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171.
Thierry Jolicoeur Evgeni Burovsky Giuliano Orso 《The European physical journal. Special topics》2013,219(1):3-12
We present 2D steady concentration profiles of confined layers of off-critical polymer blends. The layer rests on a solid substrate and has a flat free surface due to very high surface tension. The profiles correspond to non-linear steady solutions of the Cahn-Hilliard equation in a rectangular domain. The free polymer-gas interface is considered to be sharp, while the internal interfaces are diffuse. We explore the rich solution structure (including laterally structured layers, stratified layers, checkerboard structures, oblique states and droplets) as a function of mean concentration. 相似文献
172.
Filippo Maria Denaro Giuliano De Stefano 《Theoretical and Computational Fluid Dynamics》2011,25(5):315-355
A Finite Volume-based large-eddy simulation method is proposed along with a suitable extension of the dynamic modelling procedure
that takes into account for the integral formulation of the governing filtered equations. Discussion about the misleading
interpretation of FV in some literature is addressed. Then, the classical Germano identity is congruently rewritten in such
a way that the determination of the modelling parameters does not require any arbitrary averaging procedure and thus retains
a fully local character. The numerical modelling of stratified turbulence is the specific problem considered in this study,
as an archetypal of simple geophysical flows. The original scaling formulation of the dynamic sub-grid scale model proposed by Wong and Lilly (Phys. Fluids 6(6), 1994) is suitably extended to the present integral formulation. This approach is preferred with respect to traditional
ones since the eddy coefficients can be independently computed by avoiding the addition of unjustified buoyancy production
terms in the constitutive equations. Simple scaling arguments allow us not to use the equilibrium hypothesis according to
which the dissipation rate should equal the sub-grid scale energy production. A careful a priori analysis of the relevance
of the test filter shape as well as the filter-to-grid ratio is reported. Large-eddy simulation results are a posteriori compared
with a reference pseudo-spectral direct numerical solution that is suitably post-filtered in order to have a meaningful comparison.
In particular, the spectral distribution of kinetic and thermal energy as well as the viscosity and diffusivity sub-grid scale
profiles are illustrated. The good performances of the proposed method, in terms of both evolutions of global quantities and
statistics, are very promising for the future development and application of the method. 相似文献
173.
Giuliano Gargiulo Elvira Zappale 《Mathematical Methods in the Applied Sciences》2011,34(12):1541-1552
We provide some lower semicontinuity results in the space of special functions of bounded deformation for energies of the type and give some examples and applications to minimum problems, arising in Fracture Mechanics for linearly elastic materials. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
174.
Steric control on the redox chemistry of (η5-C9H7)2Yb(II)(THF)2 by 6-aryl substituted iminopyridines
Trifonov AA Shestakov BG Gudilenkov ID Fukin GK Giambastiani G Bianchini C Rossin A Luconi L Filippi J Sorace L 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10568-10575
A steric control on the reductive capacity of ytterbocenes towards iminopyridine ligands is described. The reaction of (η(5)-C(9)H(7))(2)Yb(THF)(2) with a series of 6-organyl-2-(aldimino)pyridyl ligands (IPy) takes place with the replacement of two THF molecules by one IPy unit. In contrast to the rich reductive ytterbocene chemistry described in the presence of the unsubstituted (aldimino)pyridyl ligand, all 6-aryl substituted IPys scrutinized hereafter are involved into the metal coordination as neutral bidentate {N,N} or tridentate {N,N,S; N,N,O} ligands, with no changes of the metal oxidation state in the final complexes. A series of Yb(II) metallocene complexes of general formula (η(5)-C(9)H(7))(2)Yb(II)(η(2) or η(3))[2,6-(i)Pr(2)(C(6)H(3))N=CH(C(5)H(3)N)-6-R)] have been isolated and completely characterized. The stereo-electronic role of the aryl substituents in the IPy ligands on the ytterbocene redox chemistry has also been addressed. 相似文献
175.
Pagacz-Kostrzewa M Reva ID Bronisz R Giuliano BM Fausto R Wierzejewska M 《The journal of physical chemistry. A》2011,115(22):5693-5707
The conformational properties and the photolysis behavior of one of the simplest N-C bonded bicyclic azoles, 5-(1H-tetrazol-1-yl)-1,2,4-triazole (T), were studied in argon and xenon matrices by infrared spectroscopy. Analysis of the experimental results was supported by extensive theoretical calculations carried out at the B3LYP/6-311++G(2d,2p) level of approximation. Out of the eight T minima located on the potential energy surface, the three most stable species were detected in low temperature matrices, namely, 5-(1H-tetrazol-1-yl)-1H-1,2,4-triazole (T1) and two conformers of 5-(1H-tetrazol-1-yl)-2H-1,2,4-triazole (T2a and T2b). With increase of the substrate temperature either during deposition of the matrices or during annealing the T2b → T2a conversion took place, in agreement with the predicted low energy barrier for this transformation (5.38 kJ mol(-1)). Both broad band and narrow band laser UV irradiations of T isolated in Xe and Ar matrices induce unimolecular decomposition involving cleavage of the tetrazole ring of T1 and T2a (T2b) that leads to the production of 1H-1,2,4-triazol-5-yl carbodiimide (P1) and 1H-1,2,4-triazol-3-yl carbodiimide (P2), respectively. When the laser is used, in addition to the main P1 and P2 photoproducts, several minor products could be successfully identified in the matrices: N-cyanocarbodiimide HNCNCN (detected for the first time) associated with nitrilimine HNNCH and HCN. An interesting phenomenon of tautomer-selective photochemistry was observed for the matrix-isolated compound. It could be explained by the different LUMO-HOMO energy gaps estimated for T1, T2a, and T2b, connected with different threshold energies necessary to start the photolysis of T1 and T2a (T2b). 相似文献
176.
