Quantification of tantalum sedimentation rates in liquid embolic agents.

Background Endovascular treatment (EVT) of brain arteriovenous malformations has evolved from cyanoacrylate derivatives such as N-butyl cyanoacrylate, an adhesive glue, to ethylene vinyl copolymer-based liquid embolics such as Onyx® and SQUID® dissolved in dimethyl sulfoxide. Although these agents offer several advantages, their rapidly decreasing radiopacity, as a result of the sedimentation of tantalum powder, compromises visual control during EVT. This study aims to quantify and compare tantalum sedimentation rates of several liquid embolic agents, and determine their effects on radiopacity. Methods The rate of sedimentation of liquid embolics Onyx 18®, SQUID 12®, and SQUID 18® was measured after preparation by single x-ray exposures for a period of 30 minutes. The signal-to-noise ratios (SNRs) of the suspension of each liquid embolic was calculated at various time points as tantalum settled out of the suspension. Precipitating Hydrophobic Injectable Liquid (PHIL®) was imaged as a control. Results Onyx 18® demonstrated the fastest sedimentation rate of the liquid embolics analyzed and demonstrated a threefold faster drop in SNR compared to SQUID 18® over 30 minutes. Onyx 18® demonstrated a one and a half times faster drop in SNR compared to SQUID 12®. Although PHIL 25® maintained constant SNR over the same time, it was lower at baseline immediately after preparation compared to tantalum-based liquids. Conclusion Caution during long injections using tantalum-based agents is advised. Onyx 18® has a significantly faster drop in radiopacity compared to SQUID 12® and SQUID 18®. Covalently bonded iodine-based embolics like PHIL® demonstrate constant radiopacity over time.

Microbial mobilization of plutonium and other actinides from contaminated soil.

We examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (µ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (µ-XRF) mapping showed its association with Fe- and Ca-phases; and µ-x-ray absorption near edge structure (µ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to the soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.

Bioreduction and precipitation of uranium in ionic liquid aqueous solution by Clostridium sp.

The ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], N-ethylpyridiniumtrifluoroacetate [EtPy][CF3COO] and N-ethylpyridiniumtetrafluoroborate [EtPy][BF4], affected the reduction and precipitation of uranium by Clostridium sp. to a varying degree. Characterization of uranium association with the ionic liquids showed that uranium formed a monodentate complex with the anion BF4(-) and PF6(-) of [EtPy][BF4] and [BMIM][PF6], respectively; and a bidentate complex with carboxylate of [EtPy][CF3COO]. Bioreduction of U(VI) was influenced by the type of complex formed: monodentate complexes were readily reduced whereas the bidentate complex of U(VI) with [CF3COO] was recalcitrant. [EtPy][BF4] affected the rate and extent of precipitation of the reduced uranium; at higher concentration the reduced U(IV) remained in the solution phase. The results suggest that by tuning the properties of ionic liquids they may be valuable candidates for uranium biotreatment.

Immobilization of Cr(VI) and its reduction to Cr(III) phosphate by granular biofilms comprising a mixture of microbes.

We assessed the potential of mixed microbial consortia, in the form of granular biofilms, to reduce chromate and remove it from synthetic minimal medium. In batch experiments, acetate-fed granular biofilms incubated aerobically reduced 0.2 mM Cr(VI) from a minimal medium at 0.15 mM day(-1) g(-1), with reduction of 0.17 mM day(-1) g(-1) under anaerobic conditions. There was negligible removal of Cr(VI) (i) without granular biofilms, (ii) with lyophilized granular biofilms, and (iii) with granules in the absence of an electron donor. Analyses by X-ray absorption near edge spectroscopy (XANES) of the granular biofilms revealed the conversion of soluble Cr(VI) to Cr(III). Extended X-ray absorption fine-structure (EXAFS) analysis of the Cr-laden granular biofilms demonstrated similarity to Cr(III) phosphate, indicating that Cr(III) was immobilized with phosphate on the biomass subsequent to microbial reduction. The sustained reduction of Cr(VI) by granular biofilms was confirmed in fed-batch experiments. Our study demonstrates the promise of granular-biofilm-based systems in treating Cr(VI)-containing effluents and wastewater.

Colloidal cutin-like substances cross-linked to siderophore decomposition products mobilizing plutonium from contaminated soils.

