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Sample records for reaction residues occurring

  1. Insights into secondary reactions occurring during atmospheric ablation of micrometeoroids

    NASA Astrophysics Data System (ADS)

    Court, Richard W.; Tan, Jonathan

    2016-06-01

    Ablation of micrometeoroids during atmospheric entry yields volatile gases such as water, carbon dioxide, and sulfur dioxide, capable of altering atmospheric chemistry and hence the climate and habitability of the planetary surface. While laboratory experiments have revealed the yields of these gases during laboratory simulations of ablation, the reactions responsible for the generation of these gases have remained unclear, with a typical assumption being that species simply undergo thermal decomposition without engaging in more complex chemistry. Here, pyrolysis-Fourier transform infrared spectroscopy reveals that mixtures of meteorite-relevant materials undergo secondary reactions during simulated ablation, with organic matter capable of taking part in carbothermic reduction of iron oxides and sulfates, resulting in yields of volatile gases that differ from those predicted by simple thermal decomposition. Sulfates are most susceptible to carbothermic reduction, producing greater yields of sulfur dioxide and carbon dioxide at lower temperatures than would be expected from simple thermal decomposition, even when mixed with meteoritically relevant abundances of low-reactivity Type IV kerogen. Iron oxides were less susceptible, with elevated yields of water, carbon dioxide, and carbon monoxide only occurring when mixed with high abundances of more reactive Type III kerogen. We use these insights to reinterpret previous ablation simulation experiments and to predict the reactions capable of occurring during ablation of carbonaceous micrometeoroids in atmospheres of different compositions.

  2. Automatic NMR-based identification of chemical reaction types in mixtures of co-occurring reactions.

    PubMed

    Latino, Diogo A R S; Aires-de-Sousa, João

    2014-01-01

    The combination of chemoinformatics approaches with NMR techniques and the increasing availability of data allow the resolution of problems far beyond the original application of NMR in structure elucidation/verification. The diversity of applications can range from process monitoring, metabolic profiling, authentication of products, to quality control. An application related to the automatic analysis of complex mixtures concerns mixtures of chemical reactions. We encoded mixtures of chemical reactions with the difference between the (1)H NMR spectra of the products and the reactants. All the signals arising from all the reactants of the co-occurring reactions were taken together (a simulated spectrum of the mixture of reactants) and the same was done for products. The difference spectrum is taken as the representation of the mixture of chemical reactions. A data set of 181 chemical reactions was used, each reaction manually assigned to one of 6 types. From this dataset, we simulated mixtures where two reactions of different types would occur simultaneously. Automatic learning methods were trained to classify the reactions occurring in a mixture from the (1)H NMR-based descriptor of the mixture. Unsupervised learning methods (self-organizing maps) produced a reasonable clustering of the mixtures by reaction type, and allowed the correct classification of 80% and 63% of the mixtures in two independent test sets of different similarity to the training set. With random forests (RF), the percentage of correct classifications was increased to 99% and 80% for the same test sets. The RF probability associated to the predictions yielded a robust indication of their reliability. This study demonstrates the possibility of applying machine learning methods to automatically identify types of co-occurring chemical reactions from NMR data. Using no explicit structural information about the reactions participants, reaction elucidation is performed without structure elucidation of

  3. Characterization of pyrotechnic reaction residue particles by SEM/EDS.

    PubMed

    Kosanke, Ken L; Dujay, Richard C; Kosanke, Bonnie

    2003-05-01

    Today the method commonly used for detecting gunshot residue is through the combined use of scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). In recent years, this same methodology began to find use in detecting and characterizing pyrotechnic reaction residue (PRR) particles whether produced by explosion or burning. This is accomplished by collecting particulate samples from a surface in the immediate area of the pyrotechnic reaction. Suspect PRR particles are identified by their morphology (typically 1 to 20 microm spheroidal particles) using an SEM; then they are analyzed for the elements they contain using X-ray EDS. This can help to identify the general type of pyrotechnic composition involved.

  4. Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers.

    PubMed

    Schubert, Michael; Paschke, Albrecht; Lau, Steffen; Geyer, Wolfgang; Knöller, Kay

    2007-02-01

    The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the "radon method" under field conditions.

  5. Naturally Occurring Radioactive Materials in Coals and Coal Combustion Residuals in the United States.

    PubMed

    Lauer, Nancy E; Hower, James C; Hsu-Kim, Heileen; Taggart, Ross K; Vengosh, Avner

    2015-09-15

    The distribution and enrichment of naturally occurring radioactive materials (NORM) in coal combustion residuals (CCRs) from different coal source basins have not been fully characterized in the United States. Here we provide a systematic analysis of the occurrence of NORM ((232)Th, (228)Ra, (238)U, (226)Ra, and (210)Pb) in coals and associated CCRs from the Illinois, Appalachian, and Powder River Basins. Illinois CCRs had the highest total Ra ((228)Ra + (226)Ra = 297 ± 46 Bq/kg) and the lowest (228)Ra/(226)Ra activity ratio (0.31 ± 0.09), followed by Appalachian CCRs (283 ± 34 Bq/kg; 0.67 ± 0.09), and Powder River CCRs (213 ± 21 Bq/kg; 0.79 ± 0.10). Total Ra and (228)Ra/(226)Ra variations in CCRs correspond to the U and Th concentrations and ash contents of their feed coals, and we show that these relationships can be used to predict total NORM concentrations in CCRs. We observed differential NORM volatility during combustion that results in (210)Pb enrichment and (210)Pb/(226)Ra ratios greater than 1 in most fly-ash samples. Overall, total NORM activities in CCRs are 7-10- and 3-5-fold higher than NORM activities in parent coals and average U.S. soil, respectively. This study lays the groundwork for future research related to the environmental and human health implications of CCR disposal and accidental release to the environment in the context of this elevated radioactivity.

  6. Emphasizing Multiple Levels of Representation to Enhance Students' Understandings of the Changes Occurring during Chemical Reactions

    ERIC Educational Resources Information Center

    Chandrasegaran, A. L.; Treagust, David F.; Mocerino, Mauro

    2009-01-01

    An alternative program of instruction was implemented with 33 high-achieving Grade 9 students (15-16 years old) in Singapore that overtly focused on the use of macroscopic, submicroscopic, and symbolic representations to describe and explain the changes that occurred during the burning of metals, reactions of dilute acids, ionic precipitations,…

  7. Conditional mutations occur predominantly in highly conserved residues of RNA polymerase II subunits.

    PubMed Central

    Scafe, C; Martin, C; Nonet, M; Podos, S; Okamura, S; Young, R A

    1990-01-01

    Conditional mutations in the Saccharomyces cerevisiae RNA polymerase II large subunit, RPB1, were obtained by introducing a mutagenized RPB1 plasmid into yeast cells, selecting for loss of the wild-type RPB1 gene, and screening the cells for heat or cold sensitivity. Sequence analysis of 10 conditional RPB1 mutations and 10 conditional RPB2 mutations revealed that the amino acid residues altered by these distinct mutations are nearly always invariant among eucaryotic RPB1 and RPB2 homologs. These results suggest that RNA polymerase mutants might be obtained in other eucaryotic organisms by alteration of these invariant residues. Images PMID:2406567

  8. Prospective audit of adverse reactions occurring in 459 primary antibody-deficient patients receiving intravenous immunoglobulin

    PubMed Central

    BRENNAN, V M; SALOMÉ-BENTLEY, N J; CHAPEL, H M

    2003-01-01

    Intravenous immunoglobulin (IVIG) is used as the standard replacement therapy for patients with primary antibody deficiencies. A previous study of adverse reactions in patients self-infusing at home over 1 year showed an overall reaction rate of 0·7%. A larger prospective study is reported here, involving a greater number of immunology centres and including children and adults who received infusions from medical or nursing staff as well as those self-infusing. Four hundred and fifty-nine patients were entered into this study and 13 508 infusions were given. The study showed that no severe reactions occurred and the reaction rate was low at 0·8%. This figure could have been lower, 0·5%, if predisposing factors responsible for some reactions had been considered before infusion. In conclusion, the study shows the importance of ongoing training for patients and staff to recognize the predisposing factors to prevent avoidable reactions. Because none of these reactions were graded as severe, the present guidance to prescribe self-injectable adrenaline for patients infusing outside hospital should be reviewed. PMID:12869031

  9. The competition plot: a simple test of whether two reactions occur at the same active site.

    PubMed Central

    Chevillard, C; Cárdenas, M L; Cornish-Bowden, A

    1993-01-01

    The competition plot is a method for determining whether or not two enzyme-catalysed reactions occur at the same active site. It is a plot of total rate against p, where p varies from 0 to 1 and specifies the concentrations (1-p)a0 and pb0 of two substrates in terms of reference concentrations a0 and b0 chosen so as to give the same rates at p = 0 and p = 1. If the two substrates react at the same site, the competition plot gives a horizontal straight line, i.e. the total rate is independent of p. Independent reactions at two separate sites give a curve with a maximum; separate reactions with cross-inhibition generate curves with either maxima or minima according to whether the Michaelis constants of the two substrates are smaller or larger than their inhibition constants in the other reactions. Although ambiguous results can sometimes arise, experimental strategies exist for avoiding them, for example working as close as possible to the lower of the two limiting rates. When tested with yeast hexokinase, the plot indicated phosphorylation of glucose and fructose at the same site. Conversely, with a mixture of yeast hexokinase and galactokinase it indicated phosphorylation of glucose and galactose at different sites. In both cases the observed behaviour agreed with the known properties of the enzymes. A slight modification to the definition of this plot allows it to be applied also to enzymes that deviate from Michaelis-Menten kinetics. PMID:8424801

  10. Combustion reaction kinetics of guarana seed residue applying isoconversional methods and consecutive reaction scheme.

    PubMed

    Lopes, Fernanda Cristina Rezende; Tannous, Katia; Rueda-Ordóñez, Yesid Javier

    2016-11-01

    This work aims the study of decomposition kinetics of guarana seed residue using thermogravimetric analyzer under synthetic air atmosphere applying heating rates of 5, 10, and 15°C/min, from room temperature to 900°C. Three thermal decomposition stages were identified: dehydration (25.1-160°C), oxidative pyrolysis (240-370°C), and combustion (350-650°C). The activation energies, reaction model, and pre-exponential factor were determined through four isoconversional methods, master plots, and linearization of the conversion rate equation, respectively. A scheme of two-consecutive reactions was applied validating the kinetic parameters of first-order reaction and two-dimensional diffusion models for the oxidative pyrolysis stage (149.57kJ/mol, 6.97×10(10)1/s) and for combustion stage (77.98kJ/mol, 98.611/s), respectively. The comparison between theoretical and experimental conversion and conversion rate showed good agreement with average deviation lower than 2%, indicating that these results could be used for modeling of guarana seed residue. PMID:27513645

  11. Combustion reaction kinetics of guarana seed residue applying isoconversional methods and consecutive reaction scheme.

    PubMed

    Lopes, Fernanda Cristina Rezende; Tannous, Katia; Rueda-Ordóñez, Yesid Javier

    2016-11-01

    This work aims the study of decomposition kinetics of guarana seed residue using thermogravimetric analyzer under synthetic air atmosphere applying heating rates of 5, 10, and 15°C/min, from room temperature to 900°C. Three thermal decomposition stages were identified: dehydration (25.1-160°C), oxidative pyrolysis (240-370°C), and combustion (350-650°C). The activation energies, reaction model, and pre-exponential factor were determined through four isoconversional methods, master plots, and linearization of the conversion rate equation, respectively. A scheme of two-consecutive reactions was applied validating the kinetic parameters of first-order reaction and two-dimensional diffusion models for the oxidative pyrolysis stage (149.57kJ/mol, 6.97×10(10)1/s) and for combustion stage (77.98kJ/mol, 98.611/s), respectively. The comparison between theoretical and experimental conversion and conversion rate showed good agreement with average deviation lower than 2%, indicating that these results could be used for modeling of guarana seed residue.

  12. Oxidative Degradation of Nadic-End-Capped Polyimides. 2; Evidence for Reactions Occurring at High Temperatures

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Johnston, J. Christopher; Cavano, Paul J.; Frimer, Aryeh A.

    1997-01-01

    The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

  13. Cardiovascular events occur independently of high on-aspirin platelet reactivity and residual COX-1 activity in stable cardiovascular patients.

    PubMed

    Nagatsuka, Kazuyuki; Miyata, Shigeki; Kada, Akiko; Kawamura, Atsushi; Nakagawara, Jyoji; Furui, Eisuke; Takiuchi, Shin; Taomoto, Katsushi; Kario, Kazuomi; Uchiyama, Shinichiro; Saito, Kozue; Nagao, Takehiko; Kitagawa, Kazuo; Hosomi, Naohisa; Tanaka, Keiji; Kaikita, Koichi; Katayama, Yasuo; Abumiya, Takeo; Nakane, Hiroshi; Wada, Hideo; Hattori, Akira; Kimura, Kazumi; Isshiki, Takaaki; Nishikawa, Masakatsu; Yamawaki, Takemori; Yonemoto, Naohiro; Okada, Hiromi; Ogawa, Hisao; Minematsu, Kazuo; Miyata, Toshiyuki

    2016-08-01

    Several studies have indicated that approximately 25 % of patients treated with aspirin exhibit high on-treatment platelet reactivity (HTPR), which is potentially associated with cardiovascular events (CVEs). However, this association is still controversial, since the mechanisms by which HTPR contributes to CVEs remain unclear and a no standardised definition of HTPR has been established. To determine whether HTPR is associated with CVE recurrence and what type of assay would best predict CVE recurrence, we conducted a multicentre prospective cohort study of 592 stable cardiovascular outpatients treated with aspirin monotherapy for secondary prevention. Their HTPR was determined by arachidonic acid- or collagen-induced aggregation assays using two different agonist concentrations. Residual cyclooxygenase (COX)-1 activity was assessed by measuring serum thromboxane (TX)B2 or urinary 11-dehydro TXB2. Shear-induced platelet thrombus formation was also examined. We followed all patients for two years to evaluate how these seven indexes were related to the recurrence of CVEs (cerebral infarction, transient ischaemic attack, myocardial infarction, unstable angina, revascularisation, other arterial thrombosis, or cardiovascular death). Of 583 patients eligible for the analysis, CVEs occurred in 69 (11.8 %). A Cox regression model identified several classical risk factors associated with CVEs. However, neither HTPR nor high residual COX-1 activity was significantly associated with CVEs, even by applying cut-off values suggested in previous reports or a receiver-operating characteristic analysis. In conclusion, recurrence of CVEs occurred independently of HTPR and residual COX-1 activity. Thus, our findings do not support the use of platelet or COX-1 functional testing for predicting clinical outcomes in stable cardiovascular patients. PMID:27098431

  14. Two-step mechanism of photodamage to photosystem II: step 1 occurs at the oxygen-evolving complex and step 2 occurs at the photochemical reaction center.

    PubMed

    Ohnishi, Norikazu; Allakhverdiev, Suleyman I; Takahashi, Shunichi; Higashi, Shoichi; Watanabe, Masakatsu; Nishiyama, Yoshitaka; Murata, Norio

    2005-06-14

    Under strong light, photosystem II (PSII) of oxygenic photosynthetic organisms is inactivated, and this phenomenon is called photoinhibition. In a widely accepted model, photoinhibition is induced by excess light energy, which is absorbed by chlorophyll but not utilized in photosynthesis. Using monochromatic light from the Okazaki Large Spectrograph and thylakoid membranes from Thermosynechococcus elongatus, we observed that UV and blue light inactivated the oxygen-evolving complex much faster than the photochemical reaction center of PSII. These observations suggested that the light-induced damage was associated with a UV- and blue light-absorbing center in the oxygen-evolving complex of PSII. The action spectrum of the primary event in photodamage to PSII revealed the strong effects of UV and blue light and differed considerably from the absorption spectra of chlorophyll and thylakoid membranes. By contrast to the photoinduced inactivation of the oxygen-evolving complex in untreated thylakoid membranes, red light efficiently induced inactivation of the PSII reaction center in Tris-treated thylakoid membranes, and the action spectrum resembled the absorption spectrum of chlorophyll. Our observations suggest that photodamage to PSII occurs in two steps. Step 1 is the light-induced inactivation of the oxygen-evolving complex. Step 2, occurring after step 1 is complete, is the inactivation of the PSII reaction center by light absorbed by chlorophyll. We confirmed our model by illumination of untreated thylakoid membranes with blue and UV light, which inactivated the oxygen-evolving complex, and then with red light, which inactivated the photochemical reaction center.

  15. Is it true that polymerization of vegetable oil occurs through Diels-Alder reaction?

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Diels-Alder reaction mechanism is known to be one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. However, our NMR study showed no evidence for Diels-Alder products. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ...

  16. A Role-Play to Illustrate the Energy Changes Occurring in an Exothermic Reaction.

    ERIC Educational Resources Information Center

    Tyas, Toby; Cabot, John

    1999-01-01

    Describes a role-play activity designed to help students understand the energy changes involved in an exothermic reaction by modeling the concepts of bond-breaking takes in energy, activation energy, temperature rise, and bond breaking gives out energy. (WRM)

  17. Reactions occurring during the sulfation of sodium chloride deposited on alumina substrates

    NASA Technical Reports Server (NTRS)

    Wu, C. S.; Birks, N.

    1986-01-01

    The reaction between solid NaCl and air containing 1 pct SO2 has been studied between 500 and 700 C. The reaction product, Na2SO4, forms not only on the surface of the NaCl but also on surrounding areas of the substrate due to the volatility of the NaCl at these temperatures. At the higher temperatures, the vapor pressure of NaCl is so high that the majority of the reaction product is distributed on the substrate. Above 625 C, the reaction product is a liquid solution of NaCl and Na2SO4 that exists only so long as NaCl is supplied from the original crystal source. Eventually, the liquid solidifies by constitutional solidification as the NaCl is converted to Na2SO4. While it exists, the liquid NaCl-Na2SO4 solution is shown to be highly corrosive to Al2O3 and, on a scale of Al2O3 growing on alloy HOS 875, particularly attacks the grain boundaries of the scale at preferred sites where chromium and iron oxides and sulfides rapidly develop. This is proposed as one mechanism by which NaCl deposition contributes to the initiation of low temperature hot corrosion.

  18. Subject Reaction to Human-Caused and Naturally-Occurring Radioactive Threat.

    ERIC Educational Resources Information Center

    Belford, Susan; Gibbs, Margaret

    While research has shown that people are adversely psychologically affected by knowledge that their communities have been toxically contaminated, it has been suggested that those who see a disaster as naturally occurring tend to be less adversely affected than those who see a disaster as caused by human acts. To examine this issue, questionnaires…

  19. Hydrogen bonding constrains free radical reaction dynamics at serine and threonine residues in peptides.

    PubMed

    Thomas, Daniel A; Sohn, Chang Ho; Gao, Jinshan; Beauchamp, J L

    2014-09-18

    Free radical-initiated peptide sequencing (FRIPS) mass spectrometry derives advantage from the introduction of highly selective low-energy dissociation pathways in target peptides. An acetyl radical, formed at the peptide N-terminus via collisional activation and subsequent dissociation of a covalently attached radical precursor, abstracts a hydrogen atom from diverse sites on the peptide, yielding sequence information through backbone cleavage as well as side-chain loss. Unique free-radical-initiated dissociation pathways observed at serine and threonine residues lead to cleavage of the neighboring N-terminal Cα-C or N-Cα bond rather than the typical Cα-C bond cleavage observed with other amino acids. These reactions were investigated by FRIPS of model peptides of the form AARAAAXAA, where X is the amino acid of interest. In combination with density functional theory (DFT) calculations, the experiments indicate the strong influence of hydrogen bonding at serine or threonine on the observed free radical chemistry. Hydrogen bonding of the side-chain hydroxyl group with a backbone carbonyl oxygen aligns the singly occupied π orbital on the β-carbon and the N-Cα bond, leading to low-barrier β-cleavage of the N-Cα bond. Interaction with the N-terminal carbonyl favors a hydrogen-atom transfer process to yield stable c and z(•) ions, whereas C-terminal interaction leads to effective cleavage of the Cα-C bond through rapid loss of isocyanic acid. Dissociation of the Cα-C bond may also occur via water loss followed by β-cleavage from a nitrogen-centered radical. These competitive dissociation pathways from a single residue illustrate the sensitivity of gas-phase free radical chemistry to subtle factors such as hydrogen bonding that affect the potential energy surface for these low-barrier processes.

  20. Secondary Structural Change Can Occur Diffusely and Not Modularly during Protein Folding and Unfolding Reactions.

    PubMed

    Malhotra, Pooja; Udgaonkar, Jayant B

    2016-05-11

    A major goal of protein folding studies is to understand the structural basis of the coupling between stabilizing interactions, which leads to cooperative conformational change. The goal is challenging because of the difficulty in simultaneously measuring global cooperativity by determining population distributions of the conformations present, and the structures of these conformations. Here, hydrogen exchange (HX) into the small protein monellin was carried out under conditions where structure-opening is rate limiting for most backbone amide sites. Detection by mass spectrometry allowed characterization of not only segment-specific structure-opening rates but also the cooperativity of unfolding of the different secondary structural segments of the protein. The segment-specific pattern of HX reveals that the backbone hydrogen-bonding network disassembles in a structurally diffuse, asynchronous manner. A comparison of the site-specific transient opening rates of secondary and tertiary structure in the protein provides a structural rationale for the observation that unfolding is hierarchical and describable by exponential kinetics, despite being diffuse. Since unfolding was studied in native conditions, the sequence of events during folding in the same conditions will be the reverse of the sequence of events observed during unfolding. Hence, the formation of secondary structural units during folding would also occur in a non-cooperative, diffuse, and asynchronous manner. PMID:27093885

  1. A single residue influences the reaction mechanism of ammonia lyases and mutases.

    PubMed

    Bartsch, Sebastian; Bornscheuer, Uwe T

    2009-01-01

    All ways lead to Rome? Computer modeling and kinetic measurements identified a distinct residue in Phe/Tyr ammonia lyases (PAL/TAL) which controls whether the Friedel-Crafts or an E(1)cB reaction mechanism takes place. Hence, Glu484 in pcPAL favors the Friedel-Crafts reaction (see picture, MIO = 4-methylidene imidazol-5-one) whereas an Asn in TAL gives an elimination reaction. These mechanistic investigations also reveal activity of a PAL mutant and a TAL towards an amino alcohol.

  2. Reaction of the N-terminal methionine residues in cyanase with diethylpyrocarbonate.

    PubMed

    Anderson, P M; Korte, J J; Holcomb, T A

    1994-11-29

    Cyanase is an inducible enzyme in Escherichia coli that catalyzes the reaction of cyanate with bicarbonate to give ammonia and carbon dioxide. The enzyme is a decamer of identical subunits (M(r) = 17,000). Previous studies have shown that modification of either the single cysteine residue or the single histidine residue in each subunit gives an active decameric derivative that dissociates reversibly to inactive dimer derivative, indicating that decameric structure is required for activity and that the SH and imidazole groups are not required for catalytic activity [Anderson, P. M., Korte, J. J., Holcomb, T. A., Cho, Y.-G., Son, C.-M., & Sung, Y.-C. (1994) J. Biol. Chem. 269, 15036-15045]. Here the effects of reaction of the reagent diethylpyrocarbonate (DEPC) with cyanase or mutant cyanases are reported. DEPC reacts stoichiometrically with the histidine residue and at one additional site in each subunit when the enzyme is in the inactive dimer form, preventing reactivation. DEPC reacts stoichiometrically (with the same result on reactivation) at only one site per subunit with the inactive dimer form of cyanase mutants in which the single histidine residue has been replaced by one of several different amino acids by site-directed mutagenesis; the site of the reaction was identified as the amino group of the N-terminal methionine. DEPC does not react with the histidine residue of the active decameric form of wild-type cyanase and does not affect activity of the active decameric form of wild-type or mutant cyanases. Reaction with the N-terminal amino group of methionine apparently prevents reactivation of the mutant enzymes by blocking association to decamer.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Just three water molecules can trigger the undesired nonenzymatic reactions of aspartic acid residues: new insight from a quantum-chemical study

    NASA Astrophysics Data System (ADS)

    Takahashi, O.

    2014-03-01

    Aspartic acid (Asp) residues in peptides and proteins (L-Asp) can undergo spontaneous, nonenzymatic reactions under physiological conditions by which abnormal L-β-Asp, D-Asp, and/or D-β-Asp residues are formed. These altered Asp residues may affect the three-dimensional structures of the peptides and proteins and hence their properties and functions. In fact, the altered Asp residues are relevant to age-related diseases such as cataract and Alzheimer's disease. Most of the above reactions of the L-Asp residue proceed via a cyclic succinimide intermediate. In this paper, I propose a detailed mechanism of cyclization of an Asp residue (forming a precursor of the succinimide) by the B3LYP/6-31+G(d,p) density functional theory calculations carried out for a small Asp-containing model compound complexed with three water molecules which act as general acid-base catalysts in proton transfers. In the proposed mechanism, the amide group on the C-terminal side of the Asp residue is first converted to the tautomeric iminol form. Then, successive reorientation of a water molecule and conformational change occur followed by the nucleophilic attack of the iminol nitrogen atom on the carboxyl carbon atom of the Asp side chain to form a five-membered ring. A satisfactory agreement was obtained between the calculated and experimental energetics.

  4. 1H-n.m.r. investigation of naturally occurring and chemically oversulphated dermatan sulphates. Identification of minor monosaccharide residues.

    PubMed Central

    Bossennec, V; Petitou, M; Perly, B

    1990-01-01

    The 1H-n.m.r. spectra of various dermatan sulphate preparations present, besides the major signals of the basic disaccharide unit, several other minor signals. We have assigned most of them by n.m.r., using two-dimensional proton-proton double-quantum-correlation and nuclear-Overhauser-effect spectroscopy experiments. This allowed us to identify 2-O-sulphated L-iduronic acid and D-glucuronic acid residues as well as 6-sulphated N-acetylgalactosamine (presumably 4-O-sulphated as well). 2-O-Sulphated iduronic acid was present to similar extents (6-10% of total uronic acids) in pig skin dermatan sulphate and pig intestine dermatan sulphate, whereas glucuronic acid represented 17% of the uronic acid of pig skin dermatan sulphate and was virtually absent (1%) from the other preparation. 6-O-Sulphated N-acetylgalactosamine was present in minor amounts in pig intestine dermatan sulphate only. The influence of sulphation of iduronic acid units on their conformation was assessed by using chemically oversulphated pig intestine dermatan sulphate. Introduction of sulphate groups in this unit in dermatan sulphate tends to shift the conformational equilibrium towards the 1C4 conformer. PMID:2339978

  5. Apolipoprotein A-I variants. Naturally occurring substitutions of proline residues affect plasma concentration of apolipoprotein A-I.

    PubMed Central

    von Eckardstein, A; Funke, H; Henke, A; Altland, K; Benninghoven, A; Assmann, G

    1989-01-01

    Six unrelated families with genetically determined structural variants of apo A-I were found in the course of an electrophoretic screening program for apo A-I variants in dried blood samples of newborns. The following structural variations were identified by the combined use of HPLC, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and automated gas phase sequencing: Pro3----Arg (1x), Pro4----Arg (1x), and Pro165----Arg (4x). All variant carriers were heterozygous for their mutant of apo A-I. Subjects heterozygous for apo A-I(Pro165----Arg) (n = 12) were found to exhibit lower mean values for apo A-I (109 +/- 16 mg/dl) and HDL cholesterol (37 +/- 9 mg/dl) than unaffected family members (n = 9): 176 +/- 41 and 64 +/- 18 mg/dl, respectively (P less than 0.001). In 9 of 12 apo A-I(Pro165----Arg) variant carriers the concentrations of apo A-I were below the fifth percentile of sex-matched controls. By two-dimensional immunoelectrophoresis as well as by densitometry the relative concentration of the variant apo A-I in heterozygous carriers of apo A-I(Pro165----Arg) was determined to account for only 30% of the total plasma apo A-I mass instead of the expected 50%. Thus, the observed apo A-I deficiency may be largely a consequence of the decreased concentration of the variant apo A-I. In the case of the apo A-I(Pro3----Arg) mutant, densitometry of HDL apolipoproteins demonstrated a distinctly increased concentration of the variant proapo A-I relative to normal proapo A-I. This phenomenon was not observed in the apo A-I(Pro4----Arg) mutant or in other mutants. This suggests that the interspecies conserved proline residue in position 3 of mature apo A-I is functionally important for the regular enzymatic conversion of proapo A-I to mature apo A-I. Images PMID:2512329

  6. Correlation of loss of activity of human aldehyde dehydrogenase with reaction of bromoacetophenone with glutamic acid-268 and cysteine-302 residues. Partial-sites reactivity of aldehyde dehydrogenase.

    PubMed Central

    Abriola, D P; MacKerell, A D; Pietruszko, R

    1990-01-01

    Bromoacetophenone (2-bromo-1-phenylethanone) has been characterized as an affinity reagent for human aldehyde dehydrogenase (EC 1.2.1.3) [MacKerell, MacWright & Pietruszko (1986) Biochemistry 25, 5182-5189], and has been shown to react specifically with the Glu-268 residue [Abriola, Fields, Stein, MacKerell & Pietruszko (1987) Biochemistry 26, 5679-5684] with an apparent inactivation stoichiometry of two molecules of bromoacetophenone per molecule of enzyme. The specificity of bromoacetophenone for reaction with Glu-268, however, is not absolute, owing to the extreme reactivity of this reagent. When bromo[14C]acetophenone was used to label the human cytoplasmic E1 isoenzyme radioactively and tryptic fragmentation was carried out, peptides besides that containing Glu-268 were found to have reacted with reagent. These peptides were purified by h.p.l.c. and analysed by sequencing and scintillation counting to quantify radioactive label in the material from each cycle of sequencing. Reaction of bromoacetophenone with the aldehyde dehydrogenase molecule during enzyme activity loss occurs with two residues, Glu-268 and Cys-302. The activity loss, however, appears to be proportional to incorporation of label at Glu-268. The large part of incorporation of label at Cys-302 occurs after the activity loss is essentially complete. With both Glu-268 and Cys-302, however, the incorporation of label stops after one molecule of bromoacetophenone has reacted with each residue. Reaction with other residues continues after activity loss is complete. PMID:1968743

  7. Evaporation residue cross sections for the {sup 64}Ni + {sup 144,154}Sm reaction -- Energy dissipation in hot nuclei

    SciTech Connect

    Back, B.B.; Blumenthal, D.J.; Davids, C.N.

    1995-08-01

    The fission hindrance of hot nuclei was deduced recently from an enhanced emission of GDR {gamma} rays, neutrons and charged particles prior to scission of heavy nuclei. In the most recent experiments addressing this topic, namely new measurements of the pre-scission {gamma} rays and evaporation residues from the {sup 32}S + {sup 184}W reaction, a rather sharp transition from negligible to full one-body dissipation occurs over the excitation energy region E{sub exc} = 60-100 MeV. However, the cross section does not appear to level out or start to decline again at the upper end of the energy range as expected in this interpretation. It is therefore clearly desirable to extend the excitation energy range to look for such an effect in order to either corroborate or refute this interpretation.

  8. Input to Resin Column Structural Analysis if Autocatalytic Resin Reaction Occurs in HB-Line Phase II

    SciTech Connect

    Hallman, D.F.

    2001-07-10

    Solutions of plutonium in nitric acid are purified and concentrated using anion resin prior to precipitation. There have been instances of resin column explosions caused by autocatalytic reactions of anion resins in nitric acid within the DOE complex

  9. The influence of Ser-154, Cys-113, and the phosphorylated threonine residue on the catalytic reaction mechanism of Pin1.

    PubMed

    Vöhringer-Martinez, Esteban; Verstraelen, Toon; Ayers, Paul W

    2014-08-21

    Pin1 is an enzyme that specifically catalyzes the cis-trans isomerization of proline amide bonds in peptides that contain a phosphorylated threonine or serine residue in the position preceding proline. In the cell, the isomerization reaction is associated with cellular signaling and has been related to diseases such as Alzheimer and cancer. The catalytic mechanism by which Pin1 accelerates the isomerization reaction, however, is still unknown. In this study, we use molecular dynamics simulation in combination with the QM/MM methodology to disclose the influence of the residues Ser-154 and Cys-113 in the enzyme and the phosphorylated threonine residue in the peptide on the reaction mechanism. To account for the correct electrostatic interaction between the three residues and the reactive center, we derive atomic charges that account for the varying electrostatic field in the catalytic cavity. Different methods based on reproducing the molecular electrostatic potential or an atoms in molecules approach were investigated. Finally, the reaction mechanism is analyzed with the mean reaction force and the influence of the three residues is disclosed. Our results show that Pin1 specifically catalyzes the isomerization of the trans conformer in a jump-rope type of motion, as suggested by us and confirmed experimentally by others. This is accomplished by anchoring the threonine phosphate residue on one end of the peptide through electrostatic interactions with the basic triad of the enzyme and at the other end through specific enzyme-peptide hydrogen bonds. Cys-113 reduces the structural contribution to the activation free energy through the stabilization of the cis conformer, and Ser-154 in combination with Gln-131 assist in the isomerization reaction of the trans isomer. PMID:25059768

  10. Energy dependence of fusion evaporation-residue cross sections in the sup 28 Si+ sup 28 Si reaction

    SciTech Connect

    Vineyard, M.F.; Bauer, J.S.; Gosdin, C.H.; Trotter, R.S. ); Kovar, D.G.; Beck, C.; Henderson, D.J.; Janssens, R.V.F.; Wilkins, B.D.; Rosner, G.; Chowdhury, P.; Ikezoe, H.; Kuhn, W. ); Kolata, J.J.; Hinnefeld, J.D. ); Maguire, C.F. ); Mateja, J.F. ); Prosser, F.W. ); Stephans, G.S.F. )

    1990-03-01

    Velocity distributions of mass-identified evaporation residues produced in the {sup 28}Si+{sup 28}Si reaction have been measured at bombarding energies of 174, 215, 240, 309, 397, and 452 MeV using time-of-flight techniques. These distributions were used to identify evaporation residues and to separate the complete-fusion and incomplete-fusion components. Angular distributions and total cross sections were extracted at all six bombarding energies. The complete-fusion evaporation-residue cross sections and the deduced critical angular momenta are compared with lower energy data and the predictions of existing models.

  11. Comparison of long-term stability of containment systems for residues and wastes contaminated with naturally occurring radionuclides at an arid site and two humid sites

    SciTech Connect

    Winters, M.; Merry-Libby, P.; Hinchman, R.

    1985-01-01

    The long-term stability of near-surface containment systems designed for the management of radioactive wastes and residues contaminated with naturally occurring radionuclides are compared at the three different sites. The containment designs are: (1) a diked 8.9-m high mound, including a 3.2-m layered cap at a site (humid) near Lewiston, New York, (2) a 6.8-m-high mound, including a similar 3.2-m cap at a site (humid) near Oak Ridge, Tennessee, and (3) 4.8-m deep trenches with 3.0-m backfilled caps at a site (arid) near Hanford, Washington. Geological, hydrological, and biological factors affecting the long-term (1000-year) integrity of the containment systems at each site are examined, including: erosion, flooding, drought, wildfire, slope and cover failure, plant root penetration, burrowing animals, other soil-forming processes, and land-use changes. For the containment designs evaluated, releases of radon-222 at the arid site are predicted to be several orders of magnitude higher than at the two humid sites - upon initial burial and at 1000 years (after severe erosion). Transfer of wastes containing naturally occurring radionuclides from a humid to an arid environment offers little or no advantage relative to long-term stability of the containment system and has a definite disadvantage in terms of gaseous radioactive releases. 26 references, 3 figures, 4 tables.

  12. {sup 29}Si solid state NMR investigation of pozzolanic reaction occurring in lime-treated Ca-bentonite

    SciTech Connect

    Pomakhina, Elena; Deneele, Dimitri; Gaillot, Anne-Claire; Paris, Michael; Ouvrard, Guy

    2012-04-15

    Lime is widely used as additive to improve the mechanical properties of natural soil used in earthworks. However, the physico-chemical mechanisms involved are yet not well understood. In order to develop and optimize this treatment method, a better understanding of the interaction between lime and the minerals of the soils, in particular clay minerals, is required. In this study, Ca-bentonite was treated with 2, 5 and 10 wt.% of lime during 1 to 98 days. Modifications in the Si local environment were then monitored by solid state nuclear magnetic resonance to investigate the pozzolanic reaction. All the soil mineral phases contribute to the release of Si and to the pozzolanic reaction, with a rapid and total consumption of Si-polymorph and an exacerbated dissolution of montmorillonite. Mechanism of C-S-H formation, function of the Ca content in the system, was found to match the sorosilicate-tobermorite model described in cement systems.

  13. Identification of co-occurring Branchinecta fairy shrimp species from encysted embryos using multiplex polymerase chain reaction

    USGS Publications Warehouse

    Vandergast, A.G.; Wood, D.A.; Simovich, M.; Bohonak, A.J.

    2009-01-01

    Morphological identification of many fairy shrimp species is difficult because distinguishing characters are restricted to adults. We developed two multiplex polymerase chain reaction assays that differentiate among three Branchinecta fairy shrimp with distributional overlap in southern California vernal pools. Two of the species are federally listed as threatened. Molecular identification of Branchinecta from cysts allows for species surveys to be conducted during the dry season, expanding the timeframe for population assessment and providing a less intrusive method of sampling sensitive vernal pool habitats. ?? Published 2009. This article is a US Government work and is in the public domain in the USA.

  14. Determination of free acidic and alkaline residues of protein via moving reaction boundary titration in microdevice electrophoresis.

    PubMed

    Wang, Hou-yu; Li, Si; Tang, Yun-yun; Dong, Jing-yu; Fan, Liu-yin; Cao, Cheng-xi

    2013-06-21

    As two important physico-chemical parameters, the acidic and alkaline residues of protein are of evident significance for the evaluation of protein properties and the design of relevant separation and analysis. However, there is still no electrophoretic method used for the direct detection of free acidic and alkaline residues of protein. Herein, we developed the concepts of moving reaction boundary (MRB) and MRB titration, relevant MRB titration theory, and the method of microdevice electrophoresis for the determination of free acidic and alkaline residues of protein. In the MRB titration, the boundary was created with acid or alkali and target protein immobilized via highly cross-linked polyacrylamide gel (PAG). It was theoretically revealed that the number of free acidic or alkaline residues of protein was as a function of MRB displacement in the electrophoretic titration system. As a proof of concept, seven model proteins were chosen for the determination of acidic or alkaline residues of protein via MRB titration. The results showed that the numbers of free acidic and alkaline residues of proteins detected were in good agreement with those obtained from the relevant amino sequences in the NCBI database, demonstrating the feasibility of the developed concept, theory and technique. The general methodology of MRB titration has potential application for inexpensive, facilitative and informative protein structure analysis of free acidic or alkaline residues of protein.

  15. Acetylation and glycation of fibrinogen in vitro occur at specific lysine residues in a concentration dependent manner: A mass spectrometric and isotope labeling study

    SciTech Connect

    Svensson, Jan; Bergman, Ann-Charlotte; Adamson, Ulf; Blombaeck, Margareta; Wallen, Hakan; Joerneskog, Gun

    2012-05-04

    Highlights: Black-Right-Pointing-Pointer Fibrinogen was incubated in vitro with glucose or aspirin. Black-Right-Pointing-Pointer Acetylations and glycations were found at twelve lysine sites by mass spectrometry. Black-Right-Pointing-Pointer The labeling by aspirin and glucose occurred dose-dependently. Black-Right-Pointing-Pointer No competition between glucose and aspirin for binding to fibrinogen was found. -- Abstract: Aspirin may exert part of its antithrombotic effects through platelet-independent mechanisms. Diabetes is a condition in which the beneficial effects of aspirin are less prominent or absent - a phenomenon called 'aspirin resistance'. We investigated whether acetylation and glycation occur at specific sites in fibrinogen and if competition between glucose and aspirin in binding to fibrinogen occurs. Our hypothesis was that such competition might be one explanation to 'aspirin resistance' in diabetes. After incubation of fibrinogen in vitro with aspirin (0.8 mM, 24 h) or glucose (100 mM, 5-10 days), we found 12 modified sites with mass spectrometric techniques. Acetylations in the {alpha}-chain: {alpha}K191, {alpha}K208, {alpha}K224, {alpha}K429, {alpha}K457, {alpha}K539, {alpha}K562, in the {beta}-chain: {beta}K233, and in the {gamma}-chain: {gamma}K170 and {gamma}K273. Glycations were found at {beta}K133 and {gamma}K75, alternatively {gamma}K85. Notably, the lysine 539 is a site involved in FXIII-mediated cross-linking of fibrin. With isotope labeling in vitro, using [{sup 14}C-acetyl]salicylic acid and [{sup 14}C]glucose, a labeling of 0.013-0.084 and 0.12-0.5 mol of acetylated and glycated adduct/mol fibrinogen, respectively, was found for clinically (12.9-100 {mu}M aspirin) and physiologically (2-8 mM glucose) relevant plasma concentrations. No competition between acetylation and glycation could be demonstrated. Thus, fibrinogen is acetylated at several lysine residues, some of which are involved in the cross-linking of fibrinogen. This may

  16. Additive effect of waste tire on the hydrogenolysis reaction of coal liquefaction residue

    SciTech Connect

    Motoyuki Sugano; Daigorou Onda; Kiyoshi Mashimo

    2006-12-15

    A numerous amount of waste tire is landfilled or dumped all over the world, which causes environmental problems, such as destruction of natural places and the risk of fires. On the other hand, the coal liquefaction residue (CLR) is produced in 30% yield through the process supporting unit (PSU) of the NEDOL coal liquefaction process. Therefore, the investigation on an effective method for utilization of waste tire and CLR is required. In this study, the simultaneous hydrogenolysis of CLR and pulverized waste tire was carried out by using tetralin. The yields in the simultaneous hydrogenolysis were compared with algebraic sum of the yields of the individual hydrogenolyses of waste tire alone and coal alone. In the simultaneous hydrogenolysis, the synergistic effects to upgrading, such as an increase in the yield of the oil constituent and a decrease in the yield of the asphaltene constituent, occurred because of the stabilization of asphaltenic radicals from CLR with aliphatic radicals from tire. The decrease in asphaltene yield in the simultaneous hydrogenolysis was pronounced with the increase in the tire:CLR ratio because the solvent effects of liquefied tire, such as stabilization of radicals, hydrogen shuttling, and heat transfer, were enhanced. Accordingly, it is estimated that the simultaneous hydrogenolysis of CLR and waste tire is an effective method for processing both materials. 15 refs., 3 figs., 2 tabs.

  17. Quasi-classical trajectory study of the adiabatic reactions occurring on the two lowest-lying electronic states of the LiH2+ system.

    PubMed

    Pino, Ilaria; Martinazzo, Rocco; Tantardini, Gian Franco

    2008-09-28

    Quasi-classical trajectory calculations have been performed on the adiabatically allowed reactions taking place on the two lowest-lying electronic states of the LiH2+ system, using the ab initio potential energy surfaces of Martinazzo et al. (J. Chem. Phys., 2003, 119, 11 241). These reactions comprise: (i) the exoergic H2 and H2+ formation occurring through LiH+ + H and LiH + H+ collisions in the ground and in the first electronically excited state, respectively; (ii) the endoergic (ground state) LiH+ dissociation induced by collisions with H atoms; and (iii) the endoergic (excited state) Li + H2+ --> LiH + H+ reaction. The topic is of relevance for a better understanding of the lithium chemistry in the early universe. Thermal rate constants for the above reactions have been computed in the temperature range 10-5000 K and found in reasonably good agreement with estimates based on the capture model.

  18. Long-term mass transfer and mixing-controlled reactions of a DNAPL plume from persistent residuals

    NASA Astrophysics Data System (ADS)

    Liu, Yuan; Illangasekare, Tissa H.; Kitanidis, Peter K.

    2014-02-01

    Understanding and being able to predict the long-term behavior of DNAPL (i.e., PCE and TCE) residuals after active remediation has ceased have become increasingly important as attention at many sites turns from aggressive remediation to monitored natural attenuation and long-term stewardship. However, plume behavior due to mass loading and reactions during these later phases is less studied as they involve large spatial and temporal scales. We apply both theoretical analysis and pore-scale simulations to investigate mass transfer from DNAPL residuals and subsequent reactions within the generated plume, and, in particular, to show the differences between early- and late-time behaviors of the plume. In the zone of entry of the DNAPL entrapment zone where the concentration boundary layer in the flowing groundwater has not fully developed, the pore-scale simulations confirm the past findings based on laboratory studies that the mass transfer increases as a power-law function of the Peclét number, and is enhanced due to reactions in the plume. Away from the entry zone and further down gradient, the long-term reactions are limited by the available additive and mixing in the porous medium, thereby behave considerably differently from the entry zone. For the reaction between the contaminant and an additive with intrinsic second-order bimolecular kinetics, the late-time reaction demonstrates a first-order decay macroscopically with respect to the mass of the limiting additive, not with respect to that of the contaminant. The late-time decay rate only depends on the intrinsic reaction rate and the solubility of the entrapped DNAPL. At the intermediate time, the additive decays exponentially with the square of time (t2), instead of time (t). Moreover, the intermediate decay rate also depends on the initial conditions, the spatial distribution of DNAPL residuals, and the effective dispersion coefficient.

  19. Long-term mass transfer and mixing-controlled reactions of a DNAPL plume from persistent residuals.

    PubMed

    Liu, Yuan; Illangasekare, Tissa H; Kitanidis, Peter K

    2014-02-01

    Understanding and being able to predict the long-term behavior of DNAPL (i.e., PCE and TCE) residuals after active remediation has ceased have become increasingly important as attention at many sites turns from aggressive remediation to monitored natural attenuation and long-term stewardship. However, plume behavior due to mass loading and reactions during these later phases is less studied as they involve large spatial and temporal scales. We apply both theoretical analysis and pore-scale simulations to investigate mass transfer from DNAPL residuals and subsequent reactions within the generated plume, and, in particular, to show the differences between early- and late-time behaviors of the plume. In the zone of entry of the DNAPL entrapment zone where the concentration boundary layer in the flowing groundwater has not fully developed, the pore-scale simulations confirm the past findings based on laboratory studies that the mass transfer increases as a power-law function of the Peclét number, and is enhanced due to reactions in the plume. Away from the entry zone and further down gradient, the long-term reactions are limited by the available additive and mixing in the porous medium, thereby behave considerably differently from the entry zone. For the reaction between the contaminant and an additive with intrinsic second-order bimolecular kinetics, the late-time reaction demonstrates a first-order decay macroscopically with respect to the mass of the limiting additive, not with respect to that of the contaminant. The late-time decay rate only depends on the intrinsic reaction rate and the solubility of the entrapped DNAPL. At the intermediate time, the additive decays exponentially with the square of time (t(2)), instead of time (t). Moreover, the intermediate decay rate also depends on the initial conditions, the spatial distribution of DNAPL residuals, and the effective dispersion coefficient.

  20. Evaporation residue cross sections for the {sup 100}Mo + {sup 116}Cd reaction -- energy dissipation in hot nuclei

    SciTech Connect

    Back, B.B.; Blumenthal, D.J.; Davids, C.N.

    1995-08-01

    In this experiment we tried to measure the evaporation residue cross section over a wide range of beam energies for the {sup 100}Mo + {sup 116}Cd reaction using the FMA. However, because of longer-than-estimated runs needed at each beam energy, and the difficulty of bending evaporation residues at the higher energies in the FMA, data were taken only at beam energies of E{sub beam} = 460, 490, and 521 MeV, which correspond to excitation energies of E{sub exc} = 62, 78, and 95 MeV, respectively. By comparing to results for the {sup 32}S + {sup 184}W reactions measured recently, we expect to demonstrate a strong entrance channel effect related to the hindrance of complete fusion in near-symmetric heavy systems (a fusion hindrance factor of the order 7-10 is expected on the basis of the Extra-Push Model). The data are being analyzed.

  1. 40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Propen-1-ol, reaction products with... Significant New Uses for Specific Chemical Substances § 721.10445 2-Propen-1-ol, reaction products with...) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide,...

  2. 40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Propen-1-ol, reaction products with... Significant New Uses for Specific Chemical Substances § 721.10445 2-Propen-1-ol, reaction products with...) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide,...

  3. Influence of the neutron numbers of projectile and target on the evaporation residue cross sections in hot fusion reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Long; Su, Jun; Zhang, Feng-Shou

    2016-06-01

    Within the framework of a dinuclear system model, the influence of projectile and target neutron number on capture cross section, fusion probability, and survival probability for the reactions S,3634+238U and 48Ca+Pu 239 ,240 ,242 ,244 are investigated. The calculated excitation functions are in good agreement with the experimental data. To synthesize more unknown neutron-deficient isotopes of already-known superheavy elements, the possibility of using lighter calcium isotopes to induce hot fusion reactions is investigated and the maximal evaporation residual cross sections for Ca 44 ,46 ,48 -induced hot fusion reactions to produce unknown neutron-deficient superheavy nuclei with Z =112 -116 are predicted.

  4. Hanford Tank 241-C-106: Impact of Cement Reactions on Release of Contaminants from Residual Waste

    SciTech Connect

    Deutsch, William J.; Krupka, Kenneth M.; Lindberg, Michael J.; Cantrell, Kirk J.; Brown, Christopher F.; Schaef, Herbert T.

