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PubMed2005

Retention and phytoavailability of radioniobium in soils.

Radioniobium is present in long-lived nuclear waste as a result of the activation of zirconium pellets associated with the nuclear fuel. The behaviour of niobium (Nb) in the environment and especially its fate in the soil-plant system has not been thoroughly investigated so far. In safety assessment of French long-lived nuclear waste disposal, data concerning the mobility and the bioavailability of Nb in soils are needed as well as general trends of its fate in the specific environment around the site of French underground research laboratory. Therefore, we investigated the mobility of 95Nb in three different soils typical of the area of north-eastern France and its uptake by two plants, rye grass (Lolium perenne L.) and winter wheat (Triticum aestivum L.). Soil:solution distribution of 95Nb was observed in 1:10 batch experiments with deionized water for a 3-day period. Results showed that K(d) values were high (in the order of 10(3) L kg(-1)) and were still significantly increasing after 3 days. A mathematical model, fitted to describe the decrease of the radioactivity after 3 days, is proposed to calculate sorption ratios--SR--(rather than K(d) values as equilibrium was not reached) over longer periods. Soil-to-plant concentration ratios (CR) were measured in shoots and roots of the two plants after cultivation on two soils spiked with (95)Nb (406kBqkg(-1)). Soil-to-root dry weight CR were high (0.30-1.52) and could probably be due to efficient uptake into the roots. However, no transfer of Nb to plant shoots was detected in any of the soils. Nb is thus a rather immobile element in soils and its transfer to plants seems limited to underground parts. It would therefore tend to accumulate in surface horizons of soils in case of long-term continuous surface release.

Biological Availability↗
PubMed2006

Endodontic surgery using 2 different magnification devices: preliminary results of a randomized controlled study.

PURPOSE: The introduction of microsurgical instruments and magnification devices has brought advantages in root-end management and the application of root-end filling materials. The main purpose of this prospective clinical study was to monitor the outcome of ultrasonic root-end preparation using magnification loupes or an endoscope. Tooth location and the presence of post restoration were also examined as potentially affecting the outcome. MATERIALS AND METHODS: Teeth treated surgically showed a periradicular lesion of strictly endodontic origin. A total of 59 patients were included in the study, according to specific selection criteria. Following the reflection of a full mucoperiosteal tissue flap, residual soft tissues were curetted, root ends were resected, and root-end cavities were prepared ultrasonically with a zirconium nitrate tip, and zinc oxide EBA-reinforced cement root-end fillings were placed. Thirty-two root-end management procedures were performed using magnification loupes and 39 using an endoscope. All cases followed for a period of 1 year were classified into 3 groups (success, uncertain healing, and failure) according to radiographic and clinical criteria. RESULTS: Of the 71 teeth evaluated at 1-year follow-up, 67 teeth (92.95%) successfully healed, 3 teeth had uncertain healing, and 2 failed. In the group using endoscopy, 94.9% of successful healing was achieved, while for the other group, 90.6% was recorded. We found no statistically significant differences in treatment results related to the arch (P = .20), post restoration (P = .21), or type of magnification device (P = .08). CONCLUSIONS: In the present study, adherence to a strict endodontic surgical protocol and the use of modern surgical endodontic procedures, together with visual magnifications, resulted in an overall high success rate.

Adult↗
PubMed2004

Ionic charge, radius, and potential control root/soil concentration ratios of fifty cationic elements in the organic horizon of a beech (Fagus sylvatica) forest podzol.

The root/organic soil concentration ratio; R/S) of 50 cationic mineral elements was related to their ionic properties, including ionic radius (r), ionic charge (z), and ionic potential (z/r or z2/r). The materials studied were ectomycorrhizal beech (Fagus sylvatica L.) roots and their almost purely organic soil substrate, the O-horizon (mor; raw humus) of a Podzol in South Sweden, developed in a site which has been untouched by forestry or other mechanical disturbance since at least 50 years and located in an area with no local sources of pollution. Elements determined by ICP-AES were aluminium, barium, calcium, iron, potassium, magnesium, manganese, sodium and strontium. Determined by ICP-MS were silver, beryllium, bismuth, cadmium, cerium, cobalt, chromium, caesium, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, mercury, holmium, indium, lanthanum, lithium, lutetium, niobium, neodymium, nickel, lead, praseodymium, rubidium, scandium, samarium, tin, terbium, thorium, titanium, thallium, thulium, uranium, vanadium, yttrium, ytterbium, zinc and zirconium. The R/S ratios were most clearly related to the ionic potential of the cationic elements studied, which accounted for approximately 60% of the variability in R/S among elements. The ionic charge of an element was more important than the ionic radius. Elements with high ionic charge had low R/S ratios and vice versa. No clear differences in R/S between essential and non-essential plant nutrients were observed, especially when ions of similar charge were compared.

