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.     

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.     

Poly(ethylene glycol)--oligolactates with monodisperse hydrophobic blocks: preparation, characterization, and behavior in water

Methoxypoly(ethylene glycol)-b-oligo-L-lactate (mPEG-b-OLA) diblock oligomers with monodisperse OLA blocks were obtained by fractionation of polydisperse block oligomers using preparative HPLC. The fractionated oligomers were composed of an mPEG block with a molecular weight of 350, 550, or 750 and an OLA block with a degree of polymerization of 4, 6, 8, or 10. The diblock oligomers with a low PEG content were fully amorphous, with glass transition temperatures ranging from -60 to -20 degrees C, indicating that the blocks were miscible. Upon heating aqueous dispersions of the block oligomers, cloud points, depending on the PEG/OLA ratio of the block oligomer, were observed at temperatures above 40 degrees C. The monodispersity of the hydrophobic block enabled the amphiphilic molecules to form nanoparticles in water with a hydrodynamic radius of 130-300 nm, at concentrations above the critical aggregation concentration (0.4-1 mg/mL), whereas polydisperse mPEG-b-OLAs gave formation of large aggregates. Static light scattering measurements showed that the nanoparticles have a low density (0.6-25 mg/mL), indicating that the particles are highly hydrated. In agreement herewith, the (1)H NMR spectra of nanoparticles in D2O closely resembled spectra in a good solvent for both blocks (CDCl3). It is therefore suggested that the nanoparticles contain a hydrated core of mPEG-b-OLA block oligomers, stabilized by a thin outer PEG layer. The particles were stable for two weeks, except for the mPEG350 series and mPEG750-b-OLA4, indicating that both the PEG block size and the PEG weight fraction of the oligomers determine their stability. The evident self-emulsifying properties of mPEG-b-oligo-l-lactates with monodisperse hydrophobic blocks as demonstrated in this study, together with their expected biocompatibility and biodegradability, make these systems well suitable for pharmaceutical applications.     

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.     

Magnetohydrodynamic natural convection of hybrid nanofluid in a porous enclosure: numerical analysis of the entropy generation

Journal of Thermal Analysis and Calorimetry - The effect on the entropy production and MHD convection of the hybrid nanofluid Al2O3–Cu/water (water with Cu and Al2O3 nanoparticles) in a...     

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.     

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.     

General decay of solutions of a nonlinear system of viscoelastic wave equations

This work is concerned with a system of two viscoelastic wave equations with nonlinear damping and source terms acting in both equations. Under some restrictions on the nonlinearity of the damping and the source terms, we prove that, for certain class of relaxation functions and for some restrictions on the initial data, the rate of decay of the total energy depends on those of the relaxation functions. This result improves many results in the literature, such as the ones in Messaoudi and Tatar (Appl. Anal. 87(3):247–263, 2008) and Liu (Nonlinear Anal. 71:2257–2267, 2009) in which only the exponential and polynomial decay rates are considered.     

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.     

Band gap and band offsets of GaNAsBi lattice matched to GaAs substrate

In this paper, we calculate the band gap and the band discontinuities of a GaN _y AsBi _x structure lattice matched to GaAs substrate using the conduction and the valence band anticrossing models at the same time. The results obtained show a good agreement with experiment. The nitrogen and the bismuth concentrations leading to a wavelength emission of 1.55 μm have been determined (x = 3.5%, y = 2%). This structure shows a good electron confinement resulting in a high characteristic temperature.