    2006-09-01

    The CH2M HILL Hanford Group, Inc. (CH2M HILL) is producing risk/performance assessments to support the closure of single-shell tanks at the U.S. Department of Energy's Hanford Site. As part of this effort, staff at Pacific Northwest National Laboratory were asked to develop release models for contaminants of concern that are present in residual sludge remaining in tank 241-C-106 (C-106) after final retrieval of waste from the tank. Initial work to produce release models was conducted on residual tank sludge using pure water as the leaching agent. The results were reported in an earlier report. The decision has now been made to close the tanks after waste retrieval with a cementitious grout to minimize infiltration and maintain the physical integrity of the tanks. This report describes testing of the residual waste with a leaching solution that simulates the composition of water passing through the grout and contacting the residual waste at the bottom of the tank.

  5. Comparison between qualitative and real-time polymerase chain reaction to evaluate minimal residual disease in children with acute lymphoblastic leukemia

    PubMed Central

    Paula, Francisco Danilo Ferreira; Elói-Santos, Silvana Maria; Xavier, Sandra Guerra; Ganazza, Mônica Aparecida; Jotta, Patricia Yoshioka; Yunes, José Andrés; Viana, Marcos Borato; Assumpção, Juliana Godoy

    2015-01-01

    Introduction Minimal residual disease is an important independent prognostic factor that can identify poor responders among patients with acute lymphoblastic leukemia. Objective The aim of this study was to analyze minimal residual disease using immunoglobulin (Ig) and T-cell receptor (TCR) gene rearrangements by conventional polymerase chain reaction followed by homo-heteroduplex analysis and to compare this with real-time polymerase chain reaction at the end of the induction period in children with acute lymphoblastic leukemia. Methods Seventy-four patients diagnosed with acute lymphoblastic leukemia were enrolled. Minimal residual disease was evaluated by qualitative polymerase chain reaction in 57 and by both tests in 44. The Kaplan–Meier and multivariate Cox methods and the log-rank test were used for statistical analysis. Results Nine patients (15.8%) were positive for minimal residual disease by qualitative polymerase chain reaction and 11 (25%) by real-time polymerase chain reaction considering a cut-off point of 1 × 10−3 for precursor B-cell acute lymphoblastic leukemia and 1 × 10−2 for T-cell acute lymphoblastic leukemia. Using the qualitative method, the 3.5-year leukemia-free survival was significantly higher in children negative for minimal residual disease compared to those with positive results (84.1% ± 5.6% versus 41.7% ± 17.3%, respectively; p-value = 0.004). There was no significant association between leukemia-free survival and minimal residual disease by real-time polymerase chain reaction. Minimal residual disease by qualitative polymerase chain reaction was the only variable significantly correlated to leukemia-free survival. Conclusion Given the difficulties in the implementation of minimal residual disease monitoring by real-time polymerase chain reaction in most treatment centers in Brazil, the qualitative polymerase chain reaction strategy may be a cost-effective alternative. PMID:26670399

  6. Unsupported Nanoporous Gold Catalyst for Chemoselective Hydrogenation Reactions under Low Pressure: Effect of Residual Silver on the Reaction.

    PubMed

    Takale, Balaram S; Feng, Xiujuan; Lu, Ye; Bao, Ming; Jin, Tienan; Minato, Taketoshi; Yamamoto, Yoshinori

    2016-08-17

    For the first time, H-H dissociation on an unsupported nanoporous gold (AuNPore) surface is reported for chemoselective hydrogenation of C≡C, C═C, C═N, and C═O bonds under mild conditions (8 atm H2 pressure, 90 °C). Silver doping in AuNPore, which was inevitable for its preparation through a process of dealloying of Au-Ag alloy, exhibited a remarkable difference in catalytic activity between two catalysts, Au>99Ag1NPore and Au90Ag10NPore.The former was more active and the latter less active in H2 hydrogenation, while the reverse tendency was observed for O2 oxidation. This marked contrast between H2 reduction and O2 oxidation is discussed. Further, Au>99Ag1NPore showed a high chemoselectivity toward reduction of terminal alkynes in the presence of internal alkynes which was not achieved using supported gold nanoparticle catalysts and other previously known methods. Reductive amination, which has great significance in synthesis of amines due to its atom-economical nature, was also realized using Au>99Ag1NPore, and the Au>99Ag1NPore/H2 system showed a preference for the reduction of aldehydes in the presence of imines. In addition to this high chemoselectivity, easy recovery and high reusability of AuNPore make it a promising heterogeneous catalyst for hydrogenation reactions. PMID:27430955

  7. Residual Nuclei Production in the reaction {sup 136}Xe+ deuterium at 500 A MeV

    SciTech Connect

    Alcantara-Nunez, J. A.; Benlliure, J.; Perez-Loureiro, D.; Casarejos, E.; Fernandez Ordonez, M.; Pereira, J.; Armbruster, P.; Enqvist, T.; Henzl, V.; Henzlova, D.; Kelic, A.; Pleskac, R.; Ricciardi, M. V.; Schmidt, K.-H.; Schmitt, C.; Yordanov, O.; Audouin, L.; Bernas, M.; Lafriaskh, A.; Stephan, C.

    2010-04-26

    More than six hundred nuclei produced in the fragmentation of {sup 136}Xe projectiles at 500 A MeV on a liquid deuterium target were identified using inverse kinematics at the GSI Fragment Separator (FRS). These data are relevant for understanding of spallation reactions.

  8. Modification of histones by sugar β-N-acetylglucosamine (GlcNAc) occurs on multiple residues, including histone H3 serine 10, and is cell cycle-regulated.

    PubMed

    Zhang, Suisheng; Roche, Kevin; Nasheuer, Heinz-Peter; Lowndes, Noel Francis

    2011-10-28

    The monosaccharide, β-N-acetylglucosamine (GlcNAc), can be added to the hydroxyl group of either serines or threonines to generate an O-linked β-N-acetylglucosamine (O-GlcNAc) residue (Love, D. C., and Hanover, J. A. (2005) Sci. STKE 2005 312, 1-14; Hart, G. W., Housley, M. P., and Slawson, C. (2007) Nature 446, 1017-1022). This post-translational protein modification, termed O-GlcNAcylation, is reversible, analogous to phosphorylation, and has been implicated in many cellular processes. Here, we present evidence that in human cells all four core histones of the nucleosome are substrates for this glycosylation in the relative abundance H3, H4/H2B, and H2A. Increasing the intracellular level of UDP-GlcNAc, the nucleotide sugar donor substrate for O-GlcNAcylation enhanced histone O-GlcNAcylation and partially suppressed phosphorylation of histone H3 at serine 10 (H3S10ph). Expression of recombinant H3.3 harboring an S10A mutation abrogated histone H3 O-GlcNAcylation relative to its wild-type version, consistent with H3S10 being a site of histone O-GlcNAcylation (H3S10glc). Moreover, O-GlcNAcylated histones were lost from H3S10ph immunoprecipitates, whereas immunoprecipitation of either H3K4me3 or H3K9me3 (active or inactive histone marks, respectively) resulted in co-immunoprecipitation of O-GlcNAcylated histones. We also examined histone O-GlcNAcylation during cell cycle progression. Histone O-GlcNAcylation is high in G(1) cells, declines throughout the S phase, increases again during late S/early G(2), and persists through late G(2) and mitosis. Thus, O-GlcNAcylation is a novel histone post-translational modification regulating chromatin conformation during transcription and cell cycle progression.

  9. Nonenzymatic oligomerization reactions on templates containing inosinic acid or diaminopurine nucleotide residues

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1999-01-01

    The template-directed oligomerization of nucleoside-5'-phosphoro-2-methyl imidazolides on standard oligonucleotide templates has been studied extensively. Here, we describe experiments with templates in which inosinic acid (I) is substituted for guanylic acid, or 2,6-diaminopurine nucleotide (D) for adenylic acid. We find that the substitution of I for G in a template is strongly inhibitory and prevents any incorporation of C into internal positions in the oligomeric products of the reaction. The substitution of D for A, on the contrary, leads to increased incorporation of U into the products. We found no evidence for the template-directed facilitation of oligomerization of A or I through A-I base pairing. The significance of these results for prebiotic chemistry is discussed.

  10. Photoinduced chemical reactions on natural single crystals and synthesized crystallites of mercury(II) sulfide in aqueous solution containing naturally occurring amino acids.

    PubMed

    Pal, Bonamali; Ikeda, Shigeru; Ohtani, Bunsho

    2003-03-10

    Photoirradiation at >300 nm of aqueous suspensions of several natural crystal specimens and synthesized crystallites of mercury(II) sulfide (HgS) induced deaminocyclization of optically active or racemic lysine into pipecolinic acid (PCA) under deaerated conditions. This is the first example, to the best of our knowledge, of photoinduced chemical reactions of natural biological compounds over natural minerals. It was found that the natural HgS crystals had activity higher than those of synthesized ones but lower than those of other sulfides of transition metals, e.g., CdS and ZnS, belonging to the same II-IV chalcogenides. In almost all of the photoreactions, decompostion of HgS occurred to liberate hydrogen sulfide (H(2)S) and Hg(2+), and the latter seemed to have undergone in-situ reductive deposition on HgS as Hg(0) after a certain induction period (24-70 h) during the photoirradiation, as indicated by the darkened color of the suspensions. The formation of PCA, presumably through combination of oxidation of lysine and reduction of an intermediate, cyclic Schiff base, could also be seen after a certain induction time of the Hg(0) formation. This was supported by the fact that the addition of small amount of Hg(2+) (0.5 wt % of HgS) increased the PCA yield by almost 2-fold. We also tried to elucidate certain aspects of the plausible stereochemical reactions in relation to the chiral crystal structure of HgS. Although, in some experiments, slight enantiomeric excess of the product PCA was observed, the excess was below or equal to the experimental error and no other supporting analytical data could not be obtained; we cannot conclude the enantiomeric photoproduction of PCA by the natural chiral HgS specimen. PMID:12611518

  11. Scanning and transmission electron microscopy study of the microstructural changes occurring in aluminium matrix composites reinforced with SiC particles during casting and welding: interface reactions

    PubMed

    Urena; Gomez De Salazar JM; Gil; Escalera; Baldonedo

    1999-11-01

    Processing of aluminium matrix composites (AMCs), especially those constituted by a reactive system such as Al-SiC, presents great difficulties which limit their potential applications. The interface reactivity between SiC and molten Al generates an aluminium carbide which degrades the composite properties. Scanning and transmission electron microscopes equipped with energy-dispersive X-ray spectroscopes are essential tools for determining the structure and chemistry of the Al-SiC interfaces in AMCs and changes occurring during casting and arc welding. In the present work, an aluminium-copper alloy (AA2014) reinforced with three different percentages of SiC particles was subjected to controlled remelting tests, at temperatures in the range 750-900 degrees C for 10 and 30 min. Arc welding tests using a tungsten intert gas with power inputs in the range 850-2000 W were also carried out. The results of these studies showed that during remelting there is preferential SiC particle consumption with formation of Al4C3 by interface reaction between the solid SiC particle and the molten aluminium matrix. The formation of Al4C3 by the same mechanism has also been detected in molten pools of arc welded composites. However, in this case there was formation of an almost continuous layer of Al4C3, which protects the particle against further consumption, and formation of aciculate aluminium carbide on the top weld. Both are formed by fusion and dissolution of the SiC in molten aluminium followed by reaction and precipitation of the Al4C3 during cooling.

  12. Nitrogen dioxide reaction with proteins: Evidence for peptide bond cleavage at lysine residues

    SciTech Connect

    Hood, D.B.

    1991-01-01

    Nitrogen dioxide (NO{sub 2}), an air pollutant produced by burning fossil fuels and a component of cigarette smoke, is thought to contribute to the pathogenesis of pulmonary diseases, such as emphysema. To gain information on the mechanism by which NO{sub 2} damages the lung, in vitro exposures of {alpha}{sub 1}-proteinase inhibitor ({alpha}{sub 1}-PI), elastin, bovine serum albumin (BSA), human serum albumin (HSA) and synthetic poly-L-lysine were performed. A genetic deficiency of {alpha}{sup 1}-PI predisposes humans to emphysema and NO{sub 2} has been hypothesized to damage {alpha}{sub 1}-PI, which would leave proteases such as human neutrophil elastase, (HNE) free to attack lung structural proteins. The ability of {alpha}{sub 1}-PI to inhibit HNE declined with exposure to 50% of the control value at molar ratios of NO{sub 2}:{alpha}{sub 1}-PI of 400:1 and greater. Exposure of {alpha}{sub 1}-PI to NO{sub 2} resulted in a 50% lose of immunoreactivity with either monoclonal or polyclonal antibodies in an enzyme-linked immunosorbent assay at molar ratios of NO{sub 2}:{alpha}{sub 1}-PI of essentially 100:1 and greater. The mechanisms of these effects were investigated via ultraviolet-visible spectroscopy and amino acid analysis. The remaining target molecules were labeled by reductive methylation of amino groups with {sup 3}H-HCHO prior to treatment with NO{sub 2} in aqueous solutions at physiological pH. Time course exposure of 5 mg {sup 3}H-insoluble bovine ligamentum nuchae elastin suspensions with up to 120 {mu}moles of NO{sub 2} resulted in 90% solubilization of the label. Amino acid analysis of the soluble and insoluble fractions from these exposures confirmed that 80% of the {sup 3}H-dimethyllysine residues were in the soluble fraction.

  13. Evidence for the Role of Active Site Residues in the Hairpin Ribozyme from Molecular Simulations along the Reaction Path

    PubMed Central

    2015-01-01

    The hairpin ribozyme accelerates a phosphoryl transfer reaction without catalytic participation of divalent metal ions. Residues A38 and G8 have been implicated as playing roles in general acid and base catalysis, respectively. Here we explore the structure and dynamics of key active site residues using more than 1 μs of molecular dynamics simulations of the hairpin ribozyme at different stages along the catalytic pathway. Analysis of results indicates hydrogen bond interactions between the nucleophile and proR nonbridging oxygen are correlated with active inline attack conformations. Further, the simulation results suggest a possible alternative role for G8 to promote inline fitness and facilitate activation of the nucleophile by hydrogen bonding, although this does not necessarily exclude an additional role as a general base. Finally, we suggest that substitution of G8 with N7- or N3-deazaguanosine which have elevated pKa values, both with and without thio modifications at the 5′ leaving group position, would provide valuable insight into the specific role of G8 in catalysis. PMID:24842535

  14. Mechanism of the Orotidine 5’-Monophosphate Decarboxylase-Catalyzed Reaction: Importance of Residues in the Orotate Binding Site†

    PubMed Central

    Iiams, Vanessa; Desai, Bijoy J.; Fedorov, Alexander A.; Fedorov, Elena V.; Almo, Steven C.; Gerlt, John A.

    2011-01-01

    The reaction catalyzed by orotidine 5’-monophosphate decarboxylase (OMPDC) is accompanied by exceptional values for the rate enhancement [kcat/knon = 7.1 × 1016] and catalytic proficiency [(kcat/KM)/knon = 4.8 × 1022 M−1]. Although a stabilized vinyl carbanion/carbene intermediate is located on the reaction coordinate, the structural strategies by which the reduction in the activation energy barrier is realized remain incompletely understood. This laboratory recently reported that “substrate destabilization” by Asp 70 in the OMPDC from Methanothermobacter thermoautotrophicus (MtOMPDC) lowers the activation energy barrier by ~5 kcal/mol (contributing ~2.7 × 103 to the rate enhancement) [K. K. Chan, B. M. Wood, A. A. Fedorov, E. V. Fedorov, H. J. Imker, T. L. Amyes, J. P. Richard, S. C. Almo, and J. A. Gerlt (2009) Biochemistry 48, 5518–31]. We now report that substitutions of hydrophobic residues in a pocket proximal to the carboxylate group of the substrate (Ile 96, Leu 123, and Val 155) with neutral hydrophilic residues decrease the value of kcat by as much as 400-fold but have minimal effect on the value of kex for exchange of H6 of the FUMP product analog with solvent deuterium; we hypothesize that this pocket destabilizes the substrate by preventing hydration of the substrate carboxylate group. We also report that substitutions for Ser 127 that is proximal to O4 of the orotate ring decrease the value of kcat/KM, with the S127P substitution that eliminates hydrogen-bonding interactions with O4 producing a 2.5 × 106-fold reduction in the value of kcat/KM; this effect is consistent with delocalization of the negative charge of the carbanionic intermediate on O4 to produce an anionic carbene intermediate and thereby provide a structural strategy for stabilization of the intermediate. These observations provide additional information on the identities of the active site residues that contribute to the rate enhancement and, therefore, insights into the

  15. Evaporation residue excitation function measurements in 50Ti- and 54Cr-induced reactions with lanthanide targets

    NASA Astrophysics Data System (ADS)

    Mayorov, D. A.; Werke, T. A.; Alfonso, M. C.; Tereshatov, E. E.; Bennett, M. E.; Frey, M. M.; Folden, C. M.

    2015-11-01

    Cross sections for the production of shell-stabilized evaporation residues in the 50Ti+Gd160 , 159Tb, 162Dy , and 54Cr+Dy162 reactions are reported. The compound nucleus excitation energy range considered principally covers the 4 n evaporation channel with segments of the 3 n and 5 n channels also measured. The resultant production cross sections are for nuclides with Z =86 -90 . From an analysis based on a statistical model, it is concluded that a larger fission probability than that predicted by the Bohr-Wheeler transition-state theory is needed to describe the data. This outcome is attributed to the influence of collective nuclear excitations. Subsequently, the expected stability enhancement against fission due to the influence of the magic N =126 shell is not evident. The x n excitation functions measured in previous experiments in the reactions 48Ca+Gd154 , 159Tb,Dy162 , and 165Ho are combined with the present data for Z >20 projectiles to illustrate systematic behavior of measured cross sections as a function of the difference in fission barrier and neutron separation energy.

  16. Residual Water Modulates QA−-to-QB Electron Transfer in Bacterial Reaction Centers Embedded in Trehalose Amorphous Matrices

    PubMed Central

    Francia, Francesco; Palazzo, Gerardo; Mallardi, Antonia; Cordone, Lorenzo; Venturoli, Giovanni

    2003-01-01

    The role of protein dynamics in the electron transfer from the reduced primary quinone, QA−, to the secondary quinone, QB, was studied at room temperature in isolated reaction centers (RC) from the photosynthetic bacterium Rhodobacter sphaeroides by incorporating the protein in trehalose water systems of different trehalose/water ratios. The effects of dehydration on the reaction kinetics were examined by analyzing charge recombination after different regimes of RC photoexcitation (single laser pulse, double flash, and continuous light) as well as by monitoring flash-induced electrochromic effects in the near infrared spectral region. Independent approaches show that dehydration of RC-containing matrices causes reversible, inhomogeneous inhibition of QA−-to-QB electron transfer, involving two subpopulations of RCs. In one of these populations (i.e., active), the electron transfer to QB is slowed but still successfully competing with P+QA− recombination, even in the driest samples; in the other (i.e., inactive), electron transfer to QB after a laser pulse is hindered, inasmuch as only recombination of the P+QA− state is observed. Small residual water variations (∼7 wt %) modulate fully the relative fraction of the two populations, with the active one decreasing to zero in the driest samples. Analysis of charge recombination after continuous illumination indicates that, in the inactive subpopulation, the conformational changes that rate-limit electron transfer can be slowed by >4 orders of magnitude. The reported effects are consistent with conformational gating of the reaction and demonstrate that the conformational dynamics controlling electron transfer to QB is strongly enslaved to the structure and dynamics of the surrounding medium. Comparing the effects of dehydration on P+QA−→PQA recombination and QA−QB→QAQB− electron transfer suggests that conformational changes gating the latter process are distinct from those stabilizing the primary

  17. Amino acid substitutions of conserved residues in the carboxyl-terminal domain of the [alpha]I(X) chain of type X collagen occur in two unrelated families with metaphyseal chondrodysplasia type Schmid

    SciTech Connect

    Wallis, G.A.; Rash, B.; Sweetman, W.A.; Thomas, J.T.; Grant, M.E.; Boot-Handford, R.P. ); Super, M. ); Evans, G. )

    1994-02-01

    Type X collagen is a homotrimeric, short-chain, nonfibrillar extracellular-matrix component that is specifically and transiently synthesized by hypertrophic chondrocytes at the site of endochondral ossification. The precise function of type X collagen is not known, but its specific pattern of expression suggests that mutations within the encoding gene (COL10A1) that alter the structure or synthesis of the protein may cause heritable forms of chondrodysplasia. The authors used the PCR and the SSCP techniques to analyze the coding and upstream promoter regions of the COL10A1 gene in a number of individuals with forms of chondrodysplasia. Using this approach, they identified two individuals with metaphyseal chondrodysplasia type Schmid (MCDS) with SSCP changes in the region of the gene encoding the carboxyl-terminal domain. Sequence analysis demonstrated that the individuals were heterozygous for two unique single-base-pair transitions that led to the substitution of the highly conserved amino acid residue tyrosine at position 598 by aspartic acid in one person and of leucine at position 614 by proline in the other. The substitution at residue 598 segregated with the phenotype in a family of eight (five affected and three unaffected) related persons. The substitutions at residue 614 occurred in a sporadically affected individual but not in her unaffected mother and brother. Additional members of this family were not available for further study. These results suggest that certain amino acid substitutions within the carboxyl-terminal domain of the chains of the type X collagen molecule cause MCDS. These amino acid substitutions are likely to alter either chain recognition or assembly of the type X collagen molecule, thereby depleting the amount of normal type X collagen deposited in the extracellular matrix, with consequent aberrations in bone growth and development. 36 refs., 5 figs.

  18. Arylfluorosulfates Inactivate Intracellular Lipid Binding Protein(s) through Chemoselective SuFEx Reaction with a Binding Site Tyr Residue.

    PubMed

    Chen, Wentao; Dong, Jiajia; Plate, Lars; Mortenson, David E; Brighty, Gabriel J; Li, Suhua; Liu, Yu; Galmozzi, Andrea; Lee, Peter S; Hulce, Jonathan J; Cravatt, Benjamin F; Saez, Enrique; Powers, Evan T; Wilson, Ian A; Sharpless, K Barry; Kelly, Jeffery W

    2016-06-15

    Arylfluorosulfates have appeared only rarely in the literature and have not been explored as probes for covalent conjugation to proteins, possibly because they were assumed to possess high reactivity, as with other sulfur(VI) halides. However, we find that arylfluorosulfates become reactive only under certain circumstances, e.g., when fluoride displacement by a nucleophile is facilitated. Herein, we explore the reactivity of structurally simple arylfluorosulfates toward the proteome of human cells. We demonstrate that the protein reactivity of arylfluorosulfates is lower than that of the corresponding aryl sulfonyl fluorides, which are better characterized with regard to proteome reactivity. We discovered that simple hydrophobic arylfluorosulfates selectively react with a few members of the intracellular lipid binding protein (iLBP) family. A central function of iLBPs is to deliver small-molecule ligands to nuclear hormone receptors. Arylfluorosulfate probe 1 reacts with a conserved tyrosine residue in the ligand-binding site of a subset of iLBPs. Arylfluorosulfate probes 3 and 4, featuring a biphenyl core, very selectively and efficiently modify cellular retinoic acid binding protein 2 (CRABP2), both in vitro and in living cells. The X-ray crystal structure of the CRABP2-4 conjugate, when considered together with binding site mutagenesis experiments, provides insight into how CRABP2 might activate arylfluorosulfates toward site-specific reaction. Treatment of breast cancer cells with probe 4 attenuates nuclear hormone receptor activity mediated by retinoic acid, an endogenous client lipid of CRABP2. Our findings demonstrate that arylfluorosulfates can selectively target single iLBPs, making them useful for understanding iLBP function. PMID:27191344

  19. [The detection of minimal residual disease in patients with chronic B-cell lymphatic leukemia using patient-specified polymerase chain reaction].

    PubMed

    Sidorova, Iu V; Sorokina, T V; Biderman, B V; Nikulina, E E; Kisilichina, D G; Naumova, E V; Pochtar', M E; Lugovskaia, S A; Ivanova, V L; Kovaleva, L G; Ptushkin, V V; Nikitin, E A; Sudarikov, A B

    2011-12-01

    The new effective protocols of treatment of chronic B-cell lymphatic leukemia, including purine analogs and monoclonal antibodies, provide robust remissions under this disease. Accordingly, the requirements to remission quality assessment are changed too. In particular the assessment of minimal residual disease is obligatory. To assess minimal residual disease in terms of quantity in case of chronic B-cell lymphatic leukemia the technique of polymerase chain reaction was applied in real time with patient-specific primers from the area of V-D-J combinations of genes of heavy chain of immunoglobulin. The study included samples from 60 patients suffering of chronic B-cell lymphatic leukemia. In 15 of them (25%), it was impossible to apply neither the sequence analysis of genes of heavy chain of immunoglobulin nor the fitting of patient-specific primer. The results of quantitative determination of minimal residual disease were obtained in 45 patients (55 tests). The minimal residual disease was detected in 30 of 55 samples (54.5%) and was not detected in 25 of 55 samples (45.5%). At the same time, the quantitative determination of minimal residual disease was implemented in regard to the initial level of neoplastic cells. The method sensitivity qualified by serial dilutions, consisted 10(-5) or 1 neoplastic cell to 100 000 normal cells. The comparative analysis was applied to the results of determination of minimal residual disease using two methods -polymerase chain reaction in real time using patient-specified primers and four-color flow cytofluometry. The determination of minimal residual disease with both methods was implemented in 37 patients (45 tests). The results of both methods matched in 93.3% (42 tests out of 45) with maximal disparity of one degree. Then Spearman factor consisted 0.87 (p < 0.0001). In 3 out of 45 tests (6.7%) neoplastic cells were detected with only one method. In the first case, it was the method of four-color flow cytofluometry and in

  20. Calculation of the evaporation residue cross sections for the synthesis of the superheavy element Z=119 via the {sup 50}Ti+{sup 249}Bk hot fusion reaction

    SciTech Connect

    Liu Zuhua; Bao, Jing-Dong

    2011-09-15

    The evaporation residue (ER) cross sections for 3n and 4n evaporation channels in the {sup 50}Ti + {sup 249}Bk reaction leading the formation of {sup 296}119 and {sup 295}119 isotopes are evaluated by means of a modified fusion-by-diffusion model. In the model, the dynamic evolution from dinucleus to mononucleus is taken into account with the two-dimensional coupled Langenvin equations. The calculated maximum ER cross sections in 3n and 4n evaporation channels of the {sup 50}Ti + {sup 249}Bk reaction are 0.17 and 0.57 pb, respectively. The cross section of 0.57 pb is close to the present experimental limit for the registration of the evaporation residual nuclei. Therefore, superheavy element 119 may be the most hopeful new element with Z>118 to be synthesized under somehow improved experimental conditions in the near future.

  1. A sensitive spectrofluorimetric method for the quantification of melamine residue in milk powder using the Mannich reaction in aqueous solutions.

    PubMed

    Rima, Jamil; Assaker, Karine; El Omar, Fawaz; karim, Chawki bou

    2013-11-15

    The objective of this study was to develop a spectrofluorimetric method for the quantitative determination of melamine. The method was based on the complexation of melamine with a mixture of formaldehyde and chemicals including a ketone group, as described by the Mannich reaction. The complex was determined by spectrofluorimetric measurement as it is characterized by specific spectroscopic properties that are related to the chromophore of the ketone compounds. 1,3-Diphenylpropane-1,3-dione (DPPD) was tested as a ketone compound. The fluorescence spectrum of the complex presented a maximum of absorption at 325 nm.A quenching of the fluorescence occurred when melamine was added into the solution. The kinetic of fluorescence quenching was followed to determine quantitatively the melamine concentration. An internal standard was added to quantify melamine. The method was tested to determine the level of melamine in contaminated milk powder. The recovery value was 97% and the limit of detection was 0.007 μg mL(-1.)

  2. Optimization of reaction conditions for enzymatic viscosity reduction and hydrolysis of wheat arabinoxylan in an industrial ethanol fermentation residue.

    PubMed

    Sørensen, Hanne R; Pedersen, Sven; Meyer, Anne S

    2006-01-01

    This study examined enzyme-catalyzed viscosity reduction and evaluated the effects of substrate dry matter concentration on enzymatic degradation of arabinoxylan in a fermentation residue, "vinasse", resulting from industrial ethanol manufacture on wheat. Enzymatic catalysis was accomplished with a 50:50 mixture of an enzyme preparation from Humicola insolens, Ultraflo L, and a cellulolytic enzyme preparation from Trichoderma reesei, Celluclast 1.5 L. This enzyme mixture was previously shown to exhibit a synergistic action on arabinoxylan degradation. The viscosity of vinasse decreased with increased enzyme dosage and treatment time at pH 5, 50 degrees C, 5 wt % vinasse dry matter. After 24 h of enzymatic treatment, 76-84%, 75-80%, and 43-47%, respectively, of the theoretically maximal arabinose, xylose, and glucose releases were achieved, indicating that the viscosity decrease was a result of enzyme-catalyzed hydrolysis of arabinoxylan, beta-glucan, and cellulose. In designed response surface experiments, the optimal enzyme reaction conditions with respect to pH and temperature of the vinasse, the vinasse supernatant (mainly soluble material), and the vinasse sediment (mainly insoluble substances) varied from pH 5.2-6.4 and 41-49 degrees C for arabinose release and from pH 4.9-5.3 and 42-46 degrees C for xylose release. Even though only limited hydrolysis of the arabinoxylan in the vinasse sediment fraction was obtained, the results indicated that the same enzyme activities acted on the arabinoxylan in the different vinasse fractions irrespective of the state of solubility of the substrate material. The levels of liberated arabinose and xylose increased with increased dry matter concentration during enzymatic hydrolysis in the vinasse and the vinasse supernatant, but at the same time, increased substrate dry matter concentrations gave corresponding linear decreases in the hydrolytic efficiency as evaluated from levels of monosaccharide release per weight unit dry

  3. Measurement of the inelastic branch of the stellar 14O(α,p)17F reaction occurring in the explosive burning in Novae and X-ray bursters

    NASA Astrophysics Data System (ADS)

    He, J. J.; Woods, P. J.; Davinson, T.; Aliotta, M.; Buescler, J.; Clement, E.; Delahaye, P.; Hass, M.; Jenkins, D. G.; Kumar, V.; Murphy, A. St. J.; Neyskens, P.; Raabe, R.; Robinson, A. P.; van der Walle, J.; Warr, N.; Wenander, F.

    2010-03-01

    The inelastic component of the key astrophysical resonance (1-, E=6.15 MeV) in the 14O(α,p)17F reaction has been studied by using the resonant scattering of 17F+p. The experiment was done at REX-ISOLDE CERN with the Miniball setup. The thick target method in inverse kinematics was utilized in the present experiment where a 44.2 MeV 17F beam bombarded a˜40μm thick (CH2)n target. The inelastic scattering protons in coincidence with the de-excited 495 keV γ rays have been clearly seen and they are from the inelastic branch to the first excited state in 17F following decay of the 1- resonance in 18Ne. Some preliminary results are reported.

  4. Reaction of variant sperm-whale myoglobins with hydrogen peroxide: the effects of mutating a histidine residue in the haem distal pocket.

    PubMed Central

    Brittain, T; Baker, A R; Butler, C S; Little, R H; Lowe, D J; Greenwood, C; Watmough, N J

    1997-01-01

    The reaction of hydrogen peroxide with a number of variants of sperm-whale myoglobin in which the distal pocket histidine residue (His64) had been mutated was studied with a combination of stopped-flow spectroscopy and freeze-quench EPR. The rate of the initial bimolecular reaction with hydrogen peroxide in all the proteins studied was found to depend on the polarity of the amino acid side chain at position 64. In wild-type myoglobin there were no significant optical changes subsequent to this reaction, suggesting the rapid formation of the well-characterized oxyferryl species. This conclusion was supported by freeze-quench EPR data, which were consistent with the pattern of reactivity previously reported [King and Winfield (1963) J. Biol. Chem. 238, 1520-1528]. In those myoglobins bearing a mutation at position 64, the initial bimolecular reaction with hydrogen peroxide yielded an intermediate species that subsequently decayed via a second hydrogen peroxide-dependent step leading to modification or destruction of the haem. In the mutant His64-->Gln the calculated electronic absorption spectrum of the intermediate was not that of an oxyferryl species but seemed to be that of a low-spin ferric haem. Freeze-quench EPR studies of this mutant and the apolar mutant (His64-->Val) revealed the accumulation of a novel intermediate after the first hydrogen peroxide-dependent reaction. The unusual EPR characteristics of this species are provisionally assigned to a low-spin ferric haem with bound peroxide as the distal ligand. These results are interpreted in terms of a reaction scheme in which the polarity of the distal pocket governs the rate of binding of hydrogen peroxide to the haem iron and the residue at position 64 governs both the rate of heterolytic oxygen scission and the stability of the oxyferryl product. PMID:9337857

  5. Chemical reaction engineering studies on cocracking of petroleum vacuum residue with coal, plastics, and biomass (bagasse and petrocrop)

    SciTech Connect

    Ahmaruzzaman, M.; Sharma, D.K.

    2007-07-01

    This article deals with the studies on cocracking of petroleum vacuum residue (XVR) with thermosetting plastic, I. e., bakelite (BL), Samla coal (SC), biomass, I. e., bagasse (BG) or C. procera (CL) and their binary, ternary, and quaternary mixtures in a thermogravimetric analyzer (TGA). The kinetic studies were performed using the Coats and Redfern kinetic modeling equation. The overall activation energies obtained were 25 kJ/mole for petroleum vacuum residue, 99 kJ/mole for polypropylene, 21 kJ/mole for coal, 23 kJ/mole for Calotropis procera, and 25 kJ/mole for the combination of these four materials. However, other models, such as van Krevelan et al. and Horowitz and Metzger have also been used in some cases to compare the results with those obtained by the Coats and Redfern kinetic models. In the present work, the effect of catalysts on the cracking of Basra vacuum residue (BVR) has also been reported.

  6. Residual Nuclide Production from Iron, Lead, and Uranium by Neutron-Induced Reactions up to 180 MeV

    SciTech Connect

    Michel, R.; Glasser, W.; Herpers, U.; Schuhmacher, H.; Brede, H.J.; Dangendorf, V.; Nolte, R.; Malmborg, P.; Prokofiev, A.V.; Smirnov, A.N.; Rishkov, I.; Kollar, D.; Meulders, J.P.; Duijvestijn, M.; Koning, A.

    2005-05-24

    Within the HINDAS project, activation experiments with quasi mono-energetic neutrons were performed at UCL and TSL. Cross sections for the production of residual radionuclides were derived from the measured activities by unfolding, based on the neutron spectra inside the target stacks and starting from 'guess' excitation functions. Exemplary results are presented and are compared with theoretical calculations using the TALYS code.

  7. The contribution of the conserved hinge region residues of alpha1-antitrypsin to its reaction with elastase.

    PubMed

    Hopkins, P C; Stone, S R

    1995-12-01

    The hinge region of serpins is a conserved sequence of 8 amino acids located 7 residues away from the scissile bond at P8 to P15, on the edge of the protease-binding domain. In the inhibitory serpins the P8 to P12 residues of this motif are usually small side-chain amino acids, most commonly alanine. Each of these residues in alpha1-antitrypsin was mutated to a glutamate, and the effect of a hinge-region glutamic acid substitution was found. While substitutions at positions P10 and P12 affected the inhibitory characteristics of alpha1-antitrypsin, substitutions at positions P7, P8, P9, and P11 had no effect on inhibition. Thus, the conservation of residues with small side chains at the latter positions does not appear to be related to an essential function in the inhibitory mechanism. Following the glutamate substitution at P10, alpha1-antitrypsin remained a rapid inhibitor of elastase, but the elastase--serpin complex slowly broke down to yield active elastase and cleaved alpha1-antitrypsin. The glutamate substitution at P12 caused the resultant molecule (P12 Ala-->Glu) to become a partial substrate of elastase such that four moles of inhibitor were required to inhibit one mole of enzyme, and led to a 12-fold decrease in the association rate constant. The data could be interpreted in terms of the suicide substrate inhibition model for serpin-protease interactions and allowed a further refinement of the role of the hinge region in this process.

  8. Improved minimal residual disease detection by targeted quantitative polymerase chain reaction in Nucleophosmin 1 type a mutated acute myeloid leukemia.

    PubMed

    Pettersson, Louise; Levéen, Per; Axler, Olof; Dvorakova, Dana; Juliusson, Gunnar; Ehinger, Mats

    2016-10-01

    Multicolor flow cytometry (MFC) and real-time quantitative PCR (RQ-PCR) are important independent techniques to determine minimal residual disease (MRD) in acute myeloid leukemia (AML). MFC is the standard method, but may be unreliable. Therefore, MFC-based determination of MRD with an RQ-PCR-based approach targeting the nucleophosmin 1 (NPM1) type A mutation was set out to compare. Since most current NPM1 RQ-PCR MRD protocols suffer from clear definitions of quantifiability, we sought to define quantifiability in a reproducible and standardized manner. The limit of quantifiability of our RQ-PCR protocol for the NPM1 type A mutation varied between 0.002% and 0.04% residual leukemic cells depending on the features of the standard curve for each PCR experiment. The limit of detection was close to 0.001% leukemic cells. The limit of detection by MFC ranged from 0.01% to 1% depending on the phenotype of the leukemic cells as compared with non-leukemic bone marrow cells. Forty-five MRD samples from 15 patients using both NPM1 mutation specific RQ-PCR and MFC were analyzed. In 32 of the 45 samples (71%), an MRD-signal could be detected with RQ-PCR. A quantifiable NPM1 mutation signal was found in 15 samples (33%) (range 0.003%-2.6% leukemic cells). By contrast, only two follow-up samples (4%) showed residual leukemic cells (0.04% and 0.3%, respectively) by MFC. Thus, RQ-PCR of the NPM1 type A mutation was more sensitive and reliable than MFC for determination of MRD, which might have clinical implications. © 2016 Wiley Periodicals, Inc.

  9. Improved minimal residual disease detection by targeted quantitative polymerase chain reaction in Nucleophosmin 1 type a mutated acute myeloid leukemia.

    PubMed

    Pettersson, Louise; Levéen, Per; Axler, Olof; Dvorakova, Dana; Juliusson, Gunnar; Ehinger, Mats

    2016-10-01

    Multicolor flow cytometry (MFC) and real-time quantitative PCR (RQ-PCR) are important independent techniques to determine minimal residual disease (MRD) in acute myeloid leukemia (AML). MFC is the standard method, but may be unreliable. Therefore, MFC-based determination of MRD with an RQ-PCR-based approach targeting the nucleophosmin 1 (NPM1) type A mutation was set out to compare. Since most current NPM1 RQ-PCR MRD protocols suffer from clear definitions of quantifiability, we sought to define quantifiability in a reproducible and standardized manner. The limit of quantifiability of our RQ-PCR protocol for the NPM1 type A mutation varied between 0.002% and 0.04% residual leukemic cells depending on the features of the standard curve for each PCR experiment. The limit of detection was close to 0.001% leukemic cells. The limit of detection by MFC ranged from 0.01% to 1% depending on the phenotype of the leukemic cells as compared with non-leukemic bone marrow cells. Forty-five MRD samples from 15 patients using both NPM1 mutation specific RQ-PCR and MFC were analyzed. In 32 of the 45 samples (71%), an MRD-signal could be detected with RQ-PCR. A quantifiable NPM1 mutation signal was found in 15 samples (33%) (range 0.003%-2.6% leukemic cells). By contrast, only two follow-up samples (4%) showed residual leukemic cells (0.04% and 0.3%, respectively) by MFC. Thus, RQ-PCR of the NPM1 type A mutation was more sensitive and reliable than MFC for determination of MRD, which might have clinical implications. © 2016 Wiley Periodicals, Inc. PMID:27191933

  10. Quantum mechanical/molecular mechanical study of catalytic mechanism and role of key residues in methylation reactions catalyzed by dimethylxanthine methyltransferase in caffeine biosynthesis.

    PubMed

    Yue, Yufei; Guo, Hong

    2014-02-24

    The caffeine biosynthetic pathway is of considerable importance for the beverage and pharmaceutical industries which produces two blockbuster products: theobromine and caffeine. The major biochemistry in caffeine biosynthesis starts from the initial substrate of xanthosine and ends with the final product caffeine, with theobromine serving as an intermediate. The key enzyme, S-adenosyl-l-methionine (SAM) dependent 3,7-dimethyl-xanthine methyltransferase (DXMT), catalyzes two important methyl transfer steps in caffeine biosynthesis: (1) methylation of N3 of 7-methylxanthine (7mX) to form theobromine (Tb); (2) methylation of N1 of theobromine to form caffeine (Cf). Although DXMT has been structurally characterized recently, our understanding of the detailed catalytic mechanism and role of key catalytic residues is still lacking. In this work, the quantum mechanical/molecular mechanical (QM/MM) MD and free energy simulations are performed to elucidate the catalytic mechanism of the enzyme-catalyzed reactions and to explain experimental observations concerning the activity of this enzyme. The roles of certain active-site residues are studied, and the results of computer simulation seem to suggest that a histidine residue (His160) at the active site of DXMT may act as a general base/acid catalyst during the methyl transfer process.

  11. Naturally occurring esterification reactions with Bryostatin

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bryostatin structures share a commonality of a central bryophan ring, but each differs due to two groups (R1 and R2) that are attached to the bryophan ring via ester bonds. This research examines the impact that conditions such as UV light, acidic and basic conditions can have on the bryostatin stru...

  12. Residue Leu940 Has a Crucial Role in the Linkage and Reaction Specificity of the Glucansucrase GTF180 of the Probiotic Bacterium Lactobacillus reuteri 180*

    PubMed Central

    Meng, Xiangfeng; Dobruchowska, Justyna M.; Pijning, Tjaard; López, Cesar A.; Kamerling, Johannis P.; Dijkhuizen, Lubbert

    2014-01-01

    Highly conserved glycoside hydrolase family 70 glucansucrases are able to catalyze the synthesis of α-glucans with different structure from sucrose. The structural determinants of glucansucrase specificity have remained unclear. Residue Leu940 in domain B of GTF180, the glucansucrase of the probiotic bacterium Lactobacillus reuteri 180, was shown to vary in different glucansucrases and is close to the +1 glucosyl unit in the crystal structure of GTF180-ΔN in complex with maltose. Herein, we show that mutations in Leu940 of wild-type GTF180-ΔN all caused an increased percentage of (α1→6) linkages and a decreased percentage of (α1→3) linkages in the products. α-Glucans with potential different physicochemical properties (containing 67–100% of (α1→6) linkages) were produced by GTF180 and its Leu940 mutants. Mutant L940W was unable to form (α1→3) linkages and synthesized a smaller and linear glucan polysaccharide with only (α1→6) linkages. Docking studies revealed that the introduction of the large aromatic amino acid residue tryptophan at position 940 partially blocked the binding groove, preventing the isomalto-oligosaccharide acceptor to bind in an favorable orientation for the formation of (α1→3) linkages. Our data showed that the reaction specificity of GTF180 mutant was shifted either to increased polysaccharide synthesis (L940A, L940S, L940E, and L940F) or increased oligosaccharide synthesis (L940W). The L940W mutant is capable of producing a large amount of isomalto-oligosaccharides using released glucose from sucrose as acceptors. Thus, residue Leu940 in domain B is crucial for linkage and reaction specificity of GTF180. This study provides clear and novel insights into the structure-function relationships of glucansucrase enzymes. PMID:25288798

  13. Primary structural response in tryptophan residues of Anabaena sensory rhodopsin to photochromic reactions of the retinal chromophore

    NASA Astrophysics Data System (ADS)

    Inada, Seisuke; Mizuno, Misao; Kato, Yoshitaka; Kawanabe, Akira; Kandori, Hideki; Wei, Zhengrong; Takeuchi, Satoshi; Tahara, Tahei; Mizutani, Yasuhisa

    2013-06-01

    Anabaena sensory rhodopsin (ASR) is a microbial rhodopsin found in eubacteria and functions as a photosensor. The photoreaction of ASR is photochromic between all-trans, 15-anti (ASRAT), and 13-cis, 15-syn (ASR13C) isomers. To understand primary protein dynamics in the photoreaction starting in ASRAT and ASR13C, picosecond time-resolved ultraviolet resonance Raman spectra were obtained. In the intermediate state appearing in the picosecond temporal region, spectral changes of Trp bands were observed. For both ASRAT and ASR13C, the intensities of the Trp bands were bleached within the instrumental response time and recovered with a time constant of 30 ps. This suggests that the rates of structural changes in the Trp residue in the vicinity of the chromophore do not depend on the direction of the isomerization of retinal. A comparison between spectra of the wild-type and Trp mutants indicates that the structures of Trp76 and Trp46 change upon the primary photoreaction of retinal.

  14. Evaporation Residue Yields in Reactions of Heavy Neutron-Rich Radioactive Ion Beams with 64Ni and 96Zr Targets

    SciTech Connect

    Shapira, Dan; Liang, J Felix; Gross, Carl J; Varner Jr, Robert L; Beene, James R; Stracener, Daniel W; Mueller, Paul Edward; Kolata, Jim J; Roberts, Amy; Loveland, Walter; Vinodkumar, A. M.; Prisbrey, Landon; Sprunger, Peter H; Grzywacz-Jones, Kate L; Caraley, Anne L

    2009-01-01

    As hindrance sets in for the fusion of heavier systems, the effect of large neutron excess in the colliding nuclei on their probability to fuse is still an open question. The detection of evaporation residues (ERs), however, provides indisputable evidence for the fusion (complete and incomplete) in the reaction. We therefore devised a system with which we could measure ERs using low intensity neutron-rich radioactive ion beams with an efficiency close to 100%. We report on measurements of the production of ERs in collisions of {sup 132,134}Sn, {sup 134}Te and {sup 134}Sb ion beams with medium mass, neutron-rich targets. The data taken with {sup 132,134}Sn bombarding a {sup 64}Ni target are compared to available data (ERs and fusion) taken with stable Sn isotopes. Preliminary data on the fusion of {sup 132}Sn with {sup 96}Zr target are also presented.

  15. Reaction mechanism of the epsilon subunit of E. coli DNA polymerase III: insights into active site metal coordination and catalytically significant residues.

    PubMed

    Cisneros, G Andrés; Perera, Lalith; Schaaper, Roel M; Pedersen, Lars C; London, Robert E; Pedersen, Lee G; Darden, Thomas A

    2009-02-01

    The 28 kDa epsilon subunit of Escherichia coli DNA polymerase III is the exonucleotidic proofreader responsible for editing polymerase insertion errors. Here, we study the mechanism by which epsilon carries out the exonuclease activity. We performed quantum mechanics/molecular mechanics calculations on the N-terminal domain containing the exonuclease activity. Both the free-epsilon and a complex epsilon bound to a theta homologue (HOT) were studied. For the epsilon-HOT complex Mg(2+) or Mn(2+) were investigated as the essential divalent metal cofactors, while only Mg(2+) was used for free-epsilon. In all calculations a water molecule bound to the catalytic metal acts as the nucleophile for hydrolysis of the phosphate bond. Initially, a direct proton transfer to H162 is observed. Subsequently, the nucleophilic attack takes place followed by a second proton transfer to E14. Our results show that the reaction catalyzed with Mn(2+) is faster than that with Mg(2+), in agreement with experiment. In addition, the epsilon-HOT complex shows a slightly lower energy barrier compared to free-epsilon. In all cases the catalytic metal is observed to be pentacoordinated. Charge and frontier orbital analyses suggest that charge transfer may stabilize the pentacoordination. Energy decomposition analysis to study the contribution of each residue to catalysis suggests that there are several important residues. Among these, H98, D103, D129, and D146 have been implicated in catalysis by mutagenesis studies. Some of these residues were found to be structurally conserved on human TREX1, the exonuclease domains from E. coli DNA-Pol I, and the DNA polymerase of bacteriophage RB69.

  16. Description of fusion and evaporation residue formation cross sections in reactions leading to the formation of element Z =122 within the Langevin approach

    NASA Astrophysics Data System (ADS)

    Litnevsky, V. L.; Kosenko, G. I.; Ivanyuk, F. A.

    2016-06-01

    We describe the evolution of the compact system formed by the touching of two colliding ions in reactions 58Fe+248Cm → 306-x122 + xn, 64Ni+244Pu → 308-x122 + xn, and 90Zr+208Pb → 298-x122 + xn. The description is carried out within the dynamical multidimensional stochastic approach, based on Langevin equations for the shape degrees of freedom of colliding ions and the compact system. For the approach stage we take into account the shell structure of colliding ions, their orientation in the space, and the effect of tunneling of ions through the Coulomb barrier. By describing the evolution of the compact system formed after the touching of incident ions, the shell structure of the compact system is also taken into account. Within this approach we have calculated the compound nucleus and evaporation residue formation cross sections. These can be compared with the experimental data. We have also clarified the impact of the tunneling effect in the entrance channel on the fusion and evaporation residue cross sections.

  17. Liquid chromatography-electrospray ionization tandem mass spectrometry and dynamic multiple reaction monitoring method for determining multiple pesticide residues in tomato.

