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PubMed2003

Bond valence sums in coordination chemistry. The calculation of the oxidation state of cerium in complexes containing cerium bonded only to oxygen.

A total of 119 CeO(n)fragments with n = 3-12 were analyzed by using the bond valence sum, or BVS, method to yield new R(0) values for Ce(III)-O of 2.121(13) A and for Ce(IV)-O of 2.068(12) A. These R(0) values can be used to calculate the oxidation state of Ce in complexes where Ce is bonded only to O ligands. Furthermore, the average R(0) value of 2.094 A gives a good indication of whether the oxidation state of the Ce ion is +3 or +4 from the observed distances without any assumptions. The fact that complexes with coordination numbers of 10-12 are in agreement is significant since this study is the first example which indicates that high coordination numbers also follow BVS rules. The Ce-O distances used in deriving the R(0) values for the +3 and +4 complexes are tabulated as a function of coordination number and have a wide range of values, but the average Ce-O distance reflects the requirement that the BVS must equal the oxidation state. Several examples are given where the oxidation state of the Ce ion is apparently incorrectly assigned, as well as cases where problems with the X-ray structure determinations are indicated by a disagreement between the postulated and calculated oxidation state.

Journal Article↗
PubMed1976

Cerium nitrate: a new topical antiseptic for extensive burns.

The wounds of 60 burned patients were treated topically with cerium nitrate, which was applied either as a cream or in aqueous solution. Cerium nitrate has a potent antiseptic effect in human burn wounds, especially against gram negative bacteria and fungi. Pseudomonas aeruginosa was recovered from the wounds infrequently and never predominated. Fungi were practically never found. No patient treated with cerium developed a necrotizing wound infection. Analysis of the detailed bacteriological data indicated that, in contrast to previous results with use of the nitrate or sulfadiazine salts of silver, when gram negative species predominated, the flora tended to be predominantly gram positive when cerium was used. Therefore, some patients were treated simultaneously with cerium nitrate and silver sulfadiazine; this resulted in an even more efficient suppression of the wound flora than was observed previously with either cerium alone or silver salts alone; results with the simultaneous topical therapy in patients with injuries that previously were uniformly lethal were excellent. No toxicity attributable to the use of cerium was observed, although one instance of methemoglobinemia due to nitrate was documented. The adsorption of topically applied cerium essentially is nil. The use of cerium nitrate was associated with a nearly 50 percent reduction in the anticipated death rate. Cerium nitrate is a promising new topical antiseptic agent for the treatment of burns, particularly when it is used in combination with silver sulfadiazine.

Adolescent↗
PubMed1993

Cerium methods for light and electron microscopical histochemistry.

Methods based on the use of cerium to detect the activity of oxidases and phosphatases are rapidly expanding. Both classes of enzymes can be demonstrated with cerium at the electron and light microscopical level. The in situ detection of H2O2 production with cerium is another application that has great potential, particularly in experimental pathological research. The fine precipitate of the cerium-containing final reaction product, cerium perhydroxide or cerium phosphate, enables a very precise localization. With such techniques, important advances have been made in cell biology, such as the discovery of new organelles, functional subcompartmentization of peroxisomes, tubular lysosomes and the elucidation of the function of extracellular ATPases. At the light microscopical level, the activity of enzymes can be quantified in situ because the production of final reaction product in the cerium methods is proportional to enzyme activity in tissue sections or cells. Cerium precipitates have strong reflectance properties and this enables their use in confocal scanning laser microscopy. In the present review, the principles of cerium methods are outlined and applications in cell biology and pathology are discussed.

Animals↗
PubMed1992

Light microscopical demonstration of non-specific alkaline phosphatase activity with an incubation medium containing cerium and two calcium as the capturing agents. The cerium/calcium-hydrogen peroxide-P-phenylenediamine/pyrocatechol (Ce/Ca-H2O2-PPD/PC) double capture technique.

