Shape mixtures of multivariate skew-normal distributions

Classes of shape mixtures of independent and dependent multivariate skew-normal distributions are considered and some of their main properties are studied. If interpreted from a Bayesian point of view, the results obtained in this paper bring tractability to the problem of inference for the shape parameter, that is, the posterior distribution can be written in analytic form. Robust inference for location and scale parameters is also obtained under particular conditions.     

Dansylated Polyamines as Fluorescent Sensors for Metal Ions: Photophysical Properties and Stability of Copper(II) Complexes in Solution

Protonation and the Cu^II complexation constants of the dansylated polyamines N‐dansylethylenediamine ( 1 ), N‐dansyldiethylenetriamine ( 2 ), N‐dansyltriethylenetetramine ( 3 ), N′‐[2‐(dansylamino)ethyl]diethylenetriamine ( 4 ), and tris(2‐dansylaminoethyl)amine ( 5 ) were determined by glass‐electrode potentiometry in MeOH/H₂O 9 : 1 (v/v) solution. For ligands 3 and 4 , the determinations were also performed in aqueous solution. The complexes formed by these ligands in neutral form correspond to those observed for the analogous unsubstituted monoprotonated amines, whereas, when the ligands are deprotonated at the sulfonamide moiety, the species parallel those of the corresponding amines. The molecular structures of the complexes were deduced from the VIS absorption spectra. The crystal structure of the [CuL₂H₋₂] complex 6 of ligand 1 (L) was determined by X‐ray diffraction. The study of the photophysical properties of the ligands 3 – 5 showed that they are good fluorescent sensors for copper(II), which induced fluorescence quenching. Time‐resolved fluorescence measurements allowed us to clarify the sensing mechanism. The pH dependence of the quenching effect demonstrated that it occurs for all Cu²⁺ complexes, even for species in which the sulfonamide moiety is not deprotonated. Sensing of Cu²⁺ was compared with that of other metal ions (Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Hg²⁺), and selectivity was studied as a function of pH. Ligands 3 and 4 were found to be selective chemosensors for Cu²⁺ in weakly acidic solution (pH ca. 4 – 5).     

Nitroxide-mediated miniemulsion polymerization of n-butyl acrylate: synthesis of controlled homopolymers and gradient copolymers with styrene

Controlled free-radical homopolymerization of n-butyl acrylate and its copolymerization with styrene have been studied in aqueous miniemulsion, using an acyclic β-phosphonylated nitroxide as a mediator, the N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide, also called SG1. Polymerization kinetics have been studied and characterization of the (co)polymers has been performed, demonstrating the successful synthesis of well-defined poly(n-butyl acrylate) homopolymers and poly(n-butyl acrylate-co-styrene) gradient copolymers.     

Branching and crosslinking in emulsion polymerization

The seeded semibatch emulsion polymerization of butyl acrylate (BA) with allyl methacrylate (AMA) and butanediol diacrylate (BDA) was used to study the influence of the crosslinkers on the kinetics, branching and crosslinking density, gel fraction and sol MWD produced during the experiments carried out at 80°C using potassium persulfate as initiator. Surprisingly, the most reactive crosslinker, BDA, produced the less crosslinked, branched and gel containing polymer. These results were explained with the help of a mathematical model in terms of cyclization reactions and diffusion controlled propagation and termination reactions.