Systematic investigation and in vitro biocompatibility studies on mesoporous europium doped hydroxyapatite

This paper reports the systematic investigation of europium doped hydroxyapatite (Eu:HAp). A set of complementary techniques, namely Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and the Brunauer-Emmett-Teller (BET) technique were used towards attaining a detailed understanding of Eu:HAp. The XPS analysis confirmed the substitution of Ca ions by Eu ions in the Eu:HAp samples. Secondly, Eu:HAp and pure HAp present type IV isotherms with a hysteresis loop at a relative pressure (P/P₀) between 0.4 and 1.0, indicating the presence of mesopores. Finally, the in vitro biological effects of Eu:HAp nanoparticles were evaluated by focusing on the F-actin filament pattern and heat shock proteins (Hsp) expression in HEK293 human kidney cell line. Fluorescence microscopy studies of the actin protein revealed no changes of the immunolabelling profile in the renal cells cultured in the presence of Eu:HAp nanoparticles. Hsp60, Hsp70 and Hsp90 expressions measured by Western blot analysis were not affected after 24 and 48 hours exposure. Taken together, these results confirmed the lack of toxicity and the biocompatibility of the Eu:HAp nanoparticles. Consequently, the possibility of using these nanoparticles for medical purposes without affecting the renal function can be envisaged.      

Dendritic homopolymers and block copolymers: Tuning the morphology and properties

The synthesis and characterization of dendritic homopolymers and block copolymers of ?‐caprolactone and lactide (L ‐lactide and racemic lactide) were performed with multifunctional initiators in combination with living polymerization and the selective placement of branching junctures in a divergent growth strategy. A hexahydroxy‐functional 2,2‐bis(hydroxymethyl) propionic acid derivative was used as an initiator for the stannous‐2‐ethylhexanoate‐catalyzed living ring‐opening polymerization of ?‐caprolactone, L ‐lactide, and racemic L ,D ‐lactide. Branching junctions at the chain ends were introduced with benzylidene‐protected 2,2‐bis(hydroxymethyl) propionic acid. Subsequent generations were then polymerized, after deprotection, from these star‐shaped macroinitiators. Successive chain end capping and initiation produced three generations of polymers with molecular weights in excess of 130,000 g/mol and narrow polydispersities (<1.20). It was possible to prepare diblock and triblock copolymers with phase‐separated morphologies, and with L ‐lactide or D ,L ‐lactide, semicrystalline and amorphous morphologies were demonstrated. The polymers were characterized by ¹H NMR, ¹³C NMR, size exclusion chromatography, and differential scanning calorimetry. The compositions of the block copolymers and the conformational structures of the optically active polymers were also confirmed by optical rotation measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1174–1188, 2004     

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol^?1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg^?1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.     

Asymptotic analysis of solutions to parabolic systems

We study asymptotics as of solutions to a linear, parabolic system of equations with time-dependent coefficients in , where is a bounded domain. On we prescribe the homogeneous Dirichlet boundary condition. For large values of t, the coefficients in the elliptic part are close to time-independent coefficients in an integral sense which is described by a certain function . This includes in particular situations when the coefficients may take different values on different parts of and the boundaries between them can move with t but stabilize as . The main result is an asymptotic representation of solutions for large t. A consequence is that for , the solution behaves asymptotically as the solution to a parabolic system with time-independent coefficients.     

Numerical treatment of a twisted tail using extrapolation methods

Highly oscillatory integral, called a twisted tail, is proposed as a challenge in The SIAM 100-digit challenge. A Study in High-Accuracy Numerical Computing, where Drik Laurie developed numerical algorithms based on the use of Aitken’s Δ²-method, complex integration and transformation to a Fourier integral. Another algorithm is developed by Walter Gautschi based on Longman’s method; Newton’s method for solving a nonlinear equation; Gaussian quadrature; and the epsilon algorithm of Wynn for accelerating the convergence of infinite series. In the present work, nonlinear transformations for improving the convergence of oscillatory integrals are applied to the integration of this wildly oscillating function. Specifically, the transformation and its companion the W algorithm, and the G transformation are all used in the analysis of the integral. A Fortran program is developed employing each of the methods, and accuracies of up to 15 correct digits are reached in double precision.     

Isometric weighted composition operators on weighted Banach spaces of type

We characterize those weighted composition operators on weighted Banach spaces of holomorphic functions of type which are an isometry.

     

Molecular design of specific metal-binding peptide sequences from protein fragments: theory and experiment

A novel strategy is presented for designing peptides with specific metal-ion chelation sites, based on linking computationally predicted ion-specific combinations of amino acid side chains coordinated at the vertices of the desired coordination polyhedron into a single polypeptide chain. With this aim, a series of computer programs have been written that 1) creates a structural combinatorial library containing Z(i)-(X)(n)-Z(j) sequences (n=0-14; Z: amino acid that binds the metal through the side chain; X: any amino acid) from the existing protein structures in the non-redundant Protein Data Bank; 2) merges these fragments into a single Z(1)-(X)(n(1) )-Z(2)-(X)(n(2) )-Z(3)-(X)(n(3) )--Z(j) polypeptide chain; and 3) automatically performs two simple molecular mechanics calculations that make it possible to estimate the internal strain in the newly designed peptide. The application of this procedure for the most M(2+)-specific combinations of amino acid side chains (M: metal; see L. Rulísek, Z. Havlas J. Phys. Chem. B 2003, 107, 2376-2385) yielded several peptide sequences (with lengths of 6-20 amino acids) with the potential for specific binding with six metal ions (Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Hg(2+)). The gas-phase association constants of the studied metal ions with these de novo designed peptides were experimentally determined by MALDI mass spectrometry by using 3,4,5-trihydroxyacetophenone as a matrix, whereas the thermodynamic parameters of the metal-ion coordination in the condensed phase were measured by isothermal titration calorimetry (ITC), chelatometry and NMR spectroscopy methods. The data indicate that some of the computationally predicted peptides are potential M(2+)-specific metal-ion chelators.     

On non-negatively curved metrics on open five-dimensional manifolds

Let V ⁿ be an open manifold of non-negative sectional curvature with a soul Σ of co-dimension two. The universal cover of the unit normal bundle N of the soul in such a manifold is isometric to the direct product M ^n-2 × R. In the study of the metric structure of V ⁿ an important role plays the vector field X which belongs to the projection of the vertical planes distribution of the Riemannian submersion on the factor M in this metric splitting . The case n = 4 was considered in [Gromoll, D., Tapp, K.: Geom. Dedicata 99, 127–136 (2003)] where the authors prove that X is a Killing vector field while the manifold V ⁴ is isometric to the quotient of by the flow along the corresponding Killing field. Following an approach of [Gromoll, D., Tapp, K.: Geom. Dedicata 99, 127–136 (2003)] we consider the next case n = 5 and obtain the same result under the assumption that the set of zeros of X is not empty. Under this assumption we prove that both M ³ and Σ³ admit an open-book decomposition with a bending which is a closed geodesic and pages which are totally geodesic two-spheres, the vector field X is Killing, while the whole manifold V ⁵ is isometric to the quotient of by the flow along corresponding Killing field. Supported by the Faculty of Natural Sciences of the Hogskolan i Kalmar (Sweden).     

Going to extremes: "super" armed glycosyl donors in glycosylation chemistry

This concept article gives an overview of stereoelectronic effects in monosaccharide systems and how these can be used to dramatically enhance the reactivity of glycosyl donors in oligosaccharide synthesis.