Synthesis and biomimetic mineralization of l‐proline substituted polyphosphazenes as bulk and nanofiber

This work presents the synthesis of polyphosphazenes bearing L ‐proline methyl ester (ProOMe) and 4‐hydroxy‐l ‐proline methyl ester (HypOMe), aiming for new bioactive polymers for bone repair. The polymers were characterized by ¹H and ³¹P NMR, FTIR, DSC, and TGA. Electrospun fibers were prepared using poly[bis(l ‐proline methyl ester)phosphazene] (PProP), and their potential for biomimetic mineralization, as well as the bulk material, were tested in simulated body fluid (1×SBF). Samples were analyzed between 24 h and 3 weeks of incubation using SEM/EDS and FTIR. After 24 h, spherical and flower‐like shapes of calcium phosphates (CaP) were crystallized on the bulk samples. The nanofibers presented spherical CaP crystals attached to them after 48 h of incubation. The Ca/P molar ratio of the crystals varied from 1.5 to 1.6. According to this study, PProP presents bioactivity in vitro, and its fibers offer sites for CaP nucleation like the collagen fibers in bone. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1318–1327     

Retention of lysozyme activity by physical immobilization in nanocellulose aerogels and antibacterial effects

Aerogels prepared from aqueous dispersions of anionic and cationic cellulose nanofibrils (CNFs) were investigated as solid supports for enzymes and silver nanoparticles and to elicit a sustained antibacterial effect. The imparted stabilization in dry conditions was studied with aerogels that were cast after mixing the enzymes with CNFs followed by dehydration (freeze-drying). The activity of lysozyme immobilized in the given CNF system was analyzed upon storage in liquid and air media. In contrast with aqueous solutions of free, unbound enzyme, which lost activity after the first day, the enzyme immobilized physically in unmodified and cationic CNF presented better stability (activity for a longer time). However, the enzyme activity was reduced in the case of anionic CNF, which was prepared by TEMPO-mediated oxidation (TO-CNF). Both humidity and temperature reduced the stability of the enzyme immobilized in the respective CNF aerogel. The antibacterial activity of CNF aerogels carrying lysozyme was also tested against gram-negative and gram-positive bacteria. The results were compared with those obtained from CNF systems loaded with silver nanoparticles (AgNP) after in situ synthesis via UV reduction. Storage in cold or dry conditions preserved the activity and antibacterial performance of enzyme-loaded CNF aerogels. As expected, the lysozyme-containing aerogels showed lower inhibition than the AgNP-containing aerogel. In this latter case, the antibacterial activity depended on the concentration and size of the nanoparticles. Compared to unmodified CNF and TO-CNF, the aerogels prepared with cationic CNF, loaded with either lysozyme or AgNPs, showed remarkably better antibacterial activity. Similar experiments were conducted with horseradish peroxidase, which confirmed, to different degrees, the observations derived from the lysozyme systems. Overall, the results indicate that non-toxic and biodegradable CNF is a suitable support for bio-active materials and is effective in protecting and retaining enzymatic and antibacterial activities.     

A multi-scale Monte Carlo study of oxide structures on the Cu(1 0 0) surface

We present a multi-scale Monte Carlo study of the oxidation of the Cu(1 0 0) surface based on the Bortz-Kalos-Lebowitz model with the equilibrium energetics obtained from ab initio calculations. The radial and island size distribution functions are examined and Cu-O structures are analyzed at different temperatures and coverages. We concentrate on the coverages of 0.3 monolayer O or less, with variable sub-monolayer coverages of Cu. The results show that even though the ab initio calculations yield a higher barrier for O than for Cu adatom diffusion on Cu(1 0 0), the stability of Cu structures causes the O adatoms to be more mobile on the Cu(1 0 0) surface than the Cu adatoms. We are able to reproduce the c(2 × 2)-O domains seen in the experiments. However, we give an alternative explanation based on the repulsive interactions of O that, on one hand, cause the local ordering and, on the other hand, prohibits large well-ordered domains. We also give interpretation on the formation of the R45°-O reconstruction of Cu(1 0 0) above the O coverages of 0.3 monolayer based on the ab initio energetics.     

