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F Callens

Publications and source records attributed to F Callens.

At least 19 recordsLinked to original sources
PubMed2006

X- (X = O, S) ions in alkali halide lattices through density functional calculations. 1. Substitutional defect models.

Monoatomic X- (X = O, S) chalcogen centers in MZ (M = Na, K, Rb and Z = Cl, Br, I) alkali halide lattices are investigated within the framework of density functional theory with the principal aim to establish defect models. In electron paramagnetic resonance (EPR) experiments, X- defects with tetragonal, orthorhombic, and monoclinic g-tensor symmetry have been observed. In this paper, models in which X- replaces a single halide ion, with a next nearest neighbor and a nearest neighbor halide vacancy, are validated for the X- centers with tetragonal and orthorhombic symmetry, respectively. As such defect models are extended, the ability to reproduce experimental data is a stringent test for various computational approaches. Cluster in vacuo and embedded cluster schemes are used to calculate energy and EPR parameters for the two vacancy configurations. The final assignment of a defect structure is based on the qualitative and quantitative reproduction of experimental g and (super)hyperfine tensors.

Journal Article↗
PubMed2006

X- (X = O, S, Se) Ions in alkali halide lattices through density functional calculations. 2. Interstitial defect models.

Density functional theory techniques are used to investigate the defect structure of X- (X = O, S, Se) ions in MZ (M = Na, K, Rb and Z = Cl, Br) alkali halides which exhibit monoclinic-I g-tensor symmetry, using cluster in vacuo, embedded cluster, and periodic embedding schemes. Although a perturbed interstitial defect model was suggested from electron paramagnetic resonance experiments (EPR), the nature of the perturbation is still unknown. An appropriate defect model is developed theoretically by comparing structural and energetical properties of various defect configurations. Further validation is achieved by cross referencing experimental and computed EPR data. On the basis of the computational results, the following defect model is proposed: the X- ion is located interstitially with a charge compensating halide vacancy in its first coordination shell.

Journal Article↗
PubMed2006

Density functional investigation of high-spin XY (X = Cr, Mo, W and Y = C, N, O) molecules.

The performance of a density functional theory approach in calculating the equilibrium bond length, dipole moment, and harmonic vibrational frequency in a series of group 6 (Cr, Mo, W) transition metal-containing diatomic molecules is evaluated. Using flexible basis sets comprised of Slater type functions, a wide range of exchange-correlation functionals is investigated. Comparing with known experimental values and published results from high-level theoretical calculations, the most suitable functional form is selected. The importance of relativistic effects is checked, and predictions are made for several unknown dipole moments. The best agreement with experimental parameters is obtained when using a general gradient approximation, while special and hybrid functional forms give less accurate results.

Journal Article↗
PubMed2005

Multi-frequency electron paramagnetic resonance study of irradiated human finger phalanxes.

Electron paramagnetic resonance (EPR) is often used in dosimetry using biological samples such as teeth and bones. It is generally assumed that the radicals, formed after irradiation, are similar in both tissues as the mineral part of bone and tooth is carbonated hydroxyapatite. However, there is a lack of experimental evidence to support this assumption. The aim of the present study was to contribute to that field by studying powder and block samples of human finger phalanxes that were irradiated and analyzed by multi-frequency EPR. The results obtained from bones are different from the ones obtained in enamel by several respects: the ordering of the apatite crystallites is much smaller in bone, complicating the assignment of the observed CO2- radicals to a specific location, and one type of CO3(3-) radical was only found in enamel. Moreover, a major difference was found in the non-CO2- and non-CO3(3-) signals. The elucidation of the nature of these native signals (in bone and tooth enamel) still represents a big challenge.

Bone and Bones↗
PubMed2004

Effect of different sterilisation methods on the properties of bioadhesive powders and ocular minitablets, and clinical evaluation.

