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Complex formation of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid studied by time-resolved laser-induced fluorescence spectroscopy with ultra-short laser pulses.

The complex formation of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid (vanillic acid) was studied by time-resolved laser-induced fluorescence spectroscopy with ultra-short laser pulses using the fluorescence properties of 4-hydroxy-3-methoxybenzoic acid. A 2:1 complex of neptunium(V) with 4-hydroxy-3-methoxybenzoic acid was found. The stability constant of this complex was determined to be logbeta(210) = 7.33 +/- 0.10 at an ionic strength of 0.1 mol/l (NaClO(4)) and at 21 degrees C. The determination of the stability constant required an investigation of the excited-state proton transfer of 4-hydroxy-3-methoxybenzoic acid over the whole pH range. It was realized that 4-hydroxy-3-methoxybenzoic acid undergoes excited-state reactions only at pH values below 5. At pH values above 5 stability constants can be determined without kinetic calculation of the proton transfer.

Hydrogen-Ion Concentration↗

Structural variability in neptunium(V) oxalate compounds: synthesis and structural characterization of Na2NpO2(C2O4)OH.H2O.

Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions.

Crystallography, X-Ray↗

The absorption of ingested neptunium, plutonium and americium in newborn hamsters.

Hamsters aged 1, 4, 7, 22 and 30 days were given oral doses of either plutonium-239 citrate or americium-241 nitrate. The values of gastrointestinal absorption obtained were 3.5, 1.4, 0.04, 0.007 and 0.003 per cent, respectively, for plutonium and 4.5, 1.7, 0.5, 0.006 and 0.02 per cent, respectively, for americium, compared with values in adults of 0.01 per cent for plutonium and 0.05 per cent for americium. The absorption of neptunium was measured in hamsters aged 2 and 4 days and values of 2.3 and 1.7 per cent, respectively, were obtained for 239Np as the nitrate and 5.5 and 2.1 per cent, respectively, for 239Np as the bicarbonate compared with the values in adults of 0.02 per cent for both chemical forms. Thus, the absorption of plutonium, americium and neptunium at 1-2 days of age was about 100 times greater than in adults. The results for plutonium and americium show that absorption decreased rapidly with age over the suckling period. The values of absorption obtained at the time of weaning at 22 days were lower than in adults.

Aging↗

Evaluation of the efficiency of DTPA and other new chelating agents for removing neptunium from target organs.

Diethylenetriamine pentaacetic acid (DTPA) has been tested with 8 other new chelators for neptunium decorporation after systemic contamination in the rat. The ligands were injected intravenously at a dosage of 30 mumol kg-1 and the animals killed 24 h later. The results show that none of the chelators tested was efficient in removing significant amounts of the radionuclide from the body. In order to understand why these chelators were ineffective, in vitro approaches have since been developed in which high concentrations of DTPA were added to Np-bearing ligands in the blood, liver and skeleton. The main conclusions were that under our experimental conditions neptunium was not chelatable after its organ deposition.

Animals↗

Ultrastructural apoptotic lesions induced in bone marrow after neptunium-237 contamination.

This study describes the ultrastructure of lesions induced by neptunium-237 (237Np), a by-product of uranium in nuclear reactors, in the bone marrow. A group of rats were given a single injection of 237Np-nitrate solution in order to observe the acute toxicity effects of this actinide. Electron microscopy was used to describe the different lesions. Observations included the swelling of the cell membrane, nuclear membrane lyses, abnormal chromatin condensation or nucleus convolution. These ultrastructural alterations of the nucleus and the cellular membrane appeared shortly after treatment. This study demonstrates the toxic effects of neptunium and its implication in the induction of apoptosis in bone marrow.

Animals↗

Effects of fasting and/or oxidizing and reducing agents on absorption of neptunium from the gastrointestinal tract of mice and adult or neonatal rats.

Neptunium-237(V) nitrate was administered by gavage to groups of fed or fasted adult and 5-day-old rats. Some groups also received the oxidants quinhydrone or ferric iron, and others received the reducing agent ferrous iron. Adult mice received ferric or ferrous iron and 235Np. When the adult rats were killed at 7 days after gavage, measurements showed that, compared with rats that were fed, a 24-hr fast caused a fivefold increase in 237Np absorption and retention. Both quinhydrone and ferric iron caused an even greater increase in absorption in both fed and fasted rats. Ferrous iron, on the other hand, decreased absorption in fasted rats to values lower than those obtained in fed rats. Similar results were obtained in mice treated with 235Np and either ferric or ferrous iron. The highest absorption obtained after gavage of ferric iron to fasted rats and mice was about two orders of magnitude higher than the value obtained in animals that were fed before gavage. The effects of ferric and ferrous iron on neptunium absorption by neonatal rats were similar to their effects on adult animals but of lesser magnitude. These results are consistent with the hypothesis that Np(V), when given in small mass quantities to fed animals, is reduced in the gastrointestinal tract to Np(IV), which is less well absorbed than Np(V).

Aging↗

[Mechanism of distribution of neptunium and plutonium in rats].