    PubMed

    Andrade, G C R M; Monteiro, S H; Francisco, J G; Figueiredo, L A; Botelho, R G; Tornisielo, V L

    2015-05-15

    A quick and sensitive liquid chromatography-electrospray ionization tandem mass spectrometry method, using dynamic multiple reaction monitoring and a 1.8-μm particle size analytical column, was developed to determine 57 pesticides in tomato in a 13-min run. QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for samples preparations and validations was carried out in compliance with EU SANCO guidelines. The method was applied to 58 tomato samples. More than 84% of the compounds investigated showed limits of detection equal to or lower than 5 mg kg(-1). A mild (<20%), medium (20-50%), and strong (>50%) matrix effect was observed for 72%, 25%, and 3% of the pesticides studied, respectively. Eighty-one percent of the pesticides showed recoveries ranging between 70% and 120%. Twelve pesticides were detected in 35 samples, all below the maximum residue levels permitted in the Brazilian legislation; 15 samples exceeded the maximum residue levels established by the EU legislation for methamidophos; and 10 exceeded limits for acephate and four for bromuconazole. PMID:25577051

  18. Novel oxidative electrophilic coupling reactions of phenoxazine derivatives with MBTH and their applications to spectrophotometric determination of residual chlorine in drinking water and environmental water samples.

    PubMed

    Al-Okab, Riyad Ahmed; Syed, Akheel Ahmed

    2009-10-15

    Novel, sensitive and rapid spectrophotometric methods, using phenoxazine (PNZ), 2-chlorophe-noxazine (CPN) and 2-trifluoromethylphenoxazine (TPN) as chromogenic reagents for the determination of residual chlorine are proposed. The methods are based on the reduction of chlorine by an electrophilic coupling reagent, 3-methyl-2-benzothiazoline hydrazono hydrochloride hydrate (MBTH) in mild hydrochloric acid medium and subsequent coupling with PNZ, CPN or TPN. The blue color formed in the reaction showed maximum absorbance at 680-690 nm and obeyed Beer's law over the range 0.1-2.2 microg ml(-1). The molar absorptivity values with PNZ, CPN and TPN were 2.80 x 10(4), 2.67 x 10(4) and 1.91 x 10(4) l mol(-1)cm(-1) and Sandell's sensitivity values were 0.028, 0.027 and 0.028 microg cm(-2) respectively. The proposed methods were successfully applied in the determination of residual chlorine in drinking water and environmental water samples. The performance of proposed methods was evaluated in terms of Student's t-test and variance ratio F-test which indicated the significance of proposed methods over the standard spectrophotometric method.

  19. Product PCNPsurv or the "reduced" evaporation residue cross section σER/σfusion for "hot" fusion reactions studied with the dynamical cluster-decay model

    NASA Astrophysics Data System (ADS)

    Chopra, Sahila; Kaur, Arshdeep; Hemdeep, Gupta, Raj K.

    2016-04-01

    The product PCNPsurv of compound nucleus (CN) fusion probability PCN and survival probability Psurv is calculated to determine the reduced evaporation residue cross section σER/σfusion , denoted σERreduced, with (total) fusion cross section σfusion given as a sum of CN-formation cross section σCN and non-CN cross section σnCN for each reaction, where σCN is the sum of evaporation residue cross section σER and fusion-fission cross section σff and σnCN, if not measured, is estimated empirically as the difference between measured and calculated σfusion. Our calculations of PCN and Psurv, based on the dynamical cluster-decay model, were successfully made for some 17 "hot" fusion reactions, forming different CN of mass numbers ACN˜100 -300 , with deformations of nuclei up to hexadecapole deformations and "compact" orientations for both coplanar (Φc=0∘ ) and noncoplanar (Φc≠0∘ ) configurations, using various different nuclear interaction potentials. Interesting variations of σERreduced with CN excitation energy E*, fissility parameter χ , CN mass ACN, and Coulomb parameter Z1Z2 show that, independent of entrance channel, different isotopes of CN, and nuclear interaction potentials used, the dominant quantity in the product is Psurv, which classifies all the studied CN into three groups of weakly fissioning, radioactive, and strongly fissioning superheavy nuclei, with relative magnitudes of σERreduced˜1 , ˜10-6 , and ˜10-11 , which, like for PCN, get further grouped in two dependencies of (i) weakly fissioning and strongly fissioning superheavy nuclei decreasing with increasing E* and (ii) radioactive nuclei increasing with increasing E*.

  20. Measurement of evaporation residue cross-sections of the reaction 30Si + 238U at subbarrier energies

    SciTech Connect

    Nishio, K.; Ikezoe, H.; Mitsuoka, S.; Nagame, Y.; Tsukada, K.; Tsuruta, K.; Hofmann, S.; Hessberger, F. P.; Ackermann, D.; Heinz, S.; Khuyagbaatar, J.; Kindler, B.; Kojouharov, I.; Lommel, B.; Mazzocco, M.; Schoett, H. J.; Antalic, S.; Saro, S.; Comas, V. F.; Heredia, J. A.

    2007-02-26

    The reaction 30Si + 238U {yields} 268Sg* was studied at beam energies close to the Coulomb barrier. At the above barrier energy of Ec.m. = 144.0 MeV (center-of-mass energy at half thickness of the target), we measured three decay chains of 263Sg produced by evaporation of five neutrons. The cross-section was (67{sub -37}{sup +67}) pb. At subbarrier energy of Ec.m. = 133.0 MeV we measured three spontaneously fissioning nuclei which we assigned to the isotope 264Sg. The half-life of (120{sub -44}{sup +126}) ms was determined. The production cross-section was (10{sub -6}{sup +10}) pb, which is about four orders magnitude larger than the calculation based on the one-dimensional barrier penetration model in the fusion process, showing fusion enhancement caused by the prolate deformation of 238U. At Ec.m. = 128.0 MeV an upper cross-section limit of 15 pb was measured. Compared to excitation functions measured for the lighter system 16O + 238U {yields} 254Fm*, a reduction of the fusion probability was observed at low beam energies indicating increasing competition from quasifission processes.

  1. Effects of intraoperatively applied glucocorticoid-hydrogels on residual hearing and foreign-body reaction in a guinea pig model of cochlear implantation

    PubMed Central

    Honeder, Clemens; Landegger, Lukas David; Engleder, Elisabeth; Gabor, Franz; Plasenzotti, Roberto; Plenk, Hanns; Kaider, Alexandra; Hirtler, Lena; Gstoettner, Wolfgang; Arnoldner, Christoph

    2016-01-01

    Conclusion The intraoperative application of glucocorticoid-loaded hydrogels seems to cause a reduction in neutrophil infiltration. No beneficial effect on hearing thresholds was detected. Objectives To evaluate the application of dexamethasone- and triamcinolone-acetonide- loaded hydrogels for effects on hearing-preservation and foreign-body reaction in a guinea pig model for cochlear implantation. Methods 48 guinea pigs (n= 12/group) were implanted with a single channel electrode and intraoperatively treated with 50 µl of a 20% w/v poloxamer 407 hydrogel loaded with 6% dexamethasone or 30% triamcinolone-acetonide, a control hydrogel, or physiological saline. Click- and tone burst-evoked compound action potential thresholds were determined pre- and directly postoperatively as well as on days 3, 7, 14, 21 and 28. At the end of the experiment, temporal bones prepared for histological evaluation by a grinding/polishing technique with the electrode in situ. Three ears per treatment group were serially sectioned and evaluated for histological alterations. Results The intratympanic application of glucocorticoid-loaded hydrogels did not improve the preservation of residual hearing in this cochlear implant model. The foreign body reaction to the electrode appeared reduced in the glucocorticoid treated animals. No correlation was found between the histologically described trauma to the inner ear and the resulting hearing threshold-shifts. PMID:25720453

  2. Roles of the redox-active disulfide and histidine residues forming a catalytic dyad in reactions catalyzed by 2-ketopropyl coenzyme M oxidoreductase/carboxylase.

    PubMed

    Kofoed, Melissa A; Wampler, David A; Pandey, Arti S; Peters, John W; Ensign, Scott A

    2011-09-01

    NADPH:2-ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC), an atypical member of the disulfide oxidoreductase (DSOR) family of enzymes, catalyzes the reductive cleavage and carboxylation of 2-ketopropyl-coenzyme M [2-(2-ketopropylthio)ethanesulfonate; 2-KPC] to form acetoacetate and coenzyme M (CoM) in the bacterial pathway of propylene metabolism. Structural studies of 2-KPCC from Xanthobacter autotrophicus strain Py2 have revealed a distinctive active-site architecture that includes a putative catalytic triad consisting of two histidine residues that are hydrogen bonded to an ordered water molecule proposed to stabilize enolacetone formed from dithiol-mediated 2-KPC thioether bond cleavage. Site-directed mutants of 2-KPCC were constructed to test the tenets of the mechanism proposed from studies of the native enzyme. Mutagenesis of the interchange thiol of 2-KPCC (C82A) abolished all redox-dependent reactions of 2-KPCC (2-KPC carboxylation or protonation). The air-oxidized C82A mutant, as well as wild-type 2-KPCC, exhibited the characteristic charge transfer absorbance seen in site-directed variants of other DSOR enzymes but with a pK(a) value for C87 (8.8) four units higher (i.e., four orders of magnitude less acidic) than that for the flavin thiol of canonical DSOR enzymes. The same higher pK(a) value was observed in native 2-KPCC when the interchange thiol was alkylated by the CoM analog 2-bromoethanesulfonate. Mutagenesis of the flavin thiol (C87A) also resulted in an inactive enzyme for steady-state redox-dependent reactions, but this variant catalyzed a single-turnover reaction producing a 0.8:1 ratio of product to enzyme. Mutagenesis of the histidine proximal to the ordered water (H137A) led to nearly complete loss of redox-dependent 2-KPCC reactions, while mutagenesis of the distal histidine (H84A) reduced these activities by 58 to 76%. A redox-independent reaction of 2-KPCC (acetoacetate decarboxylation) was not decreased for any of the

  3. Naturally Occurring Food Toxins

    PubMed Central

    Dolan, Laurie C.; Matulka, Ray A.; Burdock, George A.

    2010-01-01

    Although many foods contain toxins as a naturally-occurring constituent or, are formed as the result of handling or processing, the incidence of adverse reactions to food is relatively low. The low incidence of adverse effects is the result of some pragmatic solutions by the US Food and Drug Administration (FDA) and other regulatory agencies through the creative use of specifications, action levels, tolerances, warning labels and prohibitions. Manufacturers have also played a role by setting limits on certain substances and developing mitigation procedures for process-induced toxins. Regardless of measures taken by regulators and food producers to protect consumers from natural food toxins, consumption of small levels of these materials is unavoidable. Although the risk for toxicity due to consumption of food toxins is fairly low, there is always the possibility of toxicity due to contamination, overconsumption, allergy or an unpredictable idiosyncratic response. The purpose of this review is to provide a toxicological and regulatory overview of some of the toxins present in some commonly consumed foods, and where possible, discuss the steps that have been taken to reduce consumer exposure, many of which are possible because of the unique process of food regulation in the United States. PMID:22069686

  4. Differences in gene expression amplitude overlie a conserved transcriptomic program occurring between the rapid and potent localized resistant reaction at the syncytium of the Glycine max genotype Peking (PI 548402) as compared to the prolonged and potent resistant reaction of PI 88788.

    PubMed

    Klink, Vincent P; Hosseini, Parsa; Matsye, Prachi D; Alkharouf, Nadim W; Matthews, Benjamin F

    2011-01-01

    Glycine max L. Merr. (soybean) resistance to Heterodera glycines Ichinohe occurs at the site of infection, a nurse cell known as the syncytium. Resistance is classified into two cytologically-defined responses, the G. max ([Peking])- and G. max ([PI 88788])-types. Each type represents a cohort of G. max genotypes. Resistance in G. max ([Peking]) occurs by a potent and rapid localized response, affecting parasitic second stage juveniles (p-J2). In contrast, resistance occurs by a potent but more prolonged reaction in the genotype G. max ([PI 88788]) that affects nematode development at the J3 and J4 stages. Microarray analyses comparing these cytologically and developmentally distinct resistant reactions reveal differences in gene expression in pericycle and surrounding cells even before infection. The differences include higher relative levels of the differentially expressed in response to arachidonic acid 1 gene (DEA1 [Gm-DEA1]) (+224.19-fold) and a protease inhibitor (+68.28-fold) in G. max ([Peking/PI 548402]) as compared to G. max ([PI 88788]). Gene pathway analyses compare the two genotypes (1) before, (2) at various times during, (3) constitutively throughout the resistant reaction and (4) at all time points prior to and during the resistant reaction. The amplified levels of transcriptional activity of defense genes may explain the rapid and potent reaction in G. max ([Peking/PI 548402]) as compared to G. max ([PI 88788]). In contrast, the shared differential expression levels of genes in G. max ([Peking/PI 548402]) and G. max ([PI 88788]) may indicate a conserved genomic program underlying the G. max resistance on which the genotype-specific gene expression programs are built off.

  5. Mechanism of the Flavoprotein L-Hydroxynicotine Oxidase: Kinetic Mechanism, Substrate Specificity, Reaction Product, and Roles of Active-Site Residues.

    PubMed

    Fitzpatrick, Paul F; Chadegani, Fatemeh; Zhang, Shengnan; Roberts, Kenneth M; Hinck, Cynthia S

    2016-02-01

    The flavoprotein L-hydroxynicotine oxidase (LHNO) catalyzes an early step in the bacterial catabolism of nicotine. Although the structure of the enzyme establishes that it is a member of the monoamine oxidase family, LHNO is generally accepted to oxidize a carbon-carbon bond in the pyrrolidine ring of the substrate and has been proposed to catalyze the subsequent tautomerization and hydrolysis of the initial oxidation product to yield 6-hydroxypseudooxynicotine [Kachalova, G., et al. (2011) Proc. Natl. Acad. Sci. U.S.A. 108, 4800-4805]. Analysis of the product of the enzyme from Arthrobacter nicotinovorans by nuclear magnetic resonance and continuous-flow mass spectrometry establishes that the enzyme catalyzes the oxidation of the pyrrolidine carbon-nitrogen bond, the expected reaction for a monoamine oxidase, and that hydrolysis of the amine to form 6-hydroxypseudooxynicotine is nonenzymatic. On the basis of the kcat/Km and kred values for (S)-hydroxynicotine and several analogues, the methyl group contributes only marginally (∼ 0.5 kcal/mol) to transition-state stabilization, while the hydroxyl oxygen and pyridyl nitrogen each contribute ∼ 4 kcal/mol. The small effects on activity of mutagenesis of His187, Glu300, or Tyr407 rule out catalytic roles for all three of these active-site residues.

  6. Characterization of biomass burning emissions from cooking fires, peat, crop residue, and other fuels with high-resolution proton-transfer-reaction time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Stockwell, C. E.; Veres, P. R.; Williams, J.; Yokelson, R. J.

    2015-01-01

    We deployed a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to measure biomass-burning emissions from peat, crop residue, cooking fires, and many other fire types during the fourth Fire Lab at Missoula Experiment (FLAME-4) laboratory campaign. A combination of gas standard calibrations and composition sensitive, mass-dependent calibration curves was applied to quantify gas-phase non-methane organic compounds (NMOCs) observed in the complex mixture of fire emissions. We used several approaches to assign the best identities to most major "exact masses", including many high molecular mass species. Using these methods, approximately 80-96% of the total NMOC mass detected by the PTR-TOF-MS and Fourier transform infrared (FTIR) spectroscopy was positively or tentatively identified for major fuel types. We report data for many rarely measured or previously unmeasured emissions in several compound classes including aromatic hydrocarbons, phenolic compounds, and furans; many of these are suspected secondary organic aerosol precursors. A large set of new emission factors (EFs) for a range of globally significant biomass fuels is presented. Measurements show that oxygenated NMOCs accounted for the largest fraction of emissions of all compound classes. In a brief study of various traditional and advanced cooking methods, the EFs for these emissions groups were greatest for open three-stone cooking in comparison to their more advanced counterparts. Several little-studied nitrogen-containing organic compounds were detected from many fuel types, that together accounted for 0.1-8.7% of the fuel nitrogen, and some may play a role in new particle formation.

  7. Characterization of biomass burning smoke from cooking fires, peat, crop residue and other fuels with high resolution proton-transfer-reaction time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Stockwell, C. E.; Veres, P. R.; Williams, J.; Yokelson, R. J.

    2014-08-01

    We deployed a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to measure biomass burning emissions from peat, crop-residue, cooking fires, and many other fire types during the fourth Fire Lab at Missoula Experiment (FLAME-4) laboratory campaign. A combination of gas standards calibrations and composition sensitive, mass dependent calibration curves were applied to quantify gas-phase non-methane organic compounds (NMOCs) observed in the complex mixture of fire emissions. We used several approaches to assign best identities to most major "exact masses" including many high molecular mass species. Using these methods approximately 80-96% of the total NMOC mass detected by PTR-TOF-MS and FTIR was positively or tentatively identified for major fuel types. We report data for many rarely measured or previously unmeasured emissions in several compound classes including aromatic hydrocarbons, phenolic compounds, and furans; many of which are suspected secondary organic aerosol precursors. A large set of new emission factors (EFs) for a range of globally significant biomass fuels is presented. Measurements show that oxygenated NMOCs accounted for the largest fraction of emissions of all compound classes. In a brief study of various traditional and advanced cooking methods, the EFs for these emissions groups were greatest for open 3-stone cooking in comparison to their more advanced counterparts. Several little-studied nitrogen-containing organic compounds were detected from many fuel types that together accounted for 0.1-8.7% of the fuel nitrogen and some may play a role in new particle formation.

  8. Chemical structure and properties of interstrand cross-links formed by reaction of guanine residues with abasic sites in duplex DNA.

    PubMed

    Catalano, Michael J; Liu, Shuo; Andersen, Nisana; Yang, Zhiyu; Johnson, Kevin M; Price, Nathan E; Wang, Yinsheng; Gates, Kent S

    2015-03-25

    A new type of interstrand cross-link resulting from the reaction of a DNA abasic site with a guanine residue on the opposing strand of the double helix was recently identified, but the chemical connectivity of the cross-link was not rigorously established. The work described here was designed to characterize the chemical structure and properties of dG-AP cross-links generated in duplex DNA. The approach involved characterization of the nucleoside cross-link "remnant" released by enzymatic digestion of DNA duplexes containing the dG-AP cross-link. We first carried out a chemical synthesis and complete spectroscopic structure determination of the putative cross-link remnant 9b composed of a 2-deoxyribose adduct attached to the exocyclic N(2)-amino group of dG. A reduced analogue of the cross-link remnant was also prepared (11b). Liquid chromatography-tandem mass spectrometric (LC-MS/MS) analysis revealed that the retention times and mass spectral properties of synthetic standards 9b and 11b matched those of the authentic cross-link remnants released by enzymatic digestion of duplexes containing the native and reduced dG-AP cross-link, respectively. These results establish the chemical connectivity of the dG-AP cross-link released from duplex DNA and provide a foundation for detection of this lesion in biological samples. The dG-AP cross-link in duplex DNA was remarkably stable, decomposing with a half-life of 22 days at pH 7 and 23 °C. The intrinsic chemical stability of the dG-AP cross-link suggests that this lesion in duplex DNA may have the power to block DNA-processing enzymes involved in transcription and replication.

  9. Co-Occurring Disorders

    MedlinePlus

    ... Care of You Top Ten Freshman Year Issues Alcohol, Substance Abuse and Depression Winter Break Survival Tips for College Students Implementing ... supporters and consumers in the mental health field. Alcohol and Drug Abuse, Addiction and Co-occurring Disorders: Co-occurring ... In Crisis? Call ...

  10. Drug Reactions

    MedlinePlus

    ... or diabetes. But medicines can also cause unwanted reactions. One problem is interactions, which may occur between ... more serious. Drug allergies are another type of reaction. They can be mild or life-threatening. Skin ...

  11. Reaction of unsaturated uronic acid residues with mercuric salts. Cleavage of the hyaluronic acid disaccharide 2-acetamido-2-deoxy-3-O-(beta-D-gluco-4-enepyranosyluronic acid)-D-glucose.

    PubMed Central

    Ludwigs, U; Elgavish, A; Esko, J D; Meezan, E; Rodén, L

    1987-01-01

    Degradation of connective-tissue polysaccharides with bacterial or fungal eliminases and subsequent characterization of the reaction products are now part of standard methodology for the analysis of these compounds. However, the scope of preparative and analytical work based on the use of eliminases has been limited by the lack of procedures for specific removal of the unsaturated uronic acid residues generated in the eliminase reactions. In the present investigation, we have shown that these residues are cleaved by mercuric salts under mild conditions that are not likely to affect other structures in an oligo- or poly-saccharide molecule. Thus the disaccharide generated from hyaluronic acid by digestion with chondroitinase AC or ABC was cleaved into a keto acid and free N-acetylglucosamine within 10 min at room temperature upon exposure to 14 mM-mercuric acetate at pH 5. The reaction of the disaccharide with mercuric salts was used for ready determination of the distribution of radioactivity between the glucuronic acid and N-acetylglucosamine moieties in radioactive hyaluronic acid that had been synthesized by IMR-90 fibroblasts from 3H-labelled monosaccharides. When the precursor was [3H]galactose, over 95% of the incorporated radioactivity was found in the glucuronic acid moiety. In contrast, cells grown in the presence of [3H]glucosamine synthesized a polysaccharide in which almost all of the label was located in the N-acetylglucosamine units. It is apparent from these experiments that the reaction of unsaturated uronic acid residues with mercuric salts provides a new tool with potential for many applications in the study of the structure and metabolism of connective-tissue polysaccharides. PMID:3663191

  12. Coincidences between light particles, evaporation residues, and complex fragments emitted in the reaction {sup 58}Ni + {sup 58}Ni at 500 MeV bombarding energy

    SciTech Connect

    Gomez del Campo, J.; Shapira, D.; Chavez, E.; Ortiz, M.E.; Dacal, A.; D`Onofrio, A.; Terrasi, F.

    1996-03-01

    Light particles (protons and alphas) were measured in coincidence with complex fragments (4 < Z < 10) and evaporation residues (Z > 40) using the large detector array HILI. A {sup 58}Ni beam of 500 MeV extracted from the HHIRF tandem accelerator was used to bombard a {sup 58}Ni target of 99% enrichment. A good account of the proton and alpha spectra in coincidences with the residues can be achieved only by including in the statistical model calculation the emission of complex fragments and allowing a small emission of a dinuclear configuration formed prior to fusion. The relative kinetic energy spectra between the complex fragments and the residues show a typical Coulomb peak consistent with emission from the compound nucleus and the out of plane angular correlation shows that the emission is coplanar.

  13. "Naturally occurring asbestos

    NASA Astrophysics Data System (ADS)

    Cagnard, F.; Lahondère, D.; Blein, O.; Lahfid, A.; Wille, G.

    2012-04-01

    The term asbestos refers to six silicate minerals from amphibole and serpentine groups. By definition, it consists in bundles of thin and flexible long fibers, with high-tensile strength, and chemical and heat resistance. In contrast to asbestos found within commercial products and mining, the specific term ''naturally occurring asbestos'' (NOA) refers to asbestiform minerals occurring within rocks or soils that can be released by human activities or weathering processes. The fact that the exposure to asbestos is related to lung pathologies is now widely demonstrated (e.g. asbestosis, mesothelioma and lung cancer). However, if health risks associated with exposure to NOA exist, they are not yet well documented. The crystallization of natural asbestos occurs in specific Mg-rich lithologies associated with peculiar structural and metamorphic conditions. By recognizing and combining such specific geologic criteria, the presence or the absence of asbestos in bedrock terrains can be reasonably predicted and maps of NOA hazard can be drawn. We present here new results of geological mapping and petrological study concerning the evaluation of the NOA hazard in the Alps and Corsica, in France. The three folds approach consists in (1) a determination of lithologies with potential NOA from a bibliographic compilation and extraction of target zones from a geological geodatabase (2) a geological mapping of the target zones followed by a petrological characterization of sampled asbestiform minerals in the laboratory (optical microscopy, TEM, SEM, and Raman spectroscopy technics), and (3) the drawing of the final map of NOA hazard, at regional-scale. Occurrence criteria can be retained as follows: 1. NOA are abundant in the internal zones of the Alps and Corsica, especially within ophiolitic complexes. Natural asbestos are mostly concentrated within ultramafic rocks but can also occur within basic lithologies such as Mg-metagabbros, metabasalts and meta-pillow-lavas, 2. Asbestos

  14. Naturally occurring insecticides.

    PubMed Central

    Soloway, S B

    1976-01-01

    Naturally occurring insecticides are abundant and varied in their effects, though but a few are articles of commerce. Even for these, pyrethrum, nicotine, rotenone, hellebore, ryania, and sabadilla, there is a paucity of information on mammalian toxicology and environmental effects. In general, these materials are characterized favorably by low acute toxicity and ready dissipation in nature. Unfavorable aspects of natural insecticides are the contained mixture of active and inactive components and the low active ingredient content on a crop yield basis pointing to a high unit cost. Natural insecticides can serve additionally as leads to unnatural mimics, of which the commercially successful synthetic pyrethroids are prime examples. The chemical nature, relationship of insecticidal activity to chemical structure, occurrence, production, and utilization, registered uses, metabolism, and insect and mammalian toxicity are reviewed. PMID:789058

  15. Specific function of the Met-Tyr-Trp adduct radical and residues Arg-418 and Asp-137 in the atypical catalase reaction of catalase-peroxidase KatG.

    PubMed

    Zhao, Xiangbo; Khajo, Abdelahad; Jarrett, Sanchez; Suarez, Javier; Levitsky, Yan; Burger, Richard M; Jarzecki, Andrzej A; Magliozzo, Richard S

    2012-10-26

    Catalase activity of the dual-function heme enzyme catalase-peroxidase (KatG) depends on several structural elements, including a unique adduct formed from covalently linked side chains of three conserved amino acids (Met-255, Tyr-229, and Trp-107, Mycobacterium tuberculosis KatG numbering) (MYW). Mutagenesis, electron paramagnetic resonance, and optical stopped-flow experiments, along with calculations using density functional theory (DFT) methods revealed the basis of the requirement for a radical on the MYW-adduct, for oxyferrous heme, and for conserved residues Arg-418 and Asp-137 in the rapid catalase reaction. The participation of an oxyferrous heme intermediate (dioxyheme) throughout the pH range of catalase activity is suggested from our finding that carbon monoxide inhibits the activity at both acidic and alkaline pH. In the presence of H(2)O(2), the MYW-adduct radical is formed normally in KatG[D137S] but this mutant is defective in forming dioxyheme and lacks catalase activity. KatG[R418L] is also catalase deficient but exhibits normal formation of the adduct radical and dioxyheme. Both mutants exhibit a coincidence between MYW-adduct radical persistence and H(2)O(2) consumption as a function of time, and enhanced subunit oligomerization during turnover, suggesting that the two mutations disrupting catalase turnover allow increased migration of the MYW-adduct radical to protein surface residues. DFT calculations showed that an interaction between the side chain of residue Arg-418 and Tyr-229 in the MYW-adduct radical favors reaction of the radical with the adjacent dioxyheme intermediate present throughout turnover in WT KatG. Release of molecular oxygen and regeneration of resting enzyme are thereby catalyzed in the last step of a proposed catalase reaction.

  16. On the Formation and Properties of Interstrand DNA-DNA Cross-links Forged by Reaction of an Abasic Site With the Opposing Guanine Residue of 5′-CAp Sequences in Duplex DNA

    PubMed Central

    Johnson, Kevin M.; Price, Nathan E.; Wang, Jin; Fekry, Mostafa I.; Dutta, Sanjay; Seiner, Derrick R.; Wang, Yinsheng; Gates, Kent S.

    2014-01-01

    We recently reported that the aldehyde residue of an abasic (Ap) site in duplex DNA can generate an interstrand cross-link via reaction with a guanine residue on the opposing strand. This finding is intriguing because the highly deleterious nature of interstrand cross-links suggests that even small amounts of Ap-derived cross-links could make a significant contribution to the biological consequences stemming from the generation of Ap sites in cellular DNA. Incubation of 21-bp duplexes containing a central 5′-CAp sequence under conditions of reductive amination (NaCNBH3, pH 5.2) generated much higher yields of cross-linked DNA than reported previously. At pH 7, in the absence of reducing agents, these Ap-containing duplexes also produced cross-linked duplexes that were readily detected on denaturing polyacrylamide gels. Cross-link formation was not highly sensitive to reaction conditions and, once formed, the cross-link was stable to a variety of work-up conditions. Results of multiple experiments including MALDI-TOF mass spectrometry, gel mobility, methoxyamine capping of the Ap aldehyde, inosine-for-guanine replacement, hydroxyl radical footprinting, and LCMS/MS were consistent with a cross-linking mechanism involving reversible reaction of the Ap aldehyde residue with the N2-amino group of the opposing guanine residue in 5′-CAp sequences to generate hemiaminal, imine, or cyclic hemiaminal cross-links (7-10) that were irreversibly converted under conditions of reductive amination (NaCNBH3/pH 5.2) to a stable amine linkage. Further support for the importance of the exocyclic N2-amino group in this reaction was provided by an experiment showing that installation of a 2-aminopurine-thymine base pair at the cross-linking site produced high yields (15-30%) of a cross-linked duplex at neutral pH, in the absence of NaCNBH3. PMID:23215239

  17. The three-dimensional structure of AKR11B4, a glycerol dehydrogenase from Gluconobacter oxydans, reveals a tryptophan residue as an accelerator of reaction turnover.

    PubMed

    Richter, Nina; Breicha, Klaus; Hummel, Werner; Niefind, Karsten

    2010-12-01

    The NADP-dependent glycerol dehydrogenase (EC 1.1.1.72) from Gluconobacter oxydans is a member of family 11 of the aldo-keto reductase (AKR) enzyme superfamily; according to the systematic nomenclature within the AKR superfamily, the term AKR11B4 has been assigned to the enzyme. AKR11B4 is a biotechnologically attractive enzyme because of its broad substrate spectrum, combined with its distinctive regioselectivity and stereoselectivity. These features can be partially rationalized based on a 2-Å crystal structure of apo-AKR11B4, which we describe and interpret here against the functional complex structures of other members of family 11 of the AKR superfamily. The structure of AKR11B4 shows the AKR-typical (β/α)(8) TIM-barrel fold, with three loops and the C-terminal tail determining the particular enzymatic properties. In comparison to AKR11B1 (its closest AKR relative), AKR11B4 has a relatively broad binding cleft for the cosubstrate NADP/NADPH. In the crystalline environment, it is completely blocked by the C-terminal segment of a neighboring protomer. The structure reveals a conspicuous tryptophan residue (Trp23) that has to adopt an unconventional and strained side-chain conformation to permit cosubstrate binding. We predict and confirm by site-directed mutagenesis that Trp23 is an accelerator of (co)substrate turnover. Furthermore, we show that, simultaneously, this tryptophan residue is a critical determinant for substrate binding by the enzyme, while enantioselectivity is probably governed by a methionine residue within the C-terminal tail. We present structural reasons for these notions based on ternary complex models of AKR11B4, NADP, and either octanal, d-glyceraldehyde, or l-glyceraldehyde.

  18. Interconversion of ketoprofen recognition in firefly luciferase-catalyzed enantioselective thioesterification reaction using from Pylocoeria miyako (PmL) and Hotaria parvura (HpL) just by mutating two amino acid residues.

    PubMed

    Kato, Dai-ichiro; Hiraishi, Yoshihiro; Maenaka, Mika; Yokoyama, Keisuke; Niwa, Kazuki; Ohmiya, Yoshihiro; Takeo, Masahiro; Negoro, Seiji

    2013-11-01

    We identified the critical amino acid residues for substrate recognition using two firefly luciferases from Pylocoeria miyako (PmL) and Hotaria parvura (HpL), as these two luciferase enzymes exhibit different activities toward ketoprofen. Specifically, PmL can catalyze the apparent enantioselective thioesterification reaction, while HpL cannot. By comparing the amino acid sequences around the active site, we identified two residues (I350 and M397 in PmL and F351 and S398 in HpL) that were different between the two enzymes, and the replacement of these amino acids resulted in changing the ketoprofen recognition pattern. The inactive HpL was converted to the active enzyme toward ketoprofen and vice versa for PmL. These residues also affected the enantioselectivity toward ketoprofen; however, the bioluminescent color was not affected. In addition, using molecular dynamics calculations, the replacement of these two amino acids induced changes in the state of hydrogen bonding between ketoprofen and the S349 side chain through the active site water. As S349 is not considered to influence color tuning, these changes specifically caused the differences in ketoprofen recognition in the enzyme.

  19. Pesticide residues in birds and mammals

    USGS Publications Warehouse

    Stickel, L.F.; Edwards, C.A.

    1973-01-01

    exposure to an organochlorine pesticide, the concentrations of residues in the different tissues are ordinarily directly correlated with each other. When the dosage is at lethal levels, or when stored residues are mobilised to lethal levels, the balanced relationship is disrupted. The concentrations of residues in the brain provide the most rigorous criteria for diagnosis of death due to these chemicals, and levels are generally similar across a wide range of species of birds and mammals. Residues in liver are closely correlated with recent dose, either from direct intake or from mobilisation from storage, and so reflect hazardous exposure. Residues in the whole carcass show the storage reserve, and so indicate the potential for adverse effects from lethal mobilisation or from the continuous slow mobilisation that occurs during the normal processes of metabolism and excretion. A synchronous, rapid, and widespread decline in weight and thickness of shells of eggs laid by many species of wild birds occurred in the late 1940's and has persisted. Birds of prey were primarily affected; exceptions apparently are the result of lesser exposure because of different food habits. Many species of fish-eating birds are also affected. Others, however, appear to be more resistant and to accumulate much higher residues before shell-thinning occurs. Seed-eating birds do not appear to have been generally affected; their exposure is ordinarily lower, but physiological factors also seem to be involved. A relationship between shell-thinning and population decline has been established for many species. In exceptional cases, such as the herring gull, persistent re-nesting and other population reactions have overcome adverse effects at the population level. The discovery of shell-thinning among natural populations, and the hypothesis that this thinning was related to the occurrence of organochlorine pesticides, stimulated experimental studies to determine wheth

  20. Lysyl-tRNA synthetase from Bacillus stearothermophilus: the Trp314 residue is shielded in a non-polar environment and is responsible for the fluorescence changes observed in the amino acid activation reaction.

    PubMed

    Takita, Teisuke; Nakagoshi, Makoto; Inouye, Kuniyo; Tonomura, Ben'ichiro

    2003-01-24

    Three Trp variants of lysyl-tRNA synthetase from Bacillus stearothermophilus, in which either one or both of the two Trp residues within the enzyme (Trp314 and Trp332) were substituted by a Phe residue, were produced by site-directed mutagenesis without appreciable loss of catalytic activity. The following two phenomena were observed with W332F and with the wild-type enzyme, but not with W314F: (1) the addition of L-lysine alone decreased the protein fluorescence of the enzyme, but the addition of ATP alone did not; (2) the subsequent addition of ATP after the addition of excess L-lysine restored the fluorescence to its original level. Fluorometry under various conditions and UV-absorption spectroscopy revealed that Trp314, which was about 20A away from the lysine binding site and was shielded in a non-polar environment, was solely responsible for the fluorescence changes of the enzyme in the L-lysine activation reaction. Furthermore, the microenvironmental conditions around the residue were made more polar upon the binding of L-lysine, though its contact with the solvent was still restricted. It was suggested that Trp314 was located in a less polar environment than was Trp332, after comparison of the wavelengths at the peaks of fluorescence emission and of the relative fluorescence quantum yields. Trp332 was thought, based on the fluorescence quenching by some perturbants and the chemical modification with N-bromosuccinimide, to be on the surface of the enzyme, whereas Trp314 was buried inside. The UV absorption difference spectra induced by the L-lysine binding indicated that the state of Trp314, including its electrostatic environment, changed during the process, but Trp332 did not change. The increased fluorescence from Trp314 at acidic pH compared with that at neutral pH suggests that carboxylate(s) are in close proximity to the Trp314 residue. PMID:12507472

  1. Lysine221 is the general base residue of the isochorismate synthase from Pseudomonas aeruginosa (PchA) in a reaction that is diffusion limited.

    PubMed

    Meneely, Kathleen M; Luo, Qianyi; Dhar, Prajnaparamita; Lamb, Audrey L

    2013-10-01

    The isochorismate synthase from Pseudomonas aeruginosa (PchA) catalyzes the conversion of chorismate to isochorismate, which is subsequently converted by a second enzyme (PchB) to salicylate for incorporation into the salicylate-capped siderophore pyochelin. PchA is a member of the MST family of enzymes, which includes the structurally homologous isochorismate synthases from Escherichia coli (EntC and MenF) and salicylate synthases from Yersinia enterocolitica (Irp9) and Mycobacterium tuberculosis (MbtI). The latter enzymes generate isochorismate as an intermediate before generating salicylate and pyruvate. General acid-general base catalysis has been proposed for isochorismate synthesis in all five enzymes, but the residues required for the isomerization are a matter of debate, with both lysine221 and glutamate313 proposed as the general base (PchA numbering). This work includes a classical characterization of PchA with steady state kinetic analysis, solvent kinetic isotope effect analysis and by measuring the effect of viscosogens on catalysis. The results suggest that isochorismate production from chorismate by the MST enzymes is the result of general acid-general base catalysis with a lysine as the base and a glutamic acid as the acid, in reverse protonation states. Chemistry is determined to not be rate limiting, favoring the hypothesis of a conformational or binding step as the slow step. PMID:23942051

  2. Lysine221 is the general base residue of the isochorismate synthase from Pseudomonas aeruginosa (PchA) in a reaction that is diffusion limited

    PubMed Central

    Meneely, Kathleen M.; Luo, Qianyi; Dhar, Prajnaparamita; Lamb, Audrey L.

    2013-01-01

    The isochorismate synthase from Pseudomonas aeruginosa (PchA) catalyzes the conversion of chorismate to isochorismate, which is subsequently converted by a second enzyme (PchB) to salicylate for incorporation into the salicylate-capped siderophore pyochelin. PchA is a member of the MST family of enzymes, which includes the structurally homologous isochorismate synthases from E. coli (EntC and MenF) and salicylate synthases from Yersinia enterocolitica (Irp9) and Mycobacterium tuberculosis (MbtI). The latter enzymes generate isochorismate as an intermediate before generating salicylate and pyruvate. General acid – general base catalysis has been proposed for isochorismate synthesis in all five enzymes, but the residues required for the isomerization are a matter of debate, with both lysine221 and glutamate313 proposed as the general base (PchA numbering). This work includes a classical characterization of PchA with steady state kinetic analysis, solvent kinetic isotope effect analysis and by measuring the effect of viscosogens on catalysis. The results suggest that isochorismate production from chorismate by the MST enzymes is the result of general acid – general base catalysis with a lysine as the base and a glutamic acid as the acid, in reverse protonation states. Chemistry is determined to not be rate limiting, favoring the hypothesis of a conformational or binding step as the slow step. PMID:23942051

  3. Quantification of minimal residual disease (MRD) in acute lymphoblastic leukemia (ALL) using amplicon-fusion-site polymerase chain reaction (AFS-PCR)

    PubMed Central

    2012-01-01

    The amplification of putative oncogenes is a common finding within the genome of various cancer types. Identification and further targeting of specific junction sites within the sequence of genomic amplicons (amplicon fusion sites, AFS) by PCR (AFS-PCR) is suitable for quantification of minimal residual disease (MRD). This approach has recently been developed and described for MYCN amplified neuroblastomas. To compare AFS-PCR directly to routinely used MRD diagnostic strategies, we mapped the amplified genomic regions (ampGR) of an iAMP21-amplicon in high resolution of a patient with acute lymphoblastic leukemia (ALL). Successfully, we established AFS-PCR covering junction sites between ampGR within the iAMP21-amplicon. Quantification of MRD by AFS-PCR was directly comparable to IgH/TCR based real time quantitative PCR and fluorescence activated cell sorting (FACS) analysis in consecutive bone marrow (BM) specimens. Our data give an additional proof of concept of AFS-PCR for quantification of MRD. The method could be taken into account for ALL patients with genomic amplifications as alternative MRD diagnostic, if no or qualitatively poor Ig/TCR-PCRs are available. PMID:23210797

  4. Lysine221 is the general base residue of the isochorismate synthase from Pseudomonas aeruginosa (PchA) in a reaction that is diffusion limited.

    PubMed

    Meneely, Kathleen M; Luo, Qianyi; Dhar, Prajnaparamita; Lamb, Audrey L

    2013-10-01

    The isochorismate synthase from Pseudomonas aeruginosa (PchA) catalyzes the conversion of chorismate to isochorismate, which is subsequently converted by a second enzyme (PchB) to salicylate for incorporation into the salicylate-capped siderophore pyochelin. PchA is a member of the MST family of enzymes, which includes the structurally homologous isochorismate synthases from Escherichia coli (EntC and MenF) and salicylate synthases from Yersinia enterocolitica (Irp9) and Mycobacterium tuberculosis (MbtI). The latter enzymes generate isochorismate as an intermediate before generating salicylate and pyruvate. General acid-general base catalysis has been proposed for isochorismate synthesis in all five enzymes, but the residues required for the isomerization are a matter of debate, with both lysine221 and glutamate313 proposed as the general base (PchA numbering). This work includes a classical characterization of PchA with steady state kinetic analysis, solvent kinetic isotope effect analysis and by measuring the effect of viscosogens on catalysis. The results suggest that isochorismate production from chorismate by the MST enzymes is the result of general acid-general base catalysis with a lysine as the base and a glutamic acid as the acid, in reverse protonation states. Chemistry is determined to not be rate limiting, favoring the hypothesis of a conformational or binding step as the slow step.

  5. Clinical Pearls: Leprosy Reactions.

    PubMed

    Wu, Jane; Boggild, Andrea K

    2016-09-01

    Leprosy reactions are acute inflammatory episodes that occur in the setting of Mycobacterium leprae infection. Precipitants of reactions can be pharmacologic and nonpharmacologic. Both type 1 and type 2 reactions typically occur before and during leprosy treatment but may also occur after treatment has been completed. Reactions cause morbidity due to nerve damage, and prompt corticosteroid therapy is warranted to minimize nerve damage due to reactions.

  6. Minimal Residual Disease-Based Risk Stratification in Chinese Childhood Acute Lymphoblastic Leukemia by Flow Cytometry and Plasma DNA Quantitative Polymerase Chain Reaction

    PubMed Central

    Cheng, Suk Hang; Lau, Kin Mang; Li, Chi Kong; Chan, Natalie P. H.; Ip, Rosalina K. L.; Cheng, Chi Keung; Lee, Vincent; Shing, Matthew M. K.; Leung, Alex W. K.; Ha, Shau Yin; Cheuk, Daniel K. L.; Lee, Anselm C. W.; Li, Chak Ho; Luk, Chung Wing; Ling, Siu Cheung; Hrusak, Ondrej; Mejstrikova, Ester; Leung, Yonna; Ng, Margaret H. L.

    2013-01-01

    Minimal residual disease, or MRD, is an important prognostic indicator in childhood acute lymphoblastic leukemia. In ALL-IC-BFM 2002 study, we employed a standardized method of flow cytometry MRD monitoring for multiple centers internationally using uniformed gating, and determined the relevant MRD-based risk stratification strategies in our local patient cohort. We also evaluated a novel method of PCR MRD quantitation using peripheral blood plasma. For the bone marrow flow MRD study, patients could be stratified into 3 risk groups according to MRD level using a single time-point at day-15 (Model I) (I-A: <0.1%, I-B: 0.1–10%, I-C: >10%), or using two time-points at day-15 and day-33 (Model II) (II-A: day-15<10% and day-33<0.01%, II-B: day-15≥10% or day-33≥0.01% but not both, II-C: day-15≥10% and day-33≥0.01%), which showed significantly superior prediction of relapse (p = .00047 and <0.0001 respectively). Importantly, patients with good outcome (frequency: 56.0%, event-free survival: 90.1%) could be more accurately predicted by Model II. In peripheral blood plasma PCR MRD investigation, patients with day-15-MRD≥10−4 were at a significantly higher risk of relapse (p = 0.0117). By multivariate analysis, MRD results from both methods could independently predict patients’ prognosis, with 20–35-fold increase in risk of relapse for flow MRD I-C and II-C respectively, and 5.8-fold for patients having plasma MRD of ≥10−4. We confirmed that MRD detection by flow cytometry is useful for prognostic evaluation in our Chinese cohort of childhood ALL after treatment. Moreover, peripheral blood plasma DNA MRD can be an alternative where bone marrow specimen is unavailable and as a less invasive method, which allows close monitoring. PMID:23936021

  7. A critical assessment of the performance criteria in confirmatory analysis for veterinary drug residue analysis using mass spectrometric detection in selected reaction monitoring mode.

    PubMed

    Berendsen, Bjorn J A; Meijer, Thijs; Wegh, Robin; Mol, Hans G J; Smyth, Wesley G; Armstrong Hewitt, S; van Ginkel, Leen; Nielen, Michel W F

    2016-05-01

    Besides the identification point system to assure adequate set-up of instrumentation, European Commission Decision 2002/657/EC includes performance criteria regarding relative ion abundances in mass spectrometry and chromatographic retention time. In confirmatory analysis, the relative abundance of two product ions, acquired in selected reaction monitoring mode, the ion ratio should be within certain ranges for confirmation of the identity of a substance. The acceptable tolerance of the ion ratio varies with the relative abundance of the two product ions and for retention time, CD 2002/657/EC allows a tolerance of 5%. Because of rapid technical advances in analytical instruments and new approaches applied in the field of contaminant testing in food products (multi-compound and multi-class methods) a critical assessment of these criteria is justified. In this study a large number of representative, though challenging sample extracts were prepared, including muscle, urine, milk and liver, spiked with 100 registered and banned veterinary drugs at levels ranging from 0.5 to 100 µg/kg. These extracts were analysed using SRM mode using different chromatographic conditions and mass spectrometers from different vendors. In the initial study, robust data was collected using four different instrumental set-ups. Based on a unique and highly relevant data set, consisting of over 39 000 data points, the ion ratio and retention time criteria for applicability in confirmatory analysis were assessed. The outcomes were verified based on a collaborative trial including laboratories from all over the world. It was concluded that the ion ratio deviation is not related to the value of the ion ratio, but rather to the intensity of the lowest product ion. Therefore a fixed ion ratio deviation tolerance of 50% (relative) is proposed, which also is applicable for compounds present at sub-ppb levels or having poor ionisation efficiency. Furthermore, it was observed that retention time

  8. A critical assessment of the performance criteria in confirmatory analysis for veterinary drug residue analysis using mass spectrometric detection in selected reaction monitoring mode.

    PubMed

    Berendsen, Bjorn J A; Meijer, Thijs; Wegh, Robin; Mol, Hans G J; Smyth, Wesley G; Armstrong Hewitt, S; van Ginkel, Leen; Nielen, Michel W F

    2016-05-01

    Besides the identification point system to assure adequate set-up of instrumentation, European Commission Decision 2002/657/EC includes performance criteria regarding relative ion abundances in mass spectrometry and chromatographic retention time. In confirmatory analysis, the relative abundance of two product ions, acquired in selected reaction monitoring mode, the ion ratio should be within certain ranges for confirmation of the identity of a substance. The acceptable tolerance of the ion ratio varies with the relative abundance of the two product ions and for retention time, CD 2002/657/EC allows a tolerance of 5%. Because of rapid technical advances in analytical instruments and new approaches applied in the field of contaminant testing in food products (multi-compound and multi-class methods) a critical assessment of these criteria is justified. In this study a large number of representative, though challenging sample extracts were prepared, including muscle, urine, milk and liver, spiked with 100 registered and banned veterinary drugs at levels ranging from 0.5 to 100 µg/kg. These extracts were analysed using SRM mode using different chromatographic conditions and mass spectrometers from different vendors. In the initial study, robust data was collected using four different instrumental set-ups. Based on a unique and highly relevant data set, consisting of over 39 000 data points, the ion ratio and retention time criteria for applicability in confirmatory analysis were assessed. The outcomes were verified based on a collaborative trial including laboratories from all over the world. It was concluded that the ion ratio deviation is not related to the value of the ion ratio, but rather to the intensity of the lowest product ion. Therefore a fixed ion ratio deviation tolerance of 50% (relative) is proposed, which also is applicable for compounds present at sub-ppb levels or having poor ionisation efficiency. Furthermore, it was observed that retention time

  9. Mechanism of the AppABLUF Photocycle Probed by Site-Specific Incorporation of Fluorotyrosine Residues: Effect of the Y21 pKa on the Forward and Reverse Ground-State Reactions.

    PubMed

    Gil, Agnieszka A; Haigney, Allison; Laptenok, Sergey P; Brust, Richard; Lukacs, Andras; Iuliano, James N; Jeng, Jessica; Melief, Eduard H; Zhao, Rui-Kun; Yoon, EunBin; Clark, Ian P; Towrie, Michael; Greetham, Gregory M; Ng, Annabelle; Truglio, James J; French, Jarrod B; Meech, Stephen R; Tonge, Peter J

    2016-01-27

    The transcriptional antirepressor AppA is a blue light using flavin (BLUF) photoreceptor that releases the transcriptional repressor PpsR upon photoexcitation. Light activation of AppA involves changes in a hydrogen-bonding network that surrounds the flavin chromophore on the nanosecond time scale, while the dark state of AppA is then recovered in a light-independent reaction with a dramatically longer half-life of 15 min. Residue Y21, a component of the hydrogen-bonding network, is known to be essential for photoactivity. Here, we directly explore the effect of the Y21 pKa on dark state recovery by replacing Y21 with fluorotyrosine analogues that increase the acidity of Y21 by 3.5 pH units. Ultrafast transient infrared measurements confirm that the structure of AppA is unperturbed by fluorotyrosine substitution, and that there is a small (3-fold) change in the photokinetics of the forward reaction over the fluorotyrosine series. However, reduction of 3.5 pH units in the pKa of Y21 increases the rate of dark state recovery by 4000-fold with a Brønsted coefficient of ∼ 1, indicating that the Y21 proton is completely transferred in the transition state leading from light to dark adapted AppA. A large solvent isotope effect of ∼ 6-8 is also observed on the rate of dark state recovery. These data establish that the acidity of Y21 is a crucial factor for stabilizing the light activated form of the protein, and have been used to propose a model for dark state recovery that will ultimately prove useful for tuning the properties of BLUF photosensors for optogenetic applications. PMID:26708408

  10. Naturally Occurring Radioactive Materials (NORM)

    SciTech Connect

    Gray, P.