The purpose of this study was to evaluate the influence of gamma-irradiation and dry heat sterilisation on the properties of a bioadhesive powder mixture containing ciprofloxacin and its corresponding ocular minitablets. The molecular weight characteristics of drum dried waxy maize starch (DDWM), employed as major component of the bioadhesive formulation, the decay kinetics of radicals, the rheological properties of the bioadhesive polymers and the microbial activity of ciprofloxacin were studied. The influence of the different sterilisation methods on the characteristics of the ocular minitablets was investigated by measuring the crushing strength, the friability, and the in vitro release of ciprofloxacin from the minitablets. Finally, the clinical value of the selected sterilised minitablets was evaluated in seven healthy volunteers. Both sterilisation methods similarly affected the properties of the bioadhesive formulation by inducing stable radicals and decreasing the molecular weight of DDWM, although no changes in the microbiological activity of ciprofloxacin were measured. An obvious influence of both sterilisation methods was observed in the in vitro release study. The crushing strength and friability of the minitablets were not significantly influenced by gamma-irradiation. Based on these data, gamma-irradiation was more adequate as sterilisation method for the bioadhesive ocular minitablets than dry heat sterilisation, because it affected the least the physical properties of the minitablets. Therefore, the gamma-sterilised minitablets were selected for an in vivo evaluation in seven volunteers. The concentration of ciprofloxacin in the tear film remained above its MIC value for the most common ocular pathogens for at least 8 h. Consequently, the gamma-irradiated minitablets containing ciprofloxacin can be considered as a promising formulation to treat bacterial keratitis and conjunctivitis.

Adhesives↗
PubMed2002

Some recent multi-frequency electron paramagnetic resonance results on systems relevant for dosimetry and dating.

Electron Paramagnetic Resonance (EPR) applications like e.g. EPR dosimetry and dating, are usually performed at X-band frequencies because of practical reasons (cost, sample size, etc.). However, it is increasingly recognized that the radiation-induced EPR signals are strongly composite, what might affect dose/age estimates. A few recent examples from both the dosimetry and dating field, illustrating the problems, will be presented. The involved spectra are mainly due to carbonate-derived radicals (CO2-, CO3(3-), etc.). Measurements at higher microwave frequencies are often recommended to improve the insight into the spectra and/or the practical signal quantification. Recent results at Q- and W-band frequencies will show that a multi-frequency approach indeed opens many interesting perspectives in this field but also that each frequency may have specific (dis)advantages depending on the EPR probe and application involved. The discussion will concern carbonate-containing apatite single crystals, shells, modern and fossil tooth enamel.

Carbon Isotopes↗
PubMed2001

Multifrequency EPR study of carbonate- and sulfate-derived radicals produced by radiation in shells and corallite.

Shells of two sea mollusks (Venus sp.), pearl oyster (Meleagrina vulgaris) and corallite (white coral) were exposed to ionizing radiation (gamma and X rays) and then examined by EPR spectroscopy in X, Q and W band. The resulting spectra were analyzed and the g values of the EPR lines in the multicomponent spectra were determined. The increased resolution in Q- and W-band spectra allowed us to assign the observed lines to CO(2)(-) ion radicals (isotropic and orthorhombic), SO(2)(-) isotropic, SO(3)(-) (isotropic and axial), and Mn(2+) species. The assignments were confirmed by simulations of the spectra. Practical implications for the use of Q and/or W band in low-dose quantitative EPR measurements for dating and for accidental dose estimation are discussed.

Animals↗
PubMed2000

Magnetic resonance study of Rh complexes in AgCl microcrystals.

X-ray or UV irradiation at room temperature of Rh3+ doped AgCl emulsion powders leads to the production of three paramagnetic Rh2+ related centres, labeled R4, R5 and R6. A combined X and Q band electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) study allowed the determination of a nearly complete structural model for these centres. In the X band ENDOR spectra of R4 and R5 interactions of the unpaired electron with nearby protons have been identified, indicating that for these centres Cl- ligands have been exchanged by H2O or OH-. The R6 centre, identified as a (RhCl6)4- complex, has been found to be fundamentally different from the dominant centre in large Rh2+ doped AgCl single crystals grown from the melt. The results are compared with recent work by other researchers in the same field.