Simone?MorpurgoEmail author Giuliano?Moretti Mario?Bossa 《Theoretical chemistry accounts》2012,131(3):1180
DFT calculations on the coordination of Cu+ to the framework oxygen atoms of Al-substituted ZSM-5 were performed by using combinations of different basis sets in order
to investigate the dependence of the results on the adopted computational level. With low-end basis sets, a large basis set
superposition error (BSSE) favors the coordination of Cu+ to three to four oxygen atoms of the framework, only two of which belong to the AlO4 tetrahedron corresponding to the investigated T-site. More extended basis sets considerably lower the BSSE and favor the
coordination of Cu+ to only two oxygen atoms of the AlO4 tetrahedron. Upon interaction with NO, the Cu+ ion is always coordinated by two oxygen atoms of the AlO4 tetrahedron, independently of the basis set adopted and of the coordination number before NO adsorption. The shift from three-
to twofold coordination caused by the Cu+–NO interaction requires a deformation energy that lowers the final adsorption energy. Such an effect is relevant with low-end
basis sets, whereas it is substantially absent with more extended basis sets, which favor the twofold coordination of Cu+ even before NO adsorption. As a result, high-end basis sets increase the NO interaction energy with respect to that calculated
by low-end basis sets, in agreement with experiments and suggesting a possible re-interpretation of the catalytic properties
of the investigated sites. Provided suitable scale factors are employed, the N–O stretching frequencies of adsorbed nitrogen
oxide calculated by sufficiently extended basis sets turned out in fair agreement with experimental findings. 相似文献
177.
The crack-tip stress fields in orthotropic bodies are derived within the framework of Eringen’s nonlocal elasticity via the Green’s function method. The modified Bessel function of second kind and order zero is considered as the nonlocal kernel. We demonstrate that if the localisation residuals are neglected, as originally proposed by Eringen, the asymptotic stress tensor and its normal derivative are continuous across the crack. We prove that the stresses attained at the crack tip are finite in nonlocal orthotropic continua for all the three fracture modes (I, II and III). The relative magnitudes of the stress components depend on the material orthotropy. Moreover, non-zero self-balanced tractions exist on the crack edges for both isotropic and orthotropic continua. The special case of a mode I Griffith crack in a nonlocal and orthotropic material is studied, with the inclusion of the T-stress term. 相似文献
178.
Valentina Lo Galbo Marianna Lauricella Michela Giuliano Sonia Emanuele Daniela Carlisi Giuseppe Calvaruso Anna De Blasio Diana Di Liberto Antonella DAnneo 《Molecules (Basel, Switzerland)》2021,26(14)
Today, an improved understanding of cancer cell response to cellular stress has become more necessary. Indeed, targeting the intracellular pro-oxidant/antioxidant balance triggering the tumor commitment to cell demise could represent an advantageous strategy to develop cancer-tailored therapies. In this scenario, the present study shows how the peel extract of mango—a tropical fruit rich in phytochemicals with nutraceutical properties—can affect the cell viability of three colon cancer cell lines (HT29, Caco-2 and HCT116), inducing an imbalance of cellular redox responses. By using hydro-alcoholic mango peel extract (MPE), we observed a consistent decline in thiol group content, which was accompanied by upregulation of MnSOD—a mitochondrial scavenger enzyme that modulates the cellular response against oxidative damage. Such an effect was the consequence of an early production of mitochondrial superoxide anions that appeared after just 30 min of exposure of colon cancer cells to MPE. The effect was accompanied by mitochondrial injury, consisting of the dissipation of mitochondrial membrane potential and a decrease in the level of proteins localized in the mitochondrial membrane—such as voltage-dependent anion-selective channel (VDAC1), mitofilin, and some members of Bcl-2 family proteins (Mcl-1, Bcl-2 and Bcl-XL)—with the mitochondrial release of apoptogenic factors (cytochrome C and AIF). The analysis of the cytotoxic effects exerted by the different constituents of MPE (gallic acid, mangiferin, citric acid, quinic acid, pentagalloyl glucose, and methyl gallate) allowed us to identify those phytochemicals responsible for the observed anticancer effects, sustaining their future employment as chemopreventive or therapeutic agents. 相似文献
179.
Benedetto Marelli Matteo Achilli Antonio Alessandrino Giuliano Freddi Maria Cristina Tanzi Silvia Farè Diego Mantovani 《Macromolecular bioscience》2012,12(11):1566-1574
None of the replacements proposed in the literature for small‐calibre blood vessels (SCBV) fully satisfies the stringent requirements that these grafts have to fulfil. Here, an electrospun silk fibroin tubular construct is hybridized with type I collagen gel to produce a biomimetic SCBV graft with physiologically relevant compliance and burst pressure and optimal cytocompatibility. The hybridization of the two polymers results in the formation of a nanofibrillar hydrated matrix, where the collagen gel enhances the mechanical properties of the SF tubular construct and improves the early response of the material to in vitro cell adhesion and proliferation.
180.
Rohanah Hussain Tamás Jávorfi Giuliano Siligardi 《Journal of synchrotron radiation》2012,19(1):132-135
Synchrotron radiation circular dichroism (SRCD) is a well established technique in structural biology. The first UV‐VIS beamline, dedicated to circular dichroism, at Diamond Light Source Ltd, a third‐generation synchrotron facility in south Oxfordshire, UK, has recently become operational and it is now available for the user community. Herein the main characteristics of the B23 SRCD beamline, the ancillary facilities available for users, and some of the recent advances achieved are summarized. 相似文献