    1997-02-01

    This paper discusses the broad problems presented by Naturally Occuring Radioactive Materials (NORM). Technologically Enhanced naturally occuring radioactive material includes any radionuclides whose physical, chemical, radiological properties or radionuclide concentration have been altered from their natural state. With regard to NORM in particular, radioactive contamination is radioactive material in an undesired location. This is a concern in a range of industries: petroleum; uranium mining; phosphorus and phosphates; fertilizers; fossil fuels; forestry products; water treatment; metal mining and processing; geothermal energy. The author discusses in more detail the problem in the petroleum industry, including the isotopes of concern, the hazards they present, the contamination which they cause, ways to dispose of contaminated materials, and regulatory issues. He points out there are three key programs to reduce legal exposure and problems due to these contaminants: waste minimization; NORM assesment (surveys); NORM compliance (training).

  11. Foliicolous microfungi occurring on Encephalartos.

    PubMed

    Crous, P W; Wood, A R; Okada, G; Groenewald, J Z

    2008-12-01

    Species of Encephalartos, commonly known as bread trees, bread palms or cycads are native to Africa; the genus encompasses more than 60 species and represents an important component of the indigenous African flora. Recently, a leaf blight disease was noted on several E. altensteinii plants growing at the foot of Table Mountain in the Kirstenbosch Botanical Gardens of South Africa. Preliminary isolations from dead and dying leaves of E. alten-steinii, E. lebomboensis and E. princeps, collected from South Africa, revealed the presence of several novel microfungi on this host. Novelties include Phaeomoniella capensis, Saccharata kirstenboschensis, Teratosphaeria altensteinii and T. encephalarti. New host records of species previously only known to occur on Proteaceae include Cladophialophora proteae and Catenulostroma microsporum, as well as a hyperparasite, Dactylaria leptosphaeriicola, occurring on ascomata of T. encephalarti. PMID:20396583

  12. POST-OPERATIONAL TREATMENT OF RESIDUAL NA COOLLANT IN EBR-2 USING CARBONATION

    SciTech Connect

    Sherman, S.; Knight, C.

    2011-03-08

    At the end of 2002, the Experimental Breeder Reactor Two (EBR-II) facility became a U.S. Resource Conservation and Recovery Act (RCRA) permitted site, and the RCRA permit1 compelled further treatment of the residual sodium in order to convert it into a less reactive chemical form and remove the by-products from the facility, so that a state of RCRA 'closure' for the facility may be achieved (42 U.S.C. 6901-6992k, 2002). In response to this regulatory driver, and in recognition of project budgetary and safety constraints, it was decided to treat the residual sodium in the EBR-II primary and secondary sodium systems using a process known as 'carbonation.' In early EBR-II post-operation documentation, this process is also called 'passivation.' In the carbonation process (Sherman and Henslee, 2005), the system containing residual sodium is flushed with humidified carbon dioxide (CO{sub 2}). The water vapor in the flush gas reacts with residual sodium to form sodium hydroxide (NaOH), and the CO{sub 2} in the flush gas reacts with the newly formed NaOH to make sodium bicarbonate (NaHCO{sub 3}). Hydrogen gas (H{sub 2}) is produced as a by-product. The chemical reactions occur at the exposed surface of the residual sodium. The NaHCO{sub 3} layer that forms is porous, and humidified carbon dioxide can penetrate the NaHCO{sub 3} layer to continue reacting residual sodium underneath. The rate of reaction is controlled by the thickness of the NaHCO{sub 3} surface layer, the moisture input rate, and the residual sodium exposed surface area. At the end of carbonation, approximately 780 liters of residual sodium in the EBR-II primary tank ({approx}70% of original inventory), and just under 190 liters of residual sodium in the EBR-II secondary sodium system ({approx}50% of original inventory), were converted into NaHCO{sub 3}. No bare surfaces of residual sodium remained after treatment, and all remaining residual sodium deposits are covered by a layer of NaHCO{sub 3}. From a

  13. Nipah virus entry can occur by macropinocytosis

    SciTech Connect

    Pernet, Olivier; Pohl, Christine; Ainouze, Michelle; Kweder, Hasan; Buckland, Robin

    2009-12-20

    Nipah virus (NiV) is a zoonotic biosafety level 4 paramyxovirus that emerged recently in Asia with high mortality in man. NiV is a member, with Hendra virus (HeV), of the Henipavirus genus in the Paramyxoviridae family. Although NiV entry, like that of other paramyxoviruses, is believed to occur via pH-independent fusion with the host cell's plasma membrane we present evidence that entry can occur by an endocytic pathway. The NiV receptor ephrinB2 has receptor kinase activity and we find that ephrinB2's cytoplasmic domain is required for entry but is dispensable for post-entry viral spread. The mutation of a single tyrosine residue (Y304F) in ephrinB2's cytoplasmic tail abrogates NiV entry. Moreover, our results show that NiV entry is inhibited by constructions and drugs specific for the endocytic pathway of macropinocytosis. Our findings could potentially permit the rapid development of novel low-cost antiviral treatments not only for NiV but also HeV.

  14. Free-radical reactions of glycerolipids and sphingolipids

    NASA Astrophysics Data System (ADS)

    Yurkova, I. L.

    2012-02-01

    Free-radical reactions of glycero- and sphingolipids occurring in their polar moiety (fragmentation) and in their hydrophobic residue (peroxidation) under the action of reactive oxygen species are considered. The main attention is focused on free-radical fragmentation; its mechanism and regularities are discussed. Lipid peroxidation has been shown to modify the residues of polyunsaturated fatty acids, while the free-radical fragmentation results in the cleavage of ester, O-glycosidic and amide bonds in lipid molecules to give glycerophosphatides, ceramides and fatty acid amides functioning as secondary messengers in biosystems. The bibliography includes 132 references.

  15. Deamination of 5-methylcytosine residues in Mammalian cells.

    PubMed

    Gromenko, E V; Spirin, P V; Kubareva, E A; Romanova, E A; Prassolov, V S; Shpanchenko, O V; Dontsova, O A

    2009-10-01

    DNA demethylation in mammalia occurs after fertilization and during embryogenesis and accompanies cell aging and cancer transformation. With the help of the primer extension reaction, MALDI MS and DNA cleavage by thymine DNA glycosylase deamination of 5-methylcytosine residues has been shown to take place when the model methylated DNA duplexes are treated with nuclear extracts from the cell lines CHO, HeLa, and Skov3. The hypothesis that deamination of 5-methylcytosine is the first stage of demethylation in mammalia has been postulated.

  16. Deamination of 5-Methylcytosine Residues in Mammalian Cells

    PubMed Central

    Gromenko, E.V.; Spirin, P.V.; Kubareva, E.A.; Romanova, E.A.; Prassolov, V.S.; Shpanchenko, O.V.

    2009-01-01

    DNA demethylation in mammalia occurs after fertilization and during embryogenesis and accompanies cell aging and cancer transformation. With the help of the primer extension reaction, MALDI MS and DNA cleavage by thymine DNA glycosylase deamination of 5-methylcytosine residues has been shown to take place when the model methylated DNA duplexes are treated with nuclear extracts from the cell lines CHO, HeLa, and Skov3. The hypothesis that deamination of 5-methylcytosine is the first stage of demethylation in mammalia has been postulated. PMID:22649624

  17. Alternate Alpha Induced Reactions for NIF Radiochemistry

    SciTech Connect

    Shaughnessy, D A; Moody, K J; Bernstein, L A

    2010-02-26

    Radiochemical analysis of NIF capsule residues has been identified as a potential diagnostic of NIF capsule performance. In particular, alpha-induced nuclear reactions that occur on tracer elements added to the NIF capsule have been shown through simulation to be a very sensitive diagnostic for mix. The short range of the alpha particles makes them representative of the hot spot where they are created through the fusion of deuterium and tritium. Reactions on elements doped into the innermost part of the capsule ablator would therefore be sensitive to material that had mixed into the hot spot. Radiochemical determinations of activated detector elements may perhaps be the only true measure of mix that occurs in a NIF capsule, particularly in cases when the capsule fails.

  18. Selective Deletion of the Internal Lysine Residue from the Peptide Sequence by Collisional Activation

    NASA Astrophysics Data System (ADS)

    Banerjee, Shibdas; Mazumdar, Shyamalava

    2012-11-01

    The gas-phase peptide ion fragmentation chemistry is always the center of attraction in proteomics to analyze the amino acid sequence of peptides and proteins. In this work, we describe the formation of an anomalous fragment ion, which corresponds to the selective deletion of the internal lysine residue from a series of lysine containing peptides upon collisional activation in the ion trap. We detected several water-loss fragment ions and the maximum number of water molecules lost from a particular fragment ion was equal to the number of lysine residues in that fragment. As a consequence of this water-loss phenomenon, internal lysine residues were found to be deleted from the peptide ion. The N,N-dimethylation of all the amine functional groups of the peptide stopped the internal lysine deletion reaction, but selective N-terminal α-amino acetylation had no effect on this process indicating involvement of the side chains of the lysine residues. The detailed mechanism of the lysine deletion was investigated by multistage CID of the modified and unmodified peptides, by isotope labeling and by energy resolved CID studies. The results suggest that the lysine deletion might occur through a unimolecular multistep mechanism involving a seven-membered cyclic imine intermediate formed by the loss of water from a lysine residue in the protonated peptide. This intermediate subsequently undergoes degradation reaction to deplete the interior imine ring from the peptide backbone leading to the deletion of an internal lysine residue.

  19. Mechanisms for control of biological electron transfer reactions

    PubMed Central

    Williamson, Heather R.; Dow, Brian A.; Davidson, Victor L.

    2014-01-01

    Electron transfer (ET) through and between proteins is a fundamental biological process. The rates and mechanisms of these ET reactions are controlled by the proteins in which the redox centers that donate and accept electrons reside. The protein influences the magnitudes of the ET parameters, the electronic coupling and reorganization energy that are associated with the ET reaction. The protein can regulate the rates of the ET reaction by requiring reaction steps to optimize the system for ET, leading to kinetic mechanisms of gated or coupled ET. Amino acid residues in the segment of the protein through which long range ET occurs can also modulate the ET rate by serving as staging points for hopping mechanisms of ET. Specific examples are presented to illustrate these mechanisms by which proteins control rates of ET reactions. PMID:25085775

  20. Caffeine, a naturally occurring acaricide.

    PubMed

    Russell, D W; Fernández-Caldas, E; Swanson, M C; Seleznick, M J; Trudeau, W L; Lockey, R F

    1991-01-01

    Since caffeine is a plant alkaloid that has been described as a naturally occurring insecticide, its acaricidal effect on Dermatophagoides pteronyssinus (Dp) was investigated. Twelve cultures were established by adding 30 Dp to 200 mg of Tetramin fish food and brewer's yeast (8:2 ratio); six cultures were treated with 20 mg of finely ground caffeine. All 12 cultures were incubated at 75% relative humidity, 25 degrees C, and observed during 8 weeks. Live mites were then counted under a stereoscope, cultures were extracted, and supernatants were analyzed for Der p I and Der f I allergen content with a two-site monoclonal RIA. Live mite counts in untreated cultures varied from 146 to 274 (215 +/- 47.1), and in caffeine-treated cultures from 0 to 3 (1 +/- 1.2; p less than or equal to 0.0001). Der p I concentrations in untreated cultures varied from 588 to 9000 ng/gm (3138.3 +/- 2990.8 ng/gm), and in caffeine-treated cultures from 52 to 117 ng/gm (78 +/- 23.8 ng/gm; p less than or equal to 0.01). Der p I was not detected in the food media or caffeine; Der f I was not detected in any of the cultures. Results demonstrate that caffeine inhibits mite growth and allergen production.

  1. Characterization and comparative study of coal combustion residues from a primary and additional flue gas secondary desulfurization process

    SciTech Connect

    Gomes, S.; Francois, M.; Evrard, O.; Pellissier, C.

    1998-11-01

    An extensive characterization and comparative study was done on two flue gas desulfurization (FGD) residues derived from the same coal. LR residues (originated from Loire/Rhone in the south of Lyon, France) are obtained after a primary desulfurization process (SO{sub 2} is trapped by reaction with CaO at a temperature of about 1100 C), and LM residues (originating from La Maxe, near Metz in the east of France) are obtained after an additional secondary desulfurization process (SO{sub 2} is removed further by reaction with Ca(OH){sub 2} at a temperature of about 120 C). Various and complementary investigation methods were used to determine their chemical, physical, and mineralogical properties: x-ray fluorescence and diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetry analysis, granulometric distribution, pycnometric density, BET specific surface area and pH, conductivity measurements, and chemical analysis of their insoluble fraction. The FGD residues contain basically two main components: a silico-aluminous fly ash part and calcic FGD phases. In the LR residues the two components can be considered as independent, whereas they are linked in the LM residues because chemical reactions have occurred, leading to the formation of silico-calcic gel CSH, hydrated aluminate AFm, and AFt phases.

  2. Enhancement of accelerated carbonation of alkaline waste residues by ultrasound.

    PubMed

    Araizi, Paris K; Hills, Colin D; Maries, Alan; Gunning, Peter J; Wray, David S

    2016-04-01

    The continuous growth of anthropogenic CO2 emissions into the atmosphere and the disposal of hazardous wastes into landfills present serious economic and environmental issues. Reaction of CO2 with alkaline residues or cementitius materials, known as accelerated carbonation, occurs rapidly under ambient temperature and pressure and is a proven and effective process of sequestering the gas. Moreover, further improvement of the reaction efficiency would increase the amount of CO2 that could be permanently sequestered into solid products. This paper examines the potential of enhancing the accelerated carbonation of air pollution control residues, cement bypass dust and ladle slag by applying ultrasound at various water-to-solid (w/s) ratios. Experimental results showed that application of ultrasound increased the CO2 uptake by up to four times at high w/s ratios, whereas the reactivity at low water content showed little change compared with controls. Upon sonication, the particle size of the waste residues decreased and the amount of calcite precipitates increased. Finally, the sonicated particles exhibited a rounded morphology when observed by scanning electron microscopy.

  3. Enhancement of accelerated carbonation of alkaline waste residues by ultrasound.

    PubMed

    Araizi, Paris K; Hills, Colin D; Maries, Alan; Gunning, Peter J; Wray, David S

    2016-04-01

    The continuous growth of anthropogenic CO2 emissions into the atmosphere and the disposal of hazardous wastes into landfills present serious economic and environmental issues. Reaction of CO2 with alkaline residues or cementitius materials, known as accelerated carbonation, occurs rapidly under ambient temperature and pressure and is a proven and effective process of sequestering the gas. Moreover, further improvement of the reaction efficiency would increase the amount of CO2 that could be permanently sequestered into solid products. This paper examines the potential of enhancing the accelerated carbonation of air pollution control residues, cement bypass dust and ladle slag by applying ultrasound at various water-to-solid (w/s) ratios. Experimental results showed that application of ultrasound increased the CO2 uptake by up to four times at high w/s ratios, whereas the reactivity at low water content showed little change compared with controls. Upon sonication, the particle size of the waste residues decreased and the amount of calcite precipitates increased. Finally, the sonicated particles exhibited a rounded morphology when observed by scanning electron microscopy. PMID:26905698

  4. 40 CFR 161.240 - Residue chemistry data requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... requirement if their residues are regulated by the Food and Drug Administration at 21 CFR 178.1010. (11... metabolism in livestock are required when residues occur on a livestock feed, or the pesticide is to...

  5. 40 CFR 161.240 - Residue chemistry data requirements.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... requirement if their residues are regulated by the Food and Drug Administration at 21 CFR 178.1010. (11... metabolism in livestock are required when residues occur on a livestock feed, or the pesticide is to...

  6. 40 CFR 161.240 - Residue chemistry data requirements.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... requirement if their residues are regulated by the Food and Drug Administration at 21 CFR 178.1010. (11... metabolism in livestock are required when residues occur on a livestock feed, or the pesticide is to...

  7. Selective Loss of Cysteine Residues and Disulphide Bonds in a Potato Proteinase Inhibitor II Family

    PubMed Central

    Li, Xiu-Qing; Zhang, Tieling; Donnelly, Danielle

    2011-01-01

    Disulphide bonds between cysteine residues in proteins play a key role in protein folding, stability, and function. Loss of a disulphide bond is often associated with functional differentiation of the protein. The evolution of disulphide bonds is still actively debated; analysis of naturally occurring variants can promote understanding of the protein evolutionary process. One of the disulphide bond-containing protein families is the potato proteinase inhibitor II (PI-II, or Pin2, for short) superfamily, which is found in most solanaceous plants and participates in plant development, stress response, and defence. Each PI-II domain contains eight cysteine residues (8C), and two similar PI-II domains form a functional protein that has eight disulphide bonds and two non-identical reaction centres. It is still unclear which patterns and processes affect cysteine residue loss in PI-II. Through cDNA sequencing and data mining, we found six natural variants missing cysteine residues involved in one or two disulphide bonds at the first reaction centre. We named these variants Pi7C and Pi6C for the proteins missing one or two pairs of cysteine residues, respectively. This PI-II-7C/6C family was found exclusively in potato. The missing cysteine residues were in bonding pairs but distant from one another at the nucleotide/protein sequence level. The non-synonymous/synonymous substitution (Ka/Ks) ratio analysis suggested a positive evolutionary gene selection for Pi6C and various Pi7C. The selective deletion of the first reaction centre cysteine residues that are structure-level-paired but sequence-level-distant in PI-II illustrates the flexibility of PI-II domains and suggests the functionality of their transient gene versions during evolution. PMID:21494600

  8. Residual stresses in welded plates

    NASA Technical Reports Server (NTRS)

    Bernstein, Edward L.

    1994-01-01

    The purpose of this project was to develop a simple model which could be used to study residual stress. The mechanism that results in residual stresses in the welding process starts with the deposition of molten weld metal which heats the immediately adjacent material. After solidification of weld material, normal thermal shrinkage is resisted by the adjacent, cooler material. When the thermal strain exceeds the elastic strain corresponding to the yield point stress, the stress level is limited by this value, which decreases with increasing temperature. Cooling then causes elastic unloading which is restrained by the adjoining material. Permanent plastic strain occurs, and tension is caused in the region immediately adjacent to the weld material. Compression arises in the metal farther from the weld in order to maintain overall static equilibrium. Subsequent repair welds may add to the level of residual stresses. The level of residual stress is related to the onset of fracture during welding. Thus, it is of great importance to be able to predict the level of residual stresses remaining after a weld procedure, and to determine the factors, such as weld speed, temperature, direction, and number of passes, which may affect the magnitude of remaining residual stress. It was hoped to use traditional analytical modeling techniques so that it would be easier to comprehend the effect of these variables on the resulting stress. This approach was chosen in place of finite element methods so as to facilitate the understanding of the physical processes. The accuracy of the results was checked with some existing experimental studies giving residual stress levels found from x-ray diffraction measurements.

  9. The formation of internal 6-methyladenine residues in eucaryotic messenger RNA.

    PubMed

    Tuck, M T

    1992-03-01

    1. The formation of internal 6-methyladenine (m6A) residues in eucaryotic messenger RNA (mRNA) is a postsynthetic modification in which S-adenosyl-L-methionine (SAM) serves as the methyl donor. 2. Of the methyl groups incorporated into mature mRNA 30-50% occur in m6A residues. 3. Although most cellular and certain viral mRNAs contain at least one m6A residue, some transcripts such as those coding for histone and globin are completely lacking in this modification. 4. 6-Methyladenine residues have also been localized to heterogeneous nuclear RNA (HnRNA), and for the most part these residues are conserved during mRNA processing. 5. In all known cases, the m6A residues are also found in a strict consensus sequence, Gm6AC or Am6AC, within the transcript. 6. Although the biological significance of internal adenine methylation in eucaryotic mRNA remains unclear, a great deal of research has indicated that this modification may be required for mRNA transport to the cytoplasm, the selection of splice sites or other RNA processing reactions. PMID:1551452

  10. Naturally occurring contamination in the Mancos Shale.

    PubMed

    Morrison, Stan J; Goodknight, Craig S; Tigar, Aaron D; Bush, Richard P; Gil, April

    2012-02-01

    Some uranium mill tailings disposal cells were constructed on dark-gray shale of the Upper Cretaceous Mancos Shale. Shale of this formation contains contaminants similar to those in mill tailings. To establish the contributions derived from the Mancos, we sampled 51 locations in Colorado, New Mexico, and Utah. Many of the groundwater samples were saline with nitrate, selenium, and uranium concentrations commonly exceeding 250, 000, 1000, and 200 μg/L, respectively. Higher concentrations were limited to groundwater associated with shale beds, but were not correlated with geographic area, stratigraphic position, or source of water. The elevated concentrations suggest that naturally occurring contamination should be considered when evaluating groundwater cleanup levels. At several locations, seep water was yellow or red, caused in part by dissolved organic carbon concentrations up to 280 mg/L. Most seeps had (234)U to (238)U activity ratios greater than 2, indicating preferential leaching of (234)U. Seeps were slightly enriched in (18)O relative to the meteoric water line, indicating limited evaporation. Conceptually, major ion chemical reactions are dominated by calcite dissolution following proton release from pyrite oxidation and subsequent exchange by calcium for sodium residing on clay mineral exchange sites. Contaminants are likely released from organic matter and mineral surfaces during weathering.

  11. TRACE ELEMENT CHEMISTRY IN RESIDUAL-TREATED SOIL: KEY CONCEPTS AND METAL BIOAVAILABILITY

    EPA Science Inventory

    Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are importan...

  12. Pauli-blocking effects in neutron-alpha reactions

    SciTech Connect

    Avrigeanu, M. |; Avrigeanu, V.; Antonov, A.N.; Chadwick, M.B.; Hodgson, P.E.; Stoitsov, M.V.

    1994-06-01

    We present a knockout model for direct (n,{alpha}) reactions in which the residual nucleus is left in a continuum excited state. The interaction of the neutron with a preformed alpha particle inside the nucleus is related to the free neutron-alpha scattering cross-section, with modifications to account for nuclear medium effects, including Fermi motion, Pauli-blocking, and barrier penetration. Phase space restrictions for the four nucleons of the alpha-particle after the knockout are imposed by a Pauli-blocking function. We apply this model, along with evaporation contributions, to analyze excitation functions of (n,{alpha} reactions on {sup 48}Ti, {sup 51}V, {sup 52}Cr, {sup 54}Fe, {sup 55}Mn, and {sup 59}Co. Good agreement is obtained between our calculations and experimental measurements. Values for the local Fermi energy in the region from where knockout occurs indicate a surface reaction.

  13. Catalytic combustion of residual fuels

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.; Tacina, R. R.

    1981-01-01

    A noble metal catalytic reactor was tested using two grades of petroleum derived residual fuels at specified inlet air temperatures, pressures, and reference velocities. Combustion efficiencies greater than 99.5 percent were obtained. Steady state operation of the catalytic reactor required inlet air temperatures of at least 800 K. At lower inlet air temperatures, upstream burning in the premixing zone occurred which was probably caused by fuel deposition and accumulation on the premixing zone walls. Increasing the inlet air temperature prevented this occurrence. Both residual fuels contained about 0.5 percent nitrogen by weight. NO sub x emissions ranged from 50 to 110 ppm by volume at 15 percent excess O2. Conversion of fuel-bound nitrogen to NO sub x ranged from 25 to 50 percent.

  14. Pesticide residues in eagles

    USGS Publications Warehouse

    Reichel, W.L.; Cromartie, E.; Lamont, T.G.; Mulhern, B.M.; Prouty, R.M.

    1969-01-01

    Bald and golden eagles found sick or dead in 18 States and Canada during 1964-1965 were analyzed for pesticide residues. Residues in bald eagles were considerably higher than in golden eagles. Residues of DDE, DDD, and dieldrin were detected in all samples of bald eagle carcasses; other compounds found, less frequently were heptachlor epoxide, endrin, and DCBP, a metabolite of DDT. DDE was detected in all samples of golden eagle carcasses; DDD, DDT, dieldrin, and heptachlor epoxide were detected less frequently.

  15. Reversible Hydrolysis Reaction with the Spore Photoproduct under Alkaline Conditions.

    PubMed

    Adhikari, Surya; Lin, Gengjie; Li, Lei

    2016-09-16

    DNA lesions may reduce the electron density at the nucleobases, making them prone to further modifications upon the alkaline treatment. The dominant DNA photolesion found in UV-irradiated bacterial endospores is a thymine dimer, 5-thyminyl-5,6-dihydrothymine, i.e., the spore photoproduct (SP). Here we report a stepwise addition/elimination reaction in the SP hydrolysis product under strong basic conditions where a ureido group is added to the carboxyl moiety to form a cyclic amide, regenerating SP after eliminating a hydroxide ion. Direct amidation of carboxylic acids by reaction with amines in the presence of a catalyst is well documented; however, it is very rare for an amidation reaction to occur without activation. This uncatalyzed SP reverse reaction in aqueous solution is even more surprising because the carboxyl moiety is not a good electrophile due to the negative charge it carries. Examination of the base-catalyzed hydrolyses of two other saturated pyrimidine lesions, 5,6-dihydro-2'-deoxyuridine and pyrimidine (6-4) pyrimidone photoproduct, reveals that neither reaction is reversible even though all three hydrolysis reactions may share the same gem-diol intermediate. Therefore, the SP structure where the two thymine residues maintain a stacked conformation likely provides the needed framework enabling this highly unusual carboxyl addition/elimination reaction. PMID:27537985

  16. Spallation reactions: A successful interplay between modeling and applications

    NASA Astrophysics Data System (ADS)

    David, J.-C.

    2015-06-01

    The spallation reactions are a type of nuclear reaction which occur in space by interaction of the cosmic rays with interstellar bodies. The first spallation reactions induced with an accelerator took place in 1947 at the Berkeley cyclotron (University of California) with 200MeV deuterons and 400MeV alpha beams. They highlighted the multiple emission of neutrons and charged particles and the production of a large number of residual nuclei far different from the target nuclei. In the same year, R. Serber described the reaction in two steps: a first and fast one with high-energy particle emission leading to an excited remnant nucleus, and a second one, much slower, the de-excitation of the remnant. In 2010 IAEA organized a workshop to present the results of the most widely used spallation codes within a benchmark of spallation models. If one of the goals was to understand the deficiencies, if any, in each code, one remarkable outcome points out the overall high-quality level of some models and so the great improvements achieved since Serber. Particle transport codes can then rely on such spallation models to treat the reactions between a light particle and an atomic nucleus with energies spanning from few tens of MeV up to some GeV. An overview of the spallation reactions modeling is presented in order to point out the incomparable contribution of models based on basic physics to numerous applications where such reactions occur. Validations or benchmarks, which are necessary steps in the improvement process, are also addressed, as well as the potential future domains of development. Spallation reactions modeling is a representative case of continuous studies aiming at understanding a reaction mechanism and which end up in a powerful tool.

  17. Antioxidant properties of roasted coffee residues.

    PubMed

    Yen, Wen-Jye; Wang, Bor-Sen; Chang, Lee-Wen; Duh, Pin-Der

    2005-04-01

    The antioxidant activity of roasted coffee residues was evaluated. Extraction with four solvents (water, methanol, ethanol, and n-hexane) showed that water extracts of roasted coffee residues (WERCR) produced higher yields and gave better protection for lipid peroxidation. WERCR showed a remarkable protective effect on oxidative damage of protein. In addition, WERCR showed scavenging of free radicals as well as the reducing ability and to bind ferrous ions, indicating that WERCR acts as both primary and secondary antioxidants. The HPLC analyses showed that phenolic acids (chlorogenic acid and caffeic acid) and nonphenolic compounds [caffeine, trigonelline, nicotinic acid, and 5-(hydroxymethyl)furfuraldehyde] remained in roasted coffee residues. These compounds showed a protective effect on a liposome model system. The concentrations of flavonoids and polyphenolic compounds in roasted coffee residues were 8,400 and 20,400 ppm, respectively. In addition, the Maillard reaction products (MRPs) remaining in roasted coffee residues were believed to show antioxidant activity. These data indicate that roasted coffee residues have excellent potential for use as a natural antioxidant source because the antioxidant compounds remained in roasted coffee residues. PMID:15796608

  18. HIV DNA loads, plasma residual viraemia and risk of virological rebound in heavily treated, virologically suppressed HIV-infected patients.

    PubMed

    Gianotti, N; Canducci, F; Galli, L; Cossarini, F; Salpietro, S; Poli, A; Nozza, S; Spagnuolo, V; Clementi, M; Sampaolo, M; Ceresola, E R; Racca, S; Lazzarin, A; Castagna, A

    2015-01-01

    In this single-centre, retrospective study, we analyzed data of 194 patients receiving antiretroviral therapy with <50 human immunodeficiency virus (HIV) RNA copies/mL in plasma and 318 HIV RNA/DNA paired samples. By kinetic polymerase chain reaction (kPCR) molecular system analysis, 104 (54%) subjects had undetectable HIV RNA and 90 (46%) had residual viraemia. Median (interquartile range) HIV DNA load was 780 (380-1930) copies/10(6) peripheral blood lymphocytes (PBL), and HIV DNA loads were independently associated with residual viraemia (p 0.002). Virological rebound occurred in 29/194 (15%) patients over a median (interquartile range) follow-up of 17.5 (13.5-31.5) months. Residual viraemia (p 0.002), but not HIV DNA load, was independently associated with virological rebound.

  19. Assessment of tetracycline, lead and cadmium residues in frozen chicken vended in Lagos and Ibadan, Nigeria.

    PubMed

    Olusola, Adetunji Victoria; Diana, Belleh Efie; Ayoade, Odetokun Ismail

    2012-09-01

    This study determined the levels of tetracycline and heavy metals (lead and cadmium) levels in frozen chicken. One hundred frozen chicken muscle samples were sourced from major markets in Lagos and Ibadan (fifty samples each). The samples were analyzed using high power liquid chromatography (HPLC) for tetracycline residue determination while atomic absorption spectroscopy (AAS) was used to determine the levels of lead and cadmium residues in the samples. Mean concentrations of tetracycline residue levels in the frozen chicken sampled ranged from 1.1589-1.0463ppm which is higher than the maximum residue limit set by international food safety agencies. Pb contents were higher in chicken muscles sampled from markets in Ibadan (0.0227 +/- 0.0069 microg dL(-2)) than Lagos (0.0207 +/- 0.0082 microg dL(-1)), while Cd levels were 0.0013 microg dL(-1) higher than in the Lagos samples (0.0065 +/- 0.0026 microg dL(-1)). These values were within maximum residue limits. There were no significant differences (p < 0.05) in levels of tetracycline, lead and cadmium levels from the two market locations (Lagos and Ibadan) and parts (wings and thigh muscles). However, significant differences occurred in tetracycline and Pb levels in frozen chicken sourced from Cotonou. Though not significant, tetracycline contents in the thigh muscles of the frozen chicken samples was higher than that of the wings muscles and this was attributed to the site of administration of antibiotic injection and failure to observe the pre-slaughter withdrawal period by the farmers. This study is of public health importance as the presence of these residues above the maximum residue limit in frozen chicken predisposes consumers to drug resistance, allergic reactions and poisoning as a result of toxicity. PMID:24163968

  20. Horseradish peroxidase compound I as a tool to investigate reactive protein-cysteine residues: from quantification to kinetics.

    PubMed

    Toledo, José Carlos; Audi, Renata; Ogusucu, Renata; Monteiro, Gisele; Netto, Luis Eduardo Soares; Augusto, Ohara

    2011-05-01

    Proteins containing reactive cysteine residues (protein-Cys) are receiving increased attention as mediators of hydrogen peroxide signaling. These proteins are mainly identified by mining the thiol proteomes of oxidized protein-Cys in cells and tissues. However, it is difficult to determine if oxidation occurs through a direct reaction with hydrogen peroxide or by thiol-disulfide exchange reactions. Kinetic studies with purified proteins provide invaluable information about the reactivity of protein-Cys residues with hydrogen peroxide. Previously, we showed that the characteristic UV-Vis spectrum of horseradish peroxidase compound I, produced from the oxidation of horseradish peroxidase by hydrogen peroxide, is a simple, reliable, and useful tool to determine the second-order rate constant of the reaction of reactive protein-Cys with hydrogen peroxide and peroxynitrite. Here, the method is fully described and extended to quantify reactive protein-Cys residues and micromolar concentrations of hydrogen peroxide. Members of the peroxiredoxin family were selected for the demonstration and validation of this methodology. In particular, we determined the pK(a) of the peroxidatic thiol of rPrx6 (5.2) and the second-order rate constant of its reactions with hydrogen peroxide ((3.4 ± 0.2) × 10⁷M⁻¹ s⁻¹) and peroxynitrite ((3.7 ± 0.4) × 10⁵ M⁻¹ s⁻¹) at pH 7.4 and 25°C.

  1. Characterization of welding residual stresses with neutron diffraction

    SciTech Connect

    Wang, X.L.; Spooner, S.; Hubbard, C.R.; Taljat, B.; Feng, Z.

    1998-03-01

    Welding residual stresses are a key concern in the fabrication and use of structural components containing welds. Residual stresses in welds are caused by non-uniform expansion and shrinkage of differently heated zones during the thermal transient of a weld pass. In some alloys, solid state phase transformations occurring during the welding transient contribute additional residual stresses. Manufacturing problems arising from welding residual stresses include cracking and dimensional distortion. During use, tensile stresses in the welded zone limit the fatigue resistance of the component under cyclic loading. In an aggressive environment, tensile welding residual stresses also create a necessary condition for stress-corrosion cracking to take place.

  2. [Significance of Minimal Residual Disease in Chronic Lymphocytic Leukemia].

    PubMed

    Doubek, M

    2015-01-01

    Newly introduced highly effective treatment options increase the importance of minimal residual disease measurement in chronic lymphocytic leukemia. Minimal residual disease is gaining interest mainly as a predictive marker; however, clinical significance of minimal residual dis-ease in chronic lymphocytic leukemia in many different situations remains unresolved. Factors with a possible impact on the clinical significance of minimal residual disease are as follows: technique for minimal residual disease quantification, treatment regimen, peripheral blood vs. bone marrow analysis or time -point for sampling. Highly sensitive methods now available to evaluate minimal residual disease can detect a single chronic lymphocytic leukemia cell in 10(-4)- 10(-5) leukocytes using either allele -specific oligonucleotide polymerase chain reaction or multicolor flow cytometry. Minimal residual disease quantification as a surrogate marker to assess treatment efficacy in routine hematological practice has to be further evaluated.

  3. Contact reactions to food.

    PubMed

    Killig, Claudia; Werfel, Thomas

    2008-05-01

    Cutaneous adverse reactions to foods, spices, and food additives can occur both in occupational and nonoccupational settings in those who grow, handle, prepare, or cook food. Because spices are also utilized in cosmetics and perfumes, other exposures are encountered that can result in adverse cutaneous reactions. This article describes the reaction patterns that can occur upon contact with foods, including irritant contact dermatitis and allergic contact dermatitis. The ingestion of culprit foods by sensitized individuals can provoke a generalized eczematous rash, referred to as systemic contact dermatitis. Other contact reactions to food include contact urticaria and protein contact dermatitis provoked by high-molecular-weight food proteins often encountered in patients with atopic dermatitis. Phototoxic and photoallergic contact dermatitis are also considered.

  4. Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides

    NASA Astrophysics Data System (ADS)

    Bertran-Vicente, Jordi; Penkert, Martin; Nieto-Garcia, Olaia; Jeckelmann, Jean-Marc; Schmieder, Peter; Krause, Eberhard; Hackenberger, Christian P. R.

    2016-09-01

    In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys phosphorylation site in IICBGlc, which is known to be involved in the carbohydrate uptake from the bacterial phosphotransferase system (PTS). This new chemical and analytical approach finally allows further investigating the functions and significance of Cys phosphorylation in a wide range of crucial cellular processes.

  5. Oxygen evolution reaction catalysis

    DOEpatents

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  6. Direct targeted glycation of the free sulfhydryl group of cysteine residue (Cys-34) of BSA. Mapping of the glycation sites of the anti-tumor Thomsen-Friedenreich neoglycoconjugate vaccine prepared by Michael addition reaction.

    PubMed

    Demian, Wael L L; Kottari, Naresh; Shiao, Tze Chieh; Randell, Edward; Roy, René; Banoub, Joseph H

    2014-12-01

    We present in this manuscript the characterization of the exact glycation sites of the Thomsen-Friedenreich antigen-BSA vaccine (TF antigen:BSA) prepared using a Michael addition reaction between the saccharide antigen as an electrophilic acceptor and the nucleophilic thiol and L-Lysine ε-amino groups of BSA using different ligation conditions. Matrix laser desorption ionization time-of-flight mass spectrometry of the neoglycoconjugates prepared with TF antigen:protein ratios of 2:1 and 8:1, allowed to observe, respectively, the protonated molecules for each neoglycoconjugates: [M + H](+) at m/z 67,599 and 70,905. The measurements of these molecular weights allowed us to confirm exactly the carbohydrate:protein ratios of these two synthetic vaccines. These were found to be closely formed by a TF antigen:BSA ratios of 2:1 and 8:1, respectively. Trypsin digestion and liquid chromatography coupled with electrospray ionization mass spectrometry allowed us to identify the series of released glycopeptide and peptide fragments. De novo sequencing affected by low-energy collision dissociation tandem mass spectrometry was then employed to unravel the precise glycation sites of these neoglycoconjugate vaccines. Finally, we identified, respectively, three diagnostic and characteristic glycated peptides for the synthetic glycoconjugate possessing a TF antigen:BSA ratio 2:1, whereas we have identified for the synthetic glycoconjugate having a TF:BSA ratio 8:1 a series of 14 glycated peptides. The net increase in the occupancy sites of these neoglycoconjugates was caused by the large number of glycoforms produced during the chemical ligation of the synthetic carbohydrate antigen onto the protein carrier.

  7. Direct targeted glycation of the free sulfhydryl group of cysteine residue (Cys-34) of BSA. Mapping of the glycation sites of the anti-tumor Thomsen-Friedenreich neoglycoconjugate vaccine prepared by Michael addition reaction.

    PubMed

    Demian, Wael L L; Kottari, Naresh; Shiao, Tze Chieh; Randell, Edward; Roy, René; Banoub, Joseph H

    2014-12-01

    We present in this manuscript the characterization of the exact glycation sites of the Thomsen-Friedenreich antigen-BSA vaccine (TF antigen:BSA) prepared using a Michael addition reaction between the saccharide antigen as an electrophilic acceptor and the nucleophilic thiol and L-Lysine ε-amino groups of BSA using different ligation conditions. Matrix laser desorption ionization time-of-flight mass spectrometry of the neoglycoconjugates prepared with TF antigen:protein ratios of 2:1 and 8:1, allowed to observe, respectively, the protonated molecules for each neoglycoconjugates: [M + H](+) at m/z 67,599 and 70,905. The measurements of these molecular weights allowed us to confirm exactly the carbohydrate:protein ratios of these two synthetic vaccines. These were found to be closely formed by a TF antigen:BSA ratios of 2:1 and 8:1, respectively. Trypsin digestion and liquid chromatography coupled with electrospray ionization mass spectrometry allowed us to identify the series of released glycopeptide and peptide fragments. De novo sequencing affected by low-energy collision dissociation tandem mass spectrometry was then employed to unravel the precise glycation sites of these neoglycoconjugate vaccines. Finally, we identified, respectively, three diagnostic and characteristic glycated peptides for the synthetic glycoconjugate possessing a TF antigen:BSA ratio 2:1, whereas we have identified for the synthetic glycoconjugate having a TF:BSA ratio 8:1 a series of 14 glycated peptides. The net increase in the occupancy sites of these neoglycoconjugates was caused by the large number of glycoforms produced during the chemical ligation of the synthetic carbohydrate antigen onto the protein carrier. PMID:25476939

  8. Conversion of direct process high-boiling residue to monosilanes

    DOEpatents

    Brinson, Jonathan Ashley; Crum, Bruce Robert; Jarvis, Jr., Robert Frank

    2000-01-01

    A process for the production of monosilanes from the high-boiling residue resulting from the reaction of hydrogen chloride with silicon metalloid in a process typically referred to as the "direct process." The process comprises contacting a high-boiling residue resulting from the reaction of hydrogen chloride and silicon metalloid, with hydrogen gas in the presence of a catalytic amount of aluminum trichloride effective in promoting conversion of the high-boiling residue to monosilanes. The present process results in conversion of the high-boiling residue to monosilanes. At least a portion of the aluminum trichloride catalyst required for conduct of the process may be formed in situ during conduct of the direct process and isolation of the high-boiling residue.

  9. Residue chemistry guidelines.

    PubMed

    Olinger, C L; Schmitt, R D; Zager, E

    1993-01-01

    Residue chemistry guidelines are designed to determine what the potential residues in food are and how much may be present as a result of pesticide application, so that a tolerance level may be established. Some requirements are established to assist in the enforcement of tolerances by the USDA, FDA, and the states. I realize I have given you a quick overview of the residue chemistry requirements. There are many documents which are available if you should require more information, such as the Subdivision O Residue Chemistry Guidelines, Standard Evaluation Procedures (which are used by reviewers when evaluating the studies), the Data Reporting Guidelines (which provide guidance on preparing final reports), and the Technical Guidance from Phase III of Reregistration. We have also released various papers on studies when additional guidance is required. Most of these documents are available from NTIS. I hope you will consider this information when auditing residue chemistry studies. As I see the efforts that you, the QA professionals, have made to educate yourselves on residue chemistry studies through programs such as this meeting, I have a little more confidence in answering the question "Do you trust them?" with a "Yes." Thank you.

  10. Nationwide residues of organochlorine compounds in starlings (Sturnus vulgaris), 1976

    USGS Publications Warehouse

    White, D.H.

    1979-01-01

    Organochlorine pesticide and PCB residues in starlings from 126 sites within the contiguous 48 states were monitored during fall 1976. The average nationwide level of DDE and PCBs has increased significantly since 1974, but the number of sites reporting PCB residues has decreased fivefold. Dieldrin residues have remained unchanged since 1974. Highest DDE levels occurred in samples from parts of Arizona, Arkansas, California, Louisiana, and New Mexico.

  11. The molecular mechanism of the catalase reaction.

    PubMed

    Alfonso-Prieto, Mercedes; Biarnés, Xevi; Vidossich, Pietro; Rovira, Carme

    2009-08-26

    Catalases are ubiquitous enzymes that prevent cell oxidative damage by degrading hydrogen peroxide to water and oxygen (2H(2)O(2) --> 2 H(2)O + O(2)) with high efficiency. The enzyme is first oxidized to a high-valent iron intermediate, known as Compound I (Cpd I) which, in contrast to other hydroperoxidases, is reduced back to the resting state by further reacting with H(2)O(2). By means of hybrid QM/MM Car-Parrinello metadynamics simulations, we have investigated the mechanism of the reduction of Compound I by H(2)O(2) in Helicobacter pylori catalase (HPC) and Penicillium vitale catalase (PVC). We found that the Cpd I-H(2)O(2) complex evolves to a Cpd II-like species through the transfer of a hydrogen atom from the peroxide to the oxoferryl unit. To complete the reaction, two mechanisms may be operative: a His-mediated (Fita-Rossmann) mechanism, which involves the distal His as an acid-base catalyst mediating the transfer of a proton (associated with an electron transfer), and a direct mechanism, in which a hydrogen atom transfer occurs. Independently of the mechanism, the reaction proceeds by two one-electron transfers rather than one two-electron transfer, as has long been the lore. The calculations provide a detailed view of the atomic and electronic reorganizations during the reaction, and highlight the key role of the distal residues to assist the reaction. Additional calculations on the in silico HPC His56Gly mutant and gas-phase models provide clues to understand the requirements for the reaction to proceed with low barriers. PMID:19653683

  12. Adverse events occurring after smallpox vaccination.

    PubMed

    Lane, J Michael; Goldstein, Joel

    2003-07-01

    We reviewed the literature on adverse events reported to occur after smallpox vaccination. Nearly one-half of the United States population is vaccinia-naïve and may be at risk for development of serious adverse events. We describe the clinical features of postvaccinial central nervous system disease, progressive vaccinia, eczema vaccinatum, accidental implantations, "generalized vaccinia," and the common erythematous and/or urticarial rashes. In the 1960s, death occurred approximately once in every million primary vaccinations, with fatalities resulting from progressive vaccinia, postvaccinial encephalitis, and eczema vaccinatum. Death in revaccinees occurred less commonly and almost entirely from progressive vaccinia. In today's population, death rates might be higher because of the increased prevalence of immune deficiency and atopic dermatitis.

  13. An In Situ Method for Sizing Insoluble Residues in Precipitation

    NASA Astrophysics Data System (ADS)

    Axson, J. L.; Creamean, J.; Bondy, A. L.; Warner, K. Y.; Ault, A. P.

    2014-12-01

    Aerosols acting as cloud condensation nuclei (CCN) and ice nuclei (IN) play an important role in the climate effects of clouds. Wet deposition of these particles via rainout, washout, or cloud seeding is an important removal mechanism for aerosols in the atmosphere. Many of these particles, especially those that serve as IN, are insoluble and remain suspended after uptake within precipitating droplets/crystals as insoluble residues. While studies have measured the dissolved ions or mass of species within collected precipitation, no studies to date have quantified the number and size of insoluble residues. Herein, we demonstrate for the first time an in situ method for determining the number concentration, number size distribution, and surface area distribution of insoluble residues < 1 μm in diameter in samples of melted snow and rain. This work evaluates the use of nanoparticle tracking analysis (NTA), a new and novel technique for determining particle size distributions in a liquid medium, to determine in situ size distributions of insoluble residue particles in precipitation and evaluate this technique versus other analytical methods, including dynamic light scattering (DLS) and transmission electron microscopy (TEM). Number size distribution modes ranged from 80-150 nm and were strongly sample dependent. Surface area distribution modes ranged from 150-400 nm. Differences were observed between concentrations and size distributions for snow collected at different locations and elevations and between rain and melted snow. These differences can indicate changes in the insoluble residues that vary with ambient aerosol concentration, cloud microphysics, and meteorological dynamics. This method has great potential for improving our understanding of the properties of the particles nucleating droplets and crystals, the surface area available for reactions to occur, and the number of particles removed by scavenging. Additionally, the snow samples were further evaluated

  14. Self-catalyzed site-specific depurination of guanine residues within gene sequences.

    PubMed

    Amosova, Olga; Coulter, Richard; Fresco, Jacques R

    2006-03-21

    A self-catalyzed, site-specific guanine-depurination activity has been found to occur in short gene sequences with a potential to form a stem-loop structure. The critical features of that catalytic intermediate are a 5'-G-T-G-G-3' loop and an adjacent 5'-T.A-3' base pair of a short duplex stem stable enough to fix the loop structure required for depurination of its 5'-G residue. That residue is uniquely depurinated with a rate some 5 orders of magnitude faster than that of random "spontaneous" depurination. In contrast, all other purine residues in the sequence depurinate at the spontaneous background rate. The reaction requires no divalent cations or other cofactors and occurs under essentially physiological conditions. Such stem-loops can form in duplex DNA under superhelical stress, and their critical sequence features have been found at numerous sites in the human genome. Self-catalyzed stem-loop-mediated depurination leading to flexible apurinic sites may therefore serve some important biological role, e.g., in nucleosome positioning, genetic recombination, or chromosome superfolding.

  15. Isomer residual ratio of odd-odd isotope {sup 180}Ta in supernova nucleosynthsis

    SciTech Connect

    Hayakawa, Takehito; Kajino, Toshitaka; Chiba, Satoshi; Mathews, Grant

    2010-06-01

    The nucleosynthesis of {sup 180}Ta has remained an unsolved problem and as its origin many nucleosynthesis mechanisms have been proposed. This isotope has the unique feature that the naturally occurring abundance of {sup 180}Ta is actually a meta-stable isomer (half-life of >=10{sup 15} yr), while the ground state is a 1{sup +} unstable state which beta-decays with a half-life of only 8.15 hr. We have made a new time-dependent calculation of {sup 180}Ta meta-stable isomer residual ratio after supernova neutrino-induced reactions. This residual isomer ratio is crucial for understanding the production and survival of this naturally occurring rare isotope. We have constructed a new model under temperature evolution after type II supernova explosion. We include the explicit linking between the isomer and all known excited states and found that the residual ratio is insensitive to astrophysical parameters such as neutrino energy spectrum, explosion energy, decay time constant. We find that the explicit time evolution of the synthesis of {sup 180}Ta avoids the overproduction relative to {sup 138}La for a neutrino process neutrino temperature of 4 MeV.

