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Cyanex 923 as the extractant in a rare earth element impurity analysis of high-purity cerium oxide.

In this work, the feasibility of employing Cyanex 923 as an extractant into the non-cerium REE (rare earth elements) impurity analysis of high-purity cerium oxide was investigated. Through investigations on the choice of the extraction medium, the optimium extraction acidity, matrix Ce4+ effect on the non-cerium REE ion extraction, the optimium extractant concentration and suitable extracting time, and oscillation strengh, it was found that when the phase ratio was at 1:1 and the acicidity was about 2% H2SO4, by gently shaking by hand for about 2 min, 10 mL of 30% Cyanex 923 could not extract even for a 20 ng amount of non-cerium REE3+ ions. However, the extraction efficiency for Ce4+ of 100 mg total amount under the same conditions was about 96%, indicating that a 25-fold preconcentration factor could be achieved. Thus, it was concluded that Cyanex 923 could be used in a REE impurity analysis of 99.9999% or so pure cerium oxide for primary sepapation to elimilate matrix-induced interferences encountered in an ICP-MS (inductively coupled plasma mass spectroscopy) determination.

Journal Article↗

Biopersistence of cerium in the human respiratory tract and ultrastructural findings.

For diagnostic purposes, mineralogical analysis was performed in bronchoalveolar lavage fluid and lung tissue from a 58-year-old patient previously exposed to asbestos and rare earth dusts. No significant retention of asbestos was demonstrated in lung tissue by light microscopy (asbestos bodies) or transmission electron microscopy analysis (uncoated fibers). Particles containing rare earth (cerium, lanthanum) and phosphorus were identified in alveolar macrophages in bronchoalveolar lavage fluid, and cerium-containing particles accounted for 70% of particles observed in the lung tissue. Ultrastructural analysis of lung tissue revealed the presence of particles containing cerium and phosphorus in interstitial macrophages and elastic fibers. These results suggest that rare earth is metabolized and should be considered as biopersistent in the human respiratory tract, since occupational inquiries revealed that exposure to cerium oxide abrasive powder had ceased at least 15 years earlier.

Asbestos↗

The cerium perhydroxide-diaminobenzidine (Ce-H2O2-DAB) procedure. New methods for light microscopic phosphatase histochemistry and immunohistochemistry.

New light microscopic visualization methods were developed for the histochemical detection of non-specific alkaline and acid phosphatase, Mg-, Ca- and Na, K-dependent adenosine triphosphatase, myosin adenosine triphosphatase, glucose-6-phosphatase, 5'-nucleotidase and thiamine pyrophosphatase with cerium ions as trapping agents in cryostat and plastic sections. The techniques are based on the conversion of cerium phosphate into cerium perhydroxide by H2O2 which decomposes at 55 degrees-60 degrees C into cerium hydroxide and oxygen radicals. These radicals are able to oxidize diaminobenzidine (DAB) to DAB brown. Addition of nickel ions to the DAB-H2O2 mixture generates bluish-black stained nickel-DAB complexes. Compared with the classical metal precipitation, azo, azoindoxyl and tetrazolium procedures the H2O2-DAB and especially the H2O2-DAB-nickel methods provided identical or superior results in catalytic phosphatase histochemistry and immunohistochemistry when using non-specific alkaline phosphatase as the enzyme label.

3,3'-Diaminobenzidine↗

Specific visualization of precipitated cerium by energy-filtered transmission electron microscopy for detection of alkaline phosphatase in immunoenzymatic double labeling of tyrosine hydroxylase and serotonin in the rat olfactory bulb.