Crystallization↗
PubMed2000

A decomposition study of the EPR spectrum of irradiated sucrose

In general, the EPR spectra of irradiated sugars are very complex because of their multicomponent character. In this study we applied a multivariate statistical method called MLCFA, maximum likelihood common factor analysis, and it predicted at least six components contributing to the total EPR spectrum of irradiated sucrose. Three dominant components have already been isolated in an irradiated sucrose single crystal using electron nuclear double resonance (ENDOR) and ENDOR induced EPR (EI-EPR). Results of EPR simulations based on the ENDOR data are in a reliable agreement with the experimental EPR spectra of irradiated sucrose single crystals.

Journal Article↗
PubMed2000

EPR spectrum deconvolution and dose assessment of fossil tooth enamel using maximum likelihood common factor analysis.

In order to determine the components which give rise to the EPR spectrum around g = 2 we have applied Maximum Likelihood Common Factor Analysis (MLCFA) on the EPR spectra of enamel sample 1126 which has previously been analysed by continuous wave and pulsed EPR as well as EPR microscopy. MLCFA yielded agreeing results on three sets of X-band spectra and the following components were identified: an orthorhombic component attributed to CO2-, an axial component (CO3(3-)), as well as four isotropic components, three of which could be attributed to SO2-, a tumbling CO2- and a central line of a dimethyl radical. The X-band results were confirmed by analysis of Q-band spectra where three additional isotropic lines were found, however, these three components could not be attributed to known radicals. The orthorhombic component was used to establish dose response curves for the assessment of the past radiation dose, D(E). The results appear to be more reliable than those based on conventional peak-to-peak EPR intensity measurements or simple Gaussian deconvolution methods.

Animals↗
PubMed2000

ESR study of elephant tooth enamel from the Kärlich-Seeufer site in Germany.

Enamel from 6 different positions in a well preserved elephant tooth from the Kärlich-Seeufer site in Germany has been irradiated up to 32 kGy. The X-band (v = 9.5 GHz) ESR spectra of two subsamples have been decomposed into three real components with Maximum Likelihood Common Factor Analysis (MLCFA). One of these components due to orthorhombic CO2- radicals is predominant. Dose response curves for the contributions of these MLCFA components and for different heights in the ESR spectra have been obtained and fitted with different models. Depending on the model, the equivalent dose for the preferably used height at g = 1.9973, due to CO2-, ranges from 70 to 130 Gy. Due to a very low uranium and thorium content in both enamel and dentine (< or = approximately 10 ppb) and to an important external y-attenuation, the ages fluctuate between 300 and 575 ka.

Animals↗
PubMed1998

Electron-nuclear double resonance of human tooth enamel heated at 400 degreesC.

Powdered tooth enamel heated at 400 degreesC has been examined with electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIEPR) methods and compared with hydroxyapatite synthesized at high temperature. The EPR spectrum of the tooth enamel sample consists mainly of signals assigned to O- and CO2- radicals, in contradistinction to the synthetic apatite sample, where signals of O- and CO33- were detected. The ENDOR results of heated enamel show that the O- radical is located at an A site and interacts with three unequivalent sets of 31P nuclei and two unequivalent protons. This supports the model proposed for synthetic apatite. The EIEPR results show that the 31P and 1H ENDOR resonances originate from both O- and CO2- radicals and that the 23Na and 19F resonances originate only from a CO2- radical located probably at the surface.

Carbon Dioxide↗
PubMed1995

An EPR study of intact and powdered human tooth enamel dried at 400 degrees C.

An EPR study of human tooth enamel dried at 400 degrees C is presented. Enamel blocks as well as powdered samples were investigated. The discussion deals mainly with three different spectral components, i.e., a CO3(3-) and two different CO2- signals. Using the anisotropic enamel block spectra, a convincing differentiation between the latter two radicals was possible. The first CO2- signal shows no dependence on the orientation of the enamel blocks, disappears from the spectrum upon heating, and was assigned to a surface radical. The second CO2- component is mainly responsible for the angular variation of the enamel blocks and is assigned to a bulk position. For the CO3(3-) ion, the (pseudo) angular variation of its isolated spectrum is presented and discussed. By means of the results presented in this study, earlier interpretation problems are considerably reduced.

Apatites↗