Neptunium administered intravenously together with the high molecular weight protein fraction of blood serum was almost completely accumulated by the liver after 60 min. Then neptunium left the liver and was partially deposited in the skeleton. Plutonium, being a component of a nonprotein and a low molecular weight protein fractions, was mainly found in the skeleton where it had been accumulated throughout the entire period of observation (14 days, 52-58%); as to the nonprotein fraction, the value of accumulation was somewhat higher.

Animals↗

Genomic analysis of Hyphomonas neptunium contradicts 16S rRNA gene-based phylogenetic analysis: implications for the taxonomy of the orders 'Rhodobacterales' and Caulobacterales.

Hyphomonas neptunium is a marine prosthecate alpha-proteobacterium currently classified as a member of the order 'Rhodobacterales'. Although this classification is supported by 16S rRNA gene sequence phylogeny, 23S rRNA gene sequence analysis, concatenated ribosomal proteins, HSP70 and EF-Tu phylogenies all support classifying Hyphomonas neptunium as a member of the Caulobacterales instead. The possible reasons why the 16S rRNA gene sequence gives conflicting results in this case are also discussed.

Alphaproteobacteria↗

Development of Defined, Minimal, and Complete Media for the Growth of Hyphomicrobium neptunium.

A complete synthetic medium containing 15 amino acids, a minimal synthetic medium (GAMS) containing 4 amino acids, and a supplemented minimal medium (GAMS + calcium pantothenate) have been developed for the cultivation of Hyphomicrobium neptunium ATCC 15444. Depending on the complexity of the synthetic media, generation times were approximately 2 to 3 times longer, and maximum cell densities were 0.3 to 0.9 log(10) lower than in ZoBell marine broth 2216. The fates of C-labeled amino acids in GAMS were monitored. Results suggested that H. neptunium was auxotrophic for methionine, utilized glutamic acid as a primary energy source, and readily anabolized and catabolized serine and aspartic acid. Individual amino acid concentrations above 125 mM induced prolonged lag periods, whereas only methionine was not growth limiting at a concentration as low as 2 mM.

Journal Article↗

Inhibition of deoxyribonucleic acid synthesis and bud formation by nalidixic acid in Hyphomicrobium neptunium.

The relationship between chromosome replication and morphogenesis in the budding bacterium Hyphomicrobium neptunium has been investigated. Nalidixic acid was found to completely inhibit deoxyribonucleic acid synthesis, but not ribonucleic acid synthesis. The antibiotic was bacteriostatic to the organism for the initial 5 h of exposure; thereafter it was bacteriocidal. Observation of inhibited cultures revealed cells that had produced abnormally long stalks, but no buds. These results indicate that bud formation is coupled to chromosome replication in H. neptunium. They do not exclude the possibilities that cross wall formation and bud separation may also be coupled to chromosome replication.

Adenine↗

[Oxidation of hydrogen sulfide with cell-free extract of Hyphomicrobium neptunium ATCC 15444].

Soluble (Fr. 1) and membrane (Fr. 2) fractions were prepared from the cell-free extract of Hyphomicrobium neptunium ATCC 15444, and their effects on the oxidization of hydrogen sulfide (H2S) were studied. When H2S gas was supplied to Fr. 1 and Fr. 2, sulfur in both fractions and the majority of thiosulfate ion in Fr. 1 were detected. The sulfide-oxidizing activity in Fr. 2 but not in Fr. 1 was inhibited by the addition of diethyldithiocarbamate, suggesting that Fr. 1 and Fr. 2 have different types of sulfide-oxidase, and that Fr. 2 would include cytochrome c dependent sulfide oxidase. It was also found that thiosulfate ion was formed from sulfur and sulfite ion by adding Fr. 1. However, the pronase-treatment of Fr. 1 did not influence on the formation of thiosulfate ion. These results suggest that H2S was oxidized to sulfur and sulfite ion by two types of sulfide oxidase and sulfur oxidase in H. neptunium ATCC 15444, and that the sulfite ion changed rapidly to thiosulfate through a non-enzymatic reaction with sulfur.

Bacteria↗

Efficacy of 3,4,3-LIHOPO for reducing neptunium retention in the rat after simulated wound contamination.

PURPOSE: The ligand 3,4,3-Li(1,2-HOPO) was tested for Np removal after intramuscular injection of 237Np nitrate in rats. MATERIALS AND METHODS: Two experiments were performed, one with simultaneous injection of neptunium and LIHOPO at dosages ranging from 3 to 200 micromol kg(-1) and the other with delayed administration of LIHOPO 30 micromol kg(-1) from 5 min to 30 min after Np injection. RESULTS: The data obtained after simultaneous injections showed that the ligand dosage effectiveness was not linear and depended on the tissues being considered. For bones, the best results were obtained with 200 micromol kg(-1) LIHOPO, where retention was reduced to 11% of controls. Maximum efficacies for removal in liver and kidney were obtained with 30 micromol kg(-1) LIHOPO, where retention was reduced to 39% and 1.6% of controls, respectively. At higher dosages, LIHOPO seemed to have a reverse effect on these tissues, demonstrated by a significant accumulation of the radionuclide. The delayed administration of LIHOPO dramatically decreased its efficacy. When administered 5 min after Np, LIHOPO was still efficient (60%, 37%, 7% of controls in bone, liver, kidneys, respectively) but not when treatment was delayed to 30 min. CONCLUSIONS: These results demonstrated that LIHOPO was able to complex Np at the wound site but not after translocation to blood.