To understand in detail the functional morphology of neuronal circuits it is important to identify at the ultrastructural level the incoming axon, its target neuron, and members of the signaling cascades involved. This, however, represents a formidable task, requiring highly sophisticated electron microscopic multiple-labeling techniques. To extend available double-labeling procedures such as combinations of immunogold and peroxidase methods, an additional, gold- and peroxidase-independent procedure would represent a considerable advantage. The present investigation therefore aimed to use alkaline phosphatase as the immunoenzymatic label at the electron microscopic level via cerium phosphate precipitates. To our surprise we found that available techniques, which are well established for the visualization of endogenous enzymes in sections from various tissues, are not suitable for application to immunocytochemistry. Careful characterization of the individual reaction conditions, however, resulted in an optimized procedure with largely increased sensitivity. The novel technique yields cerium-containing precipitates which are massive enough to allow the detection of the immunoenzymatic reaction product in the electron microscope. Using the rat olfactory bulb as the model system we showed further that our technique allows the combination with the peroxidase/diaminobenzidine system for ultrastructural double labeling. For this purpose, the alkaline phosphatase product is identified by its cerium content via energy-filtered transmission electron microscopy and thereby differentiated from cerium-free peroxidase-derived precipitates. Doing so, we found that ascending serotoninergic fibers do not establish synapses with dopaminergic periglomerular cells in the rat olfactory bulb.

Alkaline Phosphatase↗

Cerium-induced strain-dependent increase in Cyp2a-4/5 (cytochrome P4502a-4/5) expression in the liver and kidneys of inbred mice.

The murine Cyp2a-4 and Cyp2a-5 genes encode P450 isoforms catalysing testosterone 15 alpha-hydroxylase and coumarin 7-hydroxylase (COH) activities, respectively. Two days after the administration of a hepatotoxic dose of cerium chloride (2 mg/kg i.v.), COH activity was increased 3.2-fold in the liver of DBA/2 mice. Three and 4 days after the cerium treatment, coinciding with the occurrence of overt liver damage, there was a dramatic decrease in COH activity. The activities of testosterone 15 alpha-hydroxylase and the Cyp1a-1-mediated 7-ethoxyresorufin O-deethylase (EROD) were decreased in response to cerium. Much less pronounced changes in the enzyme activities occurred in the C57BL/6 mouse liver. Northern blot analysis showed a 21-fold increase in the hepatic Cyp2a-4/5 mRNA in the DBA/2 mice at day 2, whereas no increase occurred in the C57BL/6 mice. Also in the kidneys the increase in COH activity and in Cyp2a-4/5 mRNA was marked only in the DBA/2 mice. A polymerase chain reaction-mediated analysis method utilizing a unique PstI restriction site in the Cyp2a-5 cDNA was used to differentiate between the highly homologous Cyp2a-4 and Cyp2a-5 mRNAs. Cerium was found to increase the amount of hepatic and renal Cyp2a-4 and Cyp2a-5 mRNA only in the DBA/2 mice. These data indicate that the Cyp2a-4/5 complex is regulated in a different way in DBA/2 and C57BL/6 mice and that some association exists between the development of liver damage and COH induction.

Animals↗

Paradoxical effect of cerium on collagen synthesis in cardiac fibroblasts.

The present study examined the effect of cerium on collagen synthesis in cultured cardiac fibroblasts and explants. At 100 nM, a concentration comparable with that found in the cardiac tissue of patients with endomyocardial fibrosis, the element was found to enhance the incorporation of tritiated proline into collagen and non-collagen proteins while at 10 microM, it had an inhibitory effect. Cerium was found to have no effect on rates of DNA synthesis in fibroblasts at 100 nM. However, at this concentration, the element markedly enhanced the incorporation of tritiated uridine into RNA, suggesting that cerium may act at the level of transcription to stimulate collagen and non-collagen protein syntheses. The stimulatory action of very low levels of cerium on collagen synthesis may contribute to the accumulation of collagen seen in endomyocardial fibrosis.

Animals↗

Cerium nitrate in the management of burns.

