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41.
Sansone G Benedetti E Caumes JP Stagira S Vozzi C Pascolini M Poletto L Villoresi P De Silvestri S Nisoli M 《Physical review letters》2005,94(19):193903
By using a self-referencing technique, we have experimentally measured the influence of the carrier-envelope phase of femtosecond light pulses on the phase of the electric field of the radiation produced by high-order harmonic generation. We show that, in particular experimental conditions, the temporal evolution of the electric field of the attosecond pulses, is directly controlled by the carrier-envelope phase of the driving pulses. 相似文献
42.
An integrated quantum mechanical approach for the structural and magnetic characterization of flexible free radicals in solution has been applied to a model of the glycyl radical engaged in peptidic chains. The hyperfine couplings computed using hybrid density functionals and purposely tailored basis sets are in good agreement with experiment when vibrational averaging effects from low frequency motions and solvent effects (both direct H bonding and bulk) are taken into the proper account. The g tensor shows a smaller dependence on the specific form of the density functional, the extension of the basis set over a standard double-zeta+polarization level, vibrational averaging, and bulk solvent effects. However, hydrogen bridges with solvent molecules belonging to the first solvation shell play a significant role. Together with their intrinsic interest, our results show that a comprehensive and reliable computational approach is becoming available for the complete characterization of open-shell systems of biological interest in their natural environment. 相似文献
43.
Seeber M De Benedetti PG Fanelli F 《Journal of chemical information and computer sciences》2003,43(5):1520-1531
Comparative molecular dynamics simulations of the 5-HT(1A) receptor in its empty as well as agonist- (i.e. active) and antagonist-bound (i.e. nonactive) forms have been carried out. The agonists 5-HT and (R)-8-OH-DPAT as well as the antagonist WAY100635 have been employed. The results of this study strengthen the hypothesis that the receptor portions close to the E/DRY/W motif, with prominence to the cytosolic extensions of helices 3 and 6, are particularly susceptible to undergo structural modification in response to agonist binding. Despite the differences in the structural/dynamics behavior of the two agonists when docked into the 5-HT(1A) receptor, they both exert a destabilization of the intrahelical and interhelical interactions found in the empty and antagonist-bound receptor forms between the arginine of the E/DRY sequence and both D133(3.49) and E340(6.30). For both agonists, the chemical information transfer from the extracellular to the cytosolic domains is mediated by a cluster of aromatic amino acids in helix 6, following the ligand interaction with selected amino acids in the extracellular half of the receptor, such as D116(3.32), S199(5.42), Y195(5.38), and F361(6.51). A significant reduction in the bend at P360(6.50), as compared to the empty and the antagonist-bound receptor forms, is one of the features of the agonist-bound forms that is related to the breakage of the interhelical salt bridge between the E/DRY arginine and E340(6.30). Another structural feature, shared by the agonist-bound receptor forms and not by the empty and antagonist-bound forms, is the detachment of helices 2 and 4, as marked by the movement of W161(4.50) away from helix 2, toward the membrane space. 相似文献
44.
Different types of fused-silica capillaries of 75 microm inside diameter (ID) were packed, namely type A and B, and evaluated for the direct resolution of racemates of several basic compounds by enantioselective capillary electrochromatography (e-CEC). Type A was packed with a chiral stationary phase (CSP) containing teicoplanin (TE) mixed with silica microparticles (3:1 w/w) while type B contained only the TE-CSP. In both cases, particles of different sizes (3.5 and 5 microm ID) were employed. A polar-organic mobile phase containing methanol-acetonitrile (60-40% v/v and 0.05% w/v ammonium acetate was used. Several beta-blockers (alprenolol, oxprenolol, metoprolol, pindolol, salbutamol, propranolol, atenolol, acebutolol) were baseline-enantioresolved with both capillary types, in very short times. 相似文献
45.
We deal with variational problems on varying manifolds in ℝn. We represent each manifold by a positive measure μ, to which we associate a suitable notion of tangent space Tμ, of mean
curvature H(μ), and of Sobolev spaces with respect to μ on an open subset Ω ⊆ ℝn. We introduce the notions of weak and strong convergence for functions defined on varying manifolds, that is defined μh -a.e., being {μh} a weakly convergent sequence of measures. In this setting, we prove a strong-weak type compactness theorem for the pairs
(Pμ
h H(μh)), where Pμ
h are the projectors onto the tangent spaces Tμ
h. When μh belong to a suitable class of k-dimensional measures, having in particular a prescribed (k−1)-manifold as a boundary, we
enforce this result to study the convergence of energy functionals, possibly with a Dirichlet condition on ∂Ω. We also address
a perspective for optimization problems where the control variable is represented by a manifold with a prescribed boundary. 相似文献
46.
Dr. Ilaria Gamba Iria Salvadó Gustavo Rama Miriam Bertazzon Mateo I. Sánchez Prof. Víctor M. Sánchez‐Pedregal Prof. José Martínez‐Costas Rosa F. Brissos Prof. Patrick Gamez Prof. José L. Mascareñas Prof. Miguel Vázquez López Prof. M. Eugenio Vázquez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13369-13375
A new bipyridine building block has been used for the solid‐phase synthesis of dinuclear DNA‐binding ruthenium(II) metallopeptides. Detailed spectroscopic studies suggest that these compounds bind to the DNA by insertion into the DNA minor groove. Moreover, the potential of the solid‐phase peptide synthesis approach is demonstrated by the straightforward synthesis of an octaarginine derivative that shows effective cellular internalization and cytotoxicity linked with strong DNA interaction, as evidenced by steady‐state fluorescence spectroscopy and AFM studies. 相似文献
47.