A new method for the light microscopical demonstration of alPase activity in cryotome sections by using simultaneously cerium and calcium as capturing agents (double capture technique) is described. This method has an increased sensitivity compared with the single cerium-based and the Gomori based-cerium (single calcium and cerium converted) with techniques described previously. Presuming that the enzymatic activity during incubation of sections in the presence of a defined capturing agent is constant, the increased sensitivity after employment of the double capture method could be attributed to a decrease of enzyme inhibition by cerium through the presence of calcium. Based on model experiments it is assumed that calcium phosphate and cerium phosphate are the primary reaction products, the former converting into cerium phosphate already during incubation. The remaining calcium phosphate is converted completely by treatment with cerium citrate solution (conversion reaction). After oxidation with H2O2 the cerium perhydroxyphosphate was visualized in a paraphenylenediamine/pyrocatechol (Hanker-Yates reagent) solution without H2O2 to give a black reaction product. This visualization procedure is superior to the DAB or DAB-Ni mode as published earlier. Some results concerning the mode of inhibition of the pseudoperoxidase activity of the hemoglobin are presented.

Alkaline Phosphatase↗
PubMed2005

Toenail cerium levels and risk of a first acute myocardial infarction: the EURAMIC and heavy metals study.

The association between cerium status and risk of first acute myocardial infarction (AMI) was examined in a case-control study in 10 centres from Europe and Israel. Cerium in toenails was assessed by neutron activation analysis in 684 cases and 724 controls aged 70 years or younger. Mean concentrations of cerium were 186 and 173 microg/kg in cases and controls, respectively. Cerium was positively associated with low socio-economic status, smoking, mercury, zinc and scandium (p0.001). Cases had significantly higher levels of cerium than controls after adjustment for age and centre (case-control ratio 1.074; 95% CI 1.002-1.151) and increased in further adjustment for other cardiovascular risk factors 1.085; 95% CI 1.025-1.149. The risk after adjustment for age and centre was higher with increasing cerium levels (p for trend=0.02). After adjustment for BMI, history of hypertension, smoking, alcohol intake, diabetes, family history of CHD, beta-carotene, lycopene, alpha-tocopherol, selenium, mercury and scandium, the OR for the highest quintile was 1.43 (95% CI 0.85-2.41; p-trend 0.08). When we applied this same model in non-smokers the odds ratios in the 4th and 5th quintiles of cerium as compared with the lowest were 2.09 (95% CI 1.05-4.16) and 2.81 (95% CI 1.21-6.52), respectively, p-trend 0.011. Our results suggest that toenail cerium levels may be associated with an increased risk of AMI, but more research is warranted to shed further light and fully understand the plausibility and public health implications of these findings.

Case-Control Studies↗
PubMed1976

Differences in liver weight, mortality in cerium-treated mice and 144Ce levels in blood, liver, urine and faeces at various intervals after treatment with nafenopin and pregnenolone 16-alpha-carbonitrile (PCN).

Pretreatment with nafenopin and pregnenolone-16-alpha-carbonitrile (PCN) decreased the acute lethal toxicity in mice induced by cerium chloride (12 mg/kg resp. 15 mg/kg). Treatment with nafenopin and PCN increased the relative liver weight. More cerium accumulated in the liver of nafenopin- and PCN-treated animals than in controls during the first hours after injection. After 14 days the amount of cerium in the livers of nafenopin-treated animals was significantly higher. The concentration of cerium as a percentage of the injected dose calculated per mg liver was lower during the first day in the nafenopin group and higher in the PCN group than in the control group. After 6 days cerium concentration decreased significantly less in the livers of the nafenopin group. Cerium concentration in the blood was significantly lower in the nafenopin group during the first day. Only small amounts of the injected cerium were excreted in the urine, and no difference between treated and untreated animals was found. The amount of cerium excreted in faeces was somewhat smaller in the nafenopin-treated animals during the whole experiment.

Animals↗
PubMed2000

Cerium and lanthanum promote floral initiation and reproductive growth of Arabidopsis thaliana.

