Construction and characterization of models of hypercrosslinked polystyrene

A simple algorithm involving classical molecular dynamics (MD) simulations is here suggested to build up models of hypercrosslinked polystyrene showing macroporous structure. The algorithm is composed by three consecutive stages: MD simulation of a single polystyrene coil, crosslink formation, and finally relaxation of the structure. The models, which are differentiated by the crosslinker concentration in the initial polystyrene chain, can be characterized by employing tools of the small angle neutron scattering analysis and procedures associated to the crosslinking algorithm, which allows one to discriminate among the different kinds of crosslinks between phenyl rings and to calculate the crosslinking degree. A model of hypercrosslinked polystyrene so characterized is useful to simulate the behavior of a great number of systems of use in the applications of this macromolecule as substrate.     

New coumarin-urea based receptor for anions: a selective off–on fluorescence response to fluoride

A novel fluorosensor for anions, 1,11-bis(4-methylcoumarin-7-yl)-6-methyl-1,3,6,9,11-pentaazaundeca-2,10-dione (L), which contains two coumarin–urea units spaced by a flexible diethylenetriamine fragment, was easily prepared in 65% yield by a one-pot two-step procedure. The binding ability of L toward several anions (G) was evaluated by ¹H NMR, UV–vis, and fluorescence titration. It was found that L forms stable [LG] and [LG₂] species in both DMSO and CH₃CN solvents. Furthermore, the fluorescence emission of L in the visible range (400 nm) is affected by the presence of anions; it is quenched by acetate, chloride, and pyrophosphate while it is enhanced by fluoride. Thus, this novel fluorosensor provides a selective off–on response to the presence of fluoride in solution.     

Fabrication of large-area ordered and reproducible nanostructures for SERS biosensor application

We propose a large-area SERS device with efficient fluorescence quenching capability. The substrate is based on anodic porous alumina templates with various pore size and wall thickness as small as 15 and 36 nm, respectively. The nano-patterned SERS substrate, with excellent control and reproducibility of plasmon-polaritons generation, shows very efficient enhanced Raman signal in the presence of intrinsically fluorescent molecules such as cresyl violet, rhodamine, and green fluorescent protein. This work demonstrates that, when the nanostructures are properly designed and fabricated, Raman and fluorescence spectroscopy can be used in combination in order to obtain complementary molecular informations. Theoretical simulation shows excellent agreement with the experimental findings. The enhancement factor is found to be 10(3)-10(4), with respect to flat gold surface when the molecules are supposed to be closely packed, with considerable fluorescence suppression, showing a promising disposable biosensor.     

Synthesis, characterization and antiproliferative activity on mesothelioma cell lines of bis(carboxylato)platinum(IV) complexes based on picoplatin

The synthesis and characterization of a series of picoplatin-based (picoplatin = [PtCl(2)(mpy)(NH(3))], mpy = 2-methylpyridine), Pt(iv) complexes with axial carboxylato ligands of increasing length are reported. The synthesis is based on the oxidation with hydrogen peroxide of picoplatin to give the cis,cis,trans-[PtCl(2)(mpy)(NH(3))(OH)(2)] intermediate and then its transformation into the dicarboxylato complexes cis,cis,trans-[PtCl(2)(mpy)(NH(3))(RCOO)(2)] (R = CH(3)(CH(2))(n), n = 0-4) with the corresponding anhydride. Pt(iv) complexes with n = 0-2 were selected to be tested on four malignant pleural mesothelioma (MPM) cell lines, on human mesothelial cells (HMC), and on the cisplatin-sensitive ovarian A2780 cell line along with cisplatin as a metallo-drug reference. In general, the longer the axial chain, the more cytotoxic and selective the Pt(IV) complex is. Pt(IV) analogs show good activity on the MPM cell lines, approaching or in some case bypassing that of cisplatin and represent quite promising drug candidates for the treatment of tumors whose chemoresistance is mainly based on glutathione overexpression, such as MPM.     

Synthesis, characterisation and magnetic study of a cyano-substituted dysprosium double decker single-molecule magnet

Bis(octacyanophthalocyanine)dysprosium(III) (1) has been synthesised, characterised and magnetically studied. By the incorporation of cyano substituents on the phthalocyanine (Pc) rings, a starting point has been created for the chemical modification of double deckers for the purpose of surface self-assembly. The modification of the rings leaves the magnetic properties of the double decker largely unaffected.     

