Biomarkers of Fluoride in Children Exposed to Different Sources of Systemic Fluoride

There has been no comparison between fluoride concentrations in urine and nails of children exposed to different sources of systemic fluoride. The aim of this study was to compare the relationship between fluoride intake with urinary fluoride excretion and fluoride concentrations in fingernails and toenails of children receiving fluoride from artificially fluoridated water (0.6-0.8 mg F/L, n = 25), naturally fluoridated water (0.6-0.9 mg F/L, n = 21), fluoridated salt (180-200 mg F/Kg, n = 26), and fluoridated milk (0.25 mg F, n = 25). A control population was included (no systemic fluoride, n = 24). Fluoride intake from diet and dentifrice, urinary fluoride excretion, and fluoride concentrations in fingernails/toenails were evaluated. Fluoride was analyzed with an ion-selective electrode. Urinary fluoride excretion in the control community was significantly lower when compared with that in the fluoridated cities, except for the naturally fluoridated community. However, the same pattern was not as evident for nails. Both urinary fluoride output and fluoride concentrations in fingernails/toenails were significantly correlated to total fluoride intake. However, the correlation coefficients for fluoride intake and urinary fluoride output were lower (r = 0.28, p < 0.01) than those observed for fingernails/toenails (r = 0.36, p < 0.001), suggesting that nails might be slightly better indicators of fluoride intake at the individual level.

gamma-Radiation induces apoptosis via sarcoplasmatic reticulum in guinea pig ileum smooth muscle cells

We investigated the effects of gamma-radiation on cells isolated from the longitudinal smooth muscle layer of the guinea pig ileum, a relatively radioresistant tissue. Single doses (up to 50 Gy) reduced the amount of sarcoplasmatic reticulum and condensed the myofibrils, as shown by electron microscopy 3 days post-irradiation. After that, contractility of smooth muscle strips was reduced. Ca(2+) handling was altered after irradiation, as shown in fura-2 loaded cells, with elevated basal intracellular Ca(2+), reduced amount of intrareticular Ca(2+), and reduced capacitive Ca(2+) entry. Radiation also induced apoptosis, judged from flow cytometry of cells loaded with proprium iodide. Electron microscopy showed that radiation caused condensation of chromatin in dense masses around the nuclear envelope, the presence of apoptotic bodies, fragmentation of the nucleus, detachment of cells from their neighbors, and reductions in cell volume. Radiation also caused activation of caspase 12. Apoptosis was reduced by the administration of the caspase inhibitor Z-Val-Ala-Asp-fluoromethyl-ketone methyl ester (Z-VAD-FIVIK) during the 3 day period after irradiation, and by the chelator of intracellular Ca(2+), 1,2-bis(o-aminophenoxy)ethane-N,N,N`,N`-tetraacetic acid (BAPTA), from 1 h before until 2 h after irradiation. BAPTA also reduced the effects of radiation on contractility, basal intracellular Ca(2+), amount of intrareticular Ca(2+), capacitative Ca(2+) entry, and apoptosis. In conclusion, the effects of gamma radiation on contractility, Ca(2+) handling, and apoptosis appear due to a toxic action of intracellular Ca(2+). Ca(2+)-induced damage to the sarcoplasmatic reticulum seems a key event in impaired Ca(2+) handling and apoptosis induced by gamma-radiation. (c) 2008 Elsevier B.V. All rights reserved.

A study of the vacuum gamma-radiolysis of two aromatic polyimide fluoropolymers containing phenylphosphine oxide

The vacuum gamma -radiolysis of two fluorinated polyimides containing phenylphosphine oxide units, TOR-RC and TOR-RC ODPA, have been studied at 77 K and 300 K. The phenyl phosphine oxide units provide protection of the polymers towards oxidation by oxygen atoms and the bulky fluoromethyl groups reduce the colouration of the polymers by limiting donor-acceptor complex formation through the aromatic units. At 77 K the radicals formed were identified to be a mixture of neutral radicals (60%) and anion radicals. At 300 K only neutral radicals were found. The G-values for radical formation were found to be 0.50 and 0.42 at 77 K and 0.051 and 0.052 at 300 K for TOR-RC and TOR-RC ODPA, respectively. Little change was observed in the visible spectra of the polyimides following vacuum radiolysis at 300 K up to a dose of 3.3 MGy, and the polymers were shown to undergo net cross linking with a gel dose of 0.45 MGy.

