Amphiphilic graft copolymers with poly(oxyethylene) side chains: Synthesis via activated ester intermediates—properties

Amphiphilic graft copolymers were synthesized via activated ester substitution of derivatives of fumaric acid with amino-functionalized methoxypoly (oxyethylene)s (MPEO-NH₂) of different molecular weights. The monomeric activated esters, isopropyl pentachlorophenyl fumarate (PCPFA) and isopropyl succinimido fumarate (SIFA), were copolymerized with styrene (St) or N-vinyl pyrrolidone (VP) at equimolar ratio. The polymeric-activated esters proved to be good precursors for grafting of definite amounts of MPEO-NH₂. The aminolysis of the succinimide esters and VP-containing copolymers proceeded with gel formation due to extensive hydrogen bonding. The hydrodynamic behavior, the emulsifying ability, the thermal properties, and crystallinity of the graft copolymers were studied as a function of their molecular characteristics. The length of the PEO grafts and the degree of grafting are the factors which affect the melting parameters and the crystallinity of the side chains. © 1994 John Wiley & Sons, Inc.     

On the stability of Timoshenko-type systems with internal frictional dampings and discrete time delays

In this paper, we consider a vibrating system of Timoshenko-type in a bounded one-dimensional domain under Dirichlet–Dirichlet or Dirichlet–Neumann boundary conditions with one or two discrete time delays and one or two internal frictional dampings. First, we show that the system is well posed in the sens of semigroup theory. Second, we prove the exponential stability regardless to the speeds of wave propagation of the system if the weights of the time delays are smaller than the ones of the corresponding dampings, respectively. However, when the weight of one time delay is not smaller than the one of the corresponding damping, we prove the exponential stability in case of equal-speed wave propagation, and the polynomial stability in the opposite case.     

Structure refinements of cadmium substituted lead fluoroapatites by powder X-ray pattern fitting

Solid solutions of cadmium and lead fluoroapatite [Pb_(10−x)Cd_x(PO₄)₆F₂ (0?x?5)] were synthesized by a wet process in a basic medium. Replacement of lead by cadmium induces a linear variation of the crystallographic parameters “a” and “c” according to Végard's law. The cadmium content, as obtained from the refinement, is in agreement with the chemical analysis. The distribution of the lead and cadmium ions between two non-equivalent crystallographic sites, M(1) and M(2), was determined by the Rietveld method. The site-occupancy factors of atoms clearly indicate a preference of cadmium for site M(1) in the apatite structure in agreement with its smaller ionic radii. A progressive shift of the F⁻ ion toward the center of the triangles formed by the site M(2) metals has been observed with increasing cadmium content.     

Large time and space size behaviour of the heat equation in non-cylindrical domains

In this note we consider a linear parabolic problem defined on a non-cylindrical unbounded domain Q. If Ω _t denotes the section of Q above t, the Ω _t size goes to +∞, when t → +∞, i.e. the sections Ω _t become unbounded in some directions when the time t becomes large. Here a model problem is studied, but the technique used can be applied for a wide class of problems, as nonlinear ones, defined on more general domains Q as those introduced by Lions [11]. An asymptotically exponential convergence of the solutions of such problems towards the solution of an elliptic problem defined on a lower dimensional domain is established.     

Physicochemical characterization of degradable thermosensitive polymeric micelles