Commitment Versus Persuasion in the Three-Party Constrained Voter Model

In the framework of the three-party constrained voter model, where voters of two radical parties (A and B) interact with “centrists” (C and C _ζ ), we study the competition between a persuasive majority and a committed minority. In this model, A’s and B’s are incompatible voters that can convince centrists or be swayed by them. Here, radical voters are more persuasive than centrists, whose sub-population comprises susceptible agents C and a fraction ζ of centrist zealots C _ζ . Whereas C’s may adopt the opinions A and B with respective rates 1+δ _A and 1+δ _B (with δ _A ≥δ _B >0), C _ζ ’s are committed individuals that always remain centrists. Furthermore, A and B voters can become (susceptible) centrists C with a rate 1. The resulting competition between commitment and persuasion is studied in the mean field limit and for a finite population on a complete graph. At mean field level, there is a continuous transition from a coexistence phase when ζ<Δ _c =δ _A /(1+δ _A ) to a phase where centrism prevails when ζ≥Δ _c . In a finite population of size N, demographic fluctuations lead to centrism consensus and the dynamics is characterized by the mean consensus time τ. Because of the competition between commitment and persuasion, here consensus is reached much slower (ζ<Δ _c ) or faster (ζ≥Δ _c ) than in the absence of zealots (when τ～N). In fact, when ζ<Δ _c and there is an initial minority of centrists, the mean consensus time grows as τ～N ^?1/2 e ^Nγ , with N?1 and . The dynamics is thus characterized by a metastable state where the most persuasive voters and centrists coexist when δ _A >δ _B , whereas all species coexist when δ _A =δ _B . When ζ≥Δ _c and the initial density of centrists is low, one finds τ～lnN (when N?1). Our analytical findings are corroborated by stochastic simulations.     

Practical Implementation of a Test of Event-Based Corpuscular Model as an Alternative to Quantum Mechanics

We describe in detail the first experimental test that distinguishes between an event-based corpuscular model of the interaction of photons with matter and quantum mechanics. The test looks at the interference that results as a single photon passes through a Mach-Zehnder interferometer. The experimental results, obtained with a low-noise single-photon source, agree with the predictions of standard quantum mechanics.     

On the asymptotic crack-tip stress fields in nonlocal orthotropic elasticity

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.     

Critical phenomena in laminar–turbulence transitions by a mean field model

In this work, following the papers (Cortet et al., Phys Rev Lett 105:214501, 2010; Manneville, Dissipative structures and weak turbulence, 1990), we study the turbulence behavior in a fluid as a critical phenomenon related with a continuous phase transition. So that, we use the Ginzburg–Landau equation describing the evolution of the order parameter, which control the laminar–turbulence transition. While, the velocity is represented by a sum of two terms, the normal and the rotational (or turbulence) components. As a result, the rotational term is zero in the laminar phase. Then, a hydrodynamic model is formulated, which chooses as fundamental fields the components of velocity and a phase field function f. Moreover, we study the thermodynamic restrictions, a maximum theorem for the phase field and the role of the pressure in the phase transition. In the last section, we address the study of turbulence in Helium II, where it is possible to observe many analogies with the phenomena which occur in classical fluids     

The h-Vector of a Relatively Compressed Level Algebra

The purpose of this note is to supply an upper and a lower bound (which are in general sharp) for the h-vector of a level algebra which is relatively compressed with respect to any arbitrary level algebra A.

The useful concept of relatively compressed algebra was recently introduced in Migliore et al. (2005 Migliore , J. , Miró-Roig , R. , Nagel , U. ( 2005 ). Minimal resolution of relatively compressed level algebras . J. Algebra 284 ( 1 ): 337 – 370 .[Crossref] , [Google Scholar]) (whose investigations mainly focused on the particular case of A a complete intersection). The key idea of this note is the simple observation that the level algebras which are relatively compressed with respect to A coincide (after an obvious isomorphism) with the generic level quotients of suitable truncations of A. Therefore, we are able to apply to relatively compressed algebras the main result of our recent work, Zanello (2007 Zanello , F. ( 2007 ). Partial derivatives of a generic subspace of a vector space of forms: quotients of level algebras of arbitrary type . Trans. Amer. Math. Soc. 359 ( 6 ): 2675 – 2686 .[Crossref], [Web of Science ®] , [Google Scholar]).