Valerio Annovazzi-Lodi Giuseppe Aromataris Mauro Benedetti Michael Hamacher Sabina Merlo Valeria Vercesi 《Optical and Quantum Electronics》2010,42(3):143-156
In this paper, we numerically evaluate private data transmission using a three-laser scheme, consisting of a pair of twin
semiconductor lasers, driven to chaos by delayed optical feedback in a short cavity, and optically injected by a third chaotic
laser which forces them to synchronize. This laser is selected with different internal parameters with respect to the twin
pair, so that the emissions of the synchronized, matched lasers, are highly correlated, whereas their correlation with the
driver is low. The digital message modulates the emission of the transmitter, as in a standard Chaos Modulation scheme. Message
recovery is then obtained by subtracting, from the transmitted chaos-masked message, the chaos, locally generated by the synchronized
receiver laser. Simulations have been performed with the Lang-Kobayashi model, and, in view of application to private transmission,
we have investigated the effect of the parameter mismatch, between transmitter and receiver, on message recovery. A preliminary
experimental evaluation has been also performed using specially designed InP integrated modules. 相似文献
48.
Daniele Balducci Simone Contaldi Ilaria Lazzari Gianni Porzi 《Tetrahedron: Asymmetry》2009,20(12):1398-1401
A new, practical and very convenient stereocontrolled synthesis of (S)-2′,6′-dimethyltyrosine [(S)-Dmt] 4 was accomplished in a good yield, starting from the chiral synthon 1,4-N,N-[(S)-phenylethyl]-piperazine-2,5-dione 1. The procedure, which is an extension of our original strategy and occurs with a high level of stereoselectivity (>98%), is simple and inexpensive allowing us to prepare the unnatural α-aminoacid (S)-Dmt also on a multi-gram scale. 相似文献
49.
Giovanni Dinelli Antonio Segura Carretero Raffaella Di Silvestro Ilaria Marotti Shaoping Fu Stefano Benedettelli Lisetta Ghiselli Alberto Fernández Gutiérrez 《Journal of chromatography. A》2009,1216(43):7229-7240
An evaluation of the grain functional components of Italian durum wheat cultivars was conducted. The raw material was obtained from the field trial performed in 2006–2007 at the Experimental Farm of the University of Bologna, (Bologna, Italy). The aim of this study was to define the phytochemical profile of ten varieties, comprised of old and modern durum wheat genotypes, including quantitative and qualitative phenolic and flavonoid content (free and bound forms). The results showed that mean values of total phenolic compound and total flavonoid content in old wheat varieties (878.2 ± 19.0 μmol gallic acid equivalent/100 g of grain and 122.6 ± 25.4 μmol catechin equivalent/100 g of grain, respectively) did not differ significantly from those detected in modern genotypes (865.9 ± 128.9 μmol gallic acid equivalent/100 g and 123.5 ± 20.6 μmol catechin equivalent/100 g, respectively). However, the HPLC–ESI-TOF-MS analysis highlighted remarkable differences between modern and old cultivars. The interpretation of the mass spectra allowed the identification of 70 phenolic compounds, including coumarins, phenolic acids, anthocyanins, flavones, isoflavones, proanthocyanidins, stilbenes and lignans. The free extracts of ancient wheat varieties showed the presence of a mean number of phenolic compounds and isomer forms (8.7 ± 2.5 and 7.7 ± 4.7 respectively) significantly higher than in modern genotypes (4.4 ± 2.9 and 2.0 ± 2.4, respectively). A similar trend was observed also for the bound phenolic fraction. Moreover, the phytochemical profiles showed the presence of unique phenolic compounds in both free and bound fractions of some of the investigated wheat genotypes. Results highlighted that investigated old wheat cultivars may offer unique nutraceutical values for their peculiar contents in bioactive phytochemicals, suggesting their uses into a wide range of regular and specialty products naturally enriched with health-promoting compounds. 相似文献
50.
Chromogenic colour prints are known to be sensitive to storage environments. However, limited research is available on the effect of atmospheric pollutants on these materials, especially pollutants generated indoors. The stability of photographic dyes is of particular interest and the rate of their change can be best described using the standard RGB colour model. Therefore, the colourimetric method was compared to dye extraction and liquid chromatographic analysis to justify its use as a rapid, non-destructive method for quantitative assessment of the rate of change in dye content of colour photographs during degradation. The effects of typical indoor (acetic acid, formaldehyde) and outdoor (nitrogen dioxide) generated pollutants on chromogenic colour prints were then investigated at 80 °C, 60% RH. It was identified that acetic acid leads to the most pronounced changes in photographic dye concentrations, which is significant considering that acetic acid is often the most prominent pollutant in archival environments. On the other hand, formaldehyde exhibited a slight protective effect in comparison to the blank experiment. 相似文献