Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

The effect of geoacoustic characteristics of the bottom on the long-range sound propagation in an inhomogeneous ocean

The long-range sound propagation from a deep ocean to a receiving system located on the shelf is modeled. The waveguide model is constructed on the basis of the data of an acoustic-oceanographic experiment carried out in the northwestern Pacific. The sensitivity and the frequency dependence of the difference in the sound field levels at the crossing of the frontal zone on the geoacoustic characteristics of the bottom of the shelf and the continental slope are investigated. It is shown that the level difference decreases by 8.2 dB as the velocity of longitudinal waves increases by 100 m/s in the range within 1490–1820 m/s.     

Factor and term ranks for matrix union over semirings

We consider the arithmetic properties of the factor-rank and term-rank functions for matrices over semirings. In particular, we investigate the sets of matrices that satisfy the extremes of inequalities for these rank functions of matrix union. The classification of the linear transformations that keep these sets invariant is obtained. __________ Translated from Fundamentalnaya i Prikladnaya Matematika, Vol. 9, No. 3, pp. 175–197, 2003.     

On entire nonnegative solutions of quasilinear inequalities of elliptic type that vanish on a set of positive measure

In the article, it is proved that any nonnegative solution of an elliptic quasilinear inequality that vanishes on a subset of positive measure is trivial. __________ Translated from Trudy Seminara imeni I. G. Petrovskogo, No. 25, pp. 112–118, 2005.     

Prognostication of aging of polymeric composite materials

Experimental data demonstrate that a study of accelerated aging can enable prognostication of the working capacity and storage life of polymeric formulations used in aircraft components on the basis of changes in thermogravimetric constants of these polymeric formulations.     

Fundamental aspects of initiated oxidation of tridecane and polyethylene in solutions

Specific features of the initiated oxidation of polyethylene and its low-molecular-weight analogue tridecane, associated with the occurrence of the process in the short-chain mode, were studied.