Cations↗
PubMed2000

Oxygen yield from single turnover flashes in leaves: non-photochemical excitation quenching and the number of active PSII.

O(2) evolution from single turnover flashes of up to 96 micromol absorbed quanta m(-2) and from multiple turnover pulses of 8.6 and 38.6 ms duration and 12800 and 850 micromol absorbed quanta m(-2) s(-1) intensity, respectively, was measured in sunflower leaves with the help of zirconium O(2) analyser. O(2) evolution from one flash could be measured with 1% accuracy on the background of 10-50 micromol O(2) mol(-1). Before the measurements leaves were pre-adapted either at 30-60 or 1700 micromol quanta m(-2) s(-1) to induce different non-photochemical excitation quenching (q(N)). Short (1 min) exposures at the high light that created only energy-dependent, q(E) type quenching, caused no changes in the O(2) yield from saturating flashes or pulses that could be related to the q(E) quenching, but the yield from low intensity flashes and pulses decreased considerably. Long 30-60-min exposures at the high light induced a reversible inhibitory, q(I) type quenching that decreased the O(2) yield from both, saturating and limiting flashes and pulses (but more from the limiting ones), which reversed within 15 min under the low light. The results are in agreement with the notion that q(E) is caused by a quenching process in the PSII antenna and no changes occur in the PSII centres, but the reversible (15-30 min) q(I) quenching is accompanied by inactivation of a part of PSII centres.

Helianthus↗
PubMed1975

Studies on the reproducibility of glass bead antibody affinity columns.

Rabbit antibovine spleen DNase II and antihuman parotid amylase IgG were coupled to zirconium-clad (MAO, Corning) or plain (GAO, Corning) glass beads. (These were challenged with DNase II or amylase (human parotid or pancreatic), respectively. Although columns of the beads bound the enzymes whereas control columns did not, recoveries from the immune adsorbents were not only not quantitative but extremely variable. The columns also shed material absorbing in the ultraviolet. The antiamylase IgG-MAO column bound amylase so firmly, yet without inactivating it, that an insoluble enzyme reactor was formed. For these experiments, amylase was labeled with 14C in vitro without loss of activity.

Amylases↗
PubMed2002

A new, practical synthesis of 2-methoxyestradiols.

An efficient and practical approach to synthesize moderate to large amounts of 2-methoxyestradiol (2-ME2) is described. The key step in the synthesis is the regioselective introduction of an acetyl group at the C-2 position of estradiol using a zirconium tetrachloride mediated Fries rearrangement carried out on estradiol diacetate. The seven step synthetic procedure readily gave 2-ME2 in 49% overall yield. Application of this method to the synthesis of 2-methoxy-7 alpha-methylestradiol is also described.

2-Methoxyestradiol↗
PubMed2002

Ceramic and PMMA particles differentially affect osteoblast phenotype.

There is increasing evidence that wear debris particles present in periprosthetic tissues have direct effects on osteoblasts. The nature of the cell response varies with the chemistry of the particle and the number of particles. Most studies have used Ti, Ti-6Al-4V, and ultrahigh molecular weight polyethylene (UHMWPE) particles since these materials are most frequently used in implants and as a result, these particles predominate in peri-prosthetic tissues. Ceramics have also been used successfully as load-bearing surfaces in implants for years, although it is unknown how wear debris from these surfaces may contribute to aseptic bone loss. Further, particles resulting from polymethylmethacrylate (PMMA) cements used for fixation may also be involved in aseptic loosening of implants, but how these particles may affect bone formation is unknown. In the present study, we examined whether aluminum oxide (Al2O3), zirconium oxide (ZrO2), and PMMA particles exert effects on osteoblast proliferation, phenotypic expression, and local factor production, and if so, whether the effects were specific to the particle type. ZrO2 particles were produced in a custom-made axial mixer in which ZrO2 containers were filled with ZrO2 bars and 95% ethanol and then rotated continuously at room temperature. PMMA particles were prepared in a ZrO2 roller mill. Al2O3 was produced and provided by Aesculap AG. Particles were endotoxin-free with equivalent circle diameters <3 microm; Al2O3 particles were significantly smaller than ZrO2 or PMMA particles. Particle suspensions were added to confluent cultures of MG63 osteoblast-like cells after diluting them 1:100, 1:10, and 1:1 with culture medium. Cells were incubated with the particles for 24 h. Transmission electron microscopy showed that MG63 cells phagocytosed Al2O3 particles and exhibited ultrastructural changes consistent with cytotoxicity. This was supported by biochemical changes as well. Proliferation, alkaline phosphatase activity, and TGF-beta1 levels were decreased. ZrO2 and PMMA particles increased proliferation and alkaline phosphatase specific activity. The effect of ZrO2 on alkaline phosphatase was targeted to matrix vesicles, the effect of PMMA was greater on the cells. All particles increased prostaglandin E2 production. These results show that Al2O3, ZrO2, and PMMA particles elicit direct effects on osteoblasts and that cell response depends on the particle type. None of the particles tested had the same effect as noted previously for UHMWPE: increased proliferation and decreased alkaline phosphatase. These results may indicate that the response of peri-prosthetic tissues to wear particles may be modulated by the relative contributions of the various particle types present.

