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141.
Espa D Pilia L Marchiò L Artizzu F Serpe A Mercuri ML Simão D Almeida M Pizzotti M Tessore F Deplano P 《Dalton transactions (Cambridge, England : 2003)》2012,41(12):3485-3493
The mixed-ligand dithiolene complex [Pt(Bz(2)pipdt)(dcbdt)] (1) bearing the two ligands Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione and dcbdt = dicyanobenzodithiolato, has been synthesized, characterized and studied to evaluate its second-order optical nonlinearity. The dithione/dithiolato character of the two ligands gives rise to an asymmetric distribution of the charge in the molecule. This is reflected by structural data showing that in the C(2)S(2)PtS(2)C(2) dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the Pt-S bond distances involving the two ligands are similar, while the C-S bond distances in the C(2)S(2) units exhibit a significant difference in Bz(2)pipdt (dithione) and dcbdt (dithiolato). 1 shows a moderately strong absorption peak in the visible region, which can be related to a HOMO-LUMO transition, where the dcbdt ligand (dithiolato) contributes mostly to the HOMO, and the Bz(2)pipdt one (dithione) mostly to the LUMO. Thus this transition has ligand-to-ligand charge transfer (CT) character with some contribution of the metal and undergoes negative solvatochromism and molecular quadratic optical nonlinearity (μβ(0) = -1296 × 10(-48) esu), which was determined by the EFISH (electric-field-induced second-harmonic generation) technique and compared with the values of similar complexes on varying the dithiolato ligand (mnt = maleonitriledithiolato, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). Theoretical calculations help to elucidate the role of the dithiolato ligands in affecting the molecular quadratic optical nonlinearity of these complexes. 相似文献
142.
Carlos Henrique Marchi Leandro Alberto Novak Cosmo Damião Santiago Ana Paula da Silveira Vargas 《Applied Mathematical Modelling》2013,37(12-13):7386-7397
A theoretical basis is presented for the repeated Richardson extrapolation (RRE) to reduce and estimate the discretization error of numerical solutions for heat conduction. An example application is described for the 2D Laplace equation using the finite difference method, a domain discretized with uniform grids, second-order accurate approximations, several variables of interest, Dirichlet boundary conditions, grids with up to 8,193 × 8,193 nodes, a multigrid method, single, double and quadruple precisions and up to twelve Richardson extrapolations. It was found that: (1) RRE significantly reduces the discretization error (for example, from 2.25E-07 to 3.19E-32 with nine extrapolations and a 1,025 × 1,025 grid, yielding an order of accuracy of 19.1); (2) the Richardson error estimator works for numerical results obtained with RRE; (3) a higher reduction of the discretization error with RRE is achieved by using higher calculation precision, a larger number of extrapolations, a larger number of grids and correct error orders; and (4) to obtain a given value error, much less CPU time and RAM memory are required for the solution with RRE than without it. 相似文献
143.
F De Marchi R Seraglia L Molin P Traldi M De Rosso A Panighel A Dalla Vedova M Gardiman M Giust R Flamini 《Journal of mass spectrometry : JMS》2012,47(9):1113-1119
Triglyceride profile of seed oil samples from 32 hybrid grape varieties not studied before was investigated. A new method for the analysis of triacylglycerols (TAGs) has been developed based on the direct infusion in the electrospray ionization (ESI) source and employing tetrahydrofuran/methanol/water (85:10:5 v|v|v) as solvent; the formation of [M?+?Na](+) ions in high yield has been observed. TAGs were identified by ESI-tandem mass spectrometry analysis, and the matrix-assisted-laser-desorption-ionization and time-of-flight profile of samples was determined. Six were the principal TAGs identified in seed oil: trilinolein (LLL) was the most abundant (43%), followed by dilinoleoyl-oleoylglycerol (LOL, 23%), and dilinoleoyl-palmitoylglycerol (LPL, 15%). Compounds present in lower concentration were LSL and LOO (11%), LOP (6%), and LSP (2%). Compared with seed oils produced from V. Vinifera grapes, some significant differences in the relative abundances of TAGs were found, in particular hybrid grape seed oils showed higher LOL and lower LPL content, respectively. Among the samples studied, a particularly high content of LLL (rich in unsaturated fatty acids) was found in seed oils from two red varieties. Copyright ? 2012 John Wiley & Sons, Ltd. 相似文献
144.