  16. Topo-optical reactions for the identification of O-acyl sugars in amyloid deposits.

    PubMed

    Richter, Susann; Makovitzky, Josef

    2009-01-01

    The aldehyde bisulfite toluidine blue (ABT) reaction with former saponification (KOH-ABT) and periodic acid-borohydride reduction-saponification (PB-KOH-ABT) were applied to sections of human amyloid deposits in the respiratory tract. The saponification-induced increase in ABT-reactivity was confined to the presence of O-acyl sugars associated with the amyloid fibrils. The anisotropic and metachromatic effect in the ABT and KOH-ABT reaction was reduced in the corresponding PB-KOH-ABT reaction, a difference attributed to the removal of staining due to neutral carbohydrate residues. Since the periodic acid-borohydride reduction abolishes all pre-existing ABT-reactivity of neutral sugar vicinal diols, the isolated KOH-effect could be shown using the PB-KOH-ABT reaction. By application of this sequence, the problem identifying small quantities of O-acyl sugars was solved. It is suggested that the KOH-effect depends upon the removal of O-acyl substituents located on the polyhydroxy side chain (C7, C8, C9) of sialic acid residues. An advantage of such topo-optical reactions over biochemical techniques is the exact localization of O-acyl sugars in tissue sites. By means of the KOH-ABT and PB-KOH-ABT reactions we have demonstrated, for the first time, that O-acyl sugars occur within amyloid deposits.

  17. Young Children's Reports of when Learning Occurred

    ERIC Educational Resources Information Center

    Tang, Connie M.; Bartsch, Karen; Nunez, Narina

    2007-01-01

    This study investigated young children's reports of when learning occurred. A total of 96 4-, 5-, and 6-year-olds were recruited from suburban preschools and elementary schools. The children learned an animal fact and a body movement. A week later, children learned another animal fact and another body movement and then answered questions about…

  18. Naturally occurring iridoids. A review, part 1.

    PubMed

    Dinda, Biswanath; Debnath, Sudhan; Harigaya, Yoshihiro

    2007-02-01

    A compilation of new naturally occurring iridoid glycosides, iridoid aglycones, iridoid derivatives and bis-iridoids reported during 1994-2005 is provided with available physical and spectral data: mp, [alpha]D, UV, IR, 1H- and 13C-NMR as well as natural source with family and references. 418 compounds with 202 references are cited.

  19. Phonetic Recalibration Only Occurs in Speech Mode

    ERIC Educational Resources Information Center

    Vroomen, Jean; Baart, Martijn

    2009-01-01

    Upon hearing an ambiguous speech sound dubbed onto lipread speech, listeners adjust their phonetic categories in accordance with the lipread information (recalibration) that tells what the phoneme should be. Here we used sine wave speech (SWS) to show that this tuning effect occurs if the SWS sounds are perceived as speech, but not if the sounds…

  20. Preferential flow occurs in unsaturated conditions

    USGS Publications Warehouse

    Nimmo, John R.

    2012-01-01

    Because it commonly generates high-speed, high-volume flow with minimal exposure to solid earth materials, preferential flow in the unsaturated zone is a dominant influence in many problems of infiltration, recharge, contaminant transport, and ecohydrology. By definition, preferential flow occurs in a portion of a medium – that is, a preferred part, whether a pathway, pore, or macroscopic subvolume. There are many possible classification schemes, but usual consideration of preferential flow includes macropore or fracture flow, funneled flow determined by macroscale heterogeneities, and fingered flow determined by hydraulic instability rather than intrinsic heterogeneity. That preferential flow is spatially concentrated associates it with other characteristics that are typical, although not defining: it tends to be unusually fast, to transport high fluxes, and to occur with hydraulic disequilibrium within the medium. It also has a tendency to occur in association with large conduits and high water content, although these are less universal than is commonly assumed. Predictive unsaturated-zone flow models in common use employ several different criteria for when and where preferential flow occurs, almost always requiring a nearly saturated medium. A threshold to be exceeded may be specified in terms of the following (i) water content; (ii) matric potential, typically a value high enough to cause capillary filling in a macropore of minimum size; (iii) infiltration capacity or other indication of incipient surface ponding; or (iv) other conditions related to total filling of certain pores. Yet preferential flow does occur without meeting these criteria. My purpose in this commentary is to point out important exceptions and implications of ignoring them. Some of these pertain mainly to macropore flow, others to fingered or funneled flow, and others to combined or undifferentiated flow modes.

  1. A noncanonical function of sortase enables site-specific conjugation of small molecules to lysine residues in proteins.

    PubMed

    Bellucci, Joseph J; Bhattacharyya, Jayanta; Chilkoti, Ashutosh

    2015-01-01

    We provide the first demonstration that isopeptide ligation, a noncanonical activity of the enzyme sortase A, can be used to modify recombinant proteins. This reaction was used in vitro to conjugate small molecules to a peptide, an engineered targeting protein, and a full-length monoclonal antibody with an exquisite level of control over the site of conjugation. Attachment to the protein substrate occurred exclusively through isopeptide bonds at a lysine ε-amino group within a specific amino acid sequence. This reaction allows more than one molecule to be site-specifically conjugated to a protein at internal sites, thereby overcoming significant limitations of the canonical native peptide ligation reaction catalyzed by sortase A. Our method provides a unique chemical ligation procedure that is orthogonal to existing methods, supplying a new method to site-specifically modify lysine residues that will be a valuable addition to the protein conjugation toolbox. PMID:25363491

  2. A non-canonical function of sortase enables site-specific conjugation of small molecules to lysine residues in proteins**

    PubMed Central

    Bellucci, Joseph J.; Bhattacharyya, Jayanta

    2014-01-01

    We provide the first demonstration that isopeptide ligation, a non-canonical activity of the enzyme sortase A, can be used to modify recombinant proteins. This reaction was used in vitro to conjugate small molecules to a peptide, an engineered targeting protein, and a full-length monoclonal antibody with an exquisite level of control over the site of conjugation. Attachment to the protein substrate occurred exclusively through isopeptide bonds at a lysine ε-amino group within a specific amino acid sequence. This reaction allows more than one molecule to be site-specifically conjugated to a protein at internal sites, thereby overcoming significant limitations of the canonical native peptide ligation reaction catalyzed by sortase A. Our method provides a unique chemical ligation procedure that is orthogonal to existing methods, supplying a new method to site-specifically modify lysine residues that will be a valuable addition to the protein conjugation toolbox. PMID:25363491

  3. Experimental Demonstrations in Teaching Chemical Reactions.

    ERIC Educational Resources Information Center

    Hugerat, Muhamad; Basheer, Sobhi

    2001-01-01

    Presents demonstrations of chemical reactions by employing different features of various compounds that can be altered after a chemical change occurs. Experimental activities include para- and dia-magnetism in chemical reactions, aluminum reaction with base, reaction of acid with carbonates, use of electrochemical cells for demonstrating chemical…

  4. Treatment of vacuum residues in hydroconversion conditions

    NASA Astrophysics Data System (ADS)

    León, A. Y.; Mendoza, D. L.; Espinosa, J. O.; Laverde, D.

    2016-02-01

    In this paper the use of a liquid homogeneous catalyst has been studied in reactivity vacuum residues by hydroconversion under different conditions. To cover a wide range of compositions, six (6) vacuum residues were selected from crude mixtures. Hydroconversion test were performed in batch reactor with hydrogen atmosphere at about 2000psi in a temperature range between 430 and 480°C. The results allowed to establish that the reactivity hydroconversion conditions about coke formation is higher in vacuum residues with higher content of resins and asphaltenes. The reaction conditions promote distillate formation, however, with increasing stringency conditions, the distillate yield decreases due to distillate transformation into temperature range 430 and 460°C compared to the tests performed without catalyst demonstrating that the use of homogeneous catalyst is an alternative to treating vacuum residues and results are satisfactory in the conversion processes. Finally, predictive expressions have been developed in the formation of products depending on the conditions of temperature and physicochemical properties of processed vacuum residue.

  5. Biosynthesis of D-alanyl-lipoteichoic acid by Lactobacillus casei: interchain transacylation of D-alanyl ester residues

    SciTech Connect

    Childs, W.C. 3d.; Taron, D.J.; Neuhaus, F.C.

    1985-06-01

    Lipoteichoic acid (LTA) from Lactobacillus casei contains poly(glycerophosphate) substituted with D-alanyl ester residues. The distribution of these residues in the in vitro-synthesized polymer is uniform. Esterification of LTA with D-alanine may occur in one of two modes: (i) addition at random or (ii) addition at a defined locus in the poly(glycerophosphate) chain followed by redistribution of the ester residues. A time-dependent transacylation of these residues from D-(/sup 14/C)alanyl-lipophilic LTA to hydrophilic acceptor was observed. The hydrophilic acceptor was characterized as D-alanyl-hydrophilic LTA. This transacylation requires neither ATP nor the D-alanine incorporation system, i.e., the D-alanine activating enzyme and D-alanine:membrane acceptor ligase. No evidence for an enzyme-catalyzed transacylation reaction was observed. The authors propose that this process of transacylation may be responsible for the redistribution of D-alanyl residues after esterification to the poly(glycerophosphate). As a result, it is difficult to distinguish between these proposed modes of addition.

  6. Translated chemical reaction networks.

    PubMed

    Johnston, Matthew D

    2014-05-01

    Many biochemical and industrial applications involve complicated networks of simultaneously occurring chemical reactions. Under the assumption of mass action kinetics, the dynamics of these chemical reaction networks are governed by systems of polynomial ordinary differential equations. The steady states of these mass action systems have been analyzed via a variety of techniques, including stoichiometric network analysis, deficiency theory, and algebraic techniques (e.g., Gröbner bases). In this paper, we present a novel method for characterizing the steady states of mass action systems. Our method explicitly links a network's capacity to permit a particular class of steady states, called toric steady states, to topological properties of a generalized network called a translated chemical reaction network. These networks share their reaction vectors with their source network but are permitted to have different complex stoichiometries and different network topologies. We apply the results to examples drawn from the biochemical literature.

  7. Could a megaquake occur in the Himalayas?

    NASA Astrophysics Data System (ADS)

    Balcerak, Ernie

    2011-12-01

    GPS measurements of crustal deformation are showing that a magnitude 9 earthquake could occur in the Himalayas. Roger Bilham of the University of Colorado at Boulder reported at the AGU Fall Meeting that the region, known to be seismically active, could produce a much larger earthquake than previously thought. Bilham and colleagues used GPS to monitor rates of crustal deformation in the Himalayas. They found that the potential rupture zone is larger than scientists had believed—the region where strain is building is twice as wide as expected. Previous estimates, which were based on the historical earthquake record, suggested that the largest earthquake that would occur in the region would have a magnitude in the low 8s. Such an earthquake could be devastating—the Kashmir valley region alone is home to 6 million people.

  8. Young children's reports of when learning occurred.

    PubMed

    Tang, Connie M; Bartsch, Karen; Nunez, Narina

    2007-06-01

    This study investigated young children's reports of when learning occurred. A total of 96 4-, 5-, and 6-year-olds were recruited from suburban preschools and elementary schools. The children learned an animal fact and a body movement. A week later, children learned another animal fact and another body movement and then answered questions about when the different learning events occurred. Responses of children who responded correctly to control questions about time supported the hypothesis that temporal distance questions would elicit more correct responses than would temporal location questions. Partial support was also found for the hypothesis that behavior learning would generate more correct reports than would fact learning. Implications for characterizations of children's developing understanding of knowledge and for applications of those characterizations in education and eyewitness testimony are discussed. PMID:17346740

  9. Synthesis of Naturally Occurring Tropones and Tropolones

    PubMed Central

    Liu, Na; Song, Wangze; Schienebeck, Casi M.; Zhang, Min; Tang, Weiping

    2014-01-01

    Tropones and tropolones are an important class of seven-membered non-benzenoid aromatic compounds. They can be prepared directly by oxidation of seven-membered rings. They can also be derived from cyclization or cycloaddition of appropriate precursors followed by elimination or rearrangement. This review discusses the types of naturally occurring tropones and tropolones and outlines important methods developed for the synthesis of tropone and tropolone natural products. PMID:25400298

  10. spin pumping occurred under nonlinear spin precession

    NASA Astrophysics Data System (ADS)

    Zhou, Hengan; Fan, Xiaolong; Ma, Li; Zhou, Shiming; Xue, Desheng

    Spin pumping occurs when a pure-spin current is injected into a normal metal thin layer by an adjacent ferromagnetic metal layer undergoing ferromagnetic resonance, which can be understood as the inverse effect of spin torque, and gives access to the physics of magnetization dynamics and damping. An interesting question is that whether spin pumping occurring under nonlinear spin dynamics would differ from linear case. It is known that nonlinear spin dynamics differ distinctly from linear response, a variety of amplitude dependent nonlinear effect would present. It has been found that for spin precession angle above a few degrees, nonlinear damping term would present and dominated the dynamic energy/spin-moment dissipation. Since spin pumping are closely related to the damping process, it is interesting to ask whether the nonlinear damping term could be involved in spin pumping process. We studied the spin pumping effect occurring under nonlinear spin precession. A device which is a Pt/YIG microstrip coupled with coplanar waveguide was used. High power excitation resulted in spin precession entering in a nonlinear regime. Foldover resonance lineshape and nonlinear damping have been observed. Based on those nonlinear effects, we determined the values of the precession cone angles, and the maximum cone angle can reach a values as high as 21.5 degrees. We found that even in nonlinear regime, spin pumping is still linear, which means the nonlinear damping and foldover would not affect spin pumping process.

  11. Effect of residual ozone on membrane fouling reduction in ozone resisting microfiltration (MF) membrane system.

    PubMed

    Lee, S; Jang, N; Watanabe, Y

    2004-01-01

    The effect of residual ozone on reducing the membrane fouling was investigated using ozone resisting microfiltration membrane. It was found out that the fouling was reduced effectively by maintaining residual ozone in the membrane module. To clarify the reason why the residual ozone reduces the membrane fouling, research was focused on the molecular degradation reaction and particle destabilization reaction induced by residual ozone. The major reason of membrane fouling reduction was attributed to the reduction of reversible resistance induced by the cake layer. The reversible resistance was reduced due to degradation of organic substances in the cake layer. In addition to degradation reaction, the increase of fouling particle size due to residual ozone in the cake layer is another important process for fouling reduction. This effect has been referred to as ozone-induced destabilization reaction. The calcium present in the raw water influenced this reaction. The increase of fouling particles size improves the filterability through the cake layer and backwashing efficiency.

  12. Spectrophotometric method for determination of phosphine residues in cashew kernels.

    PubMed

    Rangaswamy, J R

    1988-01-01

    A spectrophotometric method reported for determination of phosphine (PH3) residues in wheat has been extended for determination of these residues in cashew kernels. Unlike the spectrum for wheat, the spectrum of PH3 residue-AgNO3 chromophore from cashew kernels does not show an absorption maximum at 400 nm; nevertheless, reading the absorbance at 400 nm afforded good recoveries of 90-98%. No interference occurred from crop materials, and crop controls showed low absorbance; the method can be applied for determinations as low as 0.01 ppm PH3 residue in cashew kernels.

  13. System and method for measuring residual stress

    DOEpatents

    Prime, Michael B.

    2002-01-01

    The present invention is a method and system for determining the residual stress within an elastic object. In the method, an elastic object is cut along a path having a known configuration. The cut creates a portion of the object having a new free surface. The free surface then deforms to a contour which is different from the path. Next, the contour is measured to determine how much deformation has occurred across the new free surface. Points defining the contour are collected in an empirical data set. The portion of the object is then modeled in a computer simulator. The points in the empirical data set are entered into the computer simulator. The computer simulator then calculates the residual stress along the path which caused the points within the object to move to the positions measured in the empirical data set. The calculated residual stress is then presented in a useful format to an analyst.

  14. Naturally occurring products in cancer therapy

    PubMed Central

    Rajesh, E.; Sankari, Leena S.; Malathi, L.; Krupaa, Jayasri R.

    2015-01-01

    Natural products have been used for the treatment of various diseases and are becoming an important research area for drug discovery. These products, especially phytochemicals have been extensively studies and have exhibited anti-carcinogenic activities by interfering with the initiation, development and progression of cancer through the modulation of various mechanisms including cellular proliferation, differentiation, apoptosis, angiogenesis, and metastasis. This concept is gaining attention because it is a cost-effective alternative to cancer treatment. In this article, we have discussed some of the naturally occurring products used in cancer treatment. PMID:26015704

  15. Naturally occurring antimicrobials for minimally processed foods.

    PubMed

    Davidson, P Michael; Critzer, Faith J; Taylor, T Matthew

    2013-01-01

    Natural antimicrobials are gaining increased interest from researchers and food manufacturers alike seeking to discover label-friendly alternatives to the widely implemented synthetic compounds. Naturally occurring antimicrobials can be applied directly to food to protect food quality, extend food shelf life by inhibiting or inactivating spoilage microorganisms, and improve food safety by inhibiting or inactivating food-borne pathogens. There are a great number of natural antimicrobials derived from animal, plant, and microbial sources. This manuscript reviews their efficacy against spoilage and pathogenic organisms, their methods of evaluation, and their application in various foods as well as the development of novel delivery systems and incorporation with other hurdles.

  16. Quinoprotein-catalysed reactions.

    PubMed Central

    Anthony, C

    1996-01-01

    This review is concerned with the structure and function of the quinoprotein enzymes, sometimes called quinoenzymes. These have prosthetic groups containing quinones, the name thus being analogous to the flavoproteins containing flavin prosthetic groups. Pyrrolo-quinoline quinone (PQQ) is non-covalently attached, whereas tryptophan tryptophylquinone (TTQ), topaquinone (TPQ) and lysine tyrosylquinone (LTQ) are derived from amino acid residues in the backbone of the enzymes. The mechanisms of the quinoproteins are reviewed and related to their recently determined three-dimensional structures. As expected, the quinone structures in the prosthetic groups play important roles in the mechanisms. A second common feature is the presence of a catalytic base (aspartate) at the active site which initiates the reactions by abstracting a proton from the substrate, and it is likely to be involved in multiple reactions in the mechanism. A third common feature of these enzymes is that the first part of the reaction produces a reduced prosthetic group; this part of the mechanism is fairly well understood. This is followed by an oxidative phase involving electron transfer reactions which remain poorly understood. In both types of dehydrogenase (containing PQQ and TTQ), electrons must pass from the reduced prosthetic group to redox centres in a second recipient protein (or protein domain), whereas in amine oxidases (containing TPQ or LTQ), electrons must be transferred to molecular oxygen by way of a redox-active copper ion in the protein. PMID:9003352

  17. Depleting methyl bromide residues in soil by reaction with bases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the...

  18. [Cumulative exposure to pesticide residues in food].

    PubMed

    Kostka, Grazyna; Urbanek-Olejnik, Katarzyna; Liszewska, Monika

    2011-01-01

    The results of food monitoring studies indicate that humans are constantly exposed to residues ofplant protection products (pesticides) in marketed food products. Hence, assessment of the risk to consumers associated with the consumption of products containing residues of the active substances of pesticides is a key stage in both the registration of pesticides and official control of foodstuffs. However there are frequent cases of exposure not only to individual active substances but also to mixtures of pesticide residues. These levels are usually low, below of effective action, and interaction such as synergism orpotentiation is not expected to occur At the same time, literature data indicate that for mixtures sharing a common MOA (Mode of Action/Mechanism of Action), the probability of additive effects is high, even after adjusting for the low levels of the mixed pesticide residues present. Accordingly, health risk assessment for consumers exposed to such mixtures (cumulative/aggregate risk) has become an issue of topical importance. EU-level initiatives regarding the development of appropriate methodology for the estimation of cumulative/aggregate risk have brought about considerable progress in this area. The article discusses various aspects of estimation of cumulative risk for consumers associated with exposure to mixtures of pesticide residues in food.

  19. Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides

    PubMed Central

    Bertran-Vicente, Jordi; Penkert, Martin; Nieto-Garcia, Olaia; Jeckelmann, Jean-Marc; Schmieder, Peter; Krause, Eberhard; Hackenberger, Christian P. R.

    2016-01-01

    In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys phosphorylation site in IICBGlc, which is known to be involved in the carbohydrate uptake from the bacterial phosphotransferase system (PTS). This new chemical and analytical approach finally allows further investigating the functions and significance of Cys phosphorylation in a wide range of crucial cellular processes. PMID:27586301

  20. Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides.

    PubMed

    Bertran-Vicente, Jordi; Penkert, Martin; Nieto-Garcia, Olaia; Jeckelmann, Jean-Marc; Schmieder, Peter; Krause, Eberhard; Hackenberger, Christian P R

    2016-01-01

    In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys phosphorylation site in IICB(Glc), which is known to be involved in the carbohydrate uptake from the bacterial phosphotransferase system (PTS). This new chemical and analytical approach finally allows further investigating the functions and significance of Cys phosphorylation in a wide range of crucial cellular processes. PMID:27586301

  1. Single‐residue posttranslational modification sites at the N‐terminus, C‐terminus or in‐between: To be or not to be exposed for enzyme access

    PubMed Central

    Sirota, Fernanda L.; Maurer‐Stroh, Sebastian; Eisenhaber, Birgit

    2015-01-01

    Many protein posttranslational modifications (PTMs) are the result of an enzymatic reaction. The modifying enzyme has to recognize the substrate protein's sequence motif containing the residue(s) to be modified; thus, the enzyme's catalytic cleft engulfs these residue(s) and the respective sequence environment. This residue accessibility condition principally limits the range where enzymatic PTMs can occur in the protein sequence. Non‐globular, flexible, intrinsically disordered segments or large loops/accessible long side chains should be preferred whereas residues buried in the core of structures should be void of what we call canonical, enzyme‐generated PTMs. We investigate whether PTM sites annotated in UniProtKB (with MOD_RES/LIPID keys) are situated within sequence ranges that can be mapped to known 3D structures. We find that N‐ or C‐termini harbor essentially exclusively canonical PTMs. We also find that the overwhelming majority of all other PTMs are also canonical though, later in the protein's life cycle, the PTM sites can become buried due to complex formation. Among the remaining cases, some can be explained (i) with autocatalysis, (ii) with modification before folding or after temporary unfolding, or (iii) as products of interaction with small, diffusible reactants. Others require further research how these PTMs are mechanistically generated in vivo. PMID:26038108

  2. Single-residue posttranslational modification sites at the N-terminus, C-terminus or in-between: To be or not to be exposed for enzyme access.

    PubMed

    Sirota, Fernanda L; Maurer-Stroh, Sebastian; Eisenhaber, Birgit; Eisenhaber, Frank

    2015-07-01

    Many protein posttranslational modifications (PTMs) are the result of an enzymatic reaction. The modifying enzyme has to recognize the substrate protein's sequence motif containing the residue(s) to be modified; thus, the enzyme's catalytic cleft engulfs these residue(s) and the respective sequence environment. This residue accessibility condition principally limits the range where enzymatic PTMs can occur in the protein sequence. Non-globular, flexible, intrinsically disordered segments or large loops/accessible long side chains should be preferred whereas residues buried in the core of structures should be void of what we call canonical, enzyme-generated PTMs. We investigate whether PTM sites annotated in UniProtKB (with MOD_RES/LIPID keys) are situated within sequence ranges that can be mapped to known 3D structures. We find that N- or C-termini harbor essentially exclusively canonical PTMs. We also find that the overwhelming majority of all other PTMs are also canonical though, later in the protein's life cycle, the PTM sites can become buried due to complex formation. Among the remaining cases, some can be explained (i) with autocatalysis, (ii) with modification before folding or after temporary unfolding, or (iii) as products of interaction with small, diffusible reactants. Others require further research how these PTMs are mechanistically generated in vivo. PMID:26038108

  3. Atypical Mycobacterium furunculosis occurring after pedicures.

    PubMed

    Redbord, Kelley Pagliai; Shearer, David A; Gloster, Hugh; Younger, Bruce; Connelly, Beverly L; Kindel, Susan E; Lucky, Anne W

    2006-03-01

    Mycobacterium fortuitum complex are rapidly-growing nontuberculous mycobacteria found ubiquitously in the environment including, water, soil, dust, and biofilms. M fortuitum has been reported to cause skin and soft-tissue infections in association with nail salon footbath use during pedicures. Four cases of M fortuitum complex furunculosis are reported that occurred after pedicures in the Cincinnati, Ohio/Northern Kentucky area. Dermatologists and clinicians should consider mycobacterial infections from the M fortuitum complex when patients present with nonhealing furuncles on the lower legs and should inquire about recent pedicures. Early recognition and institution of appropriate therapy are critical. Public health measures should be explored to protect against such infections, given the recent popularity of the nail care industry.

  4. Residual stresses in material processing

    SciTech Connect

    Kozaczek, K.J.; Watkins, T.R.; Hubbard, C.R.; Wang, Xun-Li; Spooner, S.

    1994-09-01

    Material manufacturing processes often introduce residual stresses into the product. The residual stresses affect the properties of the material and often are detrimental. Therefore, the distribution and magnitude of residual stresses in the final product are usually an important factor in manufacturing process optimization or component life prediction. The present paper briefly discusses the causes of residual stresses. It then adresses the direct, nondestructive methods of residual stress measurement by X-ray and neutron diffraction. Examples are presented to demonstrate the importance of residual stress measurement in machining and joining operations.

  5. 40 CFR 1065.705 - Residual and intermediate residual fuel.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... specifications for fuels meeting the definition of residual fuel in 40 CFR 80.2, including fuels marketed as... for Residual Fuel Characteristic Unit Category ISO-F- RMA 30 RMB 30 RMD 80 RME 180 RMF 180 RMG 380...

  6. 40 CFR 1065.705 - Residual and intermediate residual fuel.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... specifications for fuels meeting the definition of residual fuel in 40 CFR 80.2, including fuels marketed as... for Residual Fuel Characteristic Unit Category ISO-F- RMA 30 RMB 30 RMD 80 RME 180 RMF 180 RMG 380...

  7. Polymerase chain reaction detection of naturally occurring Campylobacter in commercial broiler chicken embryos.

    PubMed

    Hiett, K L; Cox, N A; Rothrock, M J

    2013-04-01

    Campylobacter, a foodborne pathogen closely associated with poultry, is recognized as a leading bacterial etiologic agent of human gastroenteritis in the United States. In this investigation, 2 trials were performed where tissues from 7-, 14/15-, and 19-d-old commercial broiler chicken embryos were tested for the presence of Campylobacter using both culturing methodology and PCR. Conventional culturing methods failed to detect Campylobacter from any samples tested during this investigation. Using a set of primers specific for the Campylobacter flagellinA short variable region (flaA SVR), Campylobacter DNA was amplified in 100, 80, and 100% of gastrointestinal tracts from 7-, 15-, and 19-d-old embryos, respectively, in the first trial. Similarly, Campylobacter DNA was detected in 100, 70, and 60% of gastrointestinal tracts of 7-, 14-, and 18-d-old embryos, respectively, in the second trial. In both trials, yolk sac, albumin, and liver/gallbladder samples from 19-d-old embryos all failed to produce amplicons indicative of Campylobacter DNA. Subsequent DNA sequence analyses of the flaA SVR PCR products were consistent with the amplicon arising from Campylobacter. Although a determination of whether the Campylobacter was living or dead within the embryos could not be made, these results demonstrate that Campylobacter-specific DNA is present within the gastrointestinal tract of broiler chicken embryos; however, the means by which it is present and the relative contribution to subsequent Campylobacter contamination of poultry flocks requires further investigation.

  8. Cosmetic tattoo pigment reaction.

    PubMed

    Greywal, Tanya; Cohen, Philip R

    2016-01-01

    BackgroundCutaneous reactions to tattoos are most commonly granulomatous or lichenoid.PurposeWe describe a woman who developed a lymphocytic reaction following a cosmetic tattoo procedure with black dye. The reaction occurred not only at the site of the tattoos (eyebrows and eyelash lines), but also in non-tattooed skin (bilateral malar cheeks).Methods and MaterialsWe reviewed PubMed for the following terms: cosmetic, dye, granuloma, granulomatous, lichenoid, lymphocytic, perivascular, pigment, pseudolymphoma, reaction, and tattoo. We also reviewed papers containing these terms and their references.ResultsHistopathologic examination of the left eyebrow and left cheek punch biopsies showed predominantly a perivascular lymphocytic reaction secondary to exogenous tattoo pigment.ConclusionsPerivascular lymphocytic reaction is an uncommonly described complication of tattooing. Our patient had an atypical presentation since she had no prior tattoos, became symptomatic only a few days after the procedure, reacted to black dye, and involved skin both within and outside the confines of the tattoos. Her symptoms and lesions resolved after treatment with systemic and topical corticosteroids and oral antihistamines. PMID:27617722

  9. SRC Residual fuel oils

    DOEpatents

    Tewari, Krishna C.; Foster, Edward P.

    1985-01-01

    Coal solids (SRC) and distillate oils are combined to afford single-phase blends of residual oils which have utility as fuel oils substitutes. The components are combined on the basis of their respective polarities, that is, on the basis of their heteroatom content, to assure complete solubilization of SRC. The resulting composition is a fuel oil blend which retains its stability and homogeneity over the long term.

  10. Water treatment residuals

    SciTech Connect

    Billings, C.H.

    1994-01-01

    Solutions to an environmental problem often create other environmental problems. That surely is the case in the water supply field. By providing new or expanded water treatment systems to comply with the maximum contaminant levels and treatment mandates of the Safe Drinking Water Act, water purveyors are generating large volumes of residuals that must be managed, ultimately disposed of, or recycled. Numerous federal, state, and local laws govern the management, transport, disposal, and recycling of wastes produced by water treatment systems. Because these laws can result in exorbitant waste disposal costs, restricting some projects entirely, water suppliers need to consider residual disposal early in the siting, selection, and design of treatment projects. To inform water suppliers about residual laws, AWWA commissioned a study published as a Water Industry Technical Action Fund report. In addition to identifying and describing applicable laws at the federal level and in six of the states, the study revealed a series of findings as to the consequences of those laws to water suppliers. This article is a brief overview of the findings of the report.

  11. Introduction to naturally occurring radioactive material

    SciTech Connect

    Egidi, P.

    1997-08-01

    Naturally occurring radioactive material (NORM) is everywhere; we are exposed to it every day. It is found in our bodies, the food we eat, the places where we live and work, and in products we use. We are also bathed in a sea of natural radiation coming from the sun and deep space. Living systems have adapted to these levels of radiation and radioactivity. But some industrial practices involving natural resources concentrate these radionuclides to a degree that they may pose risk to humans and the environment if they are not controlled. Other activities, such as flying at high altitudes, expose us to elevated levels of NORM. This session will concentrate on diffuse sources of technologically-enhanced (TE) NORM, which are generally large-volume, low-activity waste streams produced by industries such as mineral mining, ore benefication, production of phosphate Fertilizers, water treatment and purification, and oil and gas production. The majority of radionuclides in TENORM are found in the uranium and thorium decay chains. Radium and its subsequent decay products (radon) are the principal radionuclides used in characterizing the redistribution of TENORM in the environment by human activity. We will briefly review other radionuclides occurring in nature (potassium and rubidium) that contribute primarily to background doses. TENORM is found in many waste streams; for example, scrap metal, sludges, slags, fluids, and is being discovered in industries traditionally not thought of as affected by radionuclide contamination. Not only the forms and volumes, but the levels of radioactivity in TENORM vary. Current discussions about the validity of the linear no dose threshold theory are central to the TENORM issue. TENORM is not regulated by the Atomic Energy Act or other Federal regulations. Control and regulation of TENORM is not consistent from industry to industry nor from state to state. Proposed regulations are moving from concentration-based standards to dose

  12. Epigenetic Mechanisms in Commonly Occurring Cancers

    PubMed Central

    2012-01-01

    Cancer is a collection of very complex diseases that share many traits while differing in many ways as well. This makes a universal cure difficult to attain, and it highlights the importance of understanding each type of cancer at a molecular level. Although many strides have been made in identifying the genetic causes for some cancers, we now understand that simple changes in the primary DNA sequence cannot explain the many steps that are necessary to turn a normal cell into a rouge cancer cell. In recent years, some research has shifted to focusing on detailing epigenetic contributions to the development and progression of cancer. These changes occur apart from primary genomic sequences and include DNA methylation, histone modifications, and miRNA expression. Since these epigenetic modifications are reversible, drugs targeting epigenetic changes are becoming more common in clinical settings. Daily discoveries elucidating these complex epigenetic processes are leading to advances in the field of cancer research. These advances, however, come at a rapid and often overwhelming pace. This review specifically summarizes the main epigenetic mechanisms currently documented in solid tumors common in the United States and Europe. PMID:22519822

  13. Neonatal Adaptation Issues After Maternal Exposure to Prescription Drugs: Withdrawal Syndromes and Residual Pharmacological Effects.

    PubMed

    Convertino, Irma; Sansone, Alice Capogrosso; Marino, Alessandra; Galiulo, Maria T; Mantarro, Stefania; Antonioli, Luca; Fornai, Matteo; Blandizzi, Corrado; Tuccori, Marco

    2016-10-01

    Exposure to drugs during pregnancy has the potential to harm offspring. Teratogenic effects are the most feared adverse outcomes in newborns; however, a wide spectrum of less known, usually reversible and often acute, neonatal adverse events can also occur due to drug intake by mothers during pregnancy, particularly in close proximity to delivery. This narrative review is aimed at the description of drugs and drug classes for which licit maternal use in the predelivery period has been associated with neonatal non-teratogenic disorders. For each drug class, epidemiology, clinical features, biological mechanism and management of these adverse reactions have been discussed in detail. Although these adverse reactions have been described mainly for substances used illicitly for recreational purposes, several prescription drugs have also been involved; these include mainly psychotropic medications such as opioids, antidepressants, antiepileptics and antipsychotics. These effects can be partly explained by withdrawal syndromes (defined also as 'neonatal abstinence syndrome') caused by the delivery-related discontinuation of the drug disposition from the mother to the fetus, with symptoms that may include feeding disorders, tremors, irritability, hypotonia/hypertonia, vomiting and persistent crying, occurring a few hours to 1 month after delivery. Otherwise, neonatal neurological and behavioral effects can also be caused by a residual pharmacological effect due to an accumulation of the drug in the blood and tissues of the newborn, with various symptoms related to the toxic effects of the specific drug class, usually developing a few hours after birth. With few exceptions, validated protocols for the assessment and management of withdrawal or residual pharmacological effects of these drugs in neonates are often lacking or incomplete. Spontaneous reporting of these adverse reactions seems limited, although it might represent a useful tool for improving our knowledge about

  14. Structural Insights into Intermediate Steps in the Sir2 Deacetylation Reaction

    SciTech Connect

    Hawse, William F.; Hoff, Kevin G.; Fatkins, David G.; Daines, Alison; Zubkova, Olga V.; Schramm, Vern L.; Zheng, Weiping; Wolberger, Cynthia

    2010-07-22

    Sirtuin enzymes comprise a unique class of NAD{sup +}-dependent protein deacetylases. Although structures of many sirtuin complexes have been determined, structural resolution of intermediate chemical steps are needed to understand the deacetylation mechanism. We report crystal structures of the bacterial sirtuin, Sir2Tm, in complex with an S-alkylamidate intermediate, analogous to the naturally occurring O-alkylamidate intermediate, and a Sir2Tm ternary complex containing a dissociated NAD{sup +} analog and acetylated peptide. The structures and biochemical studies reveal critical roles for the invariant active site histidine in positioning the reaction intermediate, and for a conserved phenylalanine residue in shielding reaction intermediates from base exchange with nicotinamide. The new structural and biochemical studies provide key mechanistic insight into intermediate steps of the Sir2 deacetylation reaction.

  15. Proton Mobility in b2 Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides

    NASA Astrophysics Data System (ADS)

    Nelson, Carissa R.; Abutokaikah, Maha T.; Harrison, Alex G.; Bythell, Benjamin J.

    2016-03-01

    A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting.

  16. Characterisation of pleural inflammation occurring after primary spontaneous pneumothorax.

    PubMed

    De Smedt, A; Vanderlinden, E; Demanet, C; De Waele, M; Goossens, A; Noppen, M

    2004-06-01

    The aim of this study was to examine the inflammatory reaction occurring in the pleural space of patients suffering from primary spontaneous pneumothorax (PSP) using pleural lavage, which was performed in patients with PSP and in healthy control subjects (essential hyperhidrosis patients undergoing thoracoscopy for sympathicolysis treatment). Cellular and solute composition of lavage fluid, peripheral blood and parietal pleural biopsies were analysed. PSP lavage fluid showed an increase in all differentiated leucocytes, but most strikingly eosinophils and neutrophils. In the blood of patients with PSP, the total number of leucocytes and the absolute number of eosinophils, neutrophils and monocytes were also significantly increased. The time in which air was present in the pleural space was positively correlated with the increase of eosinophils in lavage fluid, parietal pleura and blood. Eosinophilic cationic protein was elevated after PSP and strongly correlated with the absolute number of lavage eosinophils. Chemo and cytokine analysis in lavage fluid showed differences in concentrations of interleukin (IL)-5, IL-6, IL-8, IL-12p40, tumour necrosis factor-alpha and RANTES, but not of eotaxin. Surprisingly, high levels of lipopolysaccharide binding protein were also measured. Primary spontaneous pnumothorax is associated with a substantial pleural inflammatory reaction. The authors hypothesise that mechanical stretch factors, lipopolysaccharide binding protein/lipopolysaccharide complexes or other environmental components trigger pleural inflammation after primary spontaneous pnumothorax. PMID:15219004

  17. Naturally occurring secoiridoids and bioactivity of naturally occurring iridoids and secoiridoids. A review, part 2.

    PubMed

    Dinda, Biswanath; Debnath, Sudhan; Harigaya, Yoshihiro

    2007-05-01

    Naturally occurring new secoiridoids published during 1994-2005 are reviewed with available physical and spectral data: mp, [alpha](D), UV, IR, (1)H- and (13)C-NMR and plant source. The works on biological and pharmacological activity of naturally occurring iridoids and secoiridoids reported during 1998-2005 are also reviewed. Bioactivities like antiallergic, antiarthritis, antibacterial, anticancer, anticoagulant, anticomplement, antifungal, antiinflammatory, antioxidative, antiprotozoal, antispasmodic, antiviral, immunomodulatory, neuroprotective, nerve growth factor potentiating and wound healing activities are highlighted.

  18. Differential dormancy of co-occurring copepods

    NASA Astrophysics Data System (ADS)

    Ohman, Mark D.; Drits, Aleksandr V.; Elizabeth Clarke, M.; Plourde, Stéphane

    1998-08-01

    Four species of planktonic calanoid copepods that co-occur in the California Current System ( Eucalanus californicus Johnson, Rhincalanus nasutus Giesbrecht, Calanus pacificus californicus Brodsky, and Metridia pacifica Brodsky) were investigated for evidence of seasonal dormancy in the San Diego Trough. Indices used to differentiate actively growing from dormant animals included developmental stage structure and vertical distribution; activity of aerobic metabolic enzymes (Citrate Synthase and the Electron Transfer System complex); investment in depot lipids (wax esters and triacylglycerols); in situ grazing activity from gut fluorescence; and egg production rates in simulated in situ conditions. None of the 4 species exhibited a canonical calanoid pattern of winter dormancy - i.e., synchronous developmental arrest as copepodid stage V, descent into deep waters, reduced metabolism, and lack of winter reproduction. Instead, Calanus pacificus californicus has a biphasic life history in this region, with an actively reproducing segment of the population in surface waters overlying a deep dormant segment in winter. Eucalanus californicus is dormant as both adult females and copepodid V's, although winter females respond relatively rapidly to elevated food and temperature conditions; they begin feeding and producing eggs within 2-3 days. Rhincalanus nasutus appears to enter dormancy as adult females, although the evidence is equivocal. Metridia pacifica shows no evidence of dormancy, with sustained active feeding, diel vertical migration behavior, and elevated activity of metabolic enzymes in December as well as in June. The four species also differ markedly in water content, classes of storage lipids, and specific activity of Citrate Synthase. These results suggest that copepod dormancy traits and structural composition reflect diverse adaptations to regional environmental conditions rather than a uniform, canonical series of traits that remain invariant among taxa

  19. Sundew adhesive: a naturally occurring hydrogel

    PubMed Central

    Huang, Yujian; Wang, Yongzhong; Sun, Leming; Agrawal, Richa; Zhang, Mingjun

    2015-01-01

    Bioadhesives have drawn increasing interest in recent years, owing to their eco-friendly, biocompatible and biodegradable nature. As a typical bioadhesive, sticky exudate observed on the stalked glands of sundew plants aids in the capture of insects and this viscoelastic adhesive has triggered extensive interests in revealing the implied adhesion mechanisms. Despite the significant progress that has been made, the structural traits of the sundew adhesive, especially the morphological characteristics in nanoscale, which may give rise to the viscous and elastic properties of this mucilage, remain unclear. Here, we show that the sundew adhesive is a naturally occurring hydrogel, consisting of nano-network architectures assembled with polysaccharides. The assembly process of the polysaccharides in this hydrogel is proposed to be driven by electrostatic interactions mediated with divalent cations. Negatively charged nanoparticles, with an average diameter of 231.9 ± 14.8 nm, are also obtained from this hydrogel and these nanoparticles are presumed to exert vital roles in the assembly of the nano-networks. Further characterization via atomic force microscopy indicates that the stretching deformation of the sundew adhesive is associated with the flexibility of its fibrous architectures. It is also observed that the adhesion strength of the sundew adhesive is susceptible to low temperatures. Both elasticity and adhesion strength of the sundew adhesive reduce in response to lowering the ambient temperature. The feasibility of applying sundew adhesive for tissue engineering is subsequently explored in this study. Results show that the fibrous scaffolds obtained from sundew adhesive are capable of increasing the adhesion of multiple types of cells, including fibroblast cells and smooth muscle cells, a property that results from the enhanced adsorption of serum proteins. In addition, in light of the weak cytotoxic activity exhibited by these scaffolds towards a variety of

  20. Diffusion control in an elementary protein folding reaction

    PubMed Central

    Jacob, Maik; Schindler, Thomas; Balbach, Jochen; Schmid, Franz X.

    1997-01-01

    The cold-shock protein CspB (from Bacillus subtilis), a very small protein of 67 residues, folds extremely fast in a reversible N ⇋ U two-state reaction. Both unfolding and refolding are strongly decelerated when the viscosity of the solvent is increased by adding ethylene glycol or sucrose. The folding of CspB thus seems to follow Kramers’ model for reactions in which the reactants must diffuse together. It indicates that the compaction of the protein chain occurs in the rate-limiting step of folding. Chain diffusion to a productively collapsed form and the crossing of a high energy barrier are thus tightly coupled in this folding reaction, and the measured reaction rate depends on both the diffusion of the protein chain in the solvent and the magnitude of the activation energy. We suggest that in protein folding an energetic barrier is essential to separate the native from the unfolded conformations of a protein. This barrier protects the ordered structure of a native protein against continuous unfolding by diffusive chain motions and leads to apparent two-state behavior. PMID:9159122

  1. Chemical accessibility of tyrosyl and lysyl residues in turnip yellow mosaic virus capsids.

    PubMed

    Re, G G; Kaper, J M

    1975-10-01

    The chemical accessibility of tyrosyl residues in TYMV capsids was studied by spectrophotometric titration and with the nitrating agent tetranitromethane. That of the lysyl residues was probed with trinitrobenzenesulfonate. Attempts to test their accessibility in virions were also made. Since some of these reactions were accompanied by structural changes, degradation of the particles were monitored with ultracentrifugation and light-scattering measurements. Alkaline titration of TYMV capsids induced ionization of two of the three tyrosyl residues per subunit at pH 11.3, but the third tyrosyl ionized with an apparent pK of 12.65, concomitantly with the degradation of the capsids. Reaction with tetranitromethane suggested that one tyrosyl residue per subunit can easily be nitrated and initiates degradation, after which the remaining residues also react. In intact capsids, five out of seven lysyl residues per subunit reacted readily with trinitrobenzenesulfonate. The other two lysyl residues were trinitrophenylated only after degradation of the capsids. On the other hand, all seven lysyl residues per subunit were easily trinitrophenylated in virions, during which reaction the virions disintegrated. The demonstrated chemical inaccessibility of specific numbers of tyrosyl and lysyl residues in TYMV capsids and the observed structural consequences to the capsids when the residues were made to react are consistent with previously published properties of the cysteinyl and tryptophanyl residues. The findings suggest that in the capsid the central region of the TYMV polypeptide chain is buried and might represent a site of contact between neighboring subunits.

  2. Thermal Insulation from Hardwood Residues

    NASA Astrophysics Data System (ADS)

    Sable, I.; Grinfelds, U.; Vikele, L.; Rozenberga, L.; Zeps, M.; Luguza, S.

    2015-11-01

    Adequate heat is one of the prerequisites for human wellbeing; therefore, building insulation is required in places where the outside temperature is not suitable for living. The climate change, with its rising temperatures and longer dry periods, promotes enlargement of the regions with conditions more convenient for hardwood species than for softwood species. Birch (Betula pendula) is the most common hardwood species in Latvia. The aim of this work was to obtain birch fibres from wood residues of plywood production and to form low-density thermal insulation boards. Board formation and production was done in the presence of water; natural binder, fire retardant and fungicide were added in different concentrations. Board properties such as density, transportability or resistance to particulate loss, thermal conductivity and reaction to fire were investigated. This study included thermal insulation boards with the density of 102-120 kg/m3; a strong correlation between density and the binder amount was found. Transportability also improved with the addition of a binder, and 0.1-0.5% of the binder was the most appropriate amount for this purpose. The measured thermal conductivity was in the range of 0.040-0.043 W/(m·K). Fire resistance increased with adding the fire retardant. We concluded that birch fibres are applicable for thermal insulation board production, and it is possible to diversify board properties, changing the amount of different additives.

  3. Catalyst deactivation in residue hydrocracking

    SciTech Connect

    Oballa, M.C.; Wong, C.; Krzywicki, A.

    1994-12-31

    The existence of a computer-controlled bench scale hydrocracking units at the authors site has made cheaper the non-stop running of experiments for long periods of time. It was, therefore possible to show, at minimal costs, when three hydrocracking catalysts in service reach their maximum lifetime. Different parameters which are helpful for catalyst life and activity predictions were calculated, e.g., relative catalyst age and the effectiveness factor. Experimental results compared well with model, giving them the minimum and maximum catalyst lifetime, as well as the deactivation profile with regard to sulfur and metals removal. Reaction rate constants for demetallization and desulfurization were also determined. Six commercial catalysts were evaluated at short term runs and the three most active were used for long term runs. Out of three catalysts tested for deactivation at long term runs, it was possible to choose one whose useful life was higher than the others. All runs were carried out in a Robinson-Mahoney continuous flow stirred tank reactor, using 50/50 volumetric mixture of Cold Lake/Lloydminster atmospheric residue and NiMo/Al{sub 2}O{sub 3} catalyst.

  4. On the torque reversal occurred in X-ray binaries

    NASA Astrophysics Data System (ADS)

    Gong, Biping

    The effect of torque reversal has been observed in a number of X-ray binaries, such as 4U1627-67, Her X-1, Cen X-3, GX 1+4, OAO 1657-415, and Vela X-1. Here we suggest that it originates in a simply mechanism, residual Doppler shift. In a binary system with periodic signals sending to an observer, the drift of the signal frequency actually changes with the varying orbital velocity, projected to line of sight at different phases of orbit. And it has been taken for granted that the net red-shift and blue-shift of an full orbit circle be cancelled out, so that the effect of Doppler shift to the signal in binary motion cannot be accumulated over the orbital period. However, taking the propagation time at each velocity state into account, the symmetry of the velocity distribution over the orbital phase is broken. Consequently, the net Doppler shift left in an orbit is non-zero. It is this Newtonian second Doppler effect that responsible for the torque reversal occurred in X-ray binaries.

  5. Secondary Reactions and Strategies to Improve Quantitative Protein Footprinting

    SciTech Connect

    Xu,G.; Kiselar, J.; He, Q.; Chance, M.

    2005-01-01

    Hydroxyl radical-mediated footprinting permits detailed examination of structure and dynamic processes of proteins and large biological assemblies, as changes in the rate of reaction of radicals with target peptides are governed by changes in the solvent accessibility of the side-chain probe residues. The precise and accurate determination of peptide reaction rates is essential to successfully probing protein structure using footprinting. In this study, we specifically examine the magnitude and mechanisms of secondary oxidation occurring after radiolytic exposure and prior to mass spectrometric analysis. Secondary oxidation results from hydrogen peroxide and other oxidative species generated during radiolysis, significantly impacting the oxidation of Met and Cys but not aromatic or other reactive residues. Secondary oxidation of Met with formation of sulfoxide degrades data reproducibility and inflates the perceived solvent accessibility of Met-containing peptides. It can be suppressed by adding trace amounts of catalase or millimolar Met-NH{sub 2} (or Met-OH) buffer immediately after irradiation; this leads to greatly improved adherence to first-order kinetics and more precise observed oxidation rates. The strategy is shown to suppress secondary oxidation in model peptides and improve data quality in examining the reactivity of peptides within the Arp2/3 protein complex. Cysteine is also subject to secondary oxidation generating disulfide as the principal product. The disulfides can be reduced before mass spectrometric analysis by reducing agents such as TCEP, while methionine sulfoxide is refractory to reduction by this reagent under typical reducing conditions.

  6. Diagnostic cyclisation reactions which follow phosphate transfer to carboxylate anion centres for energised [M-H]- anions of pTyr-containing peptides.