Alkaline Phosphatase↗
PubMed2001

Concentrations of natural radionuclides in imported mineral substances.

Levels of natural radionuclides, such as thorium-232 (232Th), radium-226 (226Ra) and potassium-40 (40K), were determined in about 2,000 samples of imported mineral substances using gamma spectrometry. The maximum concentration levels of 232Th, 226Ra and 40K were 1,260 +/- 54, 13,400 +/- 94 and 1,256 +/- 260 Bq kg(-1), respectively, in zirconium compounds. Due to relatively high concentrations of the above-mentioned radionuclides in some imported mineral substances, the National Radiation Protection Department (NRPD), as the competent authority, has established national limits (900 Bq kg(-1) for 232Th, 1800 Bq kg(-1) for 226Ra and 11,000 Bq kg(-1) for 40K), based on the external exposures, for general importation permits of these materials.

Commerce↗
PubMed1982

The origin, morphology, and function of epithelioid cells.

Epithelioid cells are cells of the mononuclear phagocyte system found in certain granulomas mainly associated with intense immunological activity. These cells show little phagocytic activity. In certain experimental granulomas such as those produced in guinea pigs sensitive to zirconium, and at sites of intense inflammatory reaction in man, they may contain varying amounts of rough endoplasmic reticulum ("secretory" epithelioid cells). In other situations such as tuberculoid leprosy and in some cases of sarcoidosis they may have the appearance of activated macrophages or take on a multivesicular appearance ("vesicular" epithelioid cells). It is suggested that "vesicular epithelioid cells could develop from "secretory" epithelioid cells by a process of degeneration. In studies comparing granulomas induced in lymph nodes draining the site of intradermal injection of mycobacteria, epithelioid cell granulomas were produced with BCG vaccine, whereas, the granulomas induced by Mycobacterium leprae contained undifferentiated macrophages that contained phagocytosed organisms. The BCG granulomas were in addition characterised by fibroblast infiltration, the presence of collagen and resolution by fibrosis. M. leprae granulomas showed little evidence of fibroblastic activity. Biochemical studies confirmed that BCG granulomas formed new collagen in vitro, whereas this did not take place with M. leprae granulomas. It is suggested that epithelioid cells could play an important role in fibrosis possibly by the secretion of a fibroblast activating factor.

Animals↗
PubMed1990

Preliminary adult soil ingestion estimates: results of a pilot study.

Six adults were evaluated for the extent to which they ingest soil. This study was originally part of a large childhood soil ingestion study and was used to validate part of the analytical methodology used in that larger study. The adult study followed the soil tracer methodology of the children's study. The principal findings of the adult study revealed that the four most reliable tracer elements based on recovery studies in a mass balance assessment [aluminum (Al), silicon (Si), yttrium (Y), and zirconium (Zr)] yielded the following mean daily adult soil ingestion estimations: Al (77 mg), Si (5 mg), Y (53 mg), and Zr (22 mg). The median daily soil ingestion estimations based on these same tracer elements were: Al (57 mg), Si (1 mg), Y (65 mg), and Zr (-4 mg). These findings represent the first published quantitative estimates of soil ingestion by adults.

Adult↗
PubMed2000

A quantitative minimally invasive assay for the detection of metals in the stratum corneum.