BACKGROUND: The introduction of early excision of the burn eschar has contributed to a reduction in burn-related mortality but is not appropriate in all circumstances. Cerium nitrate has been used since 1976, usually in combination with silver sulphadiazine, to improve outcome where early excision is not performed. However, has still not gained universal acceptance. The evidence for its use is reviewed. METHODS: A MEDLINE search was performed for the years 1966-2003 using keywords 'cerium', 'sulphadiazine', 'Flammacerium', 'lanthanides' and 'topical therapy for burns'. The reference lists of key articles were then sifted for other relevant articles. RESULTS: Cerium has been shown to reduce mortality and morbidity in the treatment of severe burns. This benefit is derived from its action on the burn eschar. It binds and denatures the lipid protein complex liberated from burnt skin that is responsible for the profound immunosuppression associated with major cutaneous burns. It has only limited antimicrobial properties. CONCLUSIONS: Cerium nitrate is an excellent topical treatment for most cutaneous burns not undergoing immediate excision and closure.

Animals↗

Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium.

Cerium↗

Observation of cerium isotope fractionation in ion-exchange chromatography of Ce(III)-malate complex.

The cerium isotope fractionation between Ce(III)-malate complex in aqueous solution and cerium ions in a cation-exchange resin was conducted by displacement chromatography. The pH and the chemical composition of the eluent were optimized for maintaining the self-sharpening band boundaries and the 21 m chromatographic migration of the Ce band underwent. Graphite slurry was coated on the tantalum filament prior to sample loading for reducing the isobaric interferences in cerium isotopic ratio determination by mass spectrometry. From the experimental results, it was found that the heavier isotope was enriched in the front boundary part of the cerium adsorption band, which meant that the heavier isotope was preferentially fractionated into the Ce3+ malate complex rather than simply hydrated Ce3+ ions. The isotope separation coefficient for the 136Ce/140Ce and 142Ce/140Ce was 5.2 x 10(-5) and -1.9 x 10(-5), respectively, at 298 K.

Cerium Isotopes↗

Cerium-induced light-microscopic demonstration of 5'-nucleotidase activity in the lymphatic capillaries of the proximal oesophagus of the rat.

Lymphatic capillaries with narrow lumina cannot be identified with certainty by means of conventional light microscopy. This, however, can be achieved with great precision by means of labelling the 5'-nucleotidase activity which is high in lymphatic capillaries. In blood capillaries, on the other hand, it is either lacking or much less pronounced depending on the organ. The reactions performed thus far occurred primarily in the presence of lead ions which had a toxic effect on the enzymes. In cerium, however, this inhibiting influence can be neglected. 2 light-microscopic procedures of labelling the 5'-nucleotidase activity, which make use of cerium, are presented and compared here for the first time. The cerium perhydroxide technique is especially suited for demonstrating the lymphatic capillaries. In comparison to the previous enzyme histochemical methods, a definitely more precise demonstration of the endothelia of small lymphatics now is possible. The reason for this is that this method only reacts to regions of high enzyme activity. As opposed to previous tests on cryostat sections, the lumen of the lymphatic capillary is nearly always identifiable as such if employing this type of reaction. These properties of the cerium-perhydroxide reaction allow definite statements regarding the distribution of the lymphatic capillaries in the tissue. Its simple and rapid course of reaction favour the use of this method in clinical problems. In the other technique presented, the manganese dioxide technique, the demonstration of lymphatic capillaries is by far less exact due to its greater sensitivity even to low enzyme activities.

5'-Nucleotidase↗

SOx removal by calcined MgAlFe hydrotalcite-like materials: effect of the chemical composition and the cerium incorporation method.

Sulfur oxides are one of the most hazardous atmospheric pollutants since they contribute directly to acid rain formation. Consequently, stringent environmental regulations limit atmospheric SOx emissions, motivating research on efficient ways to reduce them. To supply an alternative to reduce these emissions in fluid catalytic cracking units, this study discloses efficient SOx reducing materials based on calcined MgAlFe hydrotalcite-like compounds (HT's). Thus, HT materials were synthesized by several methods including cerium addition. The adsorption of SO2 was carried out by contacting the calcined solid with a mixture of SO2 (1%) in air at 650 degrees C. It was demonstrated that the isomorphic incorporation of iron increased its reduction capability which was reflected in higher reduction rates and metal sulfate reduction grade at 550 degrees C. Moreover, when cerium was present in the iron-containing materials the saturation rate was improved, because cerium oxide promotes the oxidation of SO2 to SO3. The way cerium is incorporated influences the SO2 adsorption capacity.