Relatively recently, inorganic colloids have been invoked to reconcile the apparent contradictions between expectations based on classical dissolved-phase Pu transport and field observations of "enhanced" Pu mobility (Kersting et al. Nature 1999, 397, 56-59). A new paradigm for Pu transport is mobilization and transport via biologically produced ligands. This study for the first time reports a new finding of Pu being transported, at sub-pM concentrations, by a cutin-like natural substance containing siderophore-like moieties and virtually all mobile Pu. Most likely, Pu is complexed by chelating groups derived from siderophores that are covalently bound to a backbone of cutin-derived soil degradation products, thus revealing the history of initial exposure to Pu. Features such as amphiphilicity and small size make this macromolecule an ideal collector for actinides and other metals and a vector for their dispersal. Cross-linking to the hydrophobic domains (e.g., by polysaccharides) gives this macromolecule high mobility and a means of enhancing Pu transport. This finding provides a new mechanism for Pu transport through environmental systems that would not have been predicted by Pu transport models.

Bioreduction of uranium(VI) complexed with citric acid by Clostridia affects its structure and solubility.

Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI): citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex,which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

Analysis of novel soluble chromate and uranyl reductases and generation of an improved enzyme by directed evolution.

Most polluted sites contain mixed waste. This is especially true of the U.S. Department of Energy (DOE) waste sites which hold a complex mixture of heavy metals, radionuclides, and organic solvents. In such environments enzymes that can remediate multiple pollutants are advantageous. We report here evolution of an enzyme, ChrR6 (formerly referred to as Y6), which shows a markedly enhanced capacity for remediating two of the most serious and prevalent DOE contaminants, chromate and uranyl. ChrR6 is a soluble enzyme and reduces chromate and uranyl intracellularly. Thus, the reduced product is at least partially sequestered and nucleated, minimizing the chances of reoxidation. Only one amino acid change, (Tyr)128(Asn), was responsible for the observed improvement. We show here that ChrR6 makes Pseudomonas putida and Escherichia coli more efficient agents for bioremediation if the cellular permeability barrier to the metals is decreased.

Coordination modes in the formation of the ternary Am(III), Cm(III), and Eu(III) complexes with EDTA and NTA: TRLFS, 13C NMR, EXAFS, and thermodynamics of the complexation.

The formation and the structure of the ternary complexes of trivalent Am, Cm, and Eu with mixtures of EDTA+NTA (ethylenediamine tetraacetate and nitrilotriacetate) have been studied by time-resolved laser fluorescence spectroscopy, 13C NMR, extended X-ray absorption fine structure, and two-phase metal ion equilibrium distribution at 6.60 m (NaClO4) and a hydrogen ion concentration value (pcH) between 3.60 and 11.50. In the ternary complexes, EDTA binds via four carboxylates and two nitrogens, while the binding of the NTA varies with the hydrogen ion concentration, pcH, and the concentration ratios of the metal ion and the ligand. When the concentration ratios of the metal to ligand is low (1:1:1-1:1:2), two ternary complexes, M(EDTA)(NTAH)(3-) and M(EDTA)(NTA)(4-), are formed at pcH ca. 9.00 in which NTA binds via three carboxylates, via two carboxylates and one nitrogen, or via two carboxylates and a H2O. At higher ratios (1:1:20 and 1:10:10) and pcH's of ca. 9.00 and 11.50, one ternary complex, M(EDTA)(NTA)(4-), is formed in which NTA binds via three carboxylates and not via nitrogen. The two-phase equilibrium distribution studies at tracer concentrations of Am, Cm, and Eu have also confirmed the formation of the ternary complex M(EDTA)(NTA)(4-) at temperatures between 0 and 60 degrees C. The stability constants (log beta111) for these metal ions increase with increasing temperature. The endothermic enthalpy and positive entropy indicated a significant effect of cation dehydration in the formation of the ternary complexes at high ionic strength.

Decontamination of uranium-contaminated steel surfaces by hydroxycarboxylic acid with uranium recovery.