A quantitative, minimally invasive tape-stripping assay for the detection of metals on and in skin that also has application to the detection of metallic elements on dry surfaces (where human contact could occur) has been developed. This development included construction, using commercial products, of an approximately 25 microm thick, low-metal content tape suitable both for tape-stripping and elemental analysis. Individual tapes were sequentially applied to the skin surface and then removed, taking with them a sample of the dead outer layer of the skin (stratum corneum). Analysis of such tape strip samples by particle induced X-ray emission (PIXE)--a well-characterized, sensitive, analytical technique based on X-ray spectrometry--identified and accurately quantified the metals in the sample. The assay had elemental sensitivities of approximately 1 ng/cm2 for many metals and analysis of elemental contents could be performed in as little as 5 min. The feasibility of the assay for measuring metals in the stratum corneum was demonstrated on the forearms of healthy human volunteers. Samples from approximately half the subjects were found to contain zirconium, possibly arising from the use of roll-on antiperspirants. The assay has potential as a tool: (1) for risk assessment, (2) to identify exposure levels following possible contact with a hazardous metal, and (3) to determine the effectiveness of cleanup or removal measures.

Humans↗
PubMedDate not supplied

Radiochemical analysis of 93Zr.

The zirconium isotope 93Zr is a long-lived pure beta-particle-emitting radionuclide, which is produced by nuclear fission and neutron activation of the stable isotope 92Zr. This element is a constituent of the structural components of nuclear reactor vessels. A selective liquid-liquid extraction method for radiochemical separation of Zr, based on liquid-liquid extraction with 1-(2'-thenoyl)-3,3,3-trifluoroacetone in xylene and a subsequent stripping of 93Zr by an aqueous acid solution, has been developed. The method was utilised to separate Zr from other pure beta-particle and beta-gamma emitters in different kinds of samples. Decontamination factors higher than 99% for the pure beta-particle and beta-gamma emitters and an overall chemical yield of 80% were obtained. The sensitivity of the method allows the determination of the isolated 93Zr by liquid scintillation counting and the minimum detectable activity value obtained was 0.067 Bq over a counting period of 60 min.

Journal Article↗
PubMed2002

Thin-target excitation functions, cross-sections and optimised thick-target yields for natMo(p,xn)(94g ,95m,95g,96(m + g))Tc nuclear reactions induced by protons from threshold up to 44 MeV. No Carrier Added radiochemical separation and quality control.

This work describes the method adopted in our laboratories, to produce 94gTc, 95gTc, 95mTc and 96gTc radionuclides via proton-cyclotron irradiation on molybdenum targets of natural isotopic composition. A new set of experimental thin-target excitation functions and "effective" cross-sections for direct natMo(p,xn)(A)Tc [with A = 94, 95, 95, 96] nuclear reactions, with incident proton energy in the range from threshold up to 44 MeV is presented. Some definitions of the equations used and nuclear data traceability are reported. Thick-target yield values were calculated and optimised, by numerical fitting and integration of the measured excitation functions. These values allow optimisation of production yield of one radionuclide, minimising at the same time the yield of the others. Radiochemical separation on NCA technetium radionuclides from both molybdenum target and niobium, zirconium and yttrium radioactive by-products is reported. Quality control tests of the radiotracers were developed for the applications envisaged in environmental metallo-biochemical toxicology.

Journal Article↗
PubMed2003

Mixing apparatus for preparing NMR samples under pressure.

The size limit for protein NMR spectroscopy in solution arises in large part from line broadening caused by slow molecular tumbling. One way to alleviate this problem is to increase the effective tumbling rate by reducing the viscosity of the solvent. Because proteins generally require an aqueous environment to remain folded, one approach has been to encapsulate hydrated proteins in reverse micelles formed by a detergent and to dissolve the encapsulated protein in a low-viscosity fluid. The high volatility of suitable low-viscosity fluids requires that the samples be prepared and maintained under pressure. We describe a novel apparatus used for the preparation of such samples. The apparatus includes a chamber for mixing the detergent with the low-viscosity solvent, a second chamber for mixing this with hydrated protein, and a 5-mm (o.d.) zirconium oxide NMR sample tube with shut-off valves designed to contain pressures on the order of 10 bar, sufficient for liquid propane. Liquids are moved from one location to another by introducing minor pressure differentials between two pressurization vessels. We discuss the operation of this apparatus and illustrate this with data on a 30-kDa protein complex (chymotrypsin:turkey ovomucoid third domain) encapsulated in reverse micelles of the detergent, sodium bis (2-ethylhexyl) sulfosuccinate, aerosol-ot (AOT), dissolved in liquid propane.

Animals↗
PubMed2002

Mediator-modified electrodes for catalytic NADH oxidation: high rate constants at interesting overpotentials.

Carbon paste electrodes were modified with a nitrofluorenone derivative, 2,4,7-trinitro-9-fluorenone, adsorbed on zirconium phosphate (ZP). After electrochemical reduction of the fluorenone derivative, it turns into a very efficient mediator for electrocatalytic NADH oxidation, with a formal potential of about +250 mV vs. Ag/AgCl. The electrochemistry and the electrocatalytic properties of the mediator were investigated with cyclic voltammetry and rotating disk electrode methodology. The second order rate constant with NADH was evaluated and found to be higher than 10(6) M(-1) s(-1), thus approaching true diffusion controlled currents for NADH oxidation.

