Polymerization of (E)‐1,3‐Pentadiene and (E)‐2‐methyl‐1,3‐pentadiene with neodymium catalysts: Examination of the factors that affect the stereoselectivity

(E)‐1,3‐Pentadiene (EP) and (E)‐2‐methyl‐1,3‐pentadiene (2MP) were polymerized to cis‐1,4 polymers with homogeneous and heterogeneous neodymium catalysts to examine the influence of the physical state of the catalyst on the polymerization stereoselectivity. Data on the polymerization of (E)‐1,3‐hexadiene (EH) are also reported. EP and EH gave cis‐1,4 isotactic polymers both with the homogeneous and with the heterogeneous system, whereas 2MP gave an isotactic cis‐1,4 polymer with the heterogeneous catalyst and a syndiotactic cis‐1,4 polymer, never reported earlier, with the homogeneous one. For comparison, the results obtained with the soluble CpTiCl₃‐based catalyst (Cp = cyclopentadienyl), which gives cis‐1,4 isotactic poly(2MP), are examined. A tentative interpretation is given for the mechanism of the formation of the stereoregular polymers obtained and a complete NMR characterization of the cis‐1,4‐syndiotactic poly(2MP) is reported. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3227–3232     

Microchemical and microstructural characterisation of medieval and post-medieval ceramic glaze coatings

A large number of ceramic samples (from the 10th to the 19th century), found during the excavation of Sicilian archaeological sites (Syracuse, Caltagirone, Sciacca and Piazza Armerina), have been studied by combining scanning electron microscopy, energy-dispersive X-ray spectrometry and optical microscopy. Attention has been focused on the microchemical and microstructural properties of the painted surfaces to investigate the nature of the enamels and pigments in the decorative layers. The general perspective has been the identification of consistent archeometric criteria, other than the standard stylistic considerations, which can be used for a reliable recognition of the production sites. The results collected for each ceramic typology were used to cluster the different ceramic reference groups in a wide database suitable for a reliable discrimination of the provenance of artefacts. Moreover, the same compositional and microstructural data allow the identification of the raw materials used for pigments. There is evidence of some differences with existing information found in the literature concerning the formulas used in ancient times. Finally, attention has also been devoted to identify the technological aspects of the manufacturing techniques and firing conditions adopted for each typology of glaze coating depending on different ceramic materials .PACS 81.05.Je; 82.80.-d; 68.37.Hk; 68.55.-a     

Estimates for large solutions of a quasilinear elliptic equation

Let \(\Omega \) be a bounded smooth domain of \(R^{n}\). We study the asymptotic behaviour of the solutions to the equation \(\triangle u-|Du|^{q}=f(u)\) in \(\Omega , 1<q<2,\) which satisfy the boundary condition \(u(x)\rightarrow \infty \) as \(x\rightarrow \partial \Omega \). These solutions are called large or blowup solutions. Near the boundary we give lower and upper bounds for the ratio \(\psi (u)/\delta \), where \(\psi (u) = \int _{u}^{\infty }1/\sqrt{2F}dt\), \(F'=f\), \(\delta =dist(x,\partial \Omega )\) or for the ratio \(u/\delta ^{(2-q)/(1-q)}\). When in particular the ratio \(f/F^{q/2}\)is regular at infinity, we find again known results (Bandle and Giarrusso, in Adv Diff Equ 1, 133–150, 1996; Giarrusso, in Comptes Rendus de l’Acad Sci 331, 777–782 2000).     

Isoperimetric inequalities for an ergodic stochastic control problem

In this paper we deal with blow-up solutions to an elliptic equation with a nonlinear gradient term. The problem under consideration can be seen as the ergodic limit of a stochastic control problem with state constraints. It is well known that it has a solution only when a parameter which appears in the equation assumes a particular value known as ergodic constant. For such a constant many properties similar to those of an eigenvalue hold true. We show that a Faber–Krahn inequality can be stated for the ergodic constant and that for the corresponding solution a comparison result in terms of the solution to a symmetrized problem can be proved.     

Diethylbis(2,2′‐bipyridine)iron/MAO. A Very Active and Stereospecific Catalyst for 1,3‐Diene Polymerization

Diethylbis(2,2′‐bipyridine)Fe/MAO is an extremely active catalyst for the polymerization of 1,3‐dienes. Polymers with a 1,2 or 3,4 structure are formed from butadiene, isoprene, (E)‐1,3‐pentadiene and 3‐methyl‐1,3‐pentadiene, while cis‐1,4 polymers are derived from 2,3‐dimethyl‐1,3‐butadiene. The 1,2 (3,4) polymers obtained at 25°C are amorphous, while those obtained below 0°C are crystalline, as was determined by means of X‐ray diffraction. Mechanistic implications of the results are briefly discussed.     

Polymerization of styrene to isotactic polymer with MAO-Ni(acac)2. Examination of the factors that influence activity and stereospecificity

The soluble catalyst system methylaluminoxane (MAO)-Ni(acac), (acac: acetylacetonate) gives polystyrene consisting of an amorphous (aPS) and a crystalline isotactic (ips) fraction. Al(CH₃)₃, which is always present in commercial samples of MAO, decreases both polymer yield and stereospecificity. The polymer yield increases with increasing the MAO/Ni ratio but, at the same time, the iPS/aPS ratio decreases. Addition of N(C₂H₅)₃ (mole ratio N/Ni = 1) increases the proportion of the isotactic fraction, while it decreases the polymer yield. A tentative interpretation of the stereospecificity is reported.     

Sum-rules of the response potential in the strongly-interacting limit of DFT

The response part of the exchange-correlation potential of Kohn–Sham density functional theory plays a very important role, for example for the calculation of accurate band gaps and excitation energies. Here we analyze this part of the potential in the limit of infinite interaction in density functional theory, showing that in the one-dimensional case it satisfies a very simple sum rule.     

Recent advances in the field of diolefin polymerization with transition metal catalysts

Recent advances in the field of catalysis for 1,3-diene polymerization and in the interpretation of the polymerization mechanism are examined. Catalysts prepared from methylaluminoxanes and soluble transition metal compounds are in general more active than the analogous systems prepared from AlR₃. With some catalysts, however, (e.g. lanthanide systems) a high activity is obtained only when transition metal compounds containing preformed metal-carbon bonds are used. Methylaluminoxanes affect also the stereospecificity of the polymerization. Active and stereospecific systems are obtained from monocyclopentadienyl derivatives of Ti and aluminoxanes. Recent views on the factors that determine stereospecificity are examined. Schemes are presented for the formation of iso- or syndiotactic polymers, with 1,2, cis-1,4 or trans-1,4 structure, from various dienes.     

Capillary GC-MS investigation of the metabolism and excretion of oxabolone in man

The metabolism of oxabolone cipionate, 17-(3-cyclopentyl-1-oxopropoxy)-4-hydroxyestr-4-en-3-one, a synthetic anabolic steroid, was investigated in man, the cumulative urinary excretion and the metabolism of the compounds being studied by GC-MS in both electron impact and chemical ionization modes. After administration by injection to volunteers, five different metabolities were detected in urine. The metabolites and the parent compound were detected in urine up to a week after administration.