We developed a simple, safe method to remove uranium from contaminated metallic surfaces so that the materials can be recycled or disposed of as low-level radioactive or nonradioactive waste. Surface analysis of rusted uranium-contaminated plain carbon-steel coupons by X-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy showed that uranium was predominantly associated with ferrihydrite, lepidocrocite, and magnetite, or occluded in the matrix of the corrosion product as uranyl hydroxide and schoepite (UO3 x 2H2O). Citric acid formulations, consisting of oxalic acid-hydrogen peroxidecitric acid (OPC) or citric acid-hydrogen peroxidecitric acid (CPC), were used to remove uranium from the coupons. The efficiency of uranium removal varied from 68% to 94% depending on the extent of corrosion, the association of uranium with the iron oxide matrix, and the accessibility of the occluded contaminant. Decontaminated coupons clearly showed evidence of the extensive removal of rust and uranium. The waste solutions containing uranium and iron from decontamination by OPC and CPC were treated first by subjecting them to biodegradation followed by photodegradation. Biodegradation of a CPC solution by Pseudomonas fluorescens resulted in the degradation of the citric acid with concomitant precipitation of Fe (>96%), whereas U that remained in solution was recovered (>99%) by photodegradation as schoepite. In contrast, in an OPC solution citric acid was biodegraded but not oxalic acid, and both Fe and U remained in solution. Photodegradation of this OPC solution resulted in the precipitation of iron as ferrihydrite and uranium as uranyl hydroxide.

Effect of competitive distance on energy expenditure during simulated competition.

Concepts of how athletes should expend their aerobic and anaerobic energetic reserves are generally based on results of tests where an "all out" strategy is imposed on/required from the athlete. We sought to determine how athletes spontaneously expend their energetic reserves when the only instruction was to finish the event in minimal time, as in competition. Well trained, and task habituated, road cyclists (N = 14) completed randomly ordered laboratory time trials of 500 m, 1000 m, 1500 m and 3000 m on a windload braked cycle ergometer. The pattern of aerobic and anaerobic energy use was calculated from total work accomplished and V.O (2) during the trials. The events were completed in 40.3 +/- 0.6 s, 87.4 +/- 4.1 s, 133.8 +/- 6.6 s and 296.0 +/- 7.2 s. The peak V.O (2) during the terminal 200 m of all events was similar (2.72 +/- 0.22, 3.01 +/- 0.34, 3.23 +/- 0.44 and 3.12 +/- 0.13 l x min (-1)). In all events, the initial power output and anaerobic energy use was high, and decreased to a more or less constant value over the remainder of the event. However, the subjects seemed to reserve some ability to expend energy anaerobically for a terminal acceleration which is contrary to predictions of an "all out" starting strategy. Although the total work accomplished increased with distance (23.14 +/- 4.24, 34.14 +/- 6.37, 43.54 +/- 6.12 and 78.22 +/- 8.28 kJ), the energy attributable to anaerobic sources was not significantly different between the rides (17.29 +/- 3.82, 18.68 +/- 8.51, 20.60 +/- 6.99 and 23.28 +/- 9.04 kJ). The results are consistent with the concept that athletes monitor their energetic resources and regulate their energetic output over time in a manner designed to optimize performance.

Association of uranium with iron oxides typically formed on corroding steel surfaces.

Decontamination of metal surfaces contaminated with low levels of radionuclides is a major concern at Department of Energy facilities. The development of an environmentally friendly and cost-effective decontamination process requires an understanding of their association with the corroding surfaces. We investigated the association of uranium with the amorphous and crystalline forms of iron oxides commonly formed on corroding steel surfaces. Uranium was incorporated with the oxide by addition during the formation of ferrihydrite, goethite, green rust II, lepidocrocite, maghemite, and magnetite. X-ray diffraction confirmed the mineralogical form of the oxide. EXAFS analysis at the U L(III) edge showed that uranium was present in hexavalent form as a uranyl oxyhydroxide species with goethite, maghemite, and magnetite and as a bidentate inner-sphere complex with ferrihydrite and lepidocrocite. Iron was present in the ferric form with ferrihydrite, goethite, lepidocrocite, and maghemite; whereas with magnetite and green rust II, both ferrous and ferric forms were present with characteristic ferrous:total iron ratios of 0.65 and 0.73, respectively. In the presence of the uranyl ion, green rust II was converted to magnetite with concomitantreduction of uranium to its tetravalent form. The rate and extent of uranium dissolution in dilute HCl depended on its association with the oxide: uranium present as oxyhydroxide species underwent rapid dissolution followed by a slow dissolution of iron; whereas uranium present as an inner-sphere complex with iron resulted in concomitant dissolution of the uranium and iron.