    PubMed

    Tran, T T Nha; Wang, Tianfang; Hack, Sandra; Bowie, John H

    2011-09-15

    The low-energy negative ion phosphoTyr to C-terminal -CO(2)PO(3)H(2) rearrangement occurs for energised peptide [M-H](-) anions even when there are seven amino acid residues between the pTyr and C-terminal amino acid residues. The rearranged C-terminal -CO(2)PO(2)H(O(-)) group effects characteristic S(N)i cyclisation/cleavage reactions. The most pronounced of these involves the electrophilic central backbone carbon of the penultimate amino acid residue. This reaction is aided by the intermediacy of an H-bonded intermediate in which the nucleophilic and electrophilic reaction centres are held in proximity in order for the S(N)i cyclisation/cleavage to proceed. The ΔG(reaction) is +184 kJ mol(-1) with the barrier to the S(N)i transition state being +240 kJ mol(-1) at the HF/6-31 + G(d)//AM1 level of theory. A similar phosphate rearrangement from pTyr to side chain CO(2)(-) (of Asp or Glu) may also occur for energised peptide [M-H](-) anions. The reaction is favourable: ΔG(reaction) is -44 kJ mol(-1) with a maximum barrier of +21 kJ mol(-1) (to the initial transition state) when Asp and Tyr are adjacent. The rearranged species R(1)-Tyr-NHCH(CH(2)CO(2)PO(3)H(-))COR(2) (R(1)  = CHO; R(2)  = OCH(3)) may undergo an S(N)i six-centred cyclisation/cleavage reaction to form the product anion R(1)-Tyr(NH(-)). This process has a high energy requirement [ΔG(reaction)  = +224 kJ mol(-1), with the barrier to the S(N)i transition state being +299 kJ mol(-1)].

  7. Residual Stresses in 21-6-9 Stainless Steel Warm Forgings

    SciTech Connect

    Everhart, Wesley A.; Lee, Jordan D.; Broecker, Daniel J.; Bartow, John P.; McQueen, Jamie M.; Switzner, Nathan T.; Neidt, Tod M.; Sisneros, Thomas A.; Brown, Donald W.

    2012-11-14

    Forging residual stresses are detrimental to the production and performance of derived machined parts due to machining distortions, corrosion drivers and fatigue crack drivers. Residual strains in a 21-6-9 stainless steel warm High Energy Rate Forging (HERF) were measured via neutron diffraction. The finite element analysis (FEA) method was used to predict the residual stresses that occur during forging and water quenching. The experimentally measured residual strains were used to calibrate simulations of the three-dimensional residual stress state of the forging. ABAQUS simulation tools predicted residual strains that tend to match with experimental results when varying yield strength is considered.

  8. Information Needs While A Disaster Is Occurring

    NASA Astrophysics Data System (ADS)

    Perry, S. C.

    2010-12-01

    that rainfall intensity at their homes might be less than the intensity up in the mountains where the debris flows would start. Nor did they know that debris flows travel too quickly to be outrun. These and many other examples indicate need for social and natural scientists to increase awareness of what to expect when the disaster strikes. This information must be solidly understood before the event occurs - while a disaster is unfolding there are no teachable moments. Case studies indicate that even those who come into a disaster well educated about the phenomenon can struggle to apply what they know when the real situation is at hand. In addition, psychological studies confirm diminished ability to comprehend information at times of stress.

  9. Release and fate of fluorocarbons in a shredder residue landfill cell: 2. Field investigations.

    PubMed

    Scheutz, Charlotte; Fredenslund, Anders M; Nedenskov, Jonas; Kjeldsen, Peter

    2010-11-01

    The shredder residues from automobiles, home appliances and other metal containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to determine the gas composition, attenuation, and emission of fluorocarbons in a monofill shredder residue landfill cell by field investigation. Landfill gas generated within the shredder waste primarily consisted of CH(4) (27%) and N(2) (71%), without CO(2), indicating that the gas composition was governed by chemical reactions in combination with anaerobic microbial reactions. The gas generated also contained different fluorocarbons (up to 27 μg L(-1)). The presence of HCFC-21 and HCFC-31 indicated that anaerobic degradation of CFC-11 occurred in the landfill cell, as neither of these compounds has been produced for industrial applications. This study demonstrates that a landfill cell containing shredder waste has a potential for attenuating CFC-11 released from polyurethane (PUR) insulation foam in the cell via aerobic and anaerobic biodegradation processes. In deeper, anaerobic zones of the cell, reductive dechlorination of CFCs to HCFCs was evident, while in the shallow, oxic zones, there was a high potential for biooxidation of both methane and lesser chlorinated fluorocarbons. These findings correlated well with both laboratory results (presented in a companion paper) and surface emission measurements that, with the exception from a few hot spots, indicated that surface emissions were negative or below detection. PMID:20444588

  10. Filtrates & Residues: Olfactory Titration.

    ERIC Educational Resources Information Center

    Wood, John T.; Eddy, Roberta M.

    1996-01-01

    Presents an experiment that uses a unique acid-base indicator--the odor of raw onion--to indicate the end point of the titration of sodium hydroxide with hydrochloric acid. Allows the student to detect the completion of the neutralization reaction by olfaction rather than sight. (JRH)

  11. Immediate hypersensitivity reaction with mango.

    PubMed

    Shah, Ashok; Gera, Kamal

    2014-01-01

    Hypersensitivity to the fruit mango is extremely rare and can exhibit either as immediate or delayed reactions. Since 1939, only 22 patients (10 with immediate type I reactions and 12 with delayed) have been documented with allergy to mango. History of atopy and geographical region may influence the type of reaction. Immediate reactions occurred most often in patients with history of atopy, while delayed reactions developed in non-atopic individuals. Clustering of delayed hypersensitivity reports from Australia and immediate reactions from Europe has been documented. We report a 50-year-old man with immediate type I hypersensitivity to mango, who developed cough, wheezing dyspnoea, generalised itching and abdominal discomfort after ingestion of mango. Life threatening event can also happen making it imperative to diagnose on time, so as to prevent significant morbidity and potential mortality. PMID:25133813

  12. The residual caries dilemma.

    PubMed

    Weerheijm, K L; Groen, H J

    1999-12-01

    Restorative dentistry is based on the assumption that bacterial infection of demineralized dentine should prompt operative intervention. One of the concepts of practical dentistry is to create a favourable environment for caries arrest with minimal operative intervention. The progress of remaining primary caries is key to any discussion of this concept. This discussion is important for the atraumatic restorative treatment (ART) approach, since the removal of all carious dentine is sometimes difficult using hand instruments only. In this paper the results of possible measures to guard against the effects of residual carious and its consequences are reviewed, in order to obtain an impression of the justification for (in)complete excavation of occlusal dentinal caries. Three types of measure are considered: isolating the caries process from the oral environment, excavating the carious dentine, and using a cariostatic filling material. Each of these measures contributes to the arrest of the caries process. However, none of these measures can arrest this process by itself. A combination of all three seems necessary. It is concluded that although residual caries does not seem to be the criterion for rerestoration, one has to strive for as complete caries removal as possible. If this cannot be fulfilled the sealing capacities of the filling material seem to be more important than its cariostatic properties. PMID:10600078

  13. Characterizing Solids in Residual Wastes from Single-Shell Tanks at the Hanford Site.

    SciTech Connect

    Krupka, Kenneth M.; Cantrell, Kirk J.; Schaef, Herbert T.; Arey, Bruce W.; Heald, Steve M.; Deutsch, William J.; Lindberg, Michael J.

    2010-03-03

    Solid-phase characterization methods have been used in an ongoing study of residual wastes (i.e., waste remaining after final retrieval operations) from underground single-shell storage tanks 241-C-103, 241 C 106, 241-C-202, 241-C-203, and 241-S-112 at the U.S. Department of Energy’s Hanford Site in Washington State. The results of studies completed to date show variability in the compositions of those residual wastes and the compositions, morphologies, and crystallinities of the individual phases that make up these wastes. These differences undoubtedly result from the various waste types stored and transferred into and out of each tank and the different sluicing and retrieval operations used for waste retrieval. The studies indicate that these residual wastes are chemically-complex assemblages of crystalline and amorphous solids that contain contaminants as discrete phases and/or coprecipitated within oxide/hydroxide phases. Depending on the specific tank, various solids (e.g., gibbsite; böhmite; dawsonite; cancrinite; Fe oxides/hydroxides such as hematite, goethite, and maghemite; rhodochrosite; lindbergite; whewellite; nitratine; and numerous amorphous or poorly crystalline phases) have been identified by X-ray diffraction and scanning electron microscopy/energy dispersive X-ray spectroscopy in residual wastes studied to date. The studies also show that contact of residual wastes with Ca(OH)2- and CaCO3-saturated aqueous solutions, which were used as surrogates for the compositions of pore-fluid leachants derived from young and aged cements, respectively, may alter the composition of solid phases present in the contacted wastes. Iron oxides/hydroxides have been identified in all residual wastes studied to date. They occur in these wastes as discrete particles, particles intergrown within a matrix of other phases, and surface coatings on other particles or particle aggregates. These Fe oxides/hydroxides typically contain trace concentrations of other

  14. Proton transfer reactions and hydrogen-bond networks in protein environments.

    PubMed

    Ishikita, Hiroshi; Saito, Keisuke

    2014-02-01

    In protein environments, proton transfer reactions occur along polar or charged residues and isolated water molecules. These species consist of H-bond networks that serve as proton transfer pathways; therefore, thorough understanding of H-bond energetics is essential when investigating proton transfer reactions in protein environments. When the pKa values (or proton affinity) of the H-bond donor and acceptor moieties are equal, significantly short, symmetric H-bonds can be formed between the two, and proton transfer reactions can occur in an efficient manner. However, such short, symmetric H-bonds are not necessarily stable when they are situated near the protein bulk surface, because the condition of matching pKa values is opposite to that required for the formation of strong salt bridges, which play a key role in protein-protein interactions. To satisfy the pKa matching condition and allow for proton transfer reactions, proteins often adjust the pKa via electron transfer reactions or H-bond pattern changes. In particular, when a symmetric H-bond is formed near the protein bulk surface as a result of one of these phenomena, its instability often results in breakage, leading to large changes in protein conformation.

  15. Proton transfer reactions and hydrogen-bond networks in protein environments

    PubMed Central

    Ishikita, Hiroshi; Saito, Keisuke

    2014-01-01

    In protein environments, proton transfer reactions occur along polar or charged residues and isolated water molecules. These species consist of H-bond networks that serve as proton transfer pathways; therefore, thorough understanding of H-bond energetics is essential when investigating proton transfer reactions in protein environments. When the pKa values (or proton affinity) of the H-bond donor and acceptor moieties are equal, significantly short, symmetric H-bonds can be formed between the two, and proton transfer reactions can occur in an efficient manner. However, such short, symmetric H-bonds are not necessarily stable when they are situated near the protein bulk surface, because the condition of matching pKa values is opposite to that required for the formation of strong salt bridges, which play a key role in protein–protein interactions. To satisfy the pKa matching condition and allow for proton transfer reactions, proteins often adjust the pKa via electron transfer reactions or H-bond pattern changes. In particular, when a symmetric H-bond is formed near the protein bulk surface as a result of one of these phenomena, its instability often results in breakage, leading to large changes in protein conformation. PMID:24284891

  16. Residual gas analyzer calibration

    NASA Technical Reports Server (NTRS)

    Lilienkamp, R. H.

    1972-01-01

    A technique which employs known gas mixtures to calibrate the residual gas analyzer (RGA) is described. The mass spectra from the RGA are recorded for each gas mixture. This mass spectra data and the mixture composition data each form a matrix. From the two matrices the calibration matrix may be computed. The matrix mathematics requires the number of calibration gas mixtures be equal to or greater than the number of gases included in the calibration. This technique was evaluated using a mathematical model of an RGA to generate the mass spectra. This model included shot noise errors in the mass spectra. Errors in the gas concentrations were also included in the valuation. The effects of these errors was studied by varying their magnitudes and comparing the resulting calibrations. Several methods of evaluating an actual calibration are presented. The effects of the number of gases in then, the composition of the calibration mixture, and the number of mixtures used are discussed.

  17. Seawater neutralization of alkaline bauxite residue and implications for revegetation.

    PubMed

    Menzies, N W; Fulton, I M; Morrell, W J

    2004-01-01

    Reaction of bauxite residue with seawater results in neutralization of alkalinity through precipitation of Mg-, Ca-, and Al-hydroxide and carbonate minerals. In batch studies, the initial pH neutralization reaction was rapid (<5 min), with further reaction continuing to reduce pH for several weeks. Reaction with seawater produced a residue pH of 8 to 8.5. Laboratory leaching column studies were undertaken to provide information on seawater neutralization of the coarse-textured fraction of the waste, residue sand (RS), under conditions comparable with those that might be applied in the field. An 0.80-m-deep column of RS was neutralized by the application of the equivalent of 2-m depth of seawater. In addition to lowering the pH and Na content of the residue, seawater neutralization resulted in the addition of substantial amounts of the plant nutrients Ca, Mg, and K to the profile. Similar results were also obtained from a field-scale assessment of neutralization. However, the accumulation of precipitate, consisting of hydrotalcite, aragonite, and pyroaurite, in the drainage system may preclude the use of in situ seawater neutralization as a routine rehabilitation practice. Following seawater neutralization, RS remains too saline to support plant growth and would require fresh water leaching before revegetation. PMID:15356249

  18. Pyrethroid insecticides: A naturally occurring toxin. (Latest citations from Pollution Abstracts). Published Search

    SciTech Connect

    Not Available

    1993-05-01

    The bibliography contains citations concerning the effects of pyrethrum and pyrethroid insecticides. Topics examine toxicity to fish, worms, flies, mosquitoes, and moths. Chemical residue on crops, the transportation of pyrethrum from soils to crops, and pyrethrum accumulation in ponds and lakes are among the topics discussed. Naturally occurring and synthetic pyrethroid insecticides are included. (Contains a minimum of 173 citations and includes a subject term index and title list.)

  19. Chemical modification of arginine residues in the lactose repressor

    SciTech Connect

    Whitson, P.A.; Matthews, K.S.

    1987-10-06

    The lactose repressor protein was chemically modified with 2,3-butanedione and phenylglyoxal. Arginine reaction was quantitated by either amino aced analysis or incorporation of /sup 14/C-labeled phenylglyoxal. Inducer binding activity was unaffected by the modification of arginine residues, while both operator and nonspecific DNA binding activities were diminished, although to differing degrees. The correlation of the decrease in DNA binding activities with the modification of approx. 1-2 equiv of arginine per monomer suggests increased reactivity of a functionally essential residue(s). For both reagents, operator DNA binding activity was protected by the presence of calf thymus DNA, and the extent of reaction with phenylglyoxal was simultaneously diminished. This protection presumably results from steric restriction of reagent access to an arginine(s) that is (are) essential for DNA binding interactions. These experiments suggest that there is (are) an essential reactive arginine(s) critical for repressor binding to DNA.

  20. [Transfer of pesticide residues to crops via cardboard boxes].

    PubMed

    Iwakoshi, Keiko; Takano, Ichiro; Kobayashi, Maki; Ohtsuka, Kenji; Tamura, Yasuhiro; Tomizawa, Sanae; Kamijo, Kyoko; Kageyama, Yuriko; Nagayama, Toshihiro

    2009-10-01

    Cardboard boxes used to transport crops are often reused in the distribution process, and therefore transfer of pesticides between crops might occur. So, we designed model experiments to investigate whether or not transfer of pesticide residues from crops to other crops via cardboard boxes occurs. Under severe experimental conditions, 6.2% of the pesticide residues of grapefruit was found to be transferred to spinach via cardboard boxes. In the case of the mandarin orange, 0.57% was transferred. The actual amount of transferred pesticides in the market may be less than that in these model experiments, but it is clear that transfer of pesticide residues to other crops via cardboard boxes can occur. Therefore more attention must be given to reuse of cardboard boxes in the distribution process. PMID:19897948

  1. Experimental determination of residual stress

    NASA Technical Reports Server (NTRS)

    Ferguson, Milton W.

    1991-01-01

    Residual stresses in finished parts have often been regarded as factors contributing to premature part failure and geometric distortions. Currently, residual stresses in welded structures and railroad components are being investigated. High residual stresses formed in welded structures due primarily to the differential contractions of the weld material as it cools and solidifies can have a profound effect on the surface performance of the structure. In railroad wheels, repeated use of the brakes causes high residual stresses in the rims which may lead to wheel failure and possible derailment. The goals of the study were: (1) to develop strategies for using x-ray diffraction to measure residual stress; (2) to subject samples of Inconel 718 to various mechanical and heat treatments and to measure the resulting stress using x-ray diffraction; and (3) to measure residual stresses in ferromagnetic alloys using magnetoacoustics.

  2. Death in pediatric Cushing syndrome is uncommon but still occurs

    PubMed Central

    Gkourogianni, Alexandra; Lodish, Maya B.; Zilbermint, Mihail; Lyssikatos, Charalampos; Belyavskaya, Elena; Keil, Margaret F.; Stratakis, Constantine A.

    2014-01-01

    Cushing syndrome (CS) in children is rare. Delayed diagnosis and treatment of CS may be associated with increased morbidity and, unfortunately, mortality. We performed a retrospective review of all patients with CS under the age of 18 referred to the NIH from 1998 to 2013 in order to describe deceased patients among cases of pediatric CS referred to the National Institutes of Health (NIH). The deaths of 4 children (3 females and 1 male), aged 7.5–15.5 years (mean age 11.2 years) with length of disease 2–4 years were recorded among 160 (2.5%) children seen at, or referred to the NIH over the last 15 years. All died at different institutions, prior to coming to the NIH (two of them) or after leaving NIH (two of them). Presenting symptoms included increasing weight and decreasing height gain, facial plethora, dorsocervical fat pad (webbed neck), striae, headache, vision disturbances and depression and other mood or behavior changes; there were no differences between how these patients presented and the others in our cohort. The causes of CS in the deceased patients were also not different, in fact, they spanned the entire spectrum of CS: pituitary disease (on of them), ectopic corticotropin production (one of them), and primary adrenal hyperplasia (1). In one patient, the cause of CS could not be verified. Three died of sepsis and one due to residual disease and complications of the primary tumor. Conclusions Despite advances in early diagnosis and treatment of pediatric CS, a 2.5% mortality rate was identified in a large cohort of patients with this condition referred to an experienced, tertiary care referral center (although these deaths occurred elsewhere). Pediatricians need to recognize the possibility of death, primarily due to sepsis, in a patient with pediatric CS and act accordingly. PMID:25241829

  3. Treatment Method for Fermi Barrel Sodium Metal Residues

    SciTech Connect

    Steven R. Sherman; Collin J. Knight

    2005-06-01

    Fermi barrels are 55-gallon drums that once contained bulk sodium metal from the shutdown Fermi 1 breeder reactor facility, and now contain residual sodium metal and other sodium/air reaction products. This report provides a residual sodium treatment method and proposed quality assurance steps that will ensure that all residual sodium is deactivated and removed from the Fermi barrels before disposal. The treatment method is the application of humidified carbon dioxide to the residual sodium followed by a water wash. The experimental application of the treatment method to six Fermi barrels is discussed, and recommendations are provided for further testing and evaluation of the method. Though more testing would allow for a greater refinement of the treatment technique, enough data has been gathered from the tests already performed to prove that 100% compliance with stated waste criteria can be achieved.

  4. Materials recovery from shredder residues

    SciTech Connect

    Daniels, E. J.; Jody, B. J.; Pomykala, J., Jr.

    2000-07-24

    Each year, about five (5) million ton of shredder residues are landfilled in the US. Similar quantities are landfilled in Europe and the Pacific Rim. Landfilling of these residues results in a cost to the existing recycling industry and also represents a loss of material resources that are otherwise recyclable. In this paper, the authors outline the resources recoverable from typical shredder residues and describe technology that they have developed to recover these resources.

  5. Residual protein levels on reprocessed dental instruments.

    PubMed

    Smith, A; Letters, S; Lange, A; Perrett, D; McHugh, S; Bagg, J

    2005-11-01

    Reduction of the initial bioburden on instruments, prior to sterilization, is believed to reduce transmission risks of iatrogenic Creutzfeldt-Jakob disease. Endodontic files are used in the preparation of root canals and are likely to have close contact and become contaminated with neural material from branches of the maxillary and mandibular cranial nerves. This study examined methods used by 22 dental practices to clean endodontic files, and scored visible debris and residual protein levels adhering to 220 dental endodontic files that had been used, cleaned, autoclaved and were deemed ready for re-use. Visible debris was scored after examination under a dissecting light microscope. Residual protein was quantified using a fluorescent assay based on reaction of proteins with o-phthaldialdehyde/N-acetyl cysteine. There was wide variation in the methods used by practices to clean endodontic files. The cleaning process varied from a wipe with an alcohol-impregnated cloth to hand scrubbing and/or use of an ultrasonic bath. Surface debris was visually detected on 98% of files. Residual protein was detected on all the files examined (median amount: 5.4 microg; range: 0.5-63.2 microg). These results demonstrate that the cleaning of some instruments reprocessed routinely in primary care is incomplete, and such instruments cannot be excluded as a potential source of cross-infection.

  6. Severe reactions to Cuprophan capillary dialyzers.

    PubMed

    Popli, S; Ing, T S; Daugirdas, J T; Kheirbek, A O; Viol, G W; Vilbar, R M; Gandhi, V C

    1982-08-01

    Five severe reactions occurred in four maintenance hemodialysis patients 1 to 5 minutes after initiating dialysis with Cuprophan capillary dialyzers. All reactions were life-threatening and one resulted in death. Inadequate rinsing of the dialyzers was probably the cause of the reactions. The severe reactions were managed by immediate discontinuation of dialysis and the institution of supportive treatment. Antianaphylactic measures were also attempted, but their therapeutic effectiveness remains to be determined. PMID:7181733

  7. Kinetics governing Michigan Antrim oil shale. I. Pyrolysis. II. Oxidation of carbonaceous residue

    SciTech Connect

    Rostam-Abadi, M.

    1982-01-01

    The intrinsic reaction rate kinetics for the pyrolysis of Michigan Antrim oil shale and the oxidation of the carbonaceous residue of this shale have been determined. The effect of heating rate, and oil shale minerals, particularly iron pyrite on the pyrolysis reaction was also investigated. As a part of the combustion process, the oxidation reactivity of carbonaceous residue prepared at several final pyrolysis temperatures, and the kinetics of chemisorption of oxygen on carbonaceous residue have been determined. Thermogravimetric and differential thermogravimetric techniques were employed in this research. The kinetics of the pyrolysis reaction were determined from both isothermal and nonisothermal rate data. No evidence of any reaction among the oil shale mineral constituents was observed at temperatures below 1173/sup 0/K. However, it was found that the presence of pyrite in oil shale reduces the primary devolatization rates of kerogen and increases the amount of residual char in the spent shale.

  8. Effect of lime on the availability of residual phosphorus and its extractability by dilute acid

    SciTech Connect

    Rhue, R.D.; Hensel, D.R.

    1983-01-01

    The objective of this study was to determine the long-term effects of liming an acid, P-deficient Placid sand (sandy, siliceous, hyperthermic Typic Humaquept) on the availability of residual fertilizer P to potatoes (Solanum tuberosum L.). Dolomitic limestone was applied in November 1977, at rates of 0, 2240, 4480, and 8960 kg/ha in a split-plot design with lime as main plots and P treatments as subplots. Phosphorus was applied at rates of 0, 56, 112, and 168 kg/ha in 1978. In 1979 and 1980, P plots were split with one-half fertilized with 56 kg P/ha and the other one-half not fertilized with P (residual). In 1978, maximum tuber yields and top dry weights occurred at the 2240 kg/ha lime rate which resulted in a soil pH of 5.8. Plant P concentrations were unaffected by lime at any sampling rate. In 1979, availability of residual soil P decreased with lime rates > 2240 kg/ha but not enough to significantly affect yields. However, in 1980, overliming injury was observed for tuber yields at the higher lime rates which was the result of P deficiency. Application of P at planting eliminated the overliming injury with maximum yields occurring in the pH range of 6.0 to 6.5. It appears that liming to pH 6.5 in this study resulted in fertilizer reaction products that were more soluble in dilute acid but less plant available than those formed under more acid conditions. However, the Mehlich I extractant appeared to be a suitable extractant for P on this soil if pH was taken into account when interpreting soil-test P. 23 references, 4 figures, 2 tables.

  9. Kinetics of coal liquefaction at very short reaction times

    SciTech Connect

    Huang, H.; Wang, K.; Wang, S.

    1995-12-31

    Kinetics of direct liquefaction of Illinois No. 6 Bituminous coal in tetralin has been investigated at three temperatures (309-424{degrees}C) during the first few seconds of the reaction and up to an hour. Conversion was followed by the ash content of the coal residue as determined by TGA, and changes in the reaction were followed by changes in the TGA parameters, such as Volatile Matter (VM) and Fixed Carbon (FC). The effects of temperature on the reaction kinetics were in both catalyzed and uncatalyzed liquefaction with a large excess of tetralin, there is an initial very rapid extraction of the soluble matter by the tetralin. After extraction there is an induction period followed by a slower rate of conversion of the coal structure itself. At higher temperatures, the amount of extraction increases and the induction period becomes shorter. At least two conflicting processes are occurring in the last stage: (1) breakdown of the coal structure to liquid products, and (2) formation of retrograde material (precursor of tar and coke). Catalysts such as sulfided molybdenum naphthenate in the presence of hydrogen greatly reduce the formation of retrograde products.

  10. Deuteration protects asparagine residues against racemization.

    PubMed

    Lowenson, Jonathan D; Shmanai, Vadim V; Shklyaruck, Denis; Clarke, Steven G; Shchepinov, Mikhail S

    2016-09-01

    Racemization in proteins and peptides at sites of L-asparaginyl and L-aspartyl residues contributes to their spontaneous degradation, especially in the biological aging process. Amino acid racemization involves deprotonation of the alpha carbon and replacement of the proton in the opposite stereoconfiguration; this reaction is much faster for aspartate/asparagine than for other amino acids because these residues form a succinimide ring in which resonance stabilizes the carbanion resulting from proton loss. To determine if the replacement of the hydrogen atom on the alpha carbon with a deuterium atom might decrease the rate of racemization and thus stabilize polypeptides, we synthesized a hexapeptide, VYPNGA, in which the three carbon-bound protons in the asparaginyl residue were replaced with deuterium atoms. Upon incubation of this peptide in pH 7.4 buffer at 37 °C, we found that the rate of deamidation via the succinimide intermediate was unchanged by the presence of the deuterium atoms. However, the accumulation of the D-aspartyl and D-isoaspartyl-forms resulting from racemization and hydrolysis of the succinimide was decreased more than five-fold in the deuterated peptide over a 20 day incubation at physiological temperature and pH. Additionally, we found that the succinimide intermediate arising from the degradation of the deuterated asparaginyl peptide was slightly less likely to open to the isoaspartyl configuration than was the protonated succinimide. These findings suggest that the kinetic isotope effect resulting from the presence of deuteriums in asparagine residues can limit the accumulation of at least some of the degradation products that arise as peptides and proteins age. PMID:27169868

  11. Residual injuries after recent safety improvements.

    PubMed

    Augenstein, J; Perdeck, E; Digges, K; Bahouth, G

    2006-01-01

    This study examines the residual injuries reported in NASS/CDS 1997-2004 by crash mode, crash severity, body region and occupant age. It examines how serious injuries are distributed in present day crashes and identifies opportunities for further injury reduction. In planar crashes, approximately 66% of the MAIS 3+ injuries occur in crashes less severe than 25 mph delta-V. Chest injuries predominate in these crashes, particularly among elderly occupants. A reduction in chest injuries to belted elderly occupants during low severity frontal crashes offers a prime opportunity for further improvement of safety systems. Younger occupants could also benefit from improved chest protection. PMID:16968647

  12. Gas dynamics in residual gas analyzer calibration

    SciTech Connect

    Santeler, D.J.

    1987-01-01

    Residual gas analyzers are used for measuring partial flow rates as well as for measuring partial pressures. The required calibration may also be obtained with either known flow rates or known pressures. The calibration and application procedures are straightforward when both are of the same type; however, substantial errors may occur if the two types are mixed. This report develops the basic equations required to convert between partial pressure calibrations and partial flow rate calibrations. It also discusses the question of fractionating and nonfractionating gas flow in various gas inlet and pumping systems.

  13. On tide-induced lagrangian residual current and residual transport: 1. Lagrangian residual current

    USGS Publications Warehouse

    Feng, Shizuo; Cheng, Ralph T.; Pangen, Xi

    1986-01-01

    Residual currents in tidal estuaries and coastal embayments have been recognized as fundamental factors which affect the long-term transport processes. It has been pointed out by previous studies that it is more relevant to use a Lagrangian mean velocity than an Eulerian mean velocity to determine the movements of water masses. Under weakly nonlinear approximation, the parameter k, which is the ratio of the net displacement of a labeled water mass in one tidal cycle to the tidal excursion, is assumed to be small. Solutions for tides, tidal current, and residual current have been considered for two-dimensional, barotropic estuaries and coastal seas. Particular attention has been paid to the distinction between the Lagrangian and Eulerian residual currents. When k is small, the first-order Lagrangian residual is shown to be the sum of the Eulerian residual current and the Stokes drift. The Lagrangian residual drift velocity or the second-order Lagrangian residual current has been shown to be dependent on the phase of tidal current. The Lagrangian drift velocity is induced by nonlinear interactions between tides, tidal currents, and the first-order residual currents, and it takes the form of an ellipse on a hodograph plane. Several examples are given to further demonstrate the unique properties of the Lagrangian residual current.

  14. The reaction of monochloramine and hydroxylamine: implications for ammonia–oxidizing bacteria in chloraminated drinking water

    EPA Science Inventory

    Drinking water chloramine use may promote ammonia–oxidizing bacteria (AOB) growth because of naturally occurring ammonia, residual ammonia remaining from chloramine formation, and ammonia released from chloramine decay and demand. A rapid chloramine residual loss is often associa...

  15. Fungicide residues in strawberry processing.

    PubMed

    Will, F; Krüger, E

    1999-03-01

    The fate of three fungicides (dichlofluanid, procymidone, and iprodione) applied under field conditions was studied during strawberry processing to juice, wine, and jam. An untreated control was compared to raw material treated with fungicides according to recommended doses and to a sample with 6-fold higher application rates. The highest residue values were found in the pomace after pressing. Residue values in readily produced juices and fruit wines were very low and did not exceed legally required maximum residue levels. Generally, processing steps such as pressing and clarification diminished fungicide residues from 50 to 100%. If the whole fruit is processed, as in fruit preparations or jam, the residue levels remain higher due to missing processing steps. PMID:10552381

  16. V-type nerve agents phosphonylate ubiquitin at biologically relevant lysine residues and induce intramolecular cyclization by an isopeptide bond.

    PubMed

    Schmidt, Christian; Breyer, Felicitas; Blum, Marc-Michael; Thiermann, Horst; Worek, Franz; John, Harald

    2014-08-01

    Toxic organophosphorus compounds (e.g., pesticides and nerve agents) are known to react with nucleophilic side chains of different amino acids (phosphylation), thus forming adducts with endogenous proteins. Most often binding to serine, tyrosine, or threonine residues is described as being of relevance for toxicological effects (e.g., acetylcholinesterase and neuropathy target esterase) or as biomarkers for post-exposure analysis (verification, e.g., albumin and butyrylcholinesterase). Accordingly, identification of novel protein targets might be beneficial for a better understanding of the toxicology of these compounds, revealing new bioanalytical verification tools, and improving knowledge on chemical reactivity. In the present study, we investigated the reaction of ubiquitin (Ub) with the V-type nerve agents Chinese VX, Russian VX, and VX in vitro. Ub is a ubiquitous protein with a mass of 8564.8 Da present in the extra- and intracellular space that plays an important physiological role in several essential processes (e.g., proteasomal degradation, DNA repair, protein turnover, and endocytosis). Reaction products were analyzed by matrix-assisted laser desorption/ionization-time-of-flight- mass spectrometry (MALDI-TOF MS) and μ-high-performance liquid chromatography online coupled to UV-detection and electrospray ionization MS (μHPLC-UV/ESI MS). Our results originally document that a complex mixture of at least mono-, di, and triphosphonylated Ub adducts was produced. Surprisingly, peptide mass fingerprint analysis in combination with MALDI and ESI MS/MS revealed that phosphonylation occurred with high selectivity in at least 6 of 7 surface-exposed lysine residues that are essential for the biological function of Ub. These reaction products were found not to age. In addition, we herein report for the first time that phosphonylation induced intramolecular cyclization by formation of an isopeptide bond between the ε-amino group of a formerly phosphonylated

  17. V-type nerve agents phosphonylate ubiquitin at biologically relevant lysine residues and induce intramolecular cyclization by an isopeptide bond.

    PubMed

    Schmidt, Christian; Breyer, Felicitas; Blum, Marc-Michael; Thiermann, Horst; Worek, Franz; John, Harald

    2014-08-01

    Toxic organophosphorus compounds (e.g., pesticides and nerve agents) are known to react with nucleophilic side chains of different amino acids (phosphylation), thus forming adducts with endogenous proteins. Most often binding to serine, tyrosine, or threonine residues is described as being of relevance for toxicological effects (e.g., acetylcholinesterase and neuropathy target esterase) or as biomarkers for post-exposure analysis (verification, e.g., albumin and butyrylcholinesterase). Accordingly, identification of novel protein targets might be beneficial for a better understanding of the toxicology of these compounds, revealing new bioanalytical verification tools, and improving knowledge on chemical reactivity. In the present study, we investigated the reaction of ubiquitin (Ub) with the V-type nerve agents Chinese VX, Russian VX, and VX in vitro. Ub is a ubiquitous protein with a mass of 8564.8 Da present in the extra- and intracellular space that plays an important physiological role in several essential processes (e.g., proteasomal degradation, DNA repair, protein turnover, and endocytosis). Reaction products were analyzed by matrix-assisted laser desorption/ionization-time-of-flight- mass spectrometry (MALDI-TOF MS) and μ-high-performance liquid chromatography online coupled to UV-detection and electrospray ionization MS (μHPLC-UV/ESI MS). Our results originally document that a complex mixture of at least mono-, di, and triphosphonylated Ub adducts was produced. Surprisingly, peptide mass fingerprint analysis in combination with MALDI and ESI MS/MS revealed that phosphonylation occurred with high selectivity in at least 6 of 7 surface-exposed lysine residues that are essential for the biological function of Ub. These reaction products were found not to age. In addition, we herein report for the first time that phosphonylation induced intramolecular cyclization by formation of an isopeptide bond between the ε-amino group of a formerly phosphonylated

  18. Co-Occurring Atomic Contacts for the Characterization of Protein Binding Hot Spots.

    PubMed

    Liu, Qian; Ren, Jing; Song, Jiangning; Li, Jinyan

    2015-01-01

    A binding hot spot is a small area at a protein-protein interface that can make significant contribution to binding free energy. This work investigates the substantial contribution made by some special co-occurring atomic contacts at a binding hot spot. A co-occurring atomic contact is a pair of atomic contacts that are close to each other with no more than three covalent-bond steps. We found that two kinds of co-occurring atomic contacts can play an important part in the accurate prediction of binding hot spot residues. One is the co-occurrence of two nearby hydrogen bonds. For example, mutations of any residue in a hydrogen bond network consisting of multiple co-occurring hydrogen bonds could disrupt the interaction considerably. The other kind of co-occurring atomic contact is the co-occurrence of a hydrophobic carbon contact and a contact between a hydrophobic carbon atom and a π ring. In fact, this co-occurrence signifies the collective effect of hydrophobic contacts. We also found that the B-factor measurements of several specific groups of amino acids are useful for the prediction of hot spots. Taking the B-factor, individual atomic contacts and the co-occurring contacts as features, we developed a new prediction method and thoroughly assessed its performance via cross-validation and independent dataset test. The results show that our method achieves higher prediction performance than well-known methods such as Robetta, FoldX and Hotpoint. We conclude that these contact descriptors, in particular the novel co-occurring atomic contacts, can be used to facilitate accurate and interpretable characterization of protein binding hot spots.

  19. Allergic reactions to rubber condoms.

    PubMed

    Rademaker, M; Forsyth, A

    1989-06-01

    With the increased use of condoms, contact dermatitis to rubber is being seen more often. To develop a rubber condom suitable for use by rubber sensitive people, a "hypoallergenic" condom, which is washed in ammonia to reduce the residues of rubber accelerators, has been manufactured. Fifty patients allergic to various rubber accelerators were patch tested with an ordinary condom and the new washed condom. Fifty patients undergoing routine patch test investigation who were not allergic to rubber were also tested as controls. Twenty two of the rubber sensitive patients had a positive reaction to the new rubber condom compared with four of the control patients. Washing rubber condoms in ammonia does not appear to reduce the residues of rubber accelerators sufficiently for their use by rubber sensitive people. A non-allergenic condom is required.

  20. Demonstration of catalytic combustion with residual fuel

    NASA Technical Reports Server (NTRS)

    Dodds, W. J.; Ekstedt, E. E.

    1981-01-01

    An experimental program was conducted to demonstrate catalytic combustion of a residual fuel oil. Three catalytic reactors, including a baseline configuration and two backup configurations based on baseline test results, were operated on No. 6 fuel oil. All reactors were multielement configurations consisting of ceramic honeycomb catalyzed with palladium on stabilized alumina. Stable operation on residual oil was demonstrated with the baseline configuration at a reactor inlet temperature of about 825 K (1025 F). At low inlet temperature, operation was precluded by apparent plugging of the catalytic reactor with residual oil. Reduced plugging tendency was demonstrated in the backup reactors by increasing the size of the catalyst channels at the reactor inlet, but plugging still occurred at inlet temperature below 725 K (845 F). Operation at the original design inlet temperature of 589 K (600 F) could not be demonstrated. Combustion efficiency above 99.5% was obtained with less than 5% reactor pressure drop. Thermally formed NO sub x levels were very low (less than 0.5 g NO2/kg fuel) but nearly 100% conversion of fuel-bound nitrogen to NO sub x was observed.

  1. Predictive hydrogeochemical modelling of bauxite residue sand in field conditions.

    PubMed

    Wissmeier, Laurin; Barry, David A; Phillips, Ian R

    2011-07-15

    The suitability of residue sand (the coarse fraction remaining from Bayer's process of bauxite refining) for constructing the surface cover of closed bauxite residue storage areas was investigated. Specifically, its properties as a medium for plant growth are of interest to ensure residue sand can support a sustainable ecosystem following site closure. The geochemical evolution of the residue sand under field conditions, its plant nutrient status and soil moisture retention were studied by integrated modelling of geochemical and hydrological processes. For the parameterization of mineral reactions, amounts and reaction kinetics of the mineral phases natron, calcite, tricalcium aluminate, sodalite, muscovite and analcime were derived from measured acid neutralization curves. The effective exchange capacity for ion adsorption was measured using three independent exchange methods. The geochemical model, which accounts for mineral reactions, cation exchange and activity corrected solution speciation, was formulated in the geochemical modelling framework PHREEQC, and partially validated in a saturated-flow column experiment. For the integration of variably saturated flow with multi-component solute transport in heterogeneous 2D domains, a coupling of PHREEQC with the multi-purpose finite-element solver COMSOL was established. The integrated hydrogeochemical model was applied to predict water availability and quality in a vertical flow lysimeter and a cover design for a storage facility using measured time series of rainfall and evaporation from southwest Western Australia. In both scenarios the sand was fertigated and gypsum-amended. Results show poor long-term retention of fertilizer ions and buffering of the pH around 10 for more than 5 y of leaching. It was concluded that fertigation, gypsum amendment and rainfall leaching alone were insufficient to render the geochemical conditions of residue sand suitable for optimal plant growth within the given timeframe. The

  2. Modulating the Redox Potential of the Stable Electron Acceptor, QB, in Mutagenized Photosystem II Reaction Centers.

    SciTech Connect

    Perrine, Zoee; Sayre, Richard

    2011-02-10

    One of the unique features of electron transfer processes in photosystem II (PSII) reaction centers (RC) is the exclusive transfer of electrons down only one of the two parallel cofactor branches. In contrast to the RC core polypeptides (psaA and psaB) of photosystem I (PSI), where electron transfer occurs down both parallel redox-active cofactor branches, there is greater protein-cofactor asymmetry between the PSII RC core polypeptides (D1 and D2). We have focused on the identification of protein-cofactor relationships that determine the branch along which primary charge separation occurs (P680+/pheophytin-(Pheo)). We have previously shown that mutagenesis of the strong hydrogen-bonding residue, D1-E130, to less polar residues (D1-E130Q,H,L) shifted the midpoint potential of the PheoD1/PheoD1- couple to more negative values, reducing the quantum yield of primary charge separation. We did not observe, however, electron transfer down the inactive branch in D1-E130 mutants. The protein residue corresponding to D1-E130 on the inactive branch is D2-Q129 which presumably has a reduced hydrogen-bonding interaction with PheoD2 relative to the D1-E130 residue with PheoD1. Analysis of the recent 2.9 Å cyanobacterial PSII crystal structure indicated, however, that the D2-Q129 residue was too distant from the PheoD2 headgroup to serve as a possible hydrogen bond donor and directly impact its midpoint potential as well as potentially determine the directionality of electron transfer. Our objective was to characterize the function of this highly conserved inactive branch residue by replacing it with a nonconservative leucine or a conservative histidine residue. Measurements of Chl fluorescence decay kinetics and thermoluminescence studies indicate that the mutagenesis of D2-Q129 decreases the redox gap between QA and QB due to a lowering of the redox potential of QB. The

  3. Production ratio of meta-stable isomer in {sup 180}Ta by neutrino-induced reactions

    SciTech Connect

    Hayakawa, Takehito; Kajino, Toshitaka; Chiba, Satoshi; Mathews, Grant

    2010-05-12

    The nucleosynthesis of {sup 180}Ta has remained an unsolved problem and as its origin many nucleosynthesis mechanisms have been proposed. This isotope has the unique feature that the naturally occurring abundance of {sup 180}Ta is actually a meta-stable isomer (half-life of >=10{sup 15} yr), while the ground state is a 1{sup +} unstable state which beta-decays with a half-life of only 8.15 hr. We have made a new time-dependent calculation of {sup 180}Ta meta-stable isomer residual ratio after supernova neutrino-induced reactions. This isomer residual ratio is crucial for understanding the production and survival of this naturally occurring rare isotope. We have constructed a new model under temperature evolution after type II supernova explosion. We include the explicit linking between the isomer and all known excited states and found that the residual ratio is insensitive to astrophysical parameters such as neutrino energy spectrum, explosion energy, decay time constant. We find that the explicit time evolution of the synthesis of {sup 180}Ta avoids the overproduction relative to {sup 138}La for a neutrino process neutrino temperature of 4 MeV.

  4. Spreadsheet program to ascertain residuals radionuclide concentrations (SPARRC), version 1.0 (for microcomputers). Software

    SciTech Connect

    1993-08-01

    Several radionuclides such as radon, radium, uranium, alpha emitters, and beta and photon emitters are to be regulated by the US Environmental Protection Agency under the Safe Drinking Water Act. When water treatment plants remove these contaminants from drinking water sources, the contaminants get transferred to the treatment plant residuals such as wash water, brines, and sludges. The presence of radionuclides in treatment plant wastes, depending on the concentration relative to allowable limits, may limit the use of less expensive disposal options for those residuals, thereby increasing the costs. Depending on the concentration of co-contaminants in residuals, thereby increasing the costs. Depending on the concentration of co-contaminants in residuals, the residuals might be classified as hazardous under the Resource Conservation and Recovery Act (RCRA). The cost of residuals disposal is also a function of the volume (and/or mass) of the residuals. Therefore, it is important to estimate the quantities, radionuclide concentrations, and co-contaminant concentrations of residuals generated from water treatment plants that remove naturally-occurring radionuclides. The Spreadsheet Program to Ascertain Residuals radionuclide Concentrations (SPARRC) can be used to estimate the waste volumes and concentrations of radionuclides (and be used co-contaminants) in the residuals from water treatment plants removing naturally-occurring radionuclides. This computer program has been developed in support of the EPA`s revision to the 1990 document entitled `Suggested Guidelines for the Disposal of Drinking Water Treatment Wastes Containing Naturally Occurring Radionuclides`.

  5. MODELING CHLORINE RESIDUALS IN DRINKING-WATER DISTRIBUTION SYSTEMS

    EPA Science Inventory

    A mass-transfer-based model is developed for predicting chlorine decay in drinking-water distribution networks. The model considers first-order reactions of chlorine to occur both in the bulk flow and at the pipe wall. The overall rate of the wall reaction is a function of the ...

  6. Nortestosterone is not a naturally occurring compound in male cattle.

    PubMed

    McEvoy, J D; McCaughey, W J; Cooper, J; Kennedy, D G; McCartan, B M

    1999-01-01

    Nortestosterone (beta-NT) is a hormonal growth promoter banned from livestock production in the EU. Following injection, the major metabolite in cattle is the 17 alpha-epimer (alpha-NT). However, this also occurs naturally in pregnant cattle. It is not known whether alpha-NT is also endogenous to intact or castrated male cattle. Three surveys were undertaken to assess whether alpha-NT is naturally produced in this subset of the population. Bile samples from a total of 1,281 cattle (73 bulls and 1,208 steers) from 366 herds were collected at slaughter and initially screened by using a semi-automated EIA with multi-analyte immunoaffinity chromatography (IAC) clean-up. Bile samples from a further 38 male cattle (10 bulls and 28 steers) were analysed by high-resolution gas chromatography-mass spectrometry (GC-MS) with IAC pretreatment. Only samples containing more than 2 ng/ml alpha-NT were subjected to GC-MS. With 2 ng/ml alpha-NT as a threshold for confirmatory testing, the false positive rate of the screening EIA was 1.8%. Bulls (n = 16) and steers (n = 179) from government farms (n = 2) and which were not treated with exogenous beta-NT, did not have measurable concentrations of alpha-NT in their bile. Bulls (n = 35) and steers (n = 606) taken from herds (n = 204) which had no previous history of illegal growth promoter abuse also did not have alpha-NT in their bile. Of 32 bulls and 451 steers of unknown treatment history sampled from herds (n = 160), 56 steers from 19 herds contained GC-MS confirmed concentrations of alpha-NT higher than the limit of quantification of the assay LOQ (0.7 ng/ml). Of these animals, two had beta-NT-containing injection sites and five had residues of the beta-agonists clenbuterol and mabuterol. Examination of the animal movement and ownership histories of the 56 confirmed positive animals strongly suggested that exogenous beta-NT had been administered at the presenting farm. It is concluded that alpha-NT is not endogenous to this subset

  7. Dehydrogenative Diels-Alder reaction.

    PubMed

    Ozawa, Takuya; Kurahashi, Takuya; Matsubara, Seijiro

    2011-10-01

    The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur. PMID:21905638

  8. Naturally occurring dominant drug resistance mutations occur infrequently in the setting of recently acquired hepatitis C

    PubMed Central

    Applegate, Tanya L; Gaudieri, Silvana; Plauzolles, Anne; Chopra, Abha; Grebely, Jason; Lucas, Michaela; Hellard, Margaret; Luciani, Fabio; Dore, Gregory J; Matthews, Gail V

    2014-01-01

    Background Directly Acting Antivirals (DAAs) are predicted to transform hepatitis C (HCV) therapy, yet little is known about the prevalence of naturally occurring resistance mutations in recently acquired HCV. This study aimed to determine the prevalence and frequency of drug resistance mutations in the viral quasispecies among HIV positive and negative individuals with recent HCV. Methods The NS3 protease, NS5A and NS5B polymerase genes were amplified from fifty genotype 1a participants of the Australian Trial in Acute Hepatitis C. Amino acid variations at sites known to be associated with possible drug resistance were analysed by ultra-deep pyrosequencing. Results Twelve percent of individuals harboured dominant resistance mutations, while 36% demonstrated non dominant resistant variants below that detectable by bulk sequencing (ie < 20%) but above a threshold of 1%. Resistance variants (< 1%) were observed at most sites associated with DAA resistance from all classes, with the exception of sofosbuvir. Conclusions Dominant resistant mutations were uncommonly observed in the setting of recent HCV. However, low level mutations to all DAA classes were observed by deep sequencing at the majority of sites, and in most individuals. The significance of these variants and impact on future treatment options remains to be determined. PMID:25105742

  9. Safety assessment of drug residues

    SciTech Connect

    Jackson, B.A.

    1980-05-15

    The safety assessment of drug residues is part of the process for defining the conditions for the safe use of drugs in food-producing animals. The information needed to assess the safety of drug residues is provided by chemical and toxicity tests. Toxicity tests are conducted to identify the type of effect produced and to determine the exposure concentrations that would be expected not to produce the effect. These tests include acute, subacute, and chronic toxicity tests, as well as reproduction studies and other special tests. The results are used to find an acceptable daily intake for drug residues that can be used to set a tolerance.

  10. Accurate assessment and identification of naturally occurring cellular cobalamins

    PubMed Central

    Hannibal, Luciana; Axhemi, Armend; Glushchenko, Alla V.; Moreira, Edward S.; Brasch, Nicola E.; Jacobsen, Donald W.

