Gamma radiolytic stability of CyMe4BTBP and the effect of nitric acid

The highly selective nitrogen donor ligand CyMe4BTBP for An(III) separation by solvent extraction was irradiated in a 60Co γ-source under varying conditions. Organic solutions of 10 mmol/L ligand in 1-octanol were contacted with different concentrations of nitric acid to observe the influence of an aqueous phase during irradiation. In subsequent liquid-liquid extraction experiments, distribution ratios of 241Am and 152Eu were determined. Distribution ratios decreased with increasing absorbed dose when irradiation was performed in the absence of nitric acid. With addition of nitric acid, initial distribution ratios remained constant over the whole examined dose range up to 300 kGy. For qualitative determination of radiolysis products, HPLC-MS measurements were performed. The protective effect of nitric acid was confirmed, since in samples irradiated with acid contact, no degradation products were observed, but only addition products of the 1-octanol molecule to the CyMe4BTBP molecule

Gamma radiolytic stability of CyMe4BTBP and the effect of nitric acid

The highly selective nitrogen donor ligand CyMe4BTBP for An(III) separation by solvent extraction was irradiated in a 60Co γ-source under varying conditions. Organic solutions of 10 mmol/L ligand in 1-octanol were contacted with different concentrations of nitric acid to observe the influence of an aqueous phase during irradiation. In subsequent liquid-liquid extraction experiments, distribution ratios of 241Am and 152Eu were determined. Distribution ratios decreased with increasing absorbed dose when irradiation was performed in the absence of nitric acid. With addition of nitric acid, initial distribution ratios remained constant over the whole examined dose range up to 300 kGy. For qualitative determination of radiolysis products, HPLC-MS measurements were performed. The protective effect of nitric acid was confirmed, since in samples irradiated with acid contact, no degradation products were observed, but only addition products of the 1-octanol molecule to the CyMe4BTBP molecule

Posterior cricoid region fluoroscopic findings: the posterior cricoid plication.

The region posterior to the cricoid cartilage is challenging to assess fluoroscopically. The purpose of this investigation is to critically evaluate the posterior cricoid (PC) region on fluoroscopy and describe patterns of common findings. This was a case control study. All fluoroscopic swallowing studies performed between June 16, 2009, and February 9, 2010, were reviewed for features seen in the PC region. These findings were categorized into distinct patterns and compared to fluoroscopic studies performed in a cohort of normal volunteers. Two hundred patient studies and 149 healthy volunteer studies were reviewed. The mean age of the referred patient cohort and the volunteer cohort was 57 years (±19) and 61 years (±16), respectively (p > 0.05). The patient cohort was 53% male and the control cohort was 56% female (p > 0.05). Four groups were identified. Pharyngoesophageal webs were seen in 7% (10/149) of controls and 14% (28/200) of patients (p = 0.03). A PC arch impression was seen in 16% of patients (32/200) and controls (24/149) (p = 1). A PC plication was demonstrated in 23% (34/149) of controls and 30% (60/200) of patients (p = 0.13). No distinctive PC region findings were seen in 54% (81/149) of controls and 42% (84/200) of referred patients (p = 0.02). Four patients (2%) had both a web and a PC plication. Four categories of PC region findings were identified (unremarkable PC region, web, PC arch impression, and PC plication). Both patients referred for swallowing studies and healthy volunteers demonstrated esophageal webs, PC arch impressions, and PC plications. Only webs were more common in patients than in control subjects (p = 0.03). The PC impression and PC plication are likely to represent normal variants that may be identified on fluoroscopic swallow studies

Improving business processes of service companies

This article considers the problem of improving business process through analysis “Highlighting areas of concern”. In the process, we formulated a number of requirements that should meet the functionality of the information system and highlighted advantages of the"Selection concerns" method

Objective and quantitative definitions of modified food textures based on sensory and rheological methodology