A study of the oxidation of two aromatic polyimide fluoropolymers containing phenylphosphine oxide by a water plasma and gamma-radiolysis in air

The oxidation of two fluorinated polyimides containing phenylphosphine oxide units, TOR-RC and TOR-RC ODPA, have been studied at 300 K for treatment by a water plasma and gamma -radiolysis in air. The changes in the O 1s/C 1s ratios obtained from x-ray photoelectron spectroscopy (XPS) analysis showed that for exposure to the water plasma the ratio increases at short exposure times and then levels to a constant value. Evidence for the formation of phosphate species was also obtained from the XPS analyses. Similar observations were made for gamma -radiolysis of the polymers in air. The polymers containing phenylphosphine oxide were found to be more resistant to oxidation in the water plasma than Kapton(R). Radiolysis of the polymers in air to high doses were also accompanied by a red shift in the visible absorption spectra.

An ESR study of the gamma radiolysis of aromatic polyesters containing isomeric naphthalene links

Six polyesters were synthesised from 4,4 ' -oxy-bis(benzoyl chloride) and 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, and 2,7-naphthalenediol isomers. The structures of the polyesters were characterised by means of IR, inherent viscosities in tetrachloroethane (TCE), solutions at 303 K and thermal analysis. The glass transition temperatures were in the range of 425-494 K by DSC thermal analysis. All of the polyesters were irradiated in an AECL Gammacell 220 unit at a dose rate of approximately 6.7 kGy/h to doses in the range of 0-15 kGy at 77 and 300 K. ESR spectroscopy was used to examine the radicals formed during radiolysis and to measure their yields. The G-values for radical formation in the polyesters were found to be in the range 0.18-1.41 at 77 K and 0.19-0.78 at 300 K. At 77 K, up to 15% of the radicals formed on radiolysis were found to be photo-bleachable anion radicals. Annealing experiments were carried out in order to identify the neutral radicals, which were assigned to naphthyl- or phenyl- and phenoxyl-type radicals. (C) 2001 Elsevier Science Ltd. All rights reserved.

An ESR study on gamma-irradiated poly(vinyl alcohol)

The formation of radicals in poly(vinyl alcohol), PVA, powder irradiated at 77 K by gamma -rays and the transformations of these radicals during photolysis with visible wavelengths and on thermal annealing have been studied. After irradiation a four-line ESR spectrum was observed. It was assigned to a triplet of the C-alpha-radical (38%), with a splitting of 3.27 mT, superimposed on a doublet (62%) with a splitting of 2.7 mT. The doublet appears to be composed of two radicals, one of which is photo-bleachable (58%) and the other which is not photo-bleachable (42%). This suggests that the latter radical is a neutral radical. The photo-bleachable component of the doublet has been assigned to a carbonyl anion radical. but the second doublet due to a neutral radical is unassigned. The total G-value for formation of radicals at 77 K was found to be 2.41 +/- 0.03. Upon illumination with visible light, the anion radicals were removed and the doublet components or the spectrum diminished in intensity, while the three-line spectrum of the C-alpha-radical became more clearly visible. This transition was due to the photo-detachment of electrons from traps which were proposed to be located on carbonyl groups in the polymer resulting from incomplete hydrolysis of the vinyl acetate. The photo-decay of the anion radicals could be satisfactorily described by a two-stage process. The first stage comprised the decay of approximately 80% of the anion radicals present, while the second stage was associated with the decay of the remaining 20%. Subsequent thermal annealing of a photolysed sample to 290 K led to a change in the shape of the spectrum to form a more clearly defined triplet, As the doublet of the neutral radical decays on thermal annealing between 150 and 250K, the C-alpha-radical is formed. (C) 2001 Elsevier Science Ltd. All rights reserved.

The behaviour of phenylphosphine oxide containing polyimides in a water plasma following gamma-radiolysis

The surface oxidation of two polyimides containing fluorinated phenylphosphine oxide units, TOR-RC and TOR-RC ODPA, have been studied by (XPS) spectroscopy following gamma -radiolysis under vacuum or in air and subsequent treatment in a water plasma. The changes in the O 1s/C 1s ratios obtained from (XPS) analysis showed that on exposure to the water plasma the ratio increases and then levels to a constant value which is similar to that found for exposure to the plasma without prior gamma -radiation treatment. Evidence for the formation of phosphate species was also obtained from the (XPS) analyses. (C) 2001 Elsevier Science Ltd. All rights reserved.