    2009-01-01

    Background Accurate assessment of cobalamin profiles in human serum, cells, and tissues may have clinical diagnostic value. However, non-alkyl forms of cobalamin undergo β-axial ligand exchange reactions during extraction, which leads to inaccurate profiles having little or no diagnostic value. Methods Experiments were designed to: 1) assess β-axial ligand exchange chemistry during the extraction and isolation of cobalamins from cultured bovine aortic endothelial cells, human foreskin fibroblasts, and human hepatoma HepG2 cells, and 2) to establish extraction conditions that would provide a more accurate assessment of endogenous forms containing both exchangeable and non-exchangeable β-axial ligands. Results The cobalamin profile of cells grown in the presence of [57Co]-cyanocobalamin as a source of vitamin B12 shows that the following derivatives are present: [57Co]-aquacobalamin, [57Co]-glutathionylcobalamin, [57Co]-sulfitocobalamin, [57Co]-cyanocobalamin, [57Co]-adenosylcobalamin, [57Co]-methylcobalamin, as well as other yet unidentified corrinoids. When the extraction is performed in the presence of excess cold aquacobalamin acting as a scavenger cobalamin (i.e., “cold trapping”), the recovery of both [57Co]-glutathionylcobalamin and [57Co]-sulfitocobalamin decreases to low but consistent levels. In contrast, the [57Co]-nitrocobalamin observed in extracts prepared without excess aquacobalamin is undetectable in extracts prepared with cold trapping. Conclusions This demonstrates that β-ligand exchange occurs with non-covalently bound β-ligands. The exception to this observation is cyanocobalamin with a non-covalent but non-exchangeable− CNT group. It is now possible to obtain accurate profiles of cellular cobalamins. PMID:18973458

  11. Incidents of chemical reactions in cell equipment

    SciTech Connect

    Baldwin, N.M.; Barlow, C.R.

    1991-12-31

    Strongly exothermic reactions can occur between equipment structural components and process gases under certain accident conditions in the diffusion enrichment cascades. This paper describes the conditions required for initiation of these reactions, and describes the range of such reactions experienced over nearly 50 years of equipment operation in the US uranium enrichment program. Factors are cited which can promote or limit the destructive extent of these reactions, and process operations are described which are designed to control the reactions to minimize equipment damage, downtime, and the possibility of material releases.

  12. Hypersensitivity reactions to iodinated contrast media.

    PubMed

    Guéant-Rodriguez, Rosa-Maria; Romano, Antonino; Barbaud, Annick; Brockow, Knut; Guéant, Jean-Louis

    2006-01-01

    Adverse reactions after iodinate contrast media (ICM) administration have been observed, which can be classified as immediate (i.e., occurring within one hour after administration) and delayed or non-immediate (i.e., occurring more than one hour after administration). Even though the incidence of ICM adverse reactions has been significantly reduced by the introduction of non-ionic compounds, immediate reactions still occur in about 3% of administrations. Different pathogenic mechanisms have been suggested for ICM reactions, including immunologic ones. Basophils and mast cells participate in immediate reactions through the release of mediators like histamine and tryptase, whereas a T-cell-mediated pathogenic mechanism is involved in most non-immediate reactions, particularly maculopapular rashes. Skin tests and specific IgE assays are carried out to diagnose immediate hypersensitivity reactions, while both delayed-reading intradermal tests and patch tests are usually performed to evaluate non-immediate reactions. However, in vitro specific IgE assays are not commercially available. As far as in vitro tests are concerned, a response involving ICM-related T-cell activity may be assessed by the lymphocyte transformation test. Allergologic evaluation appears to be indicated in hypersensitivity reactions to ICM, although the sensitivity, specificity, and predictive values of allergologic tests have not yet been established. This paper summarizes the current state of the art and addresses the research that is still needed on the pathogenic mechanisms, diagnosis, and prevention of ICM-induced hypersensitivity reactions.

  13. Development of indole chemistry to label tryptophan residues in protein for determination of tryptophan surface accessibility.

    PubMed

    Ladner, Carol L; Turner, Raymond J; Edwards, Robert A

    2007-06-01

    Solvent accessibility can be used to evaluate protein structural models, identify binding sites, and characterize protein conformational changes. The differential modification of amino acids at specific sites enables the accessible surface residues to be identified by mass spectrometry. Tryptophan residues within proteins can be differentially labeled with halocompounds by a photochemical reaction. In this study, tryptophan residues of carbonic anhydrase are reacted with chloroform, 2,2,2-trichloroethanol (TCE), 2,2,2-trichloroacetate (TCA), or 3-bromo-1-propanol (BP) under UV irradiation at 280 nm. The light-driven reactions with chloroform, TCE, TCA, and BP attach a formyl, hydroxyethanone, carboxylic acid, and propanol group, respectively, onto the indole ring of tryptophan. Trypsin and chymotrypsin digests of the modified carbonic anhydrase are used to map accessible tryptophan residues using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Tryptophan reactivity is determined by identifying peptides with tryptophan residues modified with the appropriate label. The reactivity is calculated from the frequency that the modification is identified and a semiquantitative measure of the amount of products formed. Both of these measures of tryptophan reactivity correlate significantly with the accessible surface area of tryptophan residues in carbonic anhydrase determined from the X-ray crystal structure. Therefore the photochemical reaction of halocompounds with tryptophan residues in carbonic anhydrase indicates the degree of solvent accessibility of these residues. PMID:17525468

  14. A method for enhancing gunshot residue patterns on dark and multicolored fabrics compared with the modified Griess test.

    PubMed

    Bailey, James A; Casanova, Ruby S; Bufkin, Kim

    2006-07-01

    In using infrared or infrared-enhanced photography to examine gunshot residue (GSR) on dark-colored clothing, the GSR particles are microscopically examined directly on the fabric followed by the modified Griess test (MGT) for nitrites. In conducting the MGT, the GSR is transferred to treated photographic paper for visualization. A positive reaction yields an orange color on specially treated photographic paper. The examiner also evaluates the size of the powder pattern based on the distribution of nitrite reaction sites or density. A false-positive reaction can occur using the MGT due to contaminants or dyes that produce an orange cloud reaction as well. A method for enhancing visualization of the pattern produced by burned and partially unburned powder is by treatment of the fabric with a solution of sodium hypochlorite. In order to evaluate the results of sodium hypochlorite treatment for GSR visualization, the MGT was used as a reference pattern. Enhancing GSR patterns on dark or multicolored clothing was performed by treating the fabric with an application of 5.25% solution of sodium hypochlorite. Bleaching the dyes in the fabric enhances visualization of the GSR pattern by eliminating the background color. Some dyes are not affected by sodium hypochlorite; therefore, bleaching may not enhance the GSR patterns in some fabrics. Sodium hypochlorite provides the investigator with a method for enhancing GSR patterns directly on the fabric. However, this study is not intended to act as a substitute for the MGT or Sodium Rhodizonate test.

  15. Americium recovery from reduction residues

    DOEpatents

    Conner, W.V.; Proctor, S.G.

    1973-12-25

    A process for separation and recovery of americium values from container or bomb'' reduction residues comprising dissolving the residues in a suitable acid, adjusting the hydrogen ion concentration to a desired level by adding a base, precipitating the americium as americium oxalate by adding oxalic acid, digesting the solution, separating the precipitate, and thereafter calcining the americium oxalate precipitate to form americium oxide. (Official Gazette)

  16. A sugar isomerization reaction established on various (βα)₈-barrel scaffolds is based on substrate-assisted catalysis.

    PubMed

    Reisinger, Bernd; Bocola, Marco; List, Felix; Claren, Jörg; Rajendran, Chitra; Sterner, Reinhard

    2012-11-01

    In the course of tryptophan biosynthesis, the isomerization of phosphoribosylanthranilate (PRA) is catalyzed by the (βα)₈-barrel enzyme TrpF. The reaction occurs via a general acid-base mechanism with an aspartate and a cysteine residue acting as acid and base, respectively. PRA isomerase activity could be established on two (βα)₈-barrel enzymes involved in histidine biosynthesis, namely HisA and HisF, and on a HisAF chimera, by introducing two aspartate-to-valine substitutions. We have analyzed the reaction mechanism underlying this engineered activity by measuring its pH dependence, solving the crystal structure of a HisF variant with bound product analogue, and applying molecular dynamics simulations and mixed quantum and molecular mechanics calculations. The results suggest that PRA is anchored by the C-terminal phosphate-binding sites of HisA, HisF and HisAF. As a consequence, a conserved aspartate residue, which is equivalent to Cys7 from TrpF, is properly positioned to act as catalytic base. However, no obvious catalytic acid corresponding to Asp126 from TrpF could be identified in the three proteins. Instead, this role appears to be carried out by the carboxylate group of the anthranilate moiety of PRA. Thus, the engineered PRA isomerization activity is based on a reaction mechanism including substrate-assisted catalysis and thus differs substantially from the naturally evolved reaction mechanism used by TrpF. PMID:23109729

  17. Adsorption Isotherms and Surface Reaction Kinetics

    ERIC Educational Resources Information Center

    Lobo, L. S.; Bernardo, C. A.

    1974-01-01

    Explains an error that occurs in calculating the conditions for a maximum value of a rate expression for a bimolecular reaction. The rate expression is derived using the Langmuir adsorption isotherm to relate gas pressures and corresponding surface coverages. (GS)

  18. Tissue reactions under piezoelectric shockwave application for the fragmentation of biliary calculi.

    PubMed

    Ell, C; Kerzel, W; Heyder, N; Rödl, W; Langer, H; Mischke, U; Giedl, J; Domschke, W

    1989-05-01

    The tissue reactions that occurred during piezoelectric shockwaves for the fragmentation of biliary calculi were investigated in 10 surgically removed stone containing human gall bladders and in acute (six dogs) and chronic (six dogs) animal experiments. Before and after shockwave (500, 1500 or 3000) in the anaesthetised dogs, computed tomography (CT), magnetic imaging (MRI) and laboratory tests were done; treatment was carried out under continuous ultrasonographic control. Shockwave applications to the human gall bladders resulted in disintegration of the stones with no macroscopically or microscopically detectable tissue changes. In acute animal experiments, small haematomas were observed in all six animals at surfaces, but also inside the liver and gall bladder (max diameter 25 mm). Perforation or intra-abdominal or pleural bleeding did not occur. In chronic experiments, no macroscopic, and only slight microscopic residual lesions (haemosiderin deposits) were seen three weeks after shockwave. In almost all instances, the lesions were detected by CT, MRI, and ultrasonography, while laboratory tests were negative.

  19. Implication of an unfavorable residue (Thr346) in intrinsic flexibility of firefly luciferase.

    PubMed

    Moradi, Maryam; Hosseinkhani, Saman; Emamzadeh, Rahman

    2012-09-10

    In order to better understand the functional role of an unusual residue (Thr346) of firefly luciferase mutagenesis at this residue was performed. Firefly luciferase, catalyzes the bioluminescence reaction and is an excellent tool as a reporter in nano-system biology studies. Nonetheless, the enzyme rapidly loses its activity at temperatures above 30 °C and this leads to reduced sensitivity and precision in analytical applications. Residue Thr346 in a connecting loop (341-348) of firefly luciferase is located in a disallowed region of Ramachandran plot. In this study, we have substituted this residue (T346) with anomalous dihedral angles with Val, Gly and Pro to clarify the role of this residue in structure and function of the enzyme using site-directed mutagenesis. Substitution of this unfavorable residue (T346) with atypical dihedral angles (ψ, φ) with other residues brought about an increase of thermostability and decrease of specific activity. Structural and functional properties of the mutants were analyzed using different spectroscopic methods. It seems that this residue is a critically conserved residue to support the functional flexibility for a fast kinetic bioluminescence reaction at the expense of lower stability.

  20. DISSOLUTION OF NEPTUNIUM OXIDE RESIDUES

    SciTech Connect

    Kyser, E

    2009-01-12

    This report describes the development of a dissolution flowsheet for neptunium (Np) oxide (NpO{sub 2}) residues (i.e., various NpO{sub 2} sources, HB-Line glovebox sweepings, and Savannah River National Laboratory (SRNL) thermogravimetric analysis samples). Samples of each type of materials proposed for processing were dissolved in a closed laboratory apparatus and the rate and total quantity of off-gas were measured. Samples of the off-gas were also analyzed. The quantity and type of solids remaining (when visible) were determined after post-dissolution filtration of the solution. Recommended conditions for dissolution of the NpO{sub 2} residues are: Solution Matrix and Loading: {approx}50 g Np/L (750 g Np in 15 L of dissolver solution), using 8 M nitric acid (HNO{sub 3}), 0.025 M potassium fluoride (KF) at greater than 100 C for at least 3 hours. Off-gas: Analysis of the off-gas indicated nitric oxide (NO), nitrogen dioxide (NO{sub 2}) and nitrous oxide (N{sub 2}O) as the only identified components. No hydrogen (H{sub 2}) was detected. The molar ratio of off-gas produced per mole of Np dissolved ranged from 0.25 to 0.4 moles of gas per mole of Np dissolved. A peak off-gas rate of {approx}0.1 scfm/kg bulk oxide was observed. Residual Solids: Pure NpO{sub 2} dissolved with little or no residue with the proposed flowsheet but the NpCo and both sweepings samples left visible solid residue after dissolution. For the NpCo and Part II Sweepings samples the residue amounted to {approx}1% of the initial material, but for the Part I Sweepings sample, the residue amounted to {approx}8 % of the initial material. These residues contained primarily aluminum (Al) and silicon (Si) compounds that did not completely dissolve under the flowsheet conditions. The residues from both sweepings samples contained minor amounts of plutonium (Pu) particles. Overall, the undissolved Np and Pu particles in the residues were a very small fraction of the total solids.

  1. Finite element calculation of residual stress in dental restorative material

    NASA Astrophysics Data System (ADS)

    Grassia, Luigi; D'Amore, Alberto

    2012-07-01

    A finite element methodology for residual stresses calculation in dental restorative materials is proposed. The material under concern is a multifunctional methacrylate-based composite for dental restorations, activated by visible light. Reaction kinetics, curing shrinkage, and viscoelastic relaxation functions were required as input data on a structural finite element solver. Post cure effects were considered in order to quantify the residual stresses coming out from natural contraction with respect to those debited to the chemical shrinkage. The analysis showed for a given test case that residual stresses frozen in the dental restoration at uniform temperature of 37°C are of the same order of magnitude of the strength of the dental composite material per se.

  2. The functions of tryptophan residues in membrane proteins

    SciTech Connect

    Schiffer, M.; Chang, C.H.; Stevens, F.J.

    1994-08-01

    Membrane proteins in general have a significantly higher Trp content than do soluble proteins. This is especially true for the M and L subunits of the photosynthetic reaction center from purple bacteria. The Trp residues are located mostly in the segments that connect the transmembrane helices. Further, they are concentrated at the periplasmic side of the complex. Within the protein subunits, many form hydrogen bonds with carbonyl oxygens of the main chain, thereby stabilizing the protein. On the surface of the molecule, they are correctly positioned to form hydrogen bonds with the lipid head groups while their hydrophobic rings are immersed in the lipid part of the bilayer. We suggest that Trp residues are involved in the translocation of protein through the membrane and that following translocation, Trp residues serve as anchors on the periplasmic side of the membrane.

  3. Cross-coupling reaction with lithium methyltriolborate.

    PubMed

    Yamamoto, Yasunori; Ikizakura, Kazuya; Ito, Hajime; Miyaura, Norio

    2012-12-28

    We newly developed lithium methyltriolborate as an air-stable white solid that is convenient to handle. The good performance of this triolborate for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions with haloarenes. Cross-coupling reaction of [MeB(OCH₂)₃CCH₃]Li with aryl halides occurred in the presence of Pd(OAc)₂/RuPhos complex in refluxing MeOH/H₂O and the absence of bases.

  4. Hypersensitivity reactions to carboplatin in children.

    PubMed

    Lazzareschi, Ilaria; Ruggiero, Antonio; Riccardi, Riccardo; Attinà, Giorgio; Colosimo, Cesare; Lasorella, Anna

    2002-05-01

    Hypersensitivity reactions to carboplatin are rare but sometimes life-threatening events may occur requiring discontinuation of treatment. In our study, we describe clinical features and diagnostic procedures of carboplatin-associated reactions in children affected by low-grade astrocytoma and treated with multiple courses of carboplatin. In 6 out of 29 children, we reported allergic events. We also report a desensitization protocol for carboplatin administration, which allowed the patients to receive effective treatment without adverse reactions.

  5. A reusable prepositioned ATP reaction chamber

    NASA Technical Reports Server (NTRS)

    Hoffman, D. G.

    1972-01-01

    Luminescence biometer detects presence of life by means of light-emitting chemical reaction of luciferin and luciferase with adenosine triphosphate (ATP) that occurs in all living cells. Amount of light in reaction chamber is measured to determine presence and extent of life.

  6. Overcoming residual stresses and machining distortion in the production of aluminum alloy satellite boxes.

    SciTech Connect

    Younger, Mandy S.; Eckelmeyer, Kenneth Hall

    2007-11-01

    Distortion frequently occurs during machining of age hardening aluminum alloys due to residual stresses introduced during the quenching step in the heat treatment process. This report quantifies, compares, and discusses the effectiveness of several methods for minimizing residual stresses and machining distortion in aluminum alloys 7075 and 6061.

  7. Residual effects of flurazepam and brotizolam on psychomotor performance

    PubMed Central

    Krueger, H.; Müller-Limmroth, W.

    1983-01-01

    1 Residual effects of brotizolam (0.25 mg) and flurazepam (30 mg) were studied in healthy young adults. Performance and subjective assessments were observed from 7 to 8 h after overnight ingestion, and effects were compared with that of placebo. 2 Visuo-motor coordination, visuo-mental processing time, visuo-motor reaction time and reading errors were not impaired with brotizolam. 3 There were residual effects with 30 mg flurazepam. Visuo-motor coordination, visuo-mental processing time, visuo-motor reaction time, and reading errors were impaired compared with placebo and 0.25 mg brotizolam. 4 Subjective assessments of performance correlated with measured performance. There was a decrease with flurazepam (visuo-motor coordination and visuo-mental processing time) compared with placebo. PMID:6661380

  8. Causes and Outcomes of Pediatric Injuries Occurring at School.

    ERIC Educational Resources Information Center

    Di Scala, Carla; Gallagher, Susan Scavo; Schneps, Sue E.

    1997-01-01

    Used the National Pediatric Trauma Registry, which collects data on child injuries requiring hospitalization, to examine causes and outcomes of injuries occurring at school. Analysis of 1,558 cases indicated that most injuries were unintentional and occurred among students age 10-14 years. Nearly half occurred in recreational areas. Falls and…

  9. Theoretical considerations for Reaction-Formed Silicon Carbide (RFSC) formation by molten silicon infiltration into slurry-derived preforms

    NASA Technical Reports Server (NTRS)

    Behrendt, D. R.; Singh, M.

    1993-01-01

    For reaction-formed silicon carbide (RFSC) ceramics produced by silicon melt infiltration of porous carbon preforms, equations are developed to relate the amount of residual silicon to the initial carbon density. Also, for a slurry derived preform containing both carbon and silicon powder, equations are derived which relate the amount of residual silicon in the RFSC to the relative density of the carbon in the preform and to the amount of silicon powder added to the slurry. For a porous carbon preform that does not have enough porosity to prevent choking-off of the silicon infiltration, these results show that complete silicon infiltration can occur by adding silicon powder to the slurry mixture used to produce these preforms.

  10. Total radioactive residues and residues of [36Cl]chlorate in market size broilers.

    PubMed

    Smith, David J; Byrd, James A; Anderson, Robin C

    2007-07-11

    The oral administration of chlorate salts reduces the numbers of Gram-negative pathogens in gastrointestinal tracts of live food animals. Although the efficacy of chlorate salts has been demonstrated repeatedly, the technology cannot be introduced into commercial settings without first demonstrating that chlorate residues, and metabolites of chlorate remaining in edible tissues, represent a negligible risk to consumers. Typically, a first step in this risk assessment is to quantify the parent compound and to identify metabolites remaining in edible tissues of animals treated with the experimental compound. The objectives of this study were to determine the pathway(s) of chlorate metabolism in market broilers and to determine the magnitude of chlorate residues remaining in edible tissues. To this end, 12 broilers (6 weeks; 2.70+/-0.34 kg) were randomly assigned to three treatments of 7.4, 15.0, and 22.5 mM sodium [36Cl]chlorate dissolved in drinking water (n=4 broilers per treatment). Exposure to chlorate, dissolved in drinking water, occurred at 0 and 24 h (250 mL per exposure), feed was withdrawn at hour 38, water was removed at hour 48, and birds were slaughtered at hour 54 (16 h after feed removal and 8 h after water removal). The radioactivity was rapidly eliminated in excreta with 69-78% of the total administered radioactivity being excreted by slaughter. Total radioactive residues were proportional to dose in all edible tissues with chloride ion comprising greater than 98.5% of the radioactive residue for the tissue (9.4-97.8 ppm chlorate equivalents). Chlorate residues were typically greatest in the skin (0.33-0.82 ppm), gizzard (0.1-0.137 ppm), and dark muscle (0.05-0.14 ppm). Adipose, liver, and white muscle tissue contained chlorate concentrations from 0.03 to 0.13 ppm. In contrast, chlorate concentrations in excreta eliminated during the 6 h period prior to slaughter ranged from 53 to 71 ppm. Collectively, these data indicate that broilers rapidly

  11. Total radioactive residues and residues of [36Cl]chlorate in market size broilers.

    PubMed

    Smith, David J; Byrd, James A; Anderson, Robin C

    2007-07-11

    The oral administration of chlorate salts reduces the numbers of Gram-negative pathogens in gastrointestinal tracts of live food animals. Although the efficacy of chlorate salts has been demonstrated repeatedly, the technology cannot be introduced into commercial settings without first demonstrating that chlorate residues, and metabolites of chlorate remaining in edible tissues, represent a negligible risk to consumers. Typically, a first step in this risk assessment is to quantify the parent compound and to identify metabolites remaining in edible tissues of animals treated with the experimental compound. The objectives of this study were to determine the pathway(s) of chlorate metabolism in market broilers and to determine the magnitude of chlorate residues remaining in edible tissues. To this end, 12 broilers (6 weeks; 2.70+/-0.34 kg) were randomly assigned to three treatments of 7.4, 15.0, and 22.5 mM sodium [36Cl]chlorate dissolved in drinking water (n=4 broilers per treatment). Exposure to chlorate, dissolved in drinking water, occurred at 0 and 24 h (250 mL per exposure), feed was withdrawn at hour 38, water was removed at hour 48, and birds were slaughtered at hour 54 (16 h after feed removal and 8 h after water removal). The radioactivity was rapidly eliminated in excreta with 69-78% of the total administered radioactivity being excreted by slaughter. Total radioactive residues were proportional to dose in all edible tissues with chloride ion comprising greater than 98.5% of the radioactive residue for the tissue (9.4-97.8 ppm chlorate equivalents). Chlorate residues were typically greatest in the skin (0.33-0.82 ppm), gizzard (0.1-0.137 ppm), and dark muscle (0.05-0.14 ppm). Adipose, liver, and white muscle tissue contained chlorate concentrations from 0.03 to 0.13 ppm. In contrast, chlorate concentrations in excreta eliminated during the 6 h period prior to slaughter ranged from 53 to 71 ppm. Collectively, these data indicate that broilers rapidly

  12. Associating gunpowder and residues from commercial ammunition using compositional analysis.

    PubMed

    MacCrehan, William A; Reardon, Michelle R; Duewer, David L

    2002-03-01

    Qualitatively identifying and quantitatively determining the additives in smokeless gunpowder to calculate a numerical propellant to stabilizer (P/S) ratio is a new approach to associate handgun-fired organic gunshot residues (OGSR) with unfired powder. In past work, the P/S values of handgun OGSR and cartridges loaded with known gunpowders were evaluated. In this study, gunpowder and residue samples were obtained from seven boxes of commercial 38 caliber ammunition with the goals of associating cartridges within a box and matching residues to unfired powders, based on the P/S value and the qualitative identity of the additives. Gunpowder samples from four of the seven boxes of ammunition could be easily differentiated. When visual comparisons of the cartridge powders were considered in addition to composition, powder samples from all seven boxes of ammunition could be reliably differentiated. Handgun OGSR was also collected and evaluated in bulk as well as for individual particles. In some cases, residues could be reliably differentiated based on P/S and additive identity. It was instructive to evaluate the composition of individual unfired gunpowder and OGSR particles. We determined that both the numerical centroid and dispersity of the P/S measurements provide information for associations and exclusions. Associating measurements from residue particles with those of residue samples collected from a test firing of the same weapon and ammunition appears to be a useful approach to account for any changes in composition that occur during the firing process.

  13. Identification of Telomerase-activating Blends From Naturally Occurring Compounds.

    PubMed

    Ait-Ghezala, Ghania; Hassan, Samira; Tweed, Miles; Paris, Daniel; Crynen, Gogce; Zakirova, Zuchra; Crynen, Stefan; Crawford, Fiona

    2016-06-01

    Context • Telomeres are repeated deoxyribonucleic acid (DNA) sequences (TTAGGG) that are located on the 5' ends of chromosomes, and they control the life span of eukaryotic cells. Compelling evidence has shown that the length of a person's life is dictated by the limited number of times that a human cell can divide. The enzyme telomerase has been shown to bind to and extend the length of telomeres. Thus, strategies for activating telomerase may help maintain telomere length and, thus, may lead to improved health during aging. Objective • The current study intended to investigate the effects of several natural compounds on telomerase activity in an established cell model of telomere shortening (ie, IMR90 cells). Design • The research team designed an in vitro study. Setting • The study was conducted at Roskamp Institute in Sarasota, FL, USA. Intervention • The tested single compounds were (1) α-lipoic acid, (1) green tea extract, (2) dimethylaminoethanol L-bitartrate (DMAE L-bitartrate), (3) N-acetyl-L-cysteine hydrochloride (HCL), (4) chlorella powder, (5) L-carnosine, (6) vitamin D3, (7) rhodiola PE 3%/1%, (8) glycine, (9) French red wine extract, (10) chia seed extract, (11) broccoli seed extract, and (12) Astragalus (TA-65). The compounds were tested singly and as blends. Outcome Measures • Telomerase activity for single compounds and blends of compounds was measured by the TeloTAGGG telomerase polymerase chain reaction (PCR) enzyme-linked immunosorbent assay (ELISA). The 4 most potent blends were investigated for their effects on cancer-cell proliferation and for their potential effects on the cytotoxicity and antiproliferative activity of a chemotherapeutic agent, the topoisomerase I inhibitor topotecan. The benefits of 6 population doublings (PDs) were measured for the single compounds, and the 4 blends were compared to 3 concentrations of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Results • Certain of the compounds increased

  14. Identification of Telomerase-activating Blends From Naturally Occurring Compounds.

    PubMed

    Ait-Ghezala, Ghania; Hassan, Samira; Tweed, Miles; Paris, Daniel; Crynen, Gogce; Zakirova, Zuchra; Crynen, Stefan; Crawford, Fiona

    2016-06-01

    Context • Telomeres are repeated deoxyribonucleic acid (DNA) sequences (TTAGGG) that are located on the 5' ends of chromosomes, and they control the life span of eukaryotic cells. Compelling evidence has shown that the length of a person's life is dictated by the limited number of times that a human cell can divide. The enzyme telomerase has been shown to bind to and extend the length of telomeres. Thus, strategies for activating telomerase may help maintain telomere length and, thus, may lead to improved health during aging. Objective • The current study intended to investigate the effects of several natural compounds on telomerase activity in an established cell model of telomere shortening (ie, IMR90 cells). Design • The research team designed an in vitro study. Setting • The study was conducted at Roskamp Institute in Sarasota, FL, USA. Intervention • The tested single compounds were (1) α-lipoic acid, (1) green tea extract, (2) dimethylaminoethanol L-bitartrate (DMAE L-bitartrate), (3) N-acetyl-L-cysteine hydrochloride (HCL), (4) chlorella powder, (5) L-carnosine, (6) vitamin D3, (7) rhodiola PE 3%/1%, (8) glycine, (9) French red wine extract, (10) chia seed extract, (11) broccoli seed extract, and (12) Astragalus (TA-65). The compounds were tested singly and as blends. Outcome Measures • Telomerase activity for single compounds and blends of compounds was measured by the TeloTAGGG telomerase polymerase chain reaction (PCR) enzyme-linked immunosorbent assay (ELISA). The 4 most potent blends were investigated for their effects on cancer-cell proliferation and for their potential effects on the cytotoxicity and antiproliferative activity of a chemotherapeutic agent, the topoisomerase I inhibitor topotecan. The benefits of 6 population doublings (PDs) were measured for the single compounds, and the 4 blends were compared to 3 concentrations of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Results • Certain of the compounds increased

  15. Drug hypersensitivity reactions involving skin.

    PubMed

    Hausmann, Oliver; Schnyder, Benno; Pichler, Werner J

    2010-01-01

    Immune reactions to drugs can cause a variety of diseases involving the skin, liver, kidney, lungs, and other organs. Beside immediate, IgE-mediated reactions of varying degrees (urticaria to anaphylactic shock), many drug hypersensitivity reactions appear delayed, namely hours to days after starting drug treatment, showing a variety of clinical manifestations from solely skin involvement to fulminant systemic diseases which may be fatal. Immunohistochemical and functional studies of drug-specific T cells in patients with delayed reactions confirmed a predominant role for T cells in the onset and maintenance of immune-mediated delayed drug hypersensitivity reactions (type IV reactions). In these reactions, drug-specific CD4+ and CD8+ T cells are stimulated by drugs through their T cell receptors (TCR). Drugs can stimulate T cells in two ways: they can act as haptens and bind covalently to larger protein structures (hapten-carrier model), inducing a specific immune response. In addition, they may accidentally bind in a labile, noncovalent way to a particular TCR of the whole TCR repertoire and possibly also major histocompatibility complex (MHC)-molecules - similar to their pharmacologic action. This seems to be sufficient to reactivate certain, probably in vivo preactivated T cells, if an additional interaction of the drug-stimulated TCR with MHC molecules occurs. The mechanism was named pharmacological interaction of a drug with (immune) receptor and thus termed the p-i concept. This new concept may explain the frequent skin symptoms in drug hypersensitivity to oral or parenteral drugs. Furthermore, the various clinical manifestations of T cell-mediated drug hypersensitivity may be explained by distinct T cell functions leading to different clinical phenotypes. These data allowed a subclassification of the delayed hypersensitivity reactions (type IV) into T cell reactions which, by releasing certain cytokines and chemokines, preferentially activate and recruit

  16. Chemical potential and reaction electronic flux in symmetry controlled reactions.

    PubMed

    Vogt-Geisse, Stefan; Toro-Labbé, Alejandro

    2016-07-15

    In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the Cs enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA'(ξ) and JA'' (ξ). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc.

  17. Residual Particle Sizes of Evaporating Droplets: Ammonium Sulfate and Aldehydes

    NASA Astrophysics Data System (ADS)

    Sedehi, N.; Galloway, M. M.; De Haan, D. O.

    2012-12-01

    The reactions of carbonyls like glyoxal, methylglyoxal, and glycolaldehyde, with ammonium salts have been proposed as significant sources of atmospheric organic aerosol. Aerosol containing these compounds was generated in the laboratory using the Vibrating Orifice Aerosol Generator (VOAG). The particles were completely dried before they were measured using a SMPS system. The nonvolatile fraction of the resulting aerosol was measured. The drying times were varied between two and twenty minutes, and for ammonium sulfate and glyoxal reactions, minimum residual particle sizes were reached after 3.5 minutes. Reactions of glyoxal, glycolaldehyde, and methylglyoxal with ammonium sulfate appeared to have lower non-volatile fractions remaining at higher starting concentrations, suggesting that a constant 'excess volume,' likely water, was present in the residual particles that could not be evaporated even after 20 minutes of drying. These excess volumes were not observed in our previous experiments with aldehydes but no ammonium sulfate present. At the highest concentrations tested (100 uM), non-volatile fractions of aldehydes present in residual particles were 16 (±17) %, 41 (±28) %, and 17(±32) % for glyoxal, glycolaldehyde, and methylglyoxal, respectively.

  18. A naturally occurring, noncanonical GTP aptamer made of simple tandem repeats.

    PubMed

    Curtis, Edward A; Liu, David R

    2014-01-01

    Recently, we used in vitro selection to identify a new class of naturally occurring GTP aptamer called the G motif. Here we report the discovery and characterization of a second class of naturally occurring GTP aptamer, the "CA motif." The primary sequence of this aptamer is unusual in that it consists entirely of tandem repeats of CA-rich motifs as short as three nucleotides. Several active variants of the CA motif aptamer lack the ability to form consecutive Watson-Crick base pairs in any register, while others consist of repeats containing only cytidine and adenosine residues, indicating that noncanonical interactions play important roles in its structure. The circular dichroism spectrum of the CA motif aptamer is distinct from that of A-form RNA and other major classes of nucleic acid structures. Bioinformatic searches indicate that the CA motif is absent from most archaeal and bacterial genomes, but occurs in at least 70 percent of approximately 400 eukaryotic genomes examined. These searches also uncovered several phylogenetically conserved examples of the CA motif in rodent (mouse and rat) genomes. Together, these results reveal the existence of a second class of naturally occurring GTP aptamer whose sequence requirements, like that of the G motif, are not consistent with those of a canonical secondary structure. They also indicate a new and unexpected potential biochemical activity of certain naturally occurring tandem repeats.

  19. [Consensus position document on the child with an allergic reaction after vaccination or an allergy to vaccine components].

    PubMed

    Echeverría Zudaire, L; Ortigosa Del Castillo, L; Alonso Lebrero, E; Álvarez García, F J; Cortés Álvarez, N; García Sánchez, N; Martorell Aragonés, A

    2015-07-01

    Vaccinations are one of the main public health tools for the control of vaccine-preventable diseases. If a child is labeled to have had an allergic reaction to a vaccine, the next immunizations will probably be suspended in that child, with the risks involved in this decision. The rate of severe allergic reactions is very low, ranging between 0.5-1/100,000 doses. The causes of allergic reactions to vaccines, more than the vaccine itself, are often due to residual protein components in the manufacturing process, such as gelatin or egg, and rarely to yeast or latex. Most of vaccine reactions are mild, localized at the site of injection, but in some circumstances, severe anaphylactic reactions can occur. If an immediate-type allergic reaction is suspected when vaccinating, or a child allergic to some of the vaccine components has to be vaccinated, a correct diagnosis of the possible allergy has to be made. The usual components of each vaccine should be known, in order to determine if vaccination can be performed safely on the child. PMID:25648960

  20. [Consensus position document on the child with an allergic reaction after vaccination or an allergy to vaccine components].

    PubMed

    Echeverría Zudaire, L; Ortigosa Del Castillo, L; Alonso Lebrero, E; Álvarez García, F J; Cortés Álvarez, N; García Sánchez, N; Martorell Aragonés, A

    2015-07-01

    Vaccinations are one of the main public health tools for the control of vaccine-preventable diseases. If a child is labeled to have had an allergic reaction to a vaccine, the next immunizations will probably be suspended in that child, with the risks involved in this decision. The rate of severe allergic reactions is very low, ranging between 0.5-1/100,000 doses. The causes of allergic reactions to vaccines, more than the vaccine itself, are often due to residual protein components in the manufacturing process, such as gelatin or egg, and rarely to yeast or latex. Most of vaccine reactions are mild, localized at the site of injection, but in some circumstances, severe anaphylactic reactions can occur. If an immediate-type allergic reaction is suspected when vaccinating, or a child allergic to some of the vaccine components has to be vaccinated, a correct diagnosis of the possible allergy has to be made. The usual components of each vaccine should be known, in order to determine if vaccination can be performed safely on the child.

  1. Application of the organic on water reactions to prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Kolb, Vera M.

    2012-10-01

    The old view that prebiotic reactions in water are hampered by the low solubility of the organic compounds in water is now being revised due to the discoveries of the reactions "on water". These reactions occur in the heterogeneous system comprising of the organic compounds and water. Unexpectedly, such reactions are extremely efficient; they often give quantitative yields, and are accelerated in the presence of water as compared to the organic solvents. These "on water" reactions are not the same as the "in water" reactions, which occur in solution, and are thus homogenous. Examples of the "on water" reactions include Diels-Alder, Claisen, Passerini and Ugi reactions, among many others. Some of these reactions are multicomponent, but give a single product. We survey a selected number of the "on water" reactions, which have a potential prebiotic applications.

  2. Dynamic Residual Complexity of the Isoliquiritigenin-Liquiritigenin Interconversion During Bioassay†

    PubMed Central

    Simmler, Charlotte; Hajirahimkhan, Atieh; Lankin, David C.; Bolton, Judy L.; Jones, Tristesse; Soejarto, Djaja D.; Chen, Shao-Nong; Pauli, Guido F.

    2013-01-01

    Bioactive components in food plants can undergo dynamic processes that involve multiple chemical species. For example, 2′-hydroxychalcones can readily isomerize into flavanones. Although chemically well documented, this reaction has barely been explored in the context of cell-based assays. The present time-resolved study fills this gap by investigating the isomerization of isoliquiritigenin (a 2′-hydroxychalcone) and liquiritigenin (a flavanone) in two culture media (DMEM and RPMI) with and without MCF-7 cells, using HPLC-DAD-ESI/APCI-MS for analysis. Both compounds isomerized and epimerized under all investigated biological conditions, leading to mixtures of isoliquiritigenin and R/S-liquiritigenin, with 19.6% R enantiomeric excess. Consequently, all three species can potentially modulate the biological responses. This exemplifies dynamic residual complexity and demonstrates how both non-chiral reactions and enantiomeric discrimination can occur in bioassay media, with or without cells. The findings highlight the importance of controlling in situ chemical reactivity, influenced by biological systems when evaluating the mode of action of bioactives. PMID:23427769

  3. Lymphangitis occurring after intralesional Candida antigen injection for verruca vulgaris.

    PubMed

    Zubritsky, Lindsey; Alikhan, Ali

    2016-01-01

    Verruca vulgaris is a common dermatological disease with many treatment options including destructive modalities and more recently, immunotherapy. Intralesional injections of Candida antigen have been described as a safe and effective treatment with the most common adverse reactions including local reactions (burning, blistering, peeling), local erythema, and pain at the injection site. We describe the first reported case of lymphangitis after intralesional Candida antigen injection for verruca vulgaris in a healthy 18-year-old woman. The lymphangitis rapidly resolved with ibuprofen and cold compresses. Physicians should be aware of this potential adverse reaction when using this treatment modality and should be familiar with appropriate treatment of subsequent lymphangitis. PMID:27617613

  4. Dry fermentation of agricultural residues

    NASA Astrophysics Data System (ADS)

    Jewell, W. J.; Chandler, J. A.; Dellorto, S.; Fanfoni, K. J.; Fast, S.; Jackson, D.; Kabrick, R. M.

    1981-09-01

    A dry fermentation process is discussed which converts agricultural residues to methane, using the residues in their as produced state. The process appears to simplify and enhance the possibilities for using crop residues as an energy source. The major process variables investigated include temperature, the amount and type of inoculum, buffer requirements, compaction, and pretreatment to control the initial available organic components that create pH problems. A pilot-scale reactor operation on corn stover at a temperature of 550 C, with 25 percent initial total solids, a seed-to-feed ratio of 2.5 percent, and a buffer-to-feed ratio of 8 percent achieved 33 percent total volatile solids destruction in 60 days. Volumetric biogas yields from this unit were greater than 1 vol/vol day for 12 days, and greater than 0.5 vol/vol day for 32 days, at a substrate density of 169 kg/m (3).

  5. Reactions among indoor pollutants.

    PubMed

    Weschler, C J

    2001-09-13

    This paper reviews recent studies in the field of "indoor chemistry"--reactions among indoor pollutants. Advances have occurred in a number of areas. A mouse bioassay procedure has shown that ozone/terpene reactions produce products that are more irritating than their precursors, although the agents responsible for the deleterious effects remain to be determined. Indoor ozone/terpene reactions have been demonstrated to produce hydroxyl radicals, hydrogen peroxide, sub-micron particles, and ultrafine particles. New analytical techniques such as LC/MS and thermal desorption mass spectrometry have greatly improved our knowledge of the condensed-phase species associated with such particles. Indeed, the latter approach has identified a number of short-lived or thermally labile species, including organic hydroperoxides, peroxy-hemiacetals, and secondary ozonides, which would be missed by more conventional techniques. Investigators are making inroads into the poorly understood area of indoor heterogeneous chemistry. Systems studied include ozone/HVAC components, ozone/paint, and ozone/carpets. Another heterogeneous process that has been further examined is the indoor formation of nitrous acid through NO2/surface chemistry. Emissions from indoor sources that contribute to, or are altered by, indoor chemistry have also received attention. Researchers have expanded our awareness of reactive chemicals that can emanate from wood coatings and other products commonly used indoors. In a related vein, a number of recent investigations have shown that emissions from materials can be significantly altered by indoor chemistry. On the theoretical side, an outdoor atmospheric chemistry model has been modified for use as an indoor air model, the effects of ventilation rates on indoor chemistry have been simulated, and initial steps have been taken in applying computational fluid dynamics (CFD) methods to indoor chemistry.

  6. A matching algorithm for catalytic residue site selection in computational enzyme design.

    PubMed

    Lei, Yulin; Luo, Wenjia; Zhu, Yushan

    2011-09-01

    A loop closure-based sequential algorithm, PRODA_MATCH, was developed to match catalytic residues onto a scaffold for enzyme design in silico. The computational complexity of this algorithm is polynomial with respect to the number of active sites, the number of catalytic residues, and the maximal iteration number of cyclic coordinate descent steps. This matching algorithm is independent of a rotamer library that enables the catalytic residue to take any required conformation during the reaction coordinate. The catalytic geometric parameters defined between functional groups of transition state (TS) and the catalytic residues are continuously optimized to identify the accurate position of the TS. Pseudo-spheres are introduced for surrounding residues, which make the algorithm take binding into account as early as during the matching process. Recapitulation of native catalytic residue sites was used as a benchmark to evaluate the novel algorithm. The calculation results for the test set show that the native catalytic residue sites were successfully identified and ranked within the top 10 designs for 7 of the 10 chemical reactions. This indicates that the matching algorithm has the potential to be used for designing industrial enzymes for desired reactions.

  7. Coatings for protection of equipment for biochemical processing of geothermal residues: Progress report FY`97

    SciTech Connect

    Allan, M.L.

    1997-11-01

    Thermal sprayed ethylene methacrylic acid (EMAA) and ethylene tetrafluoroethylene (ETFE), spray-and-bake ETFE and polyvinylidene fluoride (PVDF) and brushable ceramic-epoxy coatings were evaluated for corrosion protection in a biochemical process to treat geothermal residues. Coupon, Atlas cell, peel strength, cathodic disbondment and abrasion tests were performed in aggressive environments including geothermal sludge, hypersaline brine and sulfur-oxidizing bacteria (Thiobacillus ferrooxidans) to determine suitability for protecting storage tanks and reaction vessels. It was found that all of the coatings were resistant to chemical attack and biodegradation at the test temperature of 55 C. The EMAA coatings protected 316L stainless steel from corrosion in coupon tests. However, corrosion of mild steel substrates thermal sprayed with EMAA and ETFE occurred in Atlas cell tests that simulated a lined reactor operating environment and this resulted in decreased adhesive strength. Peel tests to measure residual adhesion revealed that failure mode was dependent on exposure conditions. Abrasion tests showed that the ceramic-epoxy had good resistance to the abrasive effects of sludge. Thermal sprayed EMAA coatings also displayed abrasion resistance. Cathodic disbondment tests in brine at room temperature indicated that EMAA coatings are resistant to disbondment at applied potentials of {minus}780 to {minus}1,070 mV SCE for the test conditions and duration. Slight disbondment of one specimen occurred at a potential of {minus}1,500 mV SCE. The EMAA may be suited to use in conjunction with cathodic protection although further long-term, higher temperature testing would be needed.

  8. COATINGS FOR PROTECTION OF EQUIPMENT FOR BIOCHEMICAL PROCESSING OF GEOTHERMAL RESIDUES: PROGRESS REPORT FY 97

    SciTech Connect

    ALLAN,M.L.

    1997-11-01

    Thermal sprayed ethylene methacrylic acid (EMAA) and ethylene tetrafluoroethylene (ETFE), spray-and-bake ETFE and polyvinylidene fluoride (PVDF) and brushable ceramic-epoxy coatings were evaluated for corrosion protection in a biochemical process to treat geothermal residues. The findings are also relevant to other moderate temperature brine environments where corrosion is a problem. Coupon, Atlas cell, peel strength, cathodic disbondment and abrasion tests were performed in aggressive environments including geothermal sludge, hypersaline brine and sulfur-oxidizing bacteria (Thiobadus ferrooxidans) to determine suitability for protecting storage tanks and reaction vessels. It was found that all of the coatings were resistant to chemical attack and biodegradation at the test temperature of 55 C. The EMAA coatings protected 316L stainless steel from corrosion in coupon tests. However, corrosion of mild steel substrates thermal sprayed with EMAA and ETFE occurred in Atlas cell tests that simulated a lined reactor operating environment and this resulted in decreased adhesive strength. Peel tests to measure residual adhesion revealed that failure mode was dependent on exposure conditions. Long-term tests on the durability of ceramic-epoxy coatings in brine and bacteria are ongoing. Initial indications are that this coating has suitable characteristics. Abrasion tests showed that the ceramic-epoxy had good resistance to the abrasive effects of sludge. Thermal sprayed EMAA coatings also displayed abrasion resistance. Cathodic disbondment tests in brine at room temperature indicated that EMAA coatings are resistant to disbondment at applied potentials of {minus}780 to {minus}1,070 mV SCE for the test conditions and duration. Slight disbondment of one specimen occurred at a potential of {minus}1,500 mV SCE. The EMAA may be suited to use in conjunction with cathodic protection although further long-term, higher temperature testing would be needed.

  9. Residual contact restraints in cryogenics

    NASA Astrophysics Data System (ADS)

    Cretegny, J. F.; Demonicault, J. M.

    The use of residual stress measurements to evaluate the state of cryogenic turbomachines, whose surfaces are worn by the working conductions in dry contact, is addressed. Their contribution to the understanding of the reasons of possible ruptures is considered. It is stated that residual stress measurements should be used as a complementary tool rather than as input data for models. It is shown, thanks to two examples concerning the ball bearings and splines of the liquid hydrogen turbopump of the Vulcain engine, what can be expected from such techniques. Total exploitation of the results has still to be done, but preliminary results are quite encouraging.

  10. Collection of sugarcane crop residue for energy

    SciTech Connect

    Eiland, B.R.; Clayton, J.E.

    1982-12-01

    Crop residue left after sugarcane harvesting was recovered using a forage harvester and a large round baler. The quantity, bulk density and moisture content of the crop residue was determined in four fields. Crop residue from 7 ha was burned in boilers at a sugar mill. Samples of this residue were tested by a laboratory and compared to sugarcane bagasse.

  11. Knockout reactions on p-shell nuclei for tests of structure and reaction models

    NASA Astrophysics Data System (ADS)

    Kuchera, A. N.; Bazin, D.; Babo, M.; Baumann, T.; Bowry, M.; Bradt, J.; Brown, J.; Deyoung, P. A.; Elman, B.; Finck, J. E.; Gade, A.; Grinyer, G. F.; Jones, M. D.; Lunderberg, E.; Redpath, T.; Rogers, W. F.; Stiefel, K.; Thoennessen, M.; Weisshaar, D.; Whitmore, K.

    2015-10-01

    A series of knockout reactions on p-shell nuclei were studied to extract exclusive cross sections and to investigate the neutron knockout mechanism. The measured cross sections provide stringent tests of shell model and ab initio calculations while measurements of neutron+residual coincidences test the accuracy and validity of reaction models used to predict cross sections. Six different beams ranging from A = 7 to 12 were produced at the NSCL totaling measurements of nine different reaction settings. The reaction settings were determined by the magnetic field of the Sweeper magnet which bends the residues into charged particle detectors. The reaction target was surrounded by the high efficiency CsI array, CAESAR, to tag gamma rays for cross section measurements of low-lying excited states. Additionally, knocked out neutrons were detected with MoNA-LISA in coincidence with the charged residuals. Preliminary results will be discussed. This work is partially supported by the National Science Foundation under Grant No. PHY11-02511 and the Department of Energy National Nuclear Security Administration under Award No. DE-NA0000979.

  12. Mapping residual transmission for malaria elimination.

    PubMed

    Reiner, Robert C; Le Menach, Arnaud; Kunene, Simon; Ntshalintshali, Nyasatu; Hsiang, Michelle S; Perkins, T Alex; Greenhouse, Bryan; Tatem, Andrew J; Cohen, Justin M; Smith, David L

    2015-12-29

    Eliminating malaria from a defined region involves draining the endemic parasite reservoir and minimizing local malaria transmission around imported malaria infections . In the last phases of malaria elimination, as universal interventions reap diminishing marginal returns, national resources must become increasingly devoted to identifying where residual transmission is occurring. The needs for accurate measures of progress and practical advice about how to allocate scarce resources require new analytical methods to quantify fine-grained heterogeneity in malaria risk. Using routine national surveillance data from Swaziland (a sub-Saharan country on the verge of elimination), we estimated individual reproductive numbers. Fine-grained maps of reproductive numbers and local malaria importation rates were combined to show 'malariogenic potential', a first for malaria elimination. As countries approach elimination, these individual-based measures of transmission risk provide meaningful metrics for planning programmatic responses and prioritizing areas where interventions will contribute most to malaria elimination.

  13. Method For Characterizing Residual Stress In Metals

    DOEpatents

    Jacobson, Loren A.; Michel, David J.; Wyatt, Jeffrey R.