Introduction: Patients who suffer from chewing and swallowing disorders, i.e. dysphagia, may have difficulties ingesting normal food and liquids. In these patients a texture modified diet may enable that the patient maintain adequate nutrition. However, there is no generally accepted definition of ‘texture’ that includes measurements describing different food textures. Objective: Objectively define and quantify categories of texture-modified food by conducting rheological measurements and sensory analyses. A further objective was to facilitate the communication and recommendations of appropriate food textures for patients with dysphagia. Design: About 15 food samples varying in texture qualities were characterized by descriptive sensory and rheological measurements. Results: Soups were perceived as homogenous; thickened soups were perceived as being easier to swallow, more melting and creamy compared with soups without thickener. Viscosity differed between the two types of soups. Texture descriptors for pâtés were characterized by high chewing resistance, firmness, and having larger particles compared with timbales and jellied products. Jellied products were perceived as wobbly, creamy, and easier to swallow. Concerning the rheological measurements, all solid products were more elastic than viscous (G′>G″), belonging to different G′ intervals: jellied products (low G′) and timbales together with pâtés (higher G′). Conclusion: By combining sensory and rheological measurements, a system of objective, quantitative, and well-defined food textures was developed that characterizes the different texture categories

Engineering tyrosine-based electron flow pathways in proteins: The case of aplysia myoglobin

Tyrosine residues can act as redox cofactors that provide an electron transfer ("hole-hopping") route that enhances the rate of ferryl heme iron reduction by externally added reductants, for example, ascorbate. Aplysia fasciata myoglobin, having no naturally occurring tyrosines but 15 phenylalanines that can be selectively mutated to tyrosine residues, provides an ideal protein with which to study such through-protein electron transfer pathways and ways to manipulate them. Two surface exposed phenylalanines that are close to the heme have been mutated to tyrosines (F42Y, F98Y). In both of these, the rate of ferryl heme reduction increased by up to 3 orders of magnitude. This result cannot be explained in terms of distance or redox potential change between donor and acceptor but indicates that tyrosines, by virtue of their ability to form radicals, act as redox cofactors in a new pathway. The mechanism is discussed in terms of the Marcus theory and the specific protonation/deprotonation states of the oxoferryl iron and tyrosine. Tyrosine radicals have been observed and quantified by EPR spectroscopy in both mutants, consistent with the proposed mechanism. The location of each radical is unambiguous and allows us to validate theoretical methods that assign radical location on the basis of EPR hyperfine structure. Mutation to tyrosine decreases the lipid peroxidase activity of this myoglobin in the presence of low concentrations of reductant, and the possibility of decreasing the intrinsic toxicity of hemoglobin by introduction of these pathways is discussed. © 2012 American Chemical Society

Mountain birch : potentially large source of sesquiterpenes into high latitude atmosphere

Emissions of volatile organic compounds (VOCs) from mountain birches were measured in Abisko, northern Sweden. Mountain birches make up the majority of the tree biomass in Scandinavian high latitudes, a region subject to significant climate warming. The measurements were carried out in two growing seasons. The emissions of four branches, each from a different individual tree, were measured in June-August 2006 and one of them again in July 2007. The measurements were conducted using a dynamic flow through chamber covered with Teflon film. The studied mountain birches were found to emit substantial amounts of linalool, monoterpenes and sesquiterpenes. The monoterpene emission was dominated by sabinene. The magnitude and composition of the sesquiterpene emission changed dramatically between the years. For example, the average alpha-farnesene emission potential in 2006 was almost 2600 ng g(dw)(-1) h(-1) (3.5 pmol g(dw)(-1) s(-1)) while in 2007 alpha-farnesene was not detected at all. Also the emissions of other sesquiterpenes decreased in 2007 to a fraction of that in 2006. One possible explanation for the change in emissions is the herbivory damage that occurred in the area in 2004. Herbivory is known to enhance the emissions of sesquiterpenes, especially those of alpha-farnesene, and the effect may last for several years.Emissions of volatile organic compounds (VOCs) from mountain birches were measured in Abisko, northern Sweden. Mountain birches make up the majority of the tree biomass in Scandinavian high latitudes, a region subject to significant climate warming. The measurements were carried out in two growing seasons. The emissions of four branches, each from a different individual tree, were measured in June-August 2006 and one of them again in July 2007. The measurements were conducted using a dynamic flow through chamber covered with Teflon film. The studied mountain birches were found to emit substantial amounts of linalool, monoterpenes and sesquiterpenes. The monoterpene emission was dominated by sabinene. The magnitude and composition of the sesquiterpene emission changed dramatically between the years. For example, the average alpha-farnesene emission potential in 2006 was almost 2600 ng g(dw)(-1) h(-1) (3.5 pmol g(dw)(-1) s(-1)) while in 2007 alpha-farnesene was not detected at all. Also the emissions of other sesquiterpenes decreased in 2007 to a fraction of that in 2006. One possible explanation for the change in emissions is the herbivory damage that occurred in the area in 2004. Herbivory is known to enhance the emissions of sesquiterpenes, especially those of alpha-farnesene, and the effect may last for several years.Emissions of volatile organic compounds (VOCs) from mountain birches were measured in Abisko, northern Sweden. Mountain birches make up the majority of the tree biomass in Scandinavian high latitudes, a region subject to significant climate warming. The measurements were carried out in two growing seasons. The emissions of four branches, each from a different individual tree, were measured in June-August 2006 and one of them again in July 2007. The measurements were conducted using a dynamic flow through chamber covered with Teflon film. The studied mountain birches were found to emit substantial amounts of linalool, monoterpenes and sesquiterpenes. The monoterpene emission was dominated by sabinene. The magnitude and composition of the sesquiterpene emission changed dramatically between the years. For example, the average alpha-farnesene emission potential in 2006 was almost 2600 ng g(dw)(-1) h(-1) (3.5 pmol g(dw)(-1) s(-1)) while in 2007 alpha-farnesene was not detected at all. Also the emissions of other sesquiterpenes decreased in 2007 to a fraction of that in 2006. One possible explanation for the change in emissions is the herbivory damage that occurred in the area in 2004. Herbivory is known to enhance the emissions of sesquiterpenes, especially those of alpha-farnesene, and the effect may last for several years.Peer reviewe