The effects of cerium and lanthanum on the vegetative growth, floral initiation and reproductive growth of Arabidopsis thaliana were studied. Addition of cerium nitrate (0.5-10 µM) or lanthanum nitrate (0.5-50 µM) to the culture medium significantly increased the lengths of primary roots, but had no significant effects on the number of rosette leaves produced per plant, plant heights and dry weights during the vegetative growth stage (17 days after seed germination). The percentage of plants bolted was significantly increased with the addition of 0.5-10.0 µM cerium nitrate or lanthanum nitrate. The combination of 0.5 µM cerium nitrate and 0.5 µM lanthanum nitrate was found to be most effective on the induction of floral initiation. The height, dry weight and average number of flower numbers of 35-day-old plants growing in media containing cerium nitrate or/and lanthanum nitrate (0.5-10.0 µM) were found to be significantly higher than those in the control medium. The endogenous levels of cytokinins (zeatin riboside, dihydrozeatin riboside and isopentenyl adenosine) and carbohydrates (sucrose, glucose and fructose) in leaf and root tissues of plants growing in the medium supplemented with 0.5 µM cerium nitrate and 0.5 µM lanthanum nitrate were not significantly different from those of plants in the control medium. Application of 0.5 µM cerium nitrate and 0.5 µM lanthanum nitrate enhanced the effects of 10(-6) M IPA on root growth, plant height and flowering. The role of cerium and lanthanum in promoting floral initiation and reproductive growth and the possibility of developing non-hormonal flowering promoting agents are discussed.

Journal Article↗
PubMed1999

Stimulation of cardiac fibroblast proliferation by cerium: a superoxide anion-mediated response.

UNLABELLED: Cardiac fibroblasts play a multifarious role in the maintenance of the functional and structural integrity of the heart. Therefore inadvertent proliferation of these fibroblasts can affect the normal functioning of the heart. The proliferation of fibroblasts could be due to various factors. We have worked on the hypothesis that low levels of cerium may stimulate cardiac fibroblasts to undergo proliferation and that free radicals act as the mediators of the stimulatory response. Cardiac fibroblasts isolated from neonatal Wistar rats were cultured. Proliferation of the cells was measured by cell count and immunohistochemical visualization for proliferating cell nuclear antigen. The response to cerium was assessed by comparison with control. A stimulatory response at low levels of cerium was observed with a peak at 0.5 micrometer concentration of cerium. A concomitant increase in the generation of free radicals was also seen. The cerium-stimulated cell proliferation and free radical generation was neutralized by the inclusion of superoxide dismutase in the culture medium. CONCLUSION: Low doses of cerium, at levels comparable to those found in the serum of patients with EMF, has a stimulatory effect on cardiac fibroblasts and the abrogation of proliferation by antioxidant superoxide dismutase indicates that superoxide anion acts as a biological intermediate in cerium-induced cardiac fibroblast proliferation.

Animals↗
PubMed2004

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

Cerium↗
PubMed1994

Lung retention of cerium in humans.

A retrospective study was conducted to evaluate lung retention of particles containing cerium in subjects with and without previous occupational exposure to mineral dusts. Analytical transmission electron microscopy was performed on 459 samples of bronchoalveolar lavage (BAL) fluid and 75 samples of lung tissue. Study of the distribution of mineralogical species in human samples showed that particles containing cerium were encountered in less than 10% of subjects. The proportion of subjects with particles containing cerium in their biological samples was not different between controls and subjects with previous occupational exposure to fibrous or nonfibrous mineral dusts. This was considered as the background level of lung retention of cerium in the general population. By contrast, determination of the absolute concentration of particles containing cerium in BAL fluid and lung tissue samples showed that 1.2% (from BAL fluid) and 1.5% (from lung tissue) of subjects with previous exposure to mineral particles had high lung retention of particles containing cerium. This study is believed to be the first one in which lung retention of cerium was estimated in the general population.

Adult↗
PubMed2007

Imidazolium ionic liquids as solvents for cerium(IV)-mediated oxidation reactions.