Carbon↗
PubMed2000

Self-propagating metathesis routes to metastable group 4 phosphides.

Group 4 phosphides, which are typically prepared at high temperatures (> 800 degrees C) over several days, are synthesized in self-propagating metathesis (exchange) reactions in seconds. These reactions produce cubic forms of zirconium phosphide (ZrP) and hafnium phosphide (HfP) which are normally made at temperatures greater than 1425 degrees C and 1600 degrees C, respectively. To test whether the high temperatures reached in the metathesis reactions are responsible for the formation of the cubic phases, inert salts are added to lower the maximum reaction temperatures. The lower temperature reactions still result in cubic phosphides, although smaller crystallites form. Further experiments with phosphorus addition indicate that the phosphorus content is not responsible for cubic phase formation. Templating is ruled out using lattice mismatched KCl and hexagonal ZnS as additives. Therefore, the direct synthesis of the high-temperature cubic phase in metathesis reactions appears to be caused by nucleation of the metastable cubic form that is then trapped by rapid cooling. Heating the cubic phase of either ZrP or HfP to 1000 degrees C for 18 h, or carrying out metathesis reactions in sealed ampules at 1000 degrees C, results only in the hexagonal phase.

Journal Article↗
PubMed2002

Synthesis, structural characterization, and reactions of cyclic organohydroborate half-zirconocene compounds.

Cyclic organohydroborate complexes of zirconium monocyclopentadienyl CpZr[(mu-H)(2)BC(5)H(10)](3), 1, and CpZr[(mu-H)(2)BC(8)H(14)](3), 2, were prepared from the reaction of CpZrCl(3) with 3 mol of K[H(2)BC(5)H(10)] and K[H(2)BC(8)H(10)], respectively, in diethyl ether. Compounds 1 and 2 react with the hydride ion abstracting agent B(C(6)F(5))(3) to form the same salt [CpZr(OEt)(OEt(2))(mu-OEt)](2)[HB(C(6)F(5))(3)](2), 5. The complexes CpZr(Cl)[(mu-H)(2)BC(8)H(14)](2), 3, and CpZr(Cl)[(mu-H)(2)BC(8)H(14)](2) [where Cp = C(5)(CH(3))(5)], 4, were prepared from the reaction of CpZrCl(3) and CpZrCl(3) with K[H(2)BC(8)H(10)] in 1:2 molar ratios, respectively. An alpha-hydrogen of a BC(8)H(14) unit forms an agostic interaction with Zr in compound 3 but not in 4. All of the compounds were characterized by single-crystal X-ray diffraction analysis.

Journal Article↗
PubMed2003

Syntheses and structures of metallocene methyltrihydroborate derivativies: Cp2ZrCl[(mu-H)2BHCH3], Cp2Zr[(mu-H)2BHCH3]2, and Cp2Ti[(mu-H)2BHCH3].

In reactions of zirconocene dichloride, Cp(2)ZrCl(2), with 1 equiv and an excess amount of LiBH(3)CH(3), the methyltrihydroborate complexes, Cp(2)ZrCl[(mu-H)(2)BHCH(3)], 1, and Cp(2)Zr[(mu-H)(2)BHCH(3)](2), 2, were isolated. The reaction of titanocene dichloride, Cp(2)TiCl(2), with an excess amount of LiBH(3)CH(3) produced the monosubstituted methyltrihydroborate complex, Cp(2)Ti[(mu-H)(2)BHCH(3)], 3. The titanium was reduced from Ti(IV) to Ti(III), producing a 17-electron, paramagnetic titanocene complex. Under a dynamic vacuum at room temperature, compound 2 decomposed and produced the zirconium hydride compound Cp(2)ZrH[(mu-H)(2)BHCH(3)]. Single crystal X-ray structures of 1, 2, and 3 were determined. Crystal data for 1: space group P2(1)/c, a = 13.7921(3) A, b = 13.4227(3) A, c = 13.0868(3) A, beta = 91.6448(12) degrees, Z = 8. Crystal data for 2: space group Pna2(1), a = 15.2949(4) A, b = 9.3417(2) A, c = 9.3211(2) A, Z = 4. Crystal data for 3: space group Fmm2, a = 9.1795(3) A, b = 13.0993(5) A, c = 8.8520(3) A, Z = 4.

Journal Article↗