Boron Abundances in Main Sequence B-type Stars: A Test of Rotational Depletion during Main Sequence Evolution

Boron abundances have been derived for seven main sequence B-type stars from HST STIS spectra around the B III 2066 A line. In two stars, boron appears to be undepleted with respect to the presumed initial abundance. In one star, boron is detectable but it is clearly depleted. In the other four stars, boron is undetectable implying depletions of 1 to 2 dex. Three of these four stars are nitrogen enriched, but the fourth shows no enrichment of nitrogen. Only rotationally induced mixing predicts that boron depletions are unaccompanied by nitrogen enrichments. The inferred rate of boron depletion from our observations is in good agreement with these predictions. Other boron-depleted nitrogen-normal stars are identified from the literature. Also, several boron-depleted nitrogen-rich stars are identified, and while all fall on the boron-nitrogen trend predicted by rotationally-induced mixing, a majority have nitrogen enrichments that are not uniquely explained by rotation. The spectra have also been used to determine iron-group (Cr, Mn, Fe, and Ni) abundances. The seven B-type stars have near solar iron-group abundances, as expected for young stars in the solar neighborhood. We have also analysed the halo B-type star, PG0832+676. We find [Fe/H] = -0.88 +/- 0.10, and the absence of the B III line gives the upper limit [B/H]<2.5. These and other published abundances are used to infer the star's evolutionary status as a post-AGB star.Comment: 31 pages, 14 figures. accepted to Ap

Gamma and pulsed electron radiolysis studies of CyMe4BTBP and CyMe4BTPhen: Identification of radiolysis products and effects on the hydrometallurgical separation of trivalent actinides and lanthanides

The radiolytic stability of the highly selective ligands CyMe4BTBP and CyMe4BTPhen against ionizing gamma radiation was studied in 1-octanol solution. CyMe4BTBP and CyMe4BTPhen are important extractants for a potential treatment of used nuclear fuel. They were studied under identical experimental conditions to directly compare the effects of gamma and pulsed electron radiolysis on the ligands and systematically study the influence of structural changes in the ligand backbone. Distribution ratios of Am3+, Cm3+ and Eu3+, the residual concentration of CyMe4BTBP and CyMe4BTPhen in solution, and the formation of radiolysis products were studied as a function of absorbed gamma dose and presence of an acidic aqueous phase during irradiation. Quantitative and semi-quantitative analyses were used to elucidate the radiolysis mechanism for both ligands. Addition products of alpha-hydroxyoctyl radicals formed through radiolysis of the 1-octanol diluent to the ligand molecules were identified as the predominant radiolysis products. These addition products also extract trivalent metal ions, as distribution ratios remained high although the parent molecule concentrations decreased. Therefore, the utilization time of a solvent using these extractants under the harsh conditions of used nuclear fuel treatment could be considerably longer than expected. Understanding the radiolysis mechanism is crucial for designing more radiation resistant extractants