Molecular weight changes and scission and crosslinking in poly(dimethyl siloxane) on gamma radiolysis

The molecular weight changes which occur on the gamma -radiolysis of poly(dimethyl siloxane) under vacuum between 77 and 373 K and in air at 303 K have been investigated using triple detection GPC to obtain the complete molecular weight distributions for the irradiated samples and to determine the number and weight average molecular weights. The results have been interpreted in terms of the relative yields of scission and crosslinking. The total yields for crosslinking predominate over those for scission at all the temperatures investigated for radiolysis under vacuum. Based on a solid-state Si-29 NMR analysis of PDMS irradiated under vacuum at 303 K, which yielded a value of G(Y) of 1.70, the values of G(S) = 1.15 +/-0.2 and G(H) = 1.45 +/-0.2 were obtained for radiolysis under vacuum at 303 K. For radiolysis in air at 303 K, crosslinking was also predominant, but the nett yield of crosslinking was much less than that observed for radiolysis under vacuum. Under the conditions of the radiolysis in air at 303 K, because of the low solubility of oxygen in PDMS, it is likely that the radiation chemistry is limited by oxygen diffusion. (C) 2001 Elsevier Science Ltd. All rights reserved.

Synthesis and stereochemistry of some bicyclic gamma-lactones from parasitic wasps (Hymenoptera : Braconidae). Utility of hydrolytic kinetic resolution of epoxides and palladium(II)-catalyzed hydroxycyclization-carbonylation-lactonization of ene-diols

A palladium(II)-catalyzed hydroxycyclization-carbonylation-lactonization sequence with appropriate pent-4-ene-1,3-diols provides efficient access to the bicyclic gamma -lactones, 5-n-butyl- and 5-n-hexyltetrahydrofuro-[3,2-b]furan-2(3H)-ones (3) and (4), respectively, in both racemic and enantiomeric forms. Some of the substrate pent-4-ene-1,3-diols of high enantiomeric excess (ee) have been derived from racemic terminal epoxides by hydrolytic kinetic resolution (HKR) using cobalt (III)-salen complexes. (9Z,12R)-(+)-Ricinoleic acid also serves as a chiral pool source of other pent-4-ene-1,3-diols. These syntheses and enantioselective gas chromatography confirm the structures and absolute stereochemistry of the lactones in some species of parasitic wasps (Hymenoptera: Braconidae). The highly abundant 5-n-hexyltetrahydrofuro-[3,2-b]furan-2(3H)-one (4) in Diachasmimorpha kraussii and D. longicaudata is of high ee (> 99%) with (3aR,5R,6aR) stereochemistry.

Isolation of a novel G-protein gamma-subunit from Arabidopsis thaliana and its interaction with G beta

There is increasing evidence that heterotrimeric G-proteins (G-proteins) are involved in many plant processes including phytohormone response, pathogen defence and stomatal control. In animal systems, each of the three G-protein subunits belong to large multigene families; however, few subunits have been isolated from plants. Here we report the cloning of a second plant G-protein γ-subunit (AGG2) from Arabidopsis thaliana. The predicted AGG2 protein sequence shows 48% identity to the first identified Arabidopsis Gγ-subunit, AGG1. Furthermore, AGG2 contains all of the conserved characteristics of γ-subunits including a small size (100 amino acids, 11.1 kDa), C-terminal CAAX box and a N-terminal α-helix region capable of forming a coiled-coil interaction with the β-subunit. A strong interaction between AGG2 and both the tobacco (TGB1) and Arabidopsis (AGB1) β-subunits was observed in vivo using the yeast two-hybrid system. The strong association between AGG2 and AGB1 was confirmed in vitro. Southern and Northern analyses showed that AGG2 is a single copy gene in Arabidopsis producing two transcripts that are present in all tissues tested. The isolation of a second γ-subunit from A. thaliana indicates that plant G-proteins, like their mammalian counterparts, may form different heterotrimer combinations that presumably regulate multiple signal transduction pathways.