7‐(2‐Oxoalkoxy)coumarins: Synthesis and Anti‐Inflammatory Activity of a Series of Substituted Coumarins

A series of 7‐(2‐oxoalkoxy)coumarins have been synthesized by conjugating substituted 7‐hydroxycoumarins with different chloroketones. The anti‐inflammatory properties of 7‐(2‐oxoalkoxy)coumarins were studied in LPS‐induced inflammatory response in J774 macrophages. Western blot was used to determine the expression of iNOS and COX‐2, NO was determined by measuring its metabolite nitrite by Griess reaction and IL‐6 was measured by ELISA. Seventeen of the studied compounds inhibited NO and IL‐6 production over 50% at 100 μM concentrations. IC₅₀ values of the best inhibitors were 21 μM/24 μM (NO/IL‐6) for compound 12 and 30 μM/10 μM (NO/IL‐6) for compound 20 . The main result was that the substitution with 7‐(2‐oxoalkoxy) group improved the anti‐inflammatory properties of most of the investigated 7‐hydroxycoumarins.     

Noncovalent complexation of glucosylthioureidocalix[4]arenes with carboxylates and their gas-phase characteristics: an ESI-FTICR mass spectrometric study

The noncovalent complexation of three glucosylcalix[4]arenes (1-3) towards 23 mono- and dicarboxylic acid anions were studied by ESI-FTICR mass spectrometry. Competitive complexation, collision-induced dissociation and gas-phase H/D-exchange experiments were performed to obtain information on selectivity of calixarenes towards carboxylates and characteristics of their complexes. The flexibility and number of glucose units of the host and the spatial disposition of the hydrogen bonding groups on the carboxylate guests were found to affect the selectivity of complexation strongly. The glucosylcalixarenes exhibited particular selectivity for dicarboxylic acid anions incorporating π-systems, and clear isomeric selectivity was observed for isophthalic among phthalic acid anions and for fumaric acid over maleic acid anion.     

Zero distribution of solutions of complex linear differential equations determines growth of coefficients

It is shown that the exponent of convergence λ(f) of any solution f of with entire coefficients A₀(z), …, A_k?2(z), satisfies λ(f) ? λ ∈ [1, ∞) if and only if the coefficients A₀(z), …, A_k?2(z) are polynomials such that for j = 0, …, k ? 2. In the unit disc analogue of this result certain intersections of weighted Bergman spaces take the role of polynomials. The key idea in the proofs is W. J. Kim’s 1969 representation of coefficients in terms of ratios of linearly independent solutions. © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

On Interpolating Blaschke Products and?Blaschke-Oscillatory Equations

This research is partially a continuation of a 2007 paper by the author. Growth estimates for generalized logarithmic derivatives of Blaschke products are provided under the assumption that the zero sequences are either uniformly separated or exponential. Such Blaschke products are known as interpolating Blaschke products. The growth estimates are then proven to be sharp in a rather strong sense. The sharpness discussion yields a solution to an open problem posed by E. Fricain and J. Mashreghi in 2008. Finally, several aspects are pointed out to illustrate that interpolating Blaschke products appear naturally in studying the oscillation of solutions of a differential equation f″+A(z)f=0, where A(z) is analytic in the unit disc. In particular, a unit disc analogue of a 1988 result due to S. Bank on prescribed zero sequences for entire solutions is obtained, and a more careful analysis of a 1955 example due to B. Schwarz on the case A(z)=\frac1+4g²(1-z²)²A(z)=\frac{1+4\gamma^{2}}{(1-z^{2})^{2}} reveals that an infinite zero sequence is always a union of two exponential sequences.