Use of imidazolium ionic liquids as solvents for organic transformations with tetravalent cerium salts as oxidizing agents was evaluated. Good solubility was found for ammonium hexanitratocerate(IV) (ceric ammonium nitrate, CAN) and cerium(IV) triflate in 1-alkyl-3-methylimidazolium triflate ionic liquids. Oxidation of benzyl alcohol to benzaldehyde in 1-ethyl-3-methylimidazolium triflate was studied by in-situ FTIR spectroscopy and 13C NMR spectroscopy on carbon-13-labeled benzyl alcohol. Careful control of the reaction conditions is necessary because ammonium hexanitratocerate(IV) dissolved in an ionic liquid can transform benzyl alcohol not only into benzaldehyde but also into benzyl nitrate or benzoic acid. The selectivity of the reaction of cerium(IV) triflate with benzyl alcohol in dry ionic liquids depends on the degree of hydration of cerium(IV) triflate: anhydrous cerium(IV) triflate transforms benzyl alcohol into dibenzyl ether, whereas hydrated cerium(IV) triflate affords benzaldehyde as the main reaction product. Reactions of ammonium hexanitratocerate(IV) with organic substrates other than benzyl alcohol have been explored. 1,4-Hydroquinone is quantitatively transformed into 1,4-quinone. Anisole and naphthalene are nitrated. For the cerium-mediated oxidation reactions in ionic liquids, high reaction temperatures are an advantage because under these conditions smaller amounts of byproducts are formed.

Journal Article↗
PubMed2005

Pharmacological properties of cerium compounds.

Cerium is a member of the lanthanide series or rare earth elements which exert diverse biological effects mainly by their resemblance to calcium. This similarity, which is particularly characteristic for the lighter members of the lanthanide series, enables these elements to replace calcium in biomolecules without necessarily substituting for it functionally. While the inhibitory effects on calcium-dependent physiological processes (such as those involved in the blood clotting cascade as well as in neuronal and muscular functions) are well-known, their relevance for the pharmacological properties of cerium are less clear. Historically, cerium oxalate was used as an antiemetic, especially in vomiting of pregnancy and kinetoses, although its mechanism of action has never been clarified. At present, cerium nitrate is available as an adjunct to silver sulfadiazine cream for the topical treatment of extensive burns not amenable to early wound excision. Apart from direct antiseptic effects, cerium helps to prevent postburn sepsis and systemic inflammatory response by fixing burn toxins. The antineoplastic potential of cerium compounds, which had fallen into oblivion, is currently being re-explored in experimental settings, though the mechanistic basis remains to be elucidated.

Animals↗
PubMed2005

Cytotoxic activity of new cerium (III) complexes of bis-coumarins.

Complexes of cerium (III) with bis-coumarins: 3,3'-benzylidene-bis(4-hydroxy-2H-1-benzopyran-2-one) and bis(4-hydroxy-2-oxo-2H-chromen-3-yl)-(1H-pyrazol-3-yl)-methane were synthesized by reaction of cerium (III) salt and the ligands, in amounts equal to metal/ligand molar ratio of 1:2. The complexes were prepared by adding an aqueous solution of cerium (III) salt to an aqueous solution of the ligand subsequently raising the pH of the mixture gradually to ca. 5.0 by adding dilute solution of sodium hydroxide. The cerium (III) complexes with bis-coumarins were characterized by different physicochemical methods--elemental analysis, IR-, 1H- and 13C-NMR-spectroscopies and mass-spectral data. The spectral data of cerium (III) complexes were interpreted on the basis of comparison with the spectra of the free ligands. This analysis showed that in the Ce (III) complexes the ligands coordinated to the metal ion through both deprotonated hydroxyl groups. On the basis of the nu(C=O) red shift observed, participation of the carbonyl groups in the coordination to the metal ion was also suggested. Cytotoxic screening by MTT assay was carried out. In the present study we performed comparative evaluation of the cytotoxic effects of the two newly synthesized cerium complexes against the acute myeloid leukemia derived HL-60 and the chronic myeloid leukemia (CML)-derived BV-173. In addition the cytotoxic effects of Ce (III) complex with 3,3'-benzylidene-bis(4-hydroxy-2H-1-benzopyran-2-one) were evaluated on the CML-derived K-562 and LAMA-84 cells, characterized by relative low responsiveness to chemotherapy. The DNA isolated from the cytosolic fraction of BV-173 cells after 24 h treatment with the same complex (at 100 and 200 microM) demonstrated a laddering phenomenon that is indicative for apoptotic cell death.

Carbon Isotopes↗
PubMed1986

Light microscopical localization of enzymes by means of cerium-based methods. I.V. Optimization procedures for acid phosphatase.

