Role of radicals in UV‐initiated postplasma grafting of poly‐ε‐caprolactone: An electron paramagnetic resonance study

Electron paramagnetic resonance (EPR) measurements were performed on poly‐ε‐caprolactone (PCL) films at different stages of the postplasma‐grafting process. PCL films prepared by solvent casting (SC) or electrospinning (ESP) yield very similar EPR spectra after Ar‐plasma treatment and subsequent exposure to air, but the EPR signal is much stronger in the PCL‐ESP films. The free radicals appear to be mainly, and possibly exclusively, oxygen centered. The radicals generated by UV irradiation in PCL‐ESP films were studied in situ with EPR, using a UV‐LED (λ = (285 ± 5) nm). Their EPR spectrum is distinctly different from the plasma‐induced signal, indicative of carbon‐centered radicals, and appears to be independent of the plasma pretreatment. UV‐induced homolytic splitting of (hydro)peroxide bonds was not observed. Both the plasma‐ and UV‐induced radicals decay at room temperature (RT), even in an inert atmosphere. This study demonstrates the potential of electrospun films and UV‐LEDs for the study of plasma‐ and UV‐generated free radicals with EPR in polyesters, and raises questions with respect to the validity of some generally accepted molecular mechanisms underpinning the postplasma grafting technique for polyesters. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Multipliers and singular integrals on exponential growth groups

We propose a simple abstract version of Calderón–Zygmund theory, which is applicable to spaces with exponential volume growth, and then show that important specific operators can be treated within this framework. Both authors are part of the European TMR network entitled ``Harmonic Analysis'. The first author was partially supported by KBN grant 5 P03A 050 20 and by the TMR network. The second author was partially supported by his university and by the Italian M.U.R.S.T     

Symmetries of BLT-Sets

We do the tentative beginnings of a study of BLT-sets of generalised quadrangles via their symmetries. In particular, the study of whorls about a line leads us to hyperbolic reflections preserving a BLT-set of Q(4, q).     

A General Deterministic Treatment of Derivatives in Particle Methods

A unified approach to approximating spatial derivatives in particle methods using integral operators is presented. The approach is an extension of particle strength exchange, originally developed for treating the Laplacian in advection–diffusion problems. Kernels of high order of accuracy are constructed that can be used to approximate derivatives of any degree. A new treatment for computing derivatives near the edge of particle coverage is introduced, using “one-sided” integrals that only look for information where it is available. The use of these integral approximations in wave propagation applications is considered and their error is analyzed in this context using Fourier methods. Finally, simple tests are performed to demonstrate the characteristics of the treatment, including an assessment of the effects of particle dispersion, and their results are discussed.     

Overcoming the Inhibition Effects of Citrate: Precipitation of Ferromagnetic Magnetite Nanoparticles with Tunable Morphology,Magnetic Properties,and Surface Charge via Ferrous Citrate Oxidation

This study demonstrates how the method of thermally assisted oxidative precipitation in water can be opened for—the so far neglected—metal organic iron(II) complexes (herein: citrate) in order to obtain, in one step, ferromagnetic magnetite nanoparticles, possessing essential ligand properties. Based on a dedicated analysis of the specific precursor in combination with the consideration of known properties of the ligand, it is possible to identify existing inhibition-attributes of the iron organyl such that these can be overcome. Moreover, they can be exploited in a targeted manner; thus, simply by changing concentrations, a variety of magnetite nanoparticle morphologies with distinct properties can be obtained. In the case of the herein investigated ferrous citrate, three major inhibition effects are identified. While two of them efficiently prevent the formation of magnetite and need to be addressed to be overcome, the third can be exploited to selectively synthesize, for example, relatively stable carboxyl group-bearing nuclei clusters, exhibiting the properties of magnetically responsive photonic crystals, or relatively large mesocrystals, whose intraparticular magnetic interactions are apparently disturbed.     

Diffusion-limited aggregation: A kinetic critical phenomenon?

Diffusion-limited aggregation (DLA) is a model which represents noisy growth limited by diffusion. This process is quite common in nature and the simple algorithm gives a good representation of the large-scale structure of many natural objects. The clusters grown in the computer and the real objects in question are tenuous and approximately self-similar. A good deal is known about the algorithm, but a complete theory is not yet available. I review the current state of knowledge about the model, its applications and theoretical analysis of the results.     

Superspace groups and superstructures: NbS3

The application of superspace groups to short-period superstructures is considered. For niobium tri-sulfide this is worked out in detail. It is shown that in that case the superspace group provides more symmetry then given by the space group of the supercell. Its consequences for the structure, the diffraction pattern and tensor-properties are discussed.