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.     

An elliptic singularly perturbed problem with two parameters I: Solution decomposition

In this paper we consider a singularly perturbed elliptic problem with two small parameters posed on the unit square. Its solution may have exponential, parabolic and corner layers. We give a decomposition of the solution into regular and layer components and derive pointwise bounds on the components and their derivatives. The estimates are obtained by the analysis of appropriate problems on unbounded domains.     

Principle of Learning Metrics for Exploratory Data Analysis

Visualization and clustering of multivariate data are usually based on mutual distances of samples, measured by heuristic means such as the Euclidean distance of vectors of extracted features. Our recently developed methods remove this arbitrariness by learning to measure important differences. The effect is equivalent to changing the metric of the data space. It is assumed that variation of the data is important only to the extent it causes variation in auxiliary data which is available paired to the primary data. The learning of the metric is supervised by the auxiliary data, whereas the data analysis in the new metric is unsupervised. We review two approaches: a clustering algorithm and another that is based on an explicitly generated metric. Applications have so far been in exploratory analysis of texts, gene function, and bankruptcy. Relationships of the two approaches are derived, which leads to new promising approaches to the clustering problem.     

Polynomiality of primal-dual affine scaling algorithms for nonlinear complementarity problems

This paper provides an analysis of the polynomiality of primal-dual interior point algorithms for nonlinear complementarity problems using a wide neighborhood. A condition for the smoothness of the mapping is used, which is related to Zhu’s scaled Lipschitz condition, but is also applicable to mappings that are not monotone. We show that a family of primal-dual affine scaling algorithms generates an approximate solution (given a precision ε) of the nonlinear complementarity problem in a finite number of iterations whose order is a polynomial ofn, ln(1/ε) and a condition number. If the mapping is linear then the results in this paper coincide with the ones in Jansen et al., SIAM Journal on Optimization 7 (1997) 126–140. Research supported in part by Grant-in-Aids for Encouragement of Young Scientists (06750066) from the Ministry of Education, Science and Culture, Japan. Research supported by Dutch Organization for Scientific Research (NWO), grant 611-304-028     

Coupling between experimental measurements and polycrystal finite element calculations for micromechanical study of metallic materials

This paper presents a methodology for multiscale coupling between the morphology and texture of a microstructure as has been characterised experimentally, and the results of mechanical strain field analysis. This methodology is based on a coupling between experimental characterisation of the microstructure, in situ and/or ex situ mechanical tests, local strain field measurements performed at the grain scale, and finite element simulations. First, with orientation imaging microscopy, a map of the microstructure is generated that can be meshed. Then, finite element calculations are carried out on this mesh, using a constitutive law which takes into account the crystallographic orientation of each grain, as has been determined by the orientation imaging itself. These numerical results are then compared to the experimental strain field as obtained by digital image correlation at the scale of the grains.     

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