The earlier described cerium based histochemical reaction for acid phosphatase [Ce-Pb-reaction, Zimmermann and Halbhuber (1985)] was optimized. The target tissues (kidney, intestine) were fixed by perfusion with glutaraldehyde in cacodylate or piperazine buffer in anesthetized animals. Postfixation of prefixed sections is not advantageous because of the detectable repressing of the enzyme activity. Moreover, the employment of unfixed cryostat sections, which were postfixed, was always connected with a complete abolition of the acid phosphatase activity. The optimal concentration of the primary capture cerium III chloride in the incubation medium is about 1 mmol. Lower concentrations lead to an incomplete histochemical detection of phosphatase activity in lysosomes. The treatment of cryostat sections of perfusion fixed tissue with borohydride (diminution of aldehyde induced cross links) or with dimethylsulfoxide (extraction of lysosomal materials or the well known vehicle property) brought about an improvement of the penetration capacity for cerium-III-cations into the target structures. After conversion of the cerium phosphate (primary specific reaction product) into cerium perhydroxide, oxalate or fluoride, the Ce-Pb-reaction was negative. Therefore, these blocking reactions represent specific inhibition controls, which indicates the formation and presence of cerium phosphate. On the basis of these reactions it is possible to check the specificity of the histochemical Ce-Pb-reaction for phosphatase activity in sections.

Acid Phosphatase↗
PubMed2006

[Cerium-induced granulomatous dermatitis].

BACKGROUND: The presence of inorganic foreign bodies in granulomatous cutaneous lesions is not infrequent. In this paper, we describe the first case of cerium-induced cutaneous granulomatous dermatitis. CASE REPORT: A 57-year-old woman seriously burned four years ago presented with papulonodular lesions affecting only the burned areas treated with topical cerium nitrate-silver sulfadiazine cream (Flammacérium). Biopsies revealed sarcoidal granuloma associated with exogenous particles. Electron probe X-ray microanalysis demonstrated a high cerium content. Screening for systemic sarcoidosis was negative. The patient was treated with hydroxychloroquine. After four months of follow-up, clinical and histological evidence of decreased infiltrate was noted. DISCUSSION: Cerium nitrate-silver sulfadiazine cream (Flammacérium) is widely used for the topical treatment of burns. The main effect of cerium is to create superficial calcification, which decreases wound colonization and prevents the formation of granulation tissue (no hypertrophic scar formation) in burns. Prior to our case, no cutaneous side-effects of cerium had been encountered. Inoculation of foreign matter may or may not induce granuloma formation or sarcoidosis in different subjects, according to their immunologic status. The favorable outcome in this case could in fact be due to a change in the pattern of cytokinin production (TH1=> TH2) rather than the effects of hydroxychloroquine therapy.

Cerium↗
PubMed1989

Intracellular localization of cerium. A microanalytical study using an electron microprobe and ionic microanalysis.

Radioactive cerium is a nuclear toxicant. Metallic cerium is used in industry. Aspects of the intracellular metabolism of this element were studied following intraperitoneal injection and aerosol exposure in rat. Two microanalytic methods, an electron microprobe and ionic microanalysis, enabled the sites of incorporation and the process of intracellular concentration of cerium to be determined in the liver, lung, kidney, bone marrow and bone tissue. The very high sensitivity of ionic analysis enabled very low concentrations of cerium to be detected with a spatial resolution of 0.5 microns. Microanalysis by electron microprobe permitted: (i) the lysosomal localization of cerium to be determined; and (ii) the lysosomal coprecipitation of cerium with phosphorus to be demonstrated. Results are discussed in relation to aspects of radiological protection.

Administration, Inhalation↗
PubMed1983

Ultrastructural localization of several phosphatases with cerium.

Cerium ions have been used as the capture agent for inorganic phosphate released during the enzymatic hydrolysis of phosphate-containing substrates by a variety of phosphatases. Cerium phosphate reaction product accumulation is proportional to the amount of enzyme present in a cell-free model system. Ultrastructurally, cerium phosphate reaction product appears as a very fine electron-dense precipitate. Cerium appears to be a better capture agent for inorganic phosphate than lead in that reaction product is usually more uniform and more consistently reproducible when cerium is used. Furthermore, nonspecific deposits of reaction product that are commonly encountered in lead-based phosphatase reactions are virtually nonexistent when cerium is the capture agent.

Acid Phosphatase↗