A new approach to monitoring exercise training.

The ability to monitor training is critical to the process of quantitating training periodization plans. To date, no method has proven successful in monitoring training during multiple types of exercise. High-intensity exercise training is particularly difficult to quantitate. In this study we evaluate the ability of the session rating of perceived exertion (RPE) method to quantitate training during non-steady state and prolonged exercise compared with an objective standard based on heart rate (HR). In a 2-part design, subjects performed steady state and interval cycle exercise or practiced basketball. Exercise bouts were quantitated using both the session RPE method and an objective HR method. During cycle exercise, the relationship between the exercise score derived using the session RPE method and the HR method was highly consistent, although the absolute score was significantly greater with the session RPE method. During basketball, there was a consistent relationship between the 2 methods of monitoring exercise, although the absolute score was also significantly greater with the session RPE method. Despite using different subjects in the 2 parts of the study, the regression relationships between the session RPE method and the HR method were nearly overlapping, suggesting the broad applicability of this method. We conclude that the session RPE method is a valid method of quantitating exercise training during a wide variety of types of exercise. As such, this technique may hold promise as a mode and intensity-independent method of quantitating exercise training and may provide a tool to allow the quantitative evaluation of training periodization plans.

Emergence characteristics of sevoflurane compared to halothane in pediatric patients undergoing bilateral pressure equalization tube insertion.

STUDY OBJECTIVE: To compare the emergence characteristics of sevoflurane with halothane in pediatric patients having bilateral myringotomy and pressure equalization tube insertion using a highly standardized and common anesthetic technique. DESIGN: Prospective, randomized, double-blind study. SETTING: University hospital. PATIENTS: 43 ASA physical status I and II healthy pediatric outpatients scheduled for initial ear tube placement by one surgeon. INTERVENTIONS: Patients were randomized to receive either halothane or sevoflurane as their sole anesthetic drug for ear tube insertion. All patients as well as the research nurse grading emergence agitation were blinded to group assignment. No premedication was administered, and all patients received a standard dose of rectal acetaminophen for postoperative pain control. MEASUREMENT AND MAIN RESULTS: The primary outcome was the percentage of patients with emergence agitation, defined as thrashing behavior requiring physical restraint for greater than three minutes. Time to discharge from the postanesthesia care unit (PACU) and from the hospital were also compared. Sevoflurane patients had a greater incidence of emergence delirium: 57% versus 27% [95% CI (1.7%-58.1%) p = 0.047]. Time to discharge from the PACU and the hospital were longer for patients who received sevoflurane: 62 versus 50 min [95% CI (1.4-23.6) p = 0.02] and 102 versus 79 mins [95% CI (9.6-37.1) p = 0.003]. CONCLUSION: In our institution there is a trend toward greater emergence agitation in ear tube placement patients given sevoflurane versus halothane anesthesia. Further, (with our discharge criteria) patients are actually discharged from the PACU and the hospital faster when given halothane as a sole anesthetic when compared to sevoflurane.

The chsA gene from Aspergillus nidulans is necessary for maximal conidiation.

A fragment from the open reading frame of the cloned chsA gene from Aspergillus nidulans was deleted and replaced with the argB gene. The resulting construct was used to replace the wild-type chsA gene in an argB deletion strain. The growth and morphology of the vegetative hyphae from the resulting chsA disruptant strain were indistinguishable from those of a wild-type strain but the chitin content of the hyphae from the disruptant was reduced to approximately 90% of that of wild-type. The disruptant showed reduced ability to produce the asexual spores (conidia) that are formed by differentiated aerial hyphae called conidiophores. The ability to form undifferentiated aerial hyphae was not impaired in the disruptant. The conidiophores and conidia produced by the disruptant were indistinguishable from those of wild-type. Conidium formation by the disruptant grown on a variety of media was reduced to about 30% of the wild-type. A chsE null strain did not show a defect in conidiation but a strain in which both chsA and chsE were inactivated produced about 3% of the conidia of wild-type. That finding supports the hypothesis that chsA and chsE encode a partially redundant function necessary for conidiophore development.

The HSSP database of protein structure-sequence alignments and family profiles.