Adsorption↗

Demonstration of enhanced K-edge angiography using a cerium target x-ray generator.

The cerium target x-ray generator is useful in order to perform enhanced K-edge angiography using a cone beam because K-series characteristic x rays from the cerium target are absorbed effectively by iodine-based contrast mediums. The x-ray generator consists of a main controller, a unit with a Cockcroft-Walton circuit and a fixed anode x-ray tube, and a personal computer. The tube is a glass-enclosed diode with a cerium target and a 0.5-mm-thick beryllium window. The maximum tube voltage and current were 65 kV and 0.4 mA, respectively, and the focal-spot sizes were 1.0 x 1.3 mm. Cerium Kalpha lines were left using a barium sulfate filter, and the x-ray intensity was 0.48 microC/kg at 1.0 m from the source with a tube voltage of 60 kV, a current of 0.40 mA, and an exposure time of 1.0 s. Angiography was performed with a computed radiography system using iodine-based microspheres. In coronary angiography of nonliving animals, we observed fine blood vessels of approximately 100 microm with high contrasts.

Angiography↗

Effects of the rare earth cerium on Escherichia coli.

The rare earth cerium was found to bind rapidly to Escherichia coli. Cerium inhibited oxygen uptake in the presence of glucose as well as the endogenous respiration of glucose-grown cells. For a cell concentration of 4 mg per ml, maximal inhibition was obtained at 120 mug per ml. Greater concentrations did not increase the inhibitory effect. Cerium inhibited (14)CO(2) evolution and (14)C uptake from uniformly labeled glucose. Marked changes in the distribution of (14)C incorporated into different chemical fractions of the cell were noted. The most striking changes occurred in the alcohol- and alcohol ether-soluble fractions, in which the (14)C activity was increased 5- to 20-fold in the presence of cerium.

Carbon Isotopes↗

Light microscopic visualization of the reaction product of cerium used for localization of peroxisomal oxidases.

The reaction product of cerium used for localization of peroxisomal oxidases is highly electron-dense but lacks sufficient contrast at the light microscopic level. We describe two methods for converting the reaction product of cerium to colored compounds visible by light microscopy. The first method is based on 3,3'-diaminobenzidine (DAB) amplification of transition metal compounds, of which cerium is one. Sections of glutaraldehyde-fixed rat liver or kidney are incubated first in media for various oxidases containing CeCl3, followed by treatment with DAB in Na acetate buffer, pH 5.3. To prevent any interference by the peroxidatic activity of catalase, NaN3 or Na pyruvate is added to the DAB amplification medium. Staining with DAB can be further intensified with NiCl2 or CoCl2. The second method is based on the conversion of the cerium reaction product with alkaline lead citrate and the final visualization of the lead compound with ammonium sulfide. These methods allow the evaluation of large sections for peroxisomal oxidases by light microscopy, making close correlation between light and electron microscopy possible.

3,3'-Diaminobenzidine↗

Enzyme histochemical demonstration of alkaline phosphatase activity in plastic-embedded tissues using a Gomori-based cerium-DAB technique.

We describe a new method for light microscopic demonstration of alkaline phosphatase (ALP) activity in plastic-embedded sections. Rat tissues were fixed in acetone (-20 degrees C), infiltrated in glycol methacrylate (GMA), and embedded at 0 degrees C. Sections were cut at 1 and 2 microns, dried at room temperature, and incubated in the conventional Gomori medium. Cerium chloride was used to convert calcium phosphate into cerium phosphate, which was subsequently converted into cerium perhydroxide. The slight yellow precipitate of cerium perhydroxide was amplified using 3,3'-diaminobenzidine tetrahydrochloride (DAB). For comparison, tissue sections were processed according to the calcium-cobalt method. The method described combines exact localization of ALP activity with optimal preservation of tissue morphology.

