtained. When the coprecipitation
method was used without reflux and aging, the smallest particles were obtained. Magnetite nanoparticles obtained from both
methods exhibited a superparamagnetic behavior and their saturation magnetization was particle size dependent. Values of 67
and 78 emu g−1 were obtained for the 27 nm and 200 nm magnetite particles, respectively. The nanoparticles were coated with silica, aminosilane,
and silica-aminosilane shell. The influence of the coating on protein absorption was studied using Bovine Serum Albumin (BSA)
protein.
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The reaction of titanium trisamidotriazacyclononane, [Ti{N(Ph)SiMe2}3tacn] (1), with C60 led to the synthesis of [Ti{N(Ph)SiMe2}3tacn]C60 (2) in high yield. Treatment of 2 with PhCH2Br led to the formation of [Ti{N(Ph)SiMe2}3tacn]Br and the radical PhCH2C60 (3). The reaction of CH3I with 1 gives two products. One is [Ti{N(Ph)SiMe2}3tacn]I (4), which results from the oxidation of 1 by an I radical. The other product, 5, resulting from a multistep reaction scheme that involves redox and nucleophilic reactions, presents an imido ligand formed by ligand rearrangement upon C-N bond cleavage. In solution, an exchange process that corresponds to a reversible 1,3-silyl shift between two Ti-bonded N atoms leads to isomers 5a and 5b. This equilibrium transforms an imido (TiNPh) into an amido ligand (Ti{NPh}SiMe2CH2Ph) with concomitant generation of an anionic moiety in the originally neutral triazacyclononane ring. In solution, either 5a or 5b displays additional fluxional processes that consist of its corresponding racemization processes. 相似文献
A simple and rapid development of a stability-indicating LC method for determination of chloroquine diphosphate in the presence of its hydrolysis, oxidative and photolysis degradation products is described. Stress testing showed that chloroquine diphosphate was degraded under basic conditions and by photolytic treatment but was stable under the other stress conditions investigated. Separation of the drug from its degradation products was achieved with a Nova Pack C18 column, 0.01 M PIC B7 and acetonitrile (40:60 v/v) pH 3.6, as mobile phase. Response was linear over the range 0.08–5.70 μg mL−1 (r = 0.996), with limits of detection and quantification (LOD and LOQ) of 0.17 and 0.35 μg mL−1, respectively.
Biginelli reactions have been monitored by direct infusion electrospray ionization mass spectrometry (ESI‐MS) and key cationic intermediates involved in this three‐component reaction have been intercepted and further characterized by tandem MS experiments (ESI‐MS/MS). Density functional theory calculations were also used to investigate the feasibility of the major competing mechanisms proposed for the Biginelli reaction. The experimental and theoretical results were found to corroborate the iminium mechanism proposed by Folkers and Johnson, whereas no intermediates directly associated with either the more energy demanding Knoevenagel or enamine mechanisms could be intercepted. 相似文献
We have used the transfer matrix technique to study the electronic structure of trans-polyacetylene, within a model Hamiltonian which includes second-neighbors interactions. The results show that the valence and conduction band widths and the energy of the localized state are dependent on the strength of the second neighbors couplings. However, for the physically reasonable range of parameters, the electronic structure of the material is only slightly modified, indicating that a simple Hückel treatment is quite accurate for this system.Work partially supported by the Brazilian Agencies FINEP and CNPq 相似文献
Up to now it has not been possible to neatly assess whether a deficient performance of a model is due to poor parametrization of the force field or the lack of inclusion of enough molecular properties. This work compares several molecular models in the framework of the same force field, which was designed to include many-body nonadditive effects: (a) a polarizable and flexible molecule with constraints that account for the quantal nature of the vibration [B. Hess, H. Saint-Martin, and H. J. C. Berendsen, J. Chem. Phys. 116, 9602 (2002), H. Saint-Martin, B. Hess, and H. J. C. Berendsen, J. Chem. Phys. 120, 11133 (2004)], (b) a polarizable and classically flexible molecule [H. Saint-Martin, J. Hernandez-Cobos, M. I. Bernal-Uruchurtu, I. Ortega-Blake, and H. J. C. Berendsen, J. Chem. Phys. 113, 10899 (2000)], (c) a polarizable and rigid molecule, and finally (d) a nonpolarizable and rigid molecule. The goal is to determine how significant the different molecular properties are. The results indicate that all factors--nonadditivity, polarizability, and intramolecular flexibility--are important. Still, approximations can be made in order to diminish the computational cost of the simulations with a small decrease in the accuracy of the predictions, provided that those approximations are counterbalanced by the proper inclusion of an effective molecular property, that is, an average molecular geometry or an average dipole. Hence instead of building an effective force field by parametrizing it in order to reproduce the properties of a specific phase, a building approach is proposed that is based on adequately restricting the molecular flexibility and/or polarizability of a model potential fitted to unimolecular properties, pair interactions, and many-body nonadditive contributions. In this manner, the same parental model can be used to simulate the same substance under a wide range of thermodynamic conditions. An additional advantage of this approach is that, as the force field improves by the quality of the molecular calculations, all levels of modeling can be improved. 相似文献
The goal of this study was to determine if there are acoustical differences between male and female voices, and if there are, where exactly do these differences lie. Extended speech samples were used. The recorded readings of a text by 31 women and by 24 men were analyzed by means of the Long-term Spectrum (LTAS), extracting the amplitude values (in decibels) at intervals of 160 Hz over a range of 8 kHz. The results showed a significant difference between genders, as well as an interaction of gender and frequency level. The female voice showed greater levels of aspiration noise, located in the spectral regions corresponding to the third formant, which causes the female voice to have a more “breathy” quality than the male voice. The lower spectral tilt in the women's voices is another consequence of this presence of greater aspiration noise. 相似文献