Animals↗

Neptunium uptake by serum transferrin.

Although of major impact in terms of biological and environmental hazards, interactions of actinide cations with biological molecules are only partially understood. Human serum transferrin (Tf) is one of the major iron carriers in charge of iron regulation in the cell cycle and consequently contamination by actinide cations is a critical issue of nuclear toxicology. Combined X-ray absorption spectroscopy (XAS) and near infrared absorption spectrometry were used to characterize a new complex between Tf and Np (IV) with the synergistic nitrilotriacetic acid (NTA) anion. Description of the neptunium polyhedron within the iron coordination site is given.

Humans↗

Subcellular and intranuclear localization of neptunium-237 (V) in rat liver.

The present investigation was aimed at establishing the distribution of 237Np within the different structures of hepatocytes. Rats were contaminated experimentally by intravenous injection of 237Np (V) and the subcellular structures of the liver were separated by ultracentrifugation. Twenty-four hours after contamination, the nuclear and cytosolic fractions bound 54 and 32%, respectively, of the total radionuclide. Purification of the nuclei followed by dissociation of the protein components in medium of increasing ionic strength showed a specific binding of neptunium to the structural proteins of the nuclear matrix.

Animals↗

Subcellular localization of neptunium-237 in lung and kidney after intratracheal administration in the rat: an ultrastructural and microanalytical study.

Chronic intratracheal administration of 237Np to rate was performed during 6 weeks. The total dose administered was 45.8 kBq. Two methods, electron microscopy and electron probe X-ray microanalysis, were used to determine the intracellular sites of localization of 237Np. Clusters of dense granules were observed in nuclei of pneumocytes and proximal tubular cells of the kidneys. These clusters have been shown to contain neptunium associated with phosphorus, sulfur and calcium. Alterations of nuclei and ultrastructural cytoplasmic lesions were observed. The absorbed doses in lungs and kidneys were very low. These results suggest that the chemical toxicity of 237Np is more important than its radiological toxicity.

Animals↗

Structural and spectroscopic trends in actinyl iodates of uranium, neptunium, and plutonium.

Two neptunyl(VI) iodates, NpO(2)(IO(3))(2)(H(2)O) (1) and NpO(2)(IO(3))(2).H(2)O (2), have been prepared from the aqueous reactions of Np(V) in HCl with KIO(4) or H(5)IO(6) at 180 degrees C and have been characterized by single crystal X-ray diffraction and Raman spectroscopy. Both compounds consist of two-dimensional arrangements of pentagonal bipyramidal [NpO(7)] polyhedra with axial neptunyl, NpO(2)(2+), dioxocations. In 1, the neptunium centers are bound in the equatorial plane by four bridging iodate anions and one terminal water molecule. The iodate anions link the [NpO(7)] units into corrugated sheets that interact with one another through intermolecular IO(3)(-)...IO(3)(-) interactions as also observed in UO(2)(IO(3))(2)(H(2)O). Compound 2 is isostructural with the recently reported PuO(2)(IO(3))(2).H(2)O, where oxygen atoms from bridging iodate anions occupy the five equatorial sites around the neptunyl moieties. The iodate anions occur as both mu(2)- and mu(3)-units and link the neptunyl polyhedra into sheets. Both types of iodate anions have their stereochemically active lone-pair of electrons aligned on one side of each layer creating a polar structure. Raman spectra of 1, UO(2)(IO(3))(2)(H(2)O), and PuO(2)(IO(3))(2).H(2)O show a sequential shift of the nu(1)(AnO(2)(2+)) stretch to lower wavenumber as the atomic number of the actinide is increased. Crystallographic data: 1, orthorhombic, space group Pcan, a = 7.684(2) A, b = 8.450(2) A, c = 12.493(3) A, Z = 4; 2, orthorhombic, space group Pna2(1), a = 7.314(1) A, b = 11.631(2) A, c = 9.449(2) A, Z = 4.

Journal Article↗

Timing of swarmer cell cycle morphogenesis and macromolecular synthesis by Hyphomicrobium neptunium in synchronous culture.

The swarmer cycle of Hyphomicrobium neptunium consists of a temporal sequence of discrete developmental events. To time morphogenesis and to investigate modulations in macromolecular synthesis, we attempted methods for synchronous culture. During synchrony, swarmer maturation occurred over 32%, hyphal growth occurred over 36%, and bud maturation occurred over 32% of the time required to complete the swarmer cycle. Daughter cells were released after 265 min. Deoxyribonucleic acid replication was discontinuous, having a G1 period of approximately 180 min. In addition, ribonucleic acid and protein syntheses were depressed during the earlier phases of development.

Bacteria↗