HSSP (http: //www.sander.embl-ebi.ac.uk/hssp/) is a derived database merging structure (3-D) and sequence (1-D) information. For each protein of known 3D structure from the Protein Data Bank (PDB), we provide a multiple sequence alignment of putative homologues and a sequence profile characteristic of the protein family, centered on the known structure. The list of homologues is the result of an iterative database search in SWISS-PROT using a position-weighted dynamic programming method for sequence profile alignment (MaxHom). The database is updated frequently. The listed putative homologues are very likely to have the same 3D structure as the PDB protein to which they have been aligned. As a result, the database not only provides aligned sequence families, but also implies secondary and tertiary structures covering 33% of all sequences in SWISS-PROT.

Infrared properties of chemical-vapor deposition polycrystalline diamond windows.

Low-resolution transmittance and reflectance spectra of high-quality chemical-vapor deposition (CVD) diamond windows were measured in the infrared in the 2.5-500-mum wavelength range (20-4000 cm(-1)). High-resolution measurements on a window with nearly parallel surfaces show well defined interference fringes at low frequencies. By standard procedures the optical constants n and k of CVD diamond were determined, for the first time to the author's knowledge, in the far-infrared region. It is shown that a window with a large wedge angle, close to 1 degrees , does not produce appreciable interference fringes. Modeling of these results confirms that interference fringes can be avoided by use of properly wedged CVD diamond windows. This result is of considerable relevance to the use of CVD diamond windows in spectroscopic applications for which fringe suppression is a major requirement.

Parental presence plus oral midazolam decreases frequency of 5% halothane inductions in children.

STUDY OBJECTIVE: To determine the frequency of 5% halothane induction and behavioral distress during inhalation induction with both oral midazolam and parental presence compared with parental presence alone. DESIGN: Randomized, controlled, double blind study. SETTING: Same day anesthesia at a university department of anesthesiology. PATIENTS: 72 ASA status I and II children, 3 to 10 years of age, scheduled for first time anesthesia. INTERVENTIONS: Children were assigned to one of two groups to receive midazolam 0.5 mg/kg orally or placebo. A parent was present during induction. Children were videotaped at baseline, after treatment, and during induction. Tapes were scored for behavioral distress using the revised Observational Scale of Behavioral Distress. MEASUREMENTS AND MAIN RESULTS: Children who received midazolam in the setting of parental presence had significantly fewer 5% halothane inductions than those who received placebo (p < 0.02). They also had less behavioral distress (p < 0.01). CONCLUSIONS: The combination of parental presence plus oral midazolam reduces the likelihood of needing a 5% rapid halothane induction when compared with parental presence without premedication.

The orlA gene from Aspergillus nidulans encodes a trehalose-6-phosphate phosphatase necessary for normal growth and chitin synthesis at elevated temperatures.

A cosmid carrying the orlA gene from Aspergillus nidulans was identified by complementation of an orlA1 mutant strain with DNA from the pKBY2 cosmid library. An orlA1 complementing fragment from the cosmid was sequenced. orlA encodes a predicted polypeptide of 227 amino acids (26360 Da) that is homologous to a 211-amino-acid domain from the polypeptide encoded by the Saccharomyces cerevisiae TPS2 gene and to almost the entire Escherichia coli otsB-encoded polypeptide. TPS2 and otsB each specify a trehalose-6-phosphate phosphatase, an enzyme that is necessary for trehalose synthesis. orlA disruptants accumulate trehalose-6-phosphate and have reduced trehalose-6-phosphatate phosphatase levels, indicating that the gene encodes a trehalose-6-phosphatate phosphatase. Disruptants have a nearly-wild-type morphology at 32 degrees C. When germinated at 42 degrees C, the conidia and hyphae from disruptants are chitin deficient, swell excessively, and lyse. The lysis is almost completely remedied by osmotic stabilizers and is partially remedied by N-acetylglucosamine (GlcNAc). The activity of glutamine:fructose-6-phosphate amido-transferase (GFAT), the first enzyme unique to aminosugar synthesis, is reduced and is labile in orlA disruption strains. The findings are consistent with the hypothesis that trehalose-6-phosphate reduces the temperature stability of GFAT and other enzymes of chitin metabolism at elevated temperatures. The results extend to filamentous organisms the observation that mutations in fungal trehalose synthesis are highly pleiotropic and affect aspects of carbohydrate metabolism that are not directly related to trehalose synthesis.