3,3'-Diaminobenzidine↗

Ultrastructural localization of phosphatase activity in the guinea pig pineal gland by the cerium technique.

Thiamine pyrophosphatase (TPPase), nucleoside diphosphatase (NDPase), and glucose-6-phosphatase (G-6-Pase) were localized by the cerium technique in guinea pig pinealocytes and compared with the corresponding lead technique. NDPase and TPPase were also compared at different pH values using the cerium technique. Vibratome sections of perfusion-fixed tissue were incubated with cerium chloride or lead nitrate. Substrates used were thiamine pyrophosphate (for TPPase), sodium inosine diphosphate (NDPase), and disodium glucose-6-phosphate (G-6-Pase). The 1-2 trans saccules of the Golgi apparatus showed TPPase and NDPase activity but none for G-6-Pase. The endoplasmic reticulum (ER) cisternae and perinuclear space had NDPase and G-6-Pase activity but not TPPase. The abluminal plasmalemma of endothelial cells and the plasmalemma of Schwann cells demonstrated TPPase and NDPase activity but the luminal plasmalemma of the endothelial cells and the plasmalemma of pinealocyte processes showed only NDPase activity. TPPase was active at all pH values tested, but NDPase was most active at pH values of 6.5 and 7.0. Lead phosphate precipitate was frequently seen in nuclei, perinuclear space, ER cisternae, and "synaptic" vesicles when lead was used as the capturing agent. These sites were usually not labeled when cerium was used.

Acid Anhydride Hydrolases↗

Study on the mechanism of cerium nitrate effects on germination of aged rice seed.

Attempts were made to promote germination of naturally and artificially aged rice seeds by treating them with cerium nitrate. The germination rate, germination index, and vigor index of aged rice seed were significantly increased by cerium. It was because the treatments of aged rice seed with cerium nitrate enhanced respiratory rate and activities of superoxide dismutase, catalase, and peroxidase, and decreased superoxide O2- and malondialdehyde contents that plasma membrane permeability was reduced. It was suggested that cerium be used for the seed treatment before sowing.

Catalase↗

Variation in mitogenic response of cardiac and pulmonary fibroblasts to cerium.

Fibroproliferative response of rat heart and lung fibroblasts to the lanthanide cerium was examined, as the element has been implicated in the causation of cardiac and pulmonary fibrosis. Fibroblasts from both of the organs were morphologically identical, and the response to fetal bovine serum, a nonspecific mitogen, was also comparable. The oxygen radical generator (hypoxanthine + xanthine oxidase [Hyp. + XO]) induced a proliferative response that was neutralized in both cardiac and lung fibroblasts by free-radical scavengers. Superoxide dismutase was more effective than catalase in reducing the mitogenic effect of Hyp. + XO. The free-radical scavenger N-acetyl-L-cysteine neutralized the free-radical-mediated changes in pulmonary fibroblasts but had a negative effect in cardiac fibroblasts, indicating a tissue-dependent variation. Reactive oxygen species are known to act as biological mediators of tissue fibrosis induced by metallic compounds. Exposure to low levels of cerium (0.5 microM) stimulated a mitogenic response in cardiac fibroblasts, but the pulmonary fibroblasts were not sensitized by the element. Tissue-dependent variation in proliferative response to cerium shows a positive association with intracellular generation of reactive oxygen species. Fibrotic changes in cerium pneumoconiosis may either be replacement fibrosis following tissue damage or mediated by nonfibroblastic cells. The study confirms that cardiac and pulmonary fibroblasts are dissimilar cellular subtypes.

Acetylcysteine↗