Core–shell nanogels by RAFT crosslinking polymerization: Synthesis and characterization

A synthetic methodology is described for the preparation of core–shell nanogels by reversible addition‐fragmentation chain transfer. Well‐defined macro chain transfer agents (macro‐CTA's) were prepared in a first step using monomers that yield sensitive polymers. In the second step, a crosslinker alone or with the addition of a functionalized comonomer were used to form a crosslinked core. The ratio of crosslinker to macro‐CTA is crucial to yield nanogels. Furthermore, the polymerization time has an impact in the architecture of the nanomaterial obtained: it evolves from a core‐crosslinked star to a core–shell nanogel. Controlling the molecular weight of the macro‐CTA and the type of comonomer in the core forming step, core–shell nanogels with hydrodynamic diameters from 22 to 168 nm and a core that represents from 35 to 77% of the size, were prepared containing functional groups in the core which could be used as catalytic scaffolds. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Pressure-driven flow of a rate-type fluid with stress threshold in an infinite channel

In this paper we extend some of our previous works on continua with stress threshold. In particular here we propose a mathematical model for a continuum which behaves as a non-linear upper convected Maxwell fluid if the stress is above a certain threshold and as a Oldroyd-B type fluid if the stress is below such a threshold. We derive the constitutive equations for each phase exploiting the theory of natural configurations (introduced by Rajagopal and co-workers) and the criterion of the maximization of the rate of dissipation. We state the mathematical problem for a one-dimensional flow driven by a constant pressure gradient and study two peculiar cases in which the velocity of the inner part of the fluid is spatially homogeneous.     

A Homeomorphism Invariant for Substitution Tiling Spaces

We derive a homeomorphism invariant for those tiling spaces which are made by rather general substitution rules on polygonal tiles, including those tilings, like the pinwheel, which contain tiles in infinitely many orientations. The invariant is a quotient of ech cohomology, is easily computed directly from the substitution rule, and distinguishes many examples, including most pinwheel-like tiling spaces. We also introduce a module structure on cohomology which is very convenient as well as of intuitive value.     

Preparation of a new chiral non-racemic sulfur-containing diselenide and applications in asymmetric synthesis

The synthesis of the new chiral non-racemic sulfur-containing diselenide, di-2-methoxy-6-[(1S)-1-(methylthio)ethyl]phenyl diselenide, is described. When treated with ammonium persulfate this diselenide is transformed into the corresponding selenenyl sulfate, which acts as a strong electrophilic reagent and adds to alkenes, in the presence of methanol or water, to afford the products of selenomethoxylation or selenohydroxylation, respectively, with excellent diastereoselectivities. Starting from alkenes containing internal nucleophiles, asymmetric cyclofunctionalization reactions also resulted in good chemical yields, complete regioselectivities, and high diastereoselectivities. This sulfur-containing diselenide can also be used in catalytic amounts to promote one-pot selenenylation-deselenenylation processes, from which several types of products can be obtained in high yield and with good enantiomeric excess.     

Beta-functionalised polythiophenes as microelectrode modifiers in low conductive media

A study on polythiophene coated microelectrodes is reported, the goal being that of checking the capability of these electrochemical systems to work in low conductive media. The possibility of electrochemically p-doping the polymer in the presence of very low concentrations or even in the absence of supporting electrolyte in the solution is ascertained, opening the way to the use of similar systems in pure solvent media. This result is obtained in such conditions that the presence of residual charges--and corresponding counterions--trapped inside the film coating can be reasonably hypothesised.     

Cosmology of a brane radiating gravitons into the extra dimension

We study in a self-consistent way the impact of the emission of bulk gravitons on the (homogeneous) cosmology of a three-brane embedded in a five-dimensional spacetime. In the low energy regime, we recover the well known result that the bulk affects the Friedmann equation only via a radiationlike term C/a(4), called dark or Weyl radiation. In the high energy regime, we find that the Weyl parameter C is no longer constant but grows rapidly. Consequently, C today is determined by the past history of the brane universe and depends on the number of relativistic degrees of freedom at the high/low energy transition.     

Laguerre geometry of surfaces with plane lines of curvature

We study surfaces with plane lines of curvature in the framework of Laguerre geometry and provide explicit representation formulae for these surfaces in terms of a potential function. As an application, we explicitly integrate allL- minimal surfaces with plane curvature lines. Partially supported by MURST 40.     

119Sn mössbauer,IR, 1H NMR spectroscopic and thermal decomposition studies on organotin(IV) adducts with glycylglycine

The complexes R₂SnCl₂·(H₂glygly), (H₂glygly = glycylglycine) (R = Me, Buⁿ, Octⁿ, Ph) and RSnCl₃·(H₂glygly)