Amphiphilic AB block copolymers consisting of thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) and poly(ethylene glycol), pHPMAmDL-b-PEG, were synthesized via a macroinitiator route. Dynamic light scattering measurements showed that these block copolymers form polymeric micelles in water with a size of around 50 nm by heating of an aqueous polymer solution from below to above the critical micelle temperature (cmt). The critical micelle concentration as well as the cmt decreased with increasing pHPMAmDL block lengths, which can be attributed to the greater hydrophobicity of the thermosensitive block with increasing molecular weight. Cryogenic transmission electron microscopy analysis revealed that the micelles have a spherical shape with a narrow size distribution. 1H NMR measurements in D2O showed that the intensity of the peaks of the protons from the pHPMAmDL block significantly decreased above the cmt, indicating that the thermosensitive blocks indeed form the solidlike core of the micelles. Static light scattering measurements demonstrated that pHPMAmDL-b-PEG micelles with relatively large pHPMAmDL blocks possess a highly packed core that is stabilized by a dense layer of swollen PEG chains. FT-IR analysis indicated that dehydration of amide bonds in the pHPMAmDL block occurs when the polymer dissolved in water is heated from below to above its cmt. The micelles were stable when an aqueous solution of micelles was incubated at 37 degrees C and at pH 5.0, where the hydrolysis rate of lactate side groups is minimized. On the other hand, at pH 9.0, where hydrolysis of the lactic acid side groups occurs, the micelles started to swell after 1.5 h of incubation and complete dissolution of micelles was observed after 4 h as a result of hydrophilization of the thermosensitive block. Fluorescence spectroscopy measurements with pyrene loaded in the hydrophobic core of the micelles showed that when these micelles were incubated at pH 8.6 and at 37 degrees C the microenvironment of pyrene became increasingly hydrated in time during this swelling phase. The results demonstrate the potential applicability of pHPMAmDL-b-PEG block copolymer micelles for the controlled delivery of hydrophobic drugs.     

Covalent modification of calcium hydroxyapatite surface by grafting phenyl phosphonate moieties

The reaction between phenyl phosphonic dichloride (C₆H₅P(O)Cl₂) and synthetic calcium hydroxy- and fluorapatite has been investigated. The presence of mono- or polymeric (C₆H₅PO) fragment bound to hydroxyapatite was evidenced by IR, and solid-state ³¹P NMR spectroscopy. X-ray powder analysis has shown that the apatitic structure remains unchanged during the reaction. In contrast, no reaction was found using fluorapatite. According to the results found for these two different apatites a mechanism was proposed for the formation of covalent P-O-P bonds as the result of a reaction between the C₆H₅P(O)Cl₂ organic reagent and (HPO₄)⁻ and/or OH⁻ ions of the hydroxyapatite.     

Well posedness and asymptotic behavior of a wave equation with distributed time‐delay and Neumann boundary conditions

This paper is concerned with the asymptotic behavior analysis of solutions to a multidimensional wave equation. Assuming that there is no displacement term in the system and taking into consideration the presence of distributed or discrete time delay, we show that the solutions exponentially converge to their stationary state. The proof mainly consists in utilizing the resolvent method. The approach adopted in this work is also used to other physical systems.     

Synthesis,X-ray structure and theoretical study of benzazole thioether and its zinc complex as corrosion inhibitors for steel in acidic medium

A ligand, 2-((benzo[d]thiazol-2-ylthio)methyl)-1H-benzo[d]imidazole, and its zinc complex have been synthesized. The structure of these compounds have been determined by spectroscopic techniques and single crystal X-ray diffraction. The corrosion inhibition study of these compounds for steel in 0.5 M H₂SO₄ medium has also been investigated using potentiodynamic polarization and EIS techniques. The quantum calculations were applied to investigate the relationship between the electronic properties and the corrosion inhibition efficiency of the two benzazoles derivatives. Surface analysis (XRF) indicated that the rust layer formed on the Cu-containing steels was enriched with Cu compounds. Polarization curves revealed that both inhibitors acted as a mixed-type inhibitor.     

Uniform and weak stability of Bresse system with two infinite memories

In this paper, we consider one-dimensional linear Bresse systems in a bounded open domain under Dirichlet–Neumann–Neumann boundary conditions with two infinite memories acting only on two equations. First, we establish the well-posedness in the sense of semigroup theory. Then, we prove two (uniform and weak) decay estimates depending on the speeds of wave propagations, the smoothness of initial data and the arbitrarily growth at infinity of the two relaxation functions.