Poly(ethylene terephthalate) copolymers containing 5‐nitroisophthalic units. II. Crystallization studies

The microstructure and crystallization behavior of a set of poly(ethylene terephthalate‐co‐5‐nitroisophthalate) copolymers (PETNI) containing 5‐nitroisophthalic units in the 10–50 mol % range were examined and compared to those of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) copolymers. A ¹³C NMR analysis of PETNI copolymers in a trifluoroacetic acid solution indicates that they are random copolymers with average sequence lengths in accordance with ideal polycondensation statistics. Differential scanning calorimetry (DSC) studies show that PETNI containing 5‐nitroisophthalic units up to 20 mol % are able to crystallize and that crystallization takes place in these copolymers at much slower rates than in PET. Wide‐angle X‐ray diffraction from powder and fibers reveals that crystallizable PETNI adopts the same triclinic crystal structure as PET, with the nitroisophthalate units being excluded from crystallites. Fourier transform infrared in combination with cross‐polarization/magic‐angle spinning ¹³C NMR spectroscopy demonstrates the occurrence of a gauche–trans conversion encompassing the crystallization process. A correlation between DSC and spectroscopic data leads us to conclude that the content of trans conformer in the noncrystallized phase of PETNI is higher than in both PET and PETI copolymers and suggests that secondary crystallization in the homopolymer must proceed by a mechanism different than that in copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1553–1564, 2001     

Ether drift experiments and electromagnetic momentum

Propagation of Aharonov-Bohm matter waves and light waves in moving media is characterized by the interaction electromagnetic momentum. Thus, recent models of light propagation in moving rarefied media justify and call for an optical experiment of the Mascart-Jamin type, capable of testing the modern interpretations of ether drift experiments.     

Carbon and nitrogen distribution in the sediments of lagoon of Ravenna (Italy)

The distribution and the origin of carbon and nitrogen in sediments of an Italian lagoon--located north-east of Ravenna town--were investigated. From 1957 to 1976, the lagoon had been affected by a strong industrial pollution due to an important petrochemical complex. At present, industrial and domestic waste waters undergo a treatment process before being discharged into the lagoon. Sediment samples from 10 locations throughout the lagoon were analysed, in order to document the spatial and vertical distribution of C and N. Data show a very strong variability (organic carbon content varies between 8.9% and 0.14%) and the highest values were found in the immediate vicinity of the industrial discharge. Sediment organic matter shows allochthonous origin in proximity of industrial discharge and autochthonous origin in the remaining areas.     

Versatile, diastereoselective additions of silyl ketene acetals, allyl tributylstannane, and Me(3)SiCN to N-acyl pyrazolines: asymmetric synthesis of densely functionalized pyrazolidines

We report the diastereoselective addition of a wide range of nucleophiles to chiral pyrazolines to provide facile access to a range of useful densely functionalized building blocks for asymmetric synthesis. Coupled with the asymmetric cycloaddition reaction of Me(3)SiCHN(2) to chiral acrylates, access to these chiral heterocycles is considerably expanded.     

About the definition of mass in (Machian) classical mechanics

We want in this note to clarify some aspects of the Machian foundation of the concept of mass in classical mechanics; specifically, we show how the relations of transitivity for the mass-ratios, necessary for a well grounded definition of mass, can be derived from Machian postulates.     

Analysis of models for the ziegler-natta stereospecific polymerization on the basis of non-bonded interactions at the catalytic site—II: Edges,steps and reliefs on the surface of layered modifications of TiCl3

The computations performed in a previous paper for hypothetical structures of the site active in the polymerization of olefins at the (110) surfaces of TiCl₃-α are extended to edges, steps and reliefs on (111) surfaces of all the layered modifications of TiCl₃. Our computations suggest that edges, steps and reliefs of all the layered modifications of TiCl₃ should behave similarly in providing active sites; polymerization should occur on these more exposed sites because of the much lower activation energies than for plain surfaces. A unique general model emerges: lower steric repulsions appear to be implied for a coordination of the polymeric chain on the more hindered octahedral position at a titanium atom and this, in turn, causes a chiral orientation of the first carbon-carbon bond of the chain. This orientation may be the main factor in determining the stereospecificity.     

Global regular and singular solutions for a model of gravitating particles

The existence of solutions of a nonlinear parabolic equation describing the gravitational interaction of particles is studied for the initial data in spaces of (generalized) pseudomeasures. This approach permits us to relax regularity assumptions on the initial conditions and to prove asymptotic stability results for the above problem.Mathematics Subject Classification (2000):35B40, 35K15, 82C21     

Regioselective cyclization of alpha,omega-alkynoic acids catalysed by TpRu complexes: synthesis of endocyclic enol lactones [Tp = hydrotris(pyrazolyl)borate

The sigma-enynyl complex [TpRu(C(Ph)=C(Ph)C identical to CPh)(P-MeiPr2)] efficiently catalyses the regioselective cyclization of alpha,omega-alkynoic acids to yield endocyclic enol lactones having ring size up to 12 atoms.     

On Logarithmic Smoothing of the Maximum Function

We consider the maximum function f resulting from a finite number of smooth functions. The logarithmic barrier function of the epigraph of f gives rise to a smooth approximation g of f itself, where >0 denotes the approximation parameter. The one-parametric family g converges – relative to a compact subset – uniformly to the function f as tends to zero. Under nondegeneracy assumptions we show that the stationary points of g and f correspond to each other, and that their respective Morse indices coincide. The latter correspondence is obtained by establishing smooth curves x() of stationary points for g , where each x() converges to the corresponding stationary point of f as tends to zero. In case of a strongly unique local minimizer, we show that the nondegeneracy assumption may be relaxed in order to obtain a smooth curve x().