Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Euler characteristics of general linear sections and polynomial Chern classes

We obtain a precise relation between the Chern–Schwartz–MacPherson class of a subvariety of projective space and the Euler characteristics of its general linear sections. In the case of a hypersurface, this leads to simple proofs of formulas of Dimca–Papadima and Huh for the degrees of the polar map of a homogeneous polynomial, extending these formula to any algebraically closed field of characteristic \(0\), and proving a conjecture of Dolgachev on ‘homaloidal’ polynomials in the same context. We generalize these formulas to subschemes of higher codimension in projective space. We also describe a simple approach to a theory of ‘polynomial Chern classes’ for varieties endowed with a morphism to projective space, recovering properties analogous to the Deligne–Grothendieck axioms from basic properties of the Euler characteristic. We prove that the polynomial Chern class defines homomorphisms from suitable relative Grothendieck rings of varieties to \(\mathbb{Z }[t]\).     

Die Kristallstruktur des l, 6-8, 13-Bis-oxido-[14]-annulens

Crystals of 1,6-8, 13-bis-oxido-[14]-annulene are monoclinic, a = 9,29, b = 9,74, c = 11,46 Å, β = 90,0°, space group P 2₁/c, with 4 molecules in the unit cell. The structure has been solved by direct methods and refined by full-matrix least-squares analysis of three-dimensional intensity data. The cis-configuration of the two oxygen bridges is confirmed, and the observed molecular parameters are in full accord with the aromatic properties of the molecule.     

Selection theorems,based on generalized variation and oscillation

In this paper we prove selection theorems for everywhere and almost everywhere convergent subsequences, based on the notion of uniformly limited oscillation, ofA, Λ-oscillation and ofA, Λ-variation, whereA is a system of intervals and Λ a sequence of reals. By this, we generalize and strengthen the selection theorems of Schrader (for oscillation) and of Waterman (for Λ-variation).     

5-vinylisoxazole

Cycloaddition of fulminic acid to 1-butyn-3-ol gave a mixture of 5-α-hydroxyethylisoxazole (I) and 4-α-hydroxyethylisoxazole (II) in the ratio 9:1. By the dehydration of 1, 5-vinylisoxazole (III) was obtained. Compound III has also been prepared by cyclization of 4-penten-2-ynal as well as its diethylacetal with hydroxylamine hydrochloride; in both instances no isomers have been obtained. Compound III spontaneously polymerizes even at room temperature yielding a polymer still containing isoxazole rings.     

Steric and kinetic effects of changing solvent and reactant in grignard reactions: Conformationally mobile versus rigid δ-keto esters

trans-7α-carbomethoxy-decal-1-one (2) yields a mixture of the two oxy-esters 6 and 7 on reacting with MeMgX. Ratios $\text{6}\text{7}$ were measured for reactions performed in benzene (with X = I) and in THF (with X = Cl). The small variations of the ratios $\text{6}\text{7}$ as compared to those obtained in analogous experiments performed with methyl (2-oxo-cyclohexyl)-propionate 4 and methyl 4-methyl-5-oxo-hexanoate 5 suggest that conformational mobility plays a fundamental role in determining the variations of stereospecificity with varying the reaction conditions. Competitive Grignard reactions among 2,4 and 5 show that their reactivities are in the order 4>2>5 ($\text{K}{}_4\text{k}{}_2$ = 1.7; $\text{k}{}_5\text{k}{}_2$=0.8) when reactions are performed in benzene with X  I and 2>4>5 ($\text{k}{}_4\text{k}{}_2$= 0.56; $\text{k}{}_5\text{k}{}_2$=0.25) when reactions are performed in THF with X  C1. The experimental data are interpreted in terms of anchimeric assistance given by the ester group to the reactions of the keto group in conformationally mobile δ-keto esters. The occurrence of this effect depends on the reaction conditions which can favour, or not, folded transition states.     

Surface ablation by excimer laser irradiation of Ti and Ti6Al4V alloy

This paper presents the surface microstructure of Ti and Ti6Al4V alloy irradiated with a high output energy XeCl ( = 308 nm) excimer laser. The treatments are carried out on both materials at two beam fluences and the effects of single- and multiple-pulse irradiation are compared. The results of the scanning electron microscopy and of the X-ray diffraction techniques suggest the possible influence of both time-behaviour and energy fluence of the laser pulse on the relative weight of the ablation rate and of the reaction product deposition rate at the sample surface.