Positano V Salani B Pepe A Santarelli MF De Marchi D Ramazzotti A Favilli B Cracolici E Midiri M Cianciulli P Lombardi M Landini L 《Magnetic resonance imaging》2009,27(2):188-197
In the clinical MRI practice, it is common to assess liver iron overload by T2* multi-echo gradient-echo images. However, there is no full consensus about the best image analysis approach for the T2* measurements. The currently used methods involve manual drawing of a region of interest (ROI) within MR images of the liver. Evaluation of a representative liver T2* value is done by fitting an appropriate model to the signal decay within the ROIs vs. the echo time. The resulting T2* value may depend on both ROI placement and choice of the signal decay model. The aim of this study was to understand how the choice of the analysis methodology may affect the accuracy of T2* measurements. A software model of the iron overloaded liver was inferred from MR images acquired from 40 thalassemia major patients. Different image analysis methods were compared exploiting the developed software model. Moreover, a method for global semiautomatic T2* measurement involving the whole liver was developed. The global method included automatic segmentation of parenchyma by an adaptive fuzzy-clustering algorithm able to compensate for signal inhomogeneities. Global liver T2* value was evaluated using a pixel-wise technique and an optimized signal decay model. The global approach was compared with the ROI-based approach used in the clinical practice. For the ROI-based approach, the intra-observer and inter-observer coefficients of variation (CoVs) were 3.7% and 5.6%, respectively. For the global analysis, the CoVs for intra-observers and inter-observers reproducibility were 0.85% and 2.87%, respectively. The variability shown by the ROI-based approach was acceptable for use in the clinical practice; however, the developed global method increased the accuracy in T2* assessment and significantly reduced the operator dependence and sampling errors. This global approach could be useful in the clinical arena for patients with borderline liver iron overload and/or requiring follow-up studies. 相似文献
145.
Paola Deplano Luciano Marchiò Flavia Artizzu Maria Laura Mercuri Luca Pilia Gloria Pintus Angela Serpe Eduard B. Yagubskii 《Monatshefte für Chemie / Chemical Monthly》2009,140(7):775-781
Abstract The novel [Ni(Me2pipdt)(dddt)] complex based on the Me2pipdt (1,4-dimethylpiperazine-3,2-dithione) and dddt (5,6-dihydro-1,4-dithine-2,3-dithiolate) ligands has been synthesised
and characterised. Structural data, vibrational marker, solvatochromic behaviour of the typical absorption in the near infrared
region, and approximate theoretical calculations suggest that an unbalanced electron distribution at the dithiolene core occurs
in the ground and excited states. In particular, the dddt ligand gives a prevailing contribution to the HOMO, and Me2pipdt to the LUMO. The charge-transfer character of the HOMO–LUMO transition makes this complex a potential second-order non-linear
optic chromophore.
Graphical Abstract
相似文献
146.
Nicola Marchi Qingshan Teng Minh T Nguyen Linda Franic Nirav K Desai Thomas Masaryk Peter Rasmussen Silvia Trasciatti Damir Janigro 《BMC neuroscience》2010,11(1):34
Background
Stem cells or immune cells targeting the central nervous system (CNS) bear significant promises for patients affected by CNS disorders. Brain or spinal cord delivery of therapeutic cells is limited by the blood-brain barrier (BBB) which remains one of the recognized rate-limiting steps. Osmotic BBB disruption (BBBD) has been shown to improve small molecule chemotherapy for brain tumors, but successful delivery of cells in conjunction with BBBD has never been reported. 相似文献147.
The computation of integrals in higher dimensions and on general domains, when no explicit cubature rules are known, can be "easily" addressed by means
of the quasi-Monte Carlo method. The method, simple in its formulation, becomes computationally inefficient when the space dimension is growing and the integration domain is particularly complex.
In this paper we present two new approaches to the quasi-Monte Carlo method for cubature based on nonnegative least squares and approximate Fekete points.
The main idea is to use less points and especially good points for solving the system of the moments. Good points are here intended as points with good interpolation properties, due to the strict connection between interpolation and cubature.
Numerical experiments show that, in average, just a tenth of the points should be used to maintain the same approximation order of the quasi-Monte Carlo method. The method has been satisfactorily applied to 2- and 3-dimensional problems on quite complex domains. 相似文献
148.
Erra L Tedesco C Immediata I Gregoli L Gaeta C Merlini M Meneghini C Brunelli M Fitch AN Neri P 《Langmuir : the ACS journal of surfaces and colloids》2012,28(22):8511-8517
The inclusion properties of a calixarene-based porous material have been studied to investigate the adsorption and the desorption of carbon tetrachloride, chloroform, and water in the zeolite-like structure. Uptake and release processes have been studied both by time-resolved powder X-ray diffraction and by thermogravimetric analysis to obtain structural and kinetic information. The selected guests are able to enter the structure with an increase in the host cell volume and with time-dependent diffusivity coefficients. Chloroform molecules act as a permanent porosity switch promoting a phase transition to non-porous triclinic form. 相似文献
149.
Bertini I Luchinat C Turano P Battaini G Casella L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2316-2322
Deoxymyoglobin has been investigated by NMR spectroscopy to determine the magnetic anisotropy through pseudocontact shifts and the total magnetic susceptibility through Evans measurements. The magnetic anisotropy values were found to be Deltachi(ax)=-2.03+/-0.08 x 10(-32) m(3) and Deltachi(rh)=-1.02+/-0.09 x 10(-32) m(3). The negative value of the axial susceptibility anisotropy originates from the z tensor axis lying in the heme plane, unlike all other heme systems investigated so far. This magnetic axis is almost exactly orthogonal to the axial histidine plane. The other two axes lie essentially in the histidine plane, the closest to the heme normal being tilted by about 36 degrees from it, towards pyrrole A on the side of the proximal histidine. From the comparison with cytochrome c' it clearly appears that the position of the one axis lying in the heme plane is related to the axial histidine orientation. Irrespective of the directions, the magnetic anisotropy is smaller than that of the analogous reduced cytochrome c' and of the order of that of low-spin iron(III). The magnetic anisotropy of the system permits the measurement of residual dipolar couplings, which, together with pseudocontact shifts, prove that the solution structure is very similar to that in the crystalline state. Magnetic measurements, at variance with previous data, demonstrate that there is an orbital contribution to the magnetic moment, micro(eff)=5.5 micro(B). Finally, from the magnetic anisotropy data, the hyperfine shifts of iron ligands could be separated in pseudocontact and contact components, and hints are provided to understand the spin-delocalisation mechanism in S=2 systems by keeping in mind the delocalisation patterns in low-spin S=1/2 and high-spin S= 5/2 iron(III) systems. 相似文献
150.
Basile F. E. Curchod Thomas J. Penfold Ursula Rothlisberger Ivano Tavernelli 《Central European Journal of Physics》2013,11(9):1059-1065
We review our recent work on ab initio nonadiabatic molecular dynamics, based on linear-response timedependent density functional theory for the calculation of the nuclear forces, potential energy surfaces, and nonadiabatic couplings. Furthermore, we describe how nuclear quantum dynamics beyond the Born-Oppenheimer approximation can be performed using quantum trajectories. Finally, the coupling and control of an external electromagnetic field with mixed quantum/classical trajectory surface hopping is discussed. 相似文献