    2002-12-03

    A method is provided for measuring the residual stress in metals. The method includes the steps of drilling one or more holes in a metal workpiece to a preselected depth and mounting one or more acoustic sensors on the metal workpiece and connecting the sensors to an electronic detecting and recording device. A liquid metal capable of penetrating into the metal workpiece placed at the bottom of the hole or holes. A recording is made over a period of time (typically within about two hours) of the magnitude and number of noise events which occur as the liquid metal penetrates into the metal workpiece. The magnitude and number of noise events are then correlated to the internal stress in the region of the workpiece at the bottom of the hole.

  14. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  15. Quantitation of the residual DNA from rice-derived recombinant human serum albumin.

    PubMed

    Chen, Zhen; Dai, Huixia; Liu, Zhenwei; Zhang, Liping; Pang, Jianlei; Ou, Jiquan; Yang, Daichang

    2014-04-01

    Residual DNA in recombinant protein pharmaceuticals can potentially cause safety issues in clinical applications; thus, maximum residual limit has been established by drug safety authorities. Assays for residual DNA in Escherichia coli, yeast, and Chinese hamster ovary (CHO) cell expression systems have been established, but no rice residual DNA assay for rice expression systems has been designed. To develop an assay for the quantification of residual DNA that is produced from rice seed, we established a sensitive assay using quantitative real-time polymerase chain reaction (qPCR) based on the 5S ribosomal RNA (rRNA) genes. We found that a 40-cycle qPCR exhibited a linear response when the template concentration was in the range of 2×10(4) to 0.2pg of DNA per reaction in TaqMan and SYBR Green I assays. The amplification efficiency was 103 to 104%, and the amount of residual DNA from recombinant human serum albumin from Oryza sativa (OsrHSA) was less than 3.8ng per dosage, which was lower than that recommended by the World Health Organization (WHO). Our results indicate that the current purification protocol could efficiently remove residual DNA during manufacturing and processing. Furthermore, this protocol could be viable in other cereal crop endosperm expression systems for developing a residual DNA quantitation assay using the highly conserved 5S rRNA gene of the crops.

  16. Quantitation of the residual DNA from rice-derived recombinant human serum albumin.

    PubMed

    Chen, Zhen; Dai, Huixia; Liu, Zhenwei; Zhang, Liping; Pang, Jianlei; Ou, Jiquan; Yang, Daichang

    2014-04-01

    Residual DNA in recombinant protein pharmaceuticals can potentially cause safety issues in clinical applications; thus, maximum residual limit has been established by drug safety authorities. Assays for residual DNA in Escherichia coli, yeast, and Chinese hamster ovary (CHO) cell expression systems have been established, but no rice residual DNA assay for rice expression systems has been designed. To develop an assay for the quantification of residual DNA that is produced from rice seed, we established a sensitive assay using quantitative real-time polymerase chain reaction (qPCR) based on the 5S ribosomal RNA (rRNA) genes. We found that a 40-cycle qPCR exhibited a linear response when the template concentration was in the range of 2×10(4) to 0.2pg of DNA per reaction in TaqMan and SYBR Green I assays. The amplification efficiency was 103 to 104%, and the amount of residual DNA from recombinant human serum albumin from Oryza sativa (OsrHSA) was less than 3.8ng per dosage, which was lower than that recommended by the World Health Organization (WHO). Our results indicate that the current purification protocol could efficiently remove residual DNA during manufacturing and processing. Furthermore, this protocol could be viable in other cereal crop endosperm expression systems for developing a residual DNA quantitation assay using the highly conserved 5S rRNA gene of the crops. PMID:24388867

  17. Peanut-induced anaphylactic reactions.

    PubMed

    Burks, W; Bannon, G A; Sicherer, S; Sampson, H A

    1999-07-01

    Food allergies, particularly to peanuts, are a common cause of anaphylaxis. Approximately 125 people die each year in the USA secondary to food-induced anaphylaxis. Clinical anaphylaxis is a syndrome of diverse etiology and dramatic presentation of symptoms associated with the classic features of type I, IgE-mediated hypersensitivity [1]. Typically the term anaphylaxis connotes an immunologically-mediated event that occurs after exposure to certain foreign substances. This reaction results from the generation and release of a variety of potent biologically active mediators and their concerted effects on various target organs. Anaphylaxis is recognized by cutaneous, respiratory, cardiovascular, and gastrointestinal signs and symptoms occurring singly or in combination. This article focuses on allergic reactions to peanuts that manifest as signs and symptoms involving multiple target organs or the cardiovascular system alone.

  18. Thermodynamics of random reaction networks.

    PubMed

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

  19. Thermodynamics of random reaction networks.

    PubMed

    Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

    2015-01-01

    Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks. PMID:25723751

  20. Spatial model of autocatalytic reactions

    NASA Astrophysics Data System (ADS)

    de Anna, Pietro; di Patti, Francesca; Fanelli, Duccio; McKane, Alan J.; Dauxois, Thierry

    2010-05-01

    Biological cells with all of their surface structure and complex interior stripped away are essentially vesicles—membranes composed of lipid bilayers which form closed sacs. Vesicles are thought to be relevant as models of primitive protocells, and they could have provided the ideal environment for prebiotic reactions to occur. In this paper, we investigate the stochastic dynamics of a set of autocatalytic reactions, within a spatially bounded domain, so as to mimic a primordial cell. The discreteness of the constituents of the autocatalytic reactions gives rise to large sustained oscillations even when the number of constituents is quite large. These oscillations are spatiotemporal in nature, unlike those found in previous studies, which consisted only of temporal oscillations. We speculate that these oscillations may have a role in seeding membrane instabilities which lead to vesicle division. In this way synchronization could be achieved between protocell growth and the reproduction rate of the constituents (the protogenetic material) in simple protocells.

  1. Light in elementary biological reactions

    NASA Astrophysics Data System (ADS)

    Sundström, Villy

    2000-09-01

    Light plays an important role in biology. In this review we discuss several processes and systems where light triggers a biological response, i.e. photosynthesis, vision, photoreceptors. For these functions Nature has chosen simple elementary chemical reactions, which occur in highly specialized and organized structures. The high efficiency and specificity of these reactions make them interesting for applications in light energy conversion and opto-electronics. In order to emphasize the synergism in studies of natural and synthetic systems we will discuss a few of each kind, with similar functions. In all cases light triggers a rapid sequence of events, which makes ultrafast spectroscopy an ideal tool to disentangle reaction mechanisms and dynamics.

  2. Regulatory problems caused by contamination, a frequently overlooked cause of veterinary drug residues.

    PubMed

    Kennedy, D G; Cannavan, A; McCracken, R J

    2000-06-16

    The occurrence of violative residues of veterinary medicines and other, unauthorised, drugs in food of animal origin is an issue of popular concern within the European Union. Violations can occur as a result of improper use of a licensed product or through the illegal use of an unlicensed substance. However, a "violative" analytical result does not necessarily mean that abuse has occurred. Contamination of animal feedingstuffs, environmental contamination and animal-to-animal transfer of drugs can also cause residue violations. This paper reviews these inadvertent causes of residues violations in food, and includes data generated using chromatographic and non-chromatographic methods of analysis.

  3. Potential hazards of fumigant residues.

    PubMed Central

    Fishbein, L

    1976-01-01

    A spectrum of fumigants (primarily ethylene dibromide, 1,2-dibromo-3-chloropropane, ethylene oxide, symdibromotetetrachloroethane, 1,3-dichloropropene, dichlorovos, carbon tetrachloride, methyl bromide) as well as their degradation products in foodstuffs and soil have been examined mainly in regard to the potential mutagenicity of their residues. PMID:789068

  4. Solidification process for sludge residue

    SciTech Connect

    Pearce, K.L.

    1998-09-10

    This report investigates the solidification process used at 100-N Basin to solidify the N Basin sediment and assesses the N Basin process for application to the K Basin sludge residue material. This report also includes a discussion of a solidification process for stabilizing filters. The solidified matrix must be compatible with the Environmental Remediation Disposal Facility acceptance criteria.

  5. Leptogenesis and residual CP symmetry

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Ding, Gui-Jun; King, Stephen F.

    2016-03-01

    We discuss flavour dependent leptogenesis in the framework of lepton flavour models based on discrete flavour and CP symmetries applied to the type-I seesaw model. Working in the flavour basis, we analyse the case of two general residual CP symmetries in the neutrino sector, which corresponds to all possible semi-direct models based on a preserved Z 2 in the neutrino sector, together with a CP symmetry, which constrains the PMNS matrix up to a single free parameter which may be fixed by the reactor angle. We systematically study and classify this case for all possible residual CP symmetries, and show that the R-matrix is tightly constrained up to a single free parameter, with only certain forms being consistent with successful leptogenesis, leading to possible connections between leptogenesis and PMNS parameters. The formalism is completely general in the sense that the two residual CP symmetries could result from any high energy discrete flavour theory which respects any CP symmetry. As a simple example, we apply the formalism to a high energy S 4 flavour symmetry with a generalized CP symmetry, broken to two residual CP symmetries in the neutrino sector, recovering familiar results for PMNS predictions, together with new results for flavour dependent leptogenesis.

  6. Allergic reactions to foods by inhalation.

    PubMed

    James, John M; Crespo, Jesús Fernández

    2007-06-01

    Although allergic reactions to foods occur most commonly after ingestion, inhalation of foods can also be an underlying cause of these reactions. For example, published reports have highlighted the inhalation of allergens from fish, shellfish, seeds, soybeans, cereal grains, hen's egg, cow's milk, and many other foods in allergic reactions. Symptoms have typically included respiratory manifestations such as rhinoconjunctivitis, coughing, wheezing, dyspnea, and asthma. In some cases, anaphylaxis has been observed. In addition, there have been many investigations of occupational asthma following the inhalation of relevant food allergens. This report reviews the current literature focusing on allergic reactions to foods by inhalation.

  7. In situ dynamics of microbial communities during decomposition of wheat, rape, and alfalfa residues.

    PubMed

    Pascault, Noémie; Cécillon, Lauric; Mathieu, Olivier; Hénault, Catherine; Sarr, Amadou; Lévêque, Jean; Farcy, Pascal; Ranjard, Lionel; Maron, Pierre-Alain

    2010-11-01

    Microbial communities are of major importance in the decomposition of soil organic matter. However, the identities and dynamics of the populations involved are still poorly documented. We investigated, in an 11-month field experiment, how the initial biochemical quality of crop residues could lead to specific decomposition patterns, linking biochemical changes undergone by the crop residues to the respiration, biomass, and genetic structure of the soil microbial communities. Wheat, alfalfa, and rape residues were incorporated into the 0-15 cm layer of the soil of field plots by tilling. Biochemical changes in the residues occurring during degradation were assessed by near-infrared spectroscopy. Qualitative modifications in the genetic structure of the bacterial communities were determined by bacterial-automated ribosomal intergenic spacer analysis. Bacterial diversity in the three crop residues at early and late stages of decomposition process was further analyzed from a molecular inventory of the 16S rDNA. The decomposition of plant residues in croplands was shown to involve specific biochemical characteristics and microbial community dynamics which were clearly related to the quality of the organic inputs. Decay stage and seasonal shifts occurred by replacement of copiotrophic bacterial groups such as proteobacteria successful on younger residues with those successful on more extensively decayed material such as Actinobacteria. However, relative abundance of proteobacteria depended greatly on the composition of the residues, with a gradient observed from alfalfa to wheat, suggesting that this bacterial group may represent a good indicator of crop residues degradability and modifications during the decomposition process.

  8. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a glass like'' material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  9. APOLLO: A computer program for the calculation of chemical equilibrium and reaction kinetics of chemical systems

    SciTech Connect

    Nguyen, H.D.

    1991-11-01

    Several of the technologies being evaluated for the treatment of waste material involve chemical reactions. Our example is the in situ vitrification (ISV) process where electrical energy is used to melt soil and waste into a ``glass like`` material that immobilizes and encapsulates any residual waste. During the ISV process, various chemical reactions may occur that produce significant amounts of products which must be contained and treated. The APOLLO program was developed to assist in predicting the composition of the gases that are formed. Although the development of this program was directed toward ISV applications, it should be applicable to other technologies where chemical reactions are of interest. This document presents the mathematical methodology of the APOLLO computer code. APOLLO is a computer code that calculates the products of both equilibrium and kinetic chemical reactions. The current version, written in FORTRAN, is readily adaptable to existing transport programs designed for the analysis of chemically reacting flow systems. Separate subroutines EQREACT and KIREACT for equilibrium ad kinetic chemistry respectively have been developed. A full detailed description of the numerical techniques used, which include both Lagrange multiplies and a third-order integrating scheme is presented. Sample test problems are presented and the results are in excellent agreement with those reported in the literature.

  10. Inhibited Release of Mobile Contaminants from Hanford Tank Residual Waste

    SciTech Connect

    Cantrell, Kirk J.; Heald, Steve M.; Arey, Bruce W.; Lindberg, Michael J.

    2011-03-03

    Investigations of contaminant release from Hanford Site tank residual waste have indicated that in some cases certain contaminants of interest (Tc and Cr) exhibit inhibited release. The percentage of Tc that dissolved from residual waste from tanks 241-C-103, 241-C-106, 241-C-202, and 241-C-203 ranged from approximately 6% to 10%. The percent leachable Cr from residual waste from tanks C-103, C 202, and C-203 ranged from approximately 1.1% to 44%. Solid phase characterization results indicate that the recalcitrant forms of these contaminants are associated with iron oxides. X-ray absorption near edge structure analysis of Tc and Cr in residual waste indicates that these contaminants occur in Fe oxide particles as their lower, less soluble oxidation states [Tc(IV) and Cr(III)]. The form of these contaminants is likely as oxides or hydroxides incorporated within the structure of the Fe oxide. Leaching behavior of U from tank residual waste was studied using deionized water, and CaCO3 and Ca(OH)2 saturated solutions as leachants. The release behavior of U from tank residual waste is complex. Initial U concentrations in water and CaCO3 leachants are high due to residual amounts of the highly soluble U mineral cejkaite. As leaching and dilution occur NaUO2PO4 {center_dot} xH2O, Na2U2O7(am) and schoepite (or a similar phase) become the solubility controlling phases for U. In the case of the Ca(OH)2 leachant, U release from tank residual waste is dramatically reduced. Thermodynamic modeling indicates that the solubility of CaUO4(c) controls release of U from residual waste in the Ca(OH)2 leachants. It is assumed the solubility controlling phase is actually a hydrated version of CaUO4 with a variable water content ranging from CaUO4 to CaUO4 {center_dot} (H2O). The critically reviewed value for CaUO4(c) (log KSP0 = 15.94) produced good agreement with our experimental data for the Ca(OH)2 leachates.

  11. L-tryptophan reacts with naturally occurring and food-occurring phenolic aldehydes to give phenolic tetrahydro-beta-carboline alkaloids: activity as antioxidants and free radical scavengers.

    PubMed

    Herraiz, Tomas; Galisteo, Juan; Chamorro, Cristina

    2003-04-01

    The reaction between the essential amino acid l-tryptophan and flavoring or naturally occurring phenyl and phenolic aldehydes was studied, and the alkaloidal reaction products were characterized by NMR and HPLC-MS. Benzaldehyde, vanillin, syringaldehyde, salicylaldehyde, and anisaldehyde condensed with l-tryptophan in aqueous-acidic media affording the corresponding phenolic tetrahydro-beta-carboline-3-carboxylic acid as two diastereoisomers, 1S,3S-cis and 1R,3S-trans. With the exception of benzaldehyde, the rest of the aldehydes needed heating conditions (70 degrees C) to significantly form tetrahydro-beta-carbolines over time with the cyclization highly favored at low pH. This suggests a likely formation of these compounds under conditions that may occur in foods, food processing, or cooking. The new phenolic tetrahydro-beta-carboline alkaloids were assayed, for the first time, for their activity as free radical scavengers and antioxidants and showed good antioxidant properties with Trolox equivalent antioxidant capacity (TEAC) values much higher than those of ascorbic acid and the water soluble vitamin E analogue, Trolox, in the 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) assay.

  12. 32 CFR 716.6 - Death occurring after active service.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 32 National Defense 5 2014-07-01 2014-07-01 false Death occurring after active service. 716.6 Section 716.6 National Defense Department of Defense (Continued) DEPARTMENT OF THE NAVY PERSONNEL DEATH GRATUITY Provisions Applicable to the Navy and the Marine Corps § 716.6 Death occurring after...

  13. 32 CFR 716.6 - Death occurring after active service.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 32 National Defense 5 2011-07-01 2011-07-01 false Death occurring after active service. 716.6 Section 716.6 National Defense Department of Defense (Continued) DEPARTMENT OF THE NAVY PERSONNEL DEATH GRATUITY Provisions Applicable to the Navy and the Marine Corps § 716.6 Death occurring after...

  14. 32 CFR 716.6 - Death occurring after active service.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 32 National Defense 5 2012-07-01 2012-07-01 false Death occurring after active service. 716.6 Section 716.6 National Defense Department of Defense (Continued) DEPARTMENT OF THE NAVY PERSONNEL DEATH GRATUITY Provisions Applicable to the Navy and the Marine Corps § 716.6 Death occurring after...

  15. 32 CFR 716.6 - Death occurring after active service.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 32 National Defense 5 2013-07-01 2013-07-01 false Death occurring after active service. 716.6 Section 716.6 National Defense Department of Defense (Continued) DEPARTMENT OF THE NAVY PERSONNEL DEATH GRATUITY Provisions Applicable to the Navy and the Marine Corps § 716.6 Death occurring after...

  16. 32 CFR 716.6 - Death occurring after active service.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 32 National Defense 5 2010-07-01 2010-07-01 false Death occurring after active service. 716.6 Section 716.6 National Defense Department of Defense (Continued) DEPARTMENT OF THE NAVY PERSONNEL DEATH GRATUITY Provisions Applicable to the Navy and the Marine Corps § 716.6 Death occurring after...

  17. Oxidation reaction by xanthine oxidase: theoretical study of reaction mechanism.

    PubMed

    Amano, Tatsuo; Ochi, Noriaki; Sato, Hirofumi; Sakaki, Shigeyoshi

    2007-07-01

    The oxidation process by molybdenum-containing enzyme, xanthine oxidase, is theoretically studied with a model complex representing the reaction center and a typical benchmark substrate, formamide. Comparisons were systematically made among reaction mechanisms proposed previously. In the concerted and stepwise mechanisms that were theoretically discussed previously, the oxidation reaction takes place with a moderate activation barrier. However, the product is less stable than the reactant complex, which indicates that these mechanisms are unlikely. Moreover, the product of the concerted mechanism is not consistent with the isotope experimental result. In addition to those mechanisms, another mechanism initiated by the deprotonation of the active site was newly investigated here. In the transition state of this reaction, the carbon atom of formamide interacts with the oxo ligand of the Mo center and the hydrogen atom is moving from the carbon atom to the thioxo ligand. This reaction takes place with a moderate activation barrier and considerably large exothermicity. Furthermore, the product by this mechanism is consistent with the isotope experimental result. Also, our computations clearly show that the deprotonation of the active site occurs with considerable exothermicity in the presence of glutamic acid and substrate. The intermediate of the stepwise mechanism could not be optimized in the case of the deprotonated active site. From all these results, it should be concluded that the one-step mechanism with the deprotonated active site is the most plausible.

  18. Organochlorine insecticide residues in the free-tailed bat (Tadarida brasiliensis) at Bracken Cave, Texas

    USGS Publications Warehouse

    Clark, D.R.; Martin, C.O.; Swineford, D.M.

    1975-01-01

    Fifty-nine free-tailed bats (Tadarida brasiliensis mexicana ) were collected at Bracken Cave, Texas, and analyzed for organochlorine insecticides and polychlorinated biphenyls (PCBs). Residues of DDE in the brain were greater in 12 young collected from the floor than in 15 young taken from the ceiling, but food deprivation, not higher residues in the brain, apparently caused young to fall....Among 18 pregnant females, residues of DDE and DDT were highest in yearlings. The first lactation by yearlings caused their residue loads to drop sharply. Thereafter, increasing age was accompanied by increasing residues but amounts generally did not exceed those in yearlings.....Residue levels in embryos were a function both of levels in the female parent and degree of embryonic development. Residues accumulated rapidly in nursing young, and lactating females may excrete from 1.3 to 16.2 (mean = 4.3) micrograms of DDE in milk per day. Maximum individual residue loads may be attained toward the end of nursing, and mobilization of these residues during southward migration may subject Bracken Cave free-tails to maximum lifetime residues in the brain....Comparison of our data with residue data for the free-tail population at Eagle Creek Cave (Arizona) in 1970 produced the following conclusions: ( 1) residues of DDE appeared similar in pregnant females, embryos, lactating females, and fallen young for the two populations; (2) residues of DDT and dieldrin appeared greater in pregnant females at Bracken Cave; (3) DDE and DDT occurred at greater levels in guano samples from Bracken Cave. On this basis, the population decline observed at Eagle Creek Cave between 1963 and 1969 does not appear to be related to the residues observed in the 1970 samples taken from that cave.

  19. Acute anaphylactoid reactions during hemodialysis in France.

    PubMed

    Forêt, M; Kuentz, F; Meftahi, H; Milongo, R; Hachache, T; Elsener, M; Dechelette, E; Cordonnier, D

    1987-04-01

    A retrospective survey of anaphylactoid reactions during dialysis in France was conducted. In 52 of 112 hemodialysis units surveyed 111 patients who had suffered one or more anaphylactoid reactions during dialysis were identified. According to the Hamilton/Adkinson classification, in 31 patients reactions were minor, in 54 patients moderate, and in 26 patients severe. Four patients died of their reactions. A preponderance of reactions (75 and 11%) occurred with cuprammonium cellulose hollow-fiber and plate dialyzers, respectively. Severe dialyzer reactions were found to occur more frequently after the long (weekend) interdialytic interval. In an in vitro study, six brands of cuprammonium cellulose hollow-fiber dialyzers were rinsed with water and the eluates analyzed by size exclusion chromatography for contaminant particles. Substantial variation in the amount of extractable material was found between dialyzers of different brands, despite the fact that all dialyzers used membranes from the same manufacturer. Previous data by others has suggested that this extractable material is a derivative of cellulose. Results of our epidemiologic survey in France are similar to those previously reported in the United States and suggest an increased incidence of dialyzer reactions with ethylene oxide-sterilized cuprammonium cellulose dialyzers. The presence of cellulose-derived particles in the rinsing fluid of such dialyzers and the possible increased incidence of reactions after the long (weekend) interdialytic interval suggest that allergy to cellulose-derived particles eluted from cellulosic dialyzers may contribute to dialyzer hypersensitivity reactions.

  20. Model for reaction kinetics in pyrolysis of wood

    SciTech Connect

    Ahuja, P.; Singh, P.C.; Upadhyay, S.N.; Kumar, S.

    1996-12-31

    A reaction model for the pyrolysis of small and large particles of wood Is developed. The chemical reactions that take place when biomass is pyrolyzed are the devolatilization reactions (primary) and due to the vapour-solid interactions (secondary). In the case of small particles, when the volatiles are immediately removed by the purge gas, only primary reactions occur and the reaction model is described by weight loss and char forming reactions. The of heterogeneous secondary reactions occur in the case of large particles due to the interaction between the volatiles and the hot nascent primary char. A chain reaction mechanism of secondary char formation is proposed. The model takes both the volatiles retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as autocatalysis into consideration. 7 refs., 3 figs., 2 tabs.

  1. 40 CFR 1065.705 - Residual and intermediate residual fuel.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... specifications for fuels meeting the definition of residual fuel in 40 CFR 80.2, including fuels marketed as... by reference in § 1065.1010). (2) Phosphorus is at or below 15 mg per kg of fuel based on the... 0.15 ISO 6245. Water, max (m3/m3) % 0.5 0.5 0.5 0.5 0.5 ISO 3733. Sulfur, max (kg/kg) % 3.50 4.00...

  2. 40 CFR 1065.705 - Residual and intermediate residual fuel.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... specifications for fuels meeting the definition of residual fuel in 40 CFR 80.2, including fuels marketed as... ISO 6245. Water, max (m3/m3)% 0.5 0.5 0.5 0.5 0.5 ISO 3733. Sulfur, max (kg/kg)% 3.50 4.00 4.50 4.50 4... the elements zinc, phosphorus, or calcium is at or below the specified limits. We consider a fuel...

  3. 40 CFR 1065.705 - Residual and intermediate residual fuel.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... specifications for fuels meeting the definition of residual fuel in 40 CFR 80.2, including fuels marketed as... ISO 6245. Water, max (m3/m3)% 0.5 0.5 0.5 0.5 0.5 ISO 3733. Sulfur, max (kg/kg)% 3.50 4.00 4.50 4.50 4... the elements zinc, phosphorus, or calcium is at or below the specified limits. We consider a fuel...

  4. Dicofol residues in eggs and carcasses of captive American kestrels

    USGS Publications Warehouse

    Wiemeyer, Stanley N.; Clark, D.R.; Spann, J.W.; Belisle, A.A.; Bunck, C.M.

    2001-01-01

    American kestrels (Falco sparverius) were fed diets containing 0 (control), 1, 3, 10, and 30 ?g/g (wet wt) of Kelthane?. Residues of dicofol and its metabolites were then analyzed in the eggs and carcasses of females. Significant differences occurred among treatments for residues of both p,p'-dicofol and p,p'-dechlorodicofol (DCD) in both eggs and carcasses and for p,p'-dicholorbenzophenone (DCBP) in eggs. Residue concentrations increased with increasing treatment exposure. Residues of p,p'-dicofol, p,p'-DCD, and p,p'-DCBP in eggs were significantly correlated with eggshell quality parameters. Significant correlations also occurred among contaminants in eggs and for individual contaminants between eggs and carcasses. The lowest-observed-dietary-effect concentration for eggshell thinning was 3 ?g/g, whereas 1 ?g/g may be considered to be near a no-observable-adverse-effect concentration. Concentrations of dicofol in potential prey items and eggs of wild birds generally have been lower than dietary-effect concentrations or concentrations in tissues or eggs associated with eggshell thinning and reduced reproductive success.

  5. Phosphorylated peptides occur in a non-helical portion of the tail of a catch muscle myosin

    SciTech Connect

    Castellani, L.; Elliott, B.W. Jr.; Cohen, C.

    1987-05-01

    Myosin from a molluscan catch muscle (the Anterior Byssus Retractor (ABRM) of Mytilus edulis) is unusual in being phosphorylated in the rod by an endogenous heavy-chain kinase. This phosphorylation enhances myosin solubility at low ionic strength and induces molecular folding of the myosin tail. Papain and chymotryptic cleavage of this myosin, phosphorylated with (..gamma..-/sup 32/P)ATP, indicates that the phosphorylated residues are associated with the carboxy-terminal end of the light meromyosin. Ion-exchange and reverse-phase HPLC of radiolabeled chymotryptic peptides allow the isolation of two different peptides with high specific activity. One of these peptides is rich in lysine and arginine residues, a finding consistent with the observation that basic residues often determine the substrate specificity of protein kinases. The second peptide contains proline residues. Taken together, these results suggest that, as in the case of Acanthamoeba myosin, phosphorylation occurs in a nonhelical portion of the rod that may also control solubility. Identification of the residues that are phosphorylated and their location in the rod may reveal how the phosphorylation-dependent changes observed in the myosin in vitro are related to changes in intermolecular interactions in the thick filaments in vivo.

  6. Diagnosis and management of postpercutaneous nephrolithotomy residual stone fragments.

    PubMed

    Skolarikos, Andreas; Papatsoris, Athanasios G

    2009-10-01

    Residual stone fragments can occur in up to 8% of patients who are treated with percutaneous nephrolithotomy (PCNL). When left untreated, approximately half of these patients will experience a stone-related event, for which more than half will need a secondary surgical intervention. Predictors of adverse events are a residual fragment larger than 2 mm that is located in the pelvis or ureter. Preventive measures for the creation of residual fragments include a carefully selected access giving exposure to the bulk of the stone, the creation of multiple tracts, the use of single pulse pneumatic lithotripsy, the prevention of stone migration with ureteral balloons or stone cones, and careful flushing of the stones from the collecting system. Plain radiography of the kidneys, ureters, and bladder, linear tomography, and ultrasonography have all been used to judge the result of PCNL and to detect the presence of residual fragments. Thin-slice, unenhanced helical CT, however, is more sensitive and should be performed at 1 month after surgery. While medical therapy and shockwave lithotripsy possess a minor role, second-look flexible nephroscopy and/or flexible ureterorenoscopy seem to be the treatments of choice for residual stone fragments after PCNL.

  7. On the auxiliary lattices and dislocation reactions at triple junctions.

    PubMed

    Gertsman, V Y

    2002-03-01

    Coincidence site and displacement shift complete lattices of triple junctions are analysed. Dislocation reactions at triple junctions are considered. It is shown that in alpha=1 junctions no trapped residual triple-junction dislocation is geometrically necessary for dislocation transmission between adjoining grain boundaries. However, the situation is different for alpha (unequal) 1 triple junctions, where in some cases the residual dislocation cannot leave the triple junction for a grain boundary without generating a stacking-fault-like defect.

  8. Investigation of the Roles of Allosteric Domain Arginine, Aspartate, and Glutamate Residues of Rhizobium etli Pyruvate Carboxylase in Relation to Its Activation by Acetyl CoA.

    PubMed

    Sirithanakorn, Chaiyos; Jitrapakdee, Sarawut; Attwood, Paul V

    2016-08-01

    The mechanism of allosteric activation of pyruvate carboxylase by acetyl CoA is not fully understood. Here we have examined the roles of residues near the acetyl CoA binding site in the allosteric activation of Rhizobium etli pyruvate carboxylase using site-directed mutagenesis. Arg429 was found to be especially important for acetyl CoA binding as substitution with serine resulted in a 100-fold increase in the Ka of acetyl CoA activation and a large decrease in the cooperativity of this activation. Asp420 and Arg424, which do not make direct contact with bound acetyl CoA, were nonetheless found to affect acetyl CoA binding when mutated, probably through changed interactions with another acetyl CoA binding residue, Arg427. Thermodynamic activation parameters for the pyruvate carboxylation reaction were determined from modified Arrhenius plots and showed that acetyl CoA acts to decrease the activation free energy of the reaction by both increasing the activation entropy and decreasing the activation enthalpy. Most importantly, mutations of Asp420, Arg424, and Arg429 enhanced the activity of the enzyme in the absence of acetyl CoA. A main focus of this work was the detailed investigation of how this increase in activity occurred in the R424S mutant. This mutation decreased the activation enthalpy of the pyruvate carboxylation reaction by an amount consistent with removal of a single hydrogen bond. It is postulated that Arg424 forms a hydrogen bonding interaction with another residue that stabilizes the asymmetrical conformation of the R. etli pyruvate carboxylase tetramer, constraining its interconversion to the symmetrical conformer that is required for catalysis. PMID:27379711

  9. Fundamental mechanisms of phosphate stabilization of divalent metals in MSW combustion scrubber residues

    SciTech Connect

    Eighmy, T.T.

    1997-12-01

    Chemical stabilization of waste materials offers the potential to reduce the leachability of heavy metals in the waste. The principal objective during stabilization is to form new mineral phases with reduced solubilities and increased geochemical stability in a leaching environment. One stabilization agent of recent interest, particularly for Pb{sup 2+}, is PO{sub 4}{sup 3{minus}}. A patented soluble phosphate treatment process, marketed by Wheelabrator Environmental Systems as the WES-PHix process, is used in 23 MSW combustion or ash processing facilities in the United States. It is also used at 7 wire recycling facilities. The process is licensed to Kurita Water Industries Ltd. of Japan where it is marketed as the ASHNITE process. It is used in over 80 MSW combustion or ash processing facilities in Japan. Phosphate combines with over 30 elements to form about 300 naturally-occurring minerals. Metal phosphates are ubiquitous secondary minerals in the oxidized zones of lead ore deposits and as assemblages around ore bodies. They also occur in soils, sediments, and phosphatic beds. As such, they are stable with respect to pH, Eh, and mineral diagenesis. Isomorphic substitutions are very common for both divalent cations (e.g. Pb{sup 2+}, for Ca{sup 2+}) and oxyanions (e.g. AsO{sub 4}{sup 3{minus}} for PO{sub 4}{sup 3{minus}}) in these minerals. This study was designed to determine the mechanisms and reaction products of chemical stabilization of dry scrubber residues treated with soluble orthophosphate. The data gleaned from various spectroscopic analyses, leaching procedures, and geochemical modeling show that precipitation/solid solution formation rather than sorption is the immobilization mechanism and that apatite minerals and solid solutions are the principal solubility-controlling reaction products. As in nature, these minerals are geochemically stable and very insoluble.

  10. Glass ceramics containment matrix for insoluble residues coming from spent fuel reprocessing

    NASA Astrophysics Data System (ADS)

    Pinet, O.; Boën, R.

    2014-04-01

    Spent fuel reprocessing by hydrometallurgical process generates insoluble residues waste streams called fines solution. Considering their radioactivity, fines solution could be considered as Intermediate Level Waste. This waste stream is usually mixed with fission products stream before vitrification. Thus fines are incorporated in glass matrix designed for High Level Waste. The withdrawal of fines from high level glass could decrease the volume of high level waste after conditioning. It could also decrease the reaction time between high level waste and additives to obtain a homogeneous melt and then increase the vitrification process capacity. Separated conditioning of fines in glass matrices has been tested. The fines content targeted value is 16 wt%. To achieve this objective, two types of glass ceramic formulations have been tested. 700 g of the two selected glass ceramics have been prepared using simulated fines. Additives used were ground glass. Melting is achieved at 1100 °C. According to the type of glass ceramic, reducing or oxidizing conditions have been performed during melting. Due to their composition and the melting redox conditions, different phases have been observed. These crystalline phases are typically RuO2, metallic Ru, metallic Pd, MoO2 and CaMoO4. In view of melting these matrices in an in can process the corrosiveness of one of the most oxidizing borosilicate glass ceramic formulation has been tested. This one has been remelted at 1100 °C in inconel 601 pot for 3 days. The oxygen fugacity measurement performed in the remelted glass leads to an oxidizing value, indicating that no significant reaction occurred between the inconel pot and the glass melt had occurred.

  11. Residual Stress Analysis in Deep Drawn Twinning Induced Plasticity (TWIP) Steels Using Neutron Diffraction Method

    NASA Astrophysics Data System (ADS)

    Hong, Seokmin; Lee, Junghoon; Lee, Sunghak; Woo, Wanchuck; Kim, Sung-Kyu; Kim, Hyoung Seop

    2014-04-01

    In Twinning Induced Plasticity (TWIP) steels, delayed fracture occurs due to residual stresses induced during deep drawing. In order to investigate the relation between residual stresses and delayed fracture, in the present study, residual stresses of deep drawn TWIP steels (22Mn-0.6C and 18Mn-2Al-0.6C steels) were investigated using the finite element method (FEM) and neutron diffraction measurements. In addition, the delayed fracture properties were examined by dipping tests of cup specimens in the boiled water. In the FEM analysis, the hoop direction residual stress was highly tensile at cup edge, and the delayed fracture was initiated by the separation of hoop direction and propagated in an axial direction. According to the neutron diffraction analysis, residual stresses in 18Mn-2Al-0.6C steel were about half the residual stresses in 22Mn-0.6C steel. From the residual strain measurement using electron back-scatter diffraction, formation of deformation twins caused a lot of grain rotation and local strain at the grain boundaries and twin boundaries. These local residual strains induce residual stress at boundaries. Al addition in TWIP steels restrained the formation of deformation twins and dynamic strain aging, resulting in more homogeneous stress and strain distributions in cup specimens. Thus, in Al-added TWIP steels, residual stress of cup specimen considerably decreased, and delayed fracture resistance was remarkably improved by the addition of Al in TWIP steels.

  12. Tirofiban-Induced Thrombocytopenia Occurring with Crohn's Disease.

    PubMed

    Ibrahim, Toni; El Karak, Fady; Araji, Assem; El Rassy, Elie

    2016-01-01

    A 69-year-old man, with severe refractory Crohn's disease, presented with acute coronary syndrome that required angioplasty. He developed severe tirofiban-induced thrombocytopenia (TIT) heralded by type I allergic reaction that required steroids and a combination of antihistamine H1 and antihistamine H2 for symptomatic management. The thrombocytopenia spontaneously resolved uneventfully in 48 hours thereafter. This case report suggests a possible association between TIT and inflammatory bowel disease. Therefore, strict monitoring of the platelet count is required in patients who develop allergic reactions to tirofiban. PMID:27144035

  13. Identifying Zn-bound histidine residues in metalloproteins using hydrogen-deuterium exchange mass spectrometry.

    PubMed

    Dong, Jia; Callahan, Katie L; Borotto, Nicholas B; Vachet, Richard W

    2014-01-01

    In this work, we have developed a method that uses hydrogen-deuterium exchange (HDX) of C2-hydrogens of histidines coupled with mass spectrometry (MS) to identify Zn-bound histidines in metalloproteins. This method relies on differences in HDX reaction rates of Zn-bound and Zn-free His residues. Using several model peptides and proteins, we find that all Zn-bound His residues have substantially lower HDX reaction rates in the presence of the metal. The vast majority of non-Zn-binding His residues undergo no significant changes in HDX reaction rates when their reactivity is compared in the presence and absence of Zn. Using this new approach, we then determined the Zn binding site of β-2-microglobulin, a protein associated with metal-induced amyloidosis. Together, these results suggest that HDX-MS of His C2-hydrogens is a promising new method for identifying Zn-bound histidines in metalloproteins.

  14. Studying Reaction Intermediates Formed at Graphenic Surfaces

    NASA Astrophysics Data System (ADS)

    Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

    2014-03-01

    We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

  15. Multicomponent reactions of cyclobutanones.

    PubMed

    Pirrung, Michael C; Wang, Jianmei

    2009-04-17

    Cyclobutanones are essentially unknown as reactants in isonitrile-based multicomponent reactions. Ugi reactions of cyclobutanone and Passerini reactions of tetramethylcyclobutane-1,3-dione have been performed in this work. These reactions are significantly enhanced by being conducted in water, a subject of recent interest whose basis is still in question but whose effects are beyond doubt. The Ugi reaction of cyclobutanone has been used in a brief synthesis of an aspartame analogue.

  16. Evaluation on double-wall-tube residual stress distribution of sodium-heated steam generator by neutron diffraction and numerical analysis

    SciTech Connect

    Kisohara, N.; Suzuki, H.; Akita, K.; Kasahara, N.

    2012-07-01

    A double-wall-tube is nominated for the steam generator heat transfer tube of future sodium fast reactors (SFRs) in Japan, to decrease the possibility of sodium/water reaction. The double-wall-tube consists of an inner tube and an outer tube, and they are mechanically contacted to keep the heat transfer of the interface between the inner and outer tubes by their residual stress. During long term SG operation, the contact stress at the interface gradually falls down due to stress relaxation. This phenomenon might increase the thermal resistance of the interface and degrade the tube heat transfer performance. The contact stress relaxation can be predicted by numerical analysis, and the analysis requires the data of the initial residual stress distributions in the tubes. However, unclear initial residual stress distributions prevent precious relaxation evaluation. In order to resolve this issue, a neutron diffraction method was employed to reveal the tri-axial (radius, hoop and longitudinal) initial residual stress distributions in the double-wall-tube. Strain gauges also were used to evaluate the contact stress. The measurement results were analyzed using a JAEA's structural computer code to determine the initial residual stress distributions. Based on the stress distributions, the structural computer code has predicted the transition of the relaxation and the decrease of the contact stress. The radial and longitudinal temperature distributions in the tubes were input to the structural analysis model. Since the radial thermal expansion difference between the inner (colder) and outer (hotter) tube reduces the contact stress and the tube inside steam pressure contributes to increasing it, the analytical model also took these effects into consideration. It has been conduced that the inner and outer tubes are contacted with sufficient stresses during the plant life time, and that effective heat transfer degradation dose not occur in the double-wall-tube SG. (authors)

  17. Pesticidal residues in animal tissues

    USGS Publications Warehouse

    DeWitt, J.B.; Menzie, C.M.; Adomaitis, V.A.; Reichel, W.L.

    1960-01-01

    Tests with penned starlings, rats, pheasants, and ducks indicated that each species differs in sensitivity to the various pesticides. Residues in tissues are proportional to the degree of exposure during area treatment and they are also found in animals shot six or more months after treatment. The presence of more than 20-30 ppm of DDT, 20 ppm of chlordan, and 6-20 ppm of heptachlor epoxide in quail tissues indicated that the birds had ingested lethal dosages of the pesticides.

  18. Calcination/dissolution residue treatment

    SciTech Connect

    Knight, R.C.; Creed, R.F.; Patello, G.K.; Hollenberg, G.W.; Buehler, M.F.; O`Rourke, S.M.; Visnapuu, A.; McLaughlin, D.F.

    1994-09-01

    Currently, high-level wastes are stored underground in steel-lined tanks at the Hanford site. Current plans call for the chemical pretreatment of these wastes before their immobilization in stable glass waste forms. One candidate pretreatment approach, calcination/dissolution, performs an alkaline fusion of the waste and creates a high-level/low-level partition based on the aqueous solubilities of the components of the product calcine. Literature and laboratory studies were conducted with the goal of finding a residue treatment technology that would decrease the quantity of high-level waste glass required following calcination/dissolution waste processing. Four elements, Fe, Ni, Bi, and U, postulated to be present in the high-level residue fraction were identified as being key to the quantity of high-level glass formed. Laboratory tests of the candidate technologies with simulant high-level residues showed reductive roasting followed by carbonyl volatilization to be successful in removing Fe, Ni, and Bi. Subsequent bench-scale tests on residues from calcination/dissolution processing of genuine Hanford Site tank waste showed Fe was separated with radioelement decontamination factors of 70 to 1,000 times with respect to total alpha activity. Thermodynamic analyses of the calcination of five typical Hanford Site tank waste compositions also were performed. The analyses showed sodium hydroxide to be the sole molten component in the waste calcine and emphasized the requirement for waste blending if fluid calcines are to be achieved. Other calcine phases identified in the thermodynamic analysis indicate the significant thermal reconstitution accomplished in calcination.

  19. Residue management at Rocky Flats

    SciTech Connect

    Olencz, J.

    1995-12-31

    Past plutonium production and manufacturing operations conducted at the Rocky Flats Environmental Technology Site (RFETS) produced a variety of plutonium-contaminated by-product materials. Residues are a category of these materials and were categorized as {open_quotes}materials in-process{close_quotes} to be recovered due to their inherent plutonium concentrations. In 1989 all RFETS plutonium production and manufacturing operations were curtailed. This report describes the management of plutonium bearing liquid and solid wastes.

  20. Residue gasification tests at TVA

    SciTech Connect

    Spencer, D.

    1984-11-01

    The Texaco gasification process was identified as an attractive way to utilise vacuum bottoms from the Exxon Donor Solvent liquefaction process to generate synthesis gas. This gas can then be upgraded to produce the hydrogen required by the EDS plant. Gasification tests were carried out at TVA's 200 t/day Muscle Shoals plant and are reported here. As a result, Texaco expects that a plant could be designed to handle EDS residue from any high-rank coal.

  1. Comparative Toxicology of Libby Amphibole and Naturally Occurring Asbestos

    EPA Science Inventory

    Summary sentence: Comparative toxicology of Libby amphibole (LA) and site-specific naturally occurring asbestos (NOA) provides new insights on physical properties influencing health effects and mechanisms of asbestos-induced inflammation, fibrosis, and tumorigenesis.Introduction/...

  2. Fetal distress during a maternal systemic allergic reaction.

    PubMed

    Klein, V R; Harris, A P; Abraham, R A; Niebyl, J R

    1984-09-01

    Systemic allergic reactions to food ingestion rarely result in life-threatening situations. When these reactions occur during pregnancy, however, the accompanying physiologic changes may result in fetal distress. A case of repetitive late decelerations in the fetal heart rate during a maternal allergic reaction is presented. Prompt and aggressive medical management brought about total resolution of maternal and fetal compromise.

  3. Geotechnical characteristics of residual soils

    SciTech Connect

    Townsend, F.C.

    1985-01-01

    Residual soils are products of chemical weathering and thus their characteristics are dependent upon environmental factors of climate, parent material, topography and drainage, and age. These conditions are optimized in the tropics where well-drained regions produce reddish lateritic soils rich in iron and aluminum sesquioxides and kaolinitic clays. Conversely, poorly drained areas tend towards montmorillonitic expansive black clays. Andosols develop over volcanic ash and rock regions and are rich in allophane (amorphous silica) and metastable halloysite. The geological origins greatly affect the resulting engineering characteristics. Both lateritic soils and andosols are susceptible to property changes upon drying, and exhibit compaction and strength properties not indicative of their classification limits. Both soils have been used successfully in earth dam construction, but attention must be given to seepage control through the weathered rock. Conversely, black soils are unpopular for embankments. Lateritic soils respond to cement stabilization and, in some cases, lime stabilization. Andosols should also respond to lime treatment and cement treatments if proper mixing can be achieved. Black expansive residual soils respond to lime treatment by demonstrating strength gains and decreased expansiveness. Rainfall induced landslides are typical of residual soil deposits.

  4. Efficient decoration of nanoparticles intended for intracellular drug targeting with targeting residues, as revealed by a new indirect analytical approach.

    PubMed

    Kaplun, Veronika; Stepensky, David

    2014-08-01

    In our previous studies, we developed a nanodrug delivery system (nano-DDS) based on poly(lactic-co-glycolic acid) PLGA nanoparticles encapsulating antigenic peptide and fluorescent marker and 3-stage approach for its decoration with peptide targeting residues. The objectives of this study were (a) to develop methods for quantitative analysis of efficiency of individual conjugation steps and (b) to determine, based on these methods, the efficiency of our 3-stage approach of nano-DDS decoration. We prepared antigenic peptide-loaded PLGA-based nano-DDSs and sequentially decorated them with specific residues using carbodiimide and Click (azide-alkyne Huisgen cycloaddition using copper(I) catalysis) reactions. The extent of cargo encapsulation and release kinetics were analyzed using HPLC-based and colorimetric analytical methods. The efficiency of residue conjugation to the nano-DDSs was analyzed using FTIR spectroscopy and by quantifying the unreacted residues in the reaction mixture (i.e., by indirect analysis of reaction efficiencies). We revealed that copper, the catalyst of the Click reactions, formed complexes with unreacted targeting residues and interfered with the analysis of their conjugation efficiency. We used penicillamine (a chelator) to disrupt these complexes, and to recover the unreacted residues. Quantitative analysis revealed that 28,800-34,000 targeting residues (corresponding to 11-13 nm(2) surface area per residue) had been conjugated to a single nano-DDS using our 3-stage decoration approach, which is much higher than previously reported conjugation efficiencies. We conclude that the applied analytical tools allow quantitative analysis of nano-DDSs and the efficiency of their conjugation with targeting residues. The 3-stage decoration approach resulted in dense conjugation of nano-DDSs with targeting residues. The present decoration and analytical approaches can be effectively applied to other types of delivery systems and other targeting

  5. Efficient decoration of nanoparticles intended for intracellular drug targeting with targeting residues, as revealed by a new indirect analytical approach.

    PubMed

    Kaplun, Veronika; Stepensky, David

    2014-08-01

    In our previous studies, we developed a nanodrug delivery system (nano-DDS) based on poly(lactic-co-glycolic acid) PLGA nanoparticles encapsulating antigenic peptide and fluorescent marker and 3-stage approach for its decoration with peptide targeting residues. The objectives of this study were (a) to develop methods for quantitative analysis of efficiency of individual conjugation steps and (b) to determine, based on these methods, the efficiency of our 3-stage approach of nano-DDS decoration. We prepared antigenic peptide-loaded PLGA-based nano-DDSs and sequentially decorated them with specific residues using carbodiimide and Click (azide-alkyne Huisgen cycloaddition using copper(I) catalysis) reactions. The extent of cargo encapsulation and release kinetics were analyzed using HPLC-based and colorimetric analytical methods. The efficiency of residue conjugation to the nano-DDSs was analyzed using FTIR spectroscopy and by quantifying the unreacted residues in the reaction mixture (i.e., by indirect analysis of reaction efficiencies). We revealed that copper, the catalyst of the Click reactions, formed complexes with unreacted targeting residues and interfered with the analysis of their conjugation efficiency. We used penicillamine (a chelator) to disrupt these complexes, and to recover the unreacted residues. Quantitative analysis revealed that 28,800-34,000 targeting residues (corresponding to 11-13 nm(2) surface area per residue) had been conjugated to a single nano-DDS using our 3-stage decoration approach, which is much higher than previously reported conjugation efficiencies. We conclude that the applied analytical tools allow quantitative analysis of nano-DDSs and the efficiency of their conjugation with targeting residues. The 3-stage decoration approach resulted in dense conjugation of nano-DDSs with targeting residues. The present decoration and analytical approaches can be effectively applied to other types of delivery systems and other targeting

  6. Internet Censorship in China: Where Does the Filtering Occur?

    NASA Astrophysics Data System (ADS)

    Xu, Xueyang; Mao, Z. Morley; Halderman, J. Alex

    China filters Internet traffic in and out of the country. In order to circumvent the firewall, it is helpful to know where the filtering occurs. In this work, we explore the AS-level topology of China's network, and probe the firewall to find the locations of filtering devices. We find that even though most filtering occurs in border ASes, choke points also exist in many provincial networks. The result suggests that two major ISPs in China have different approaches placing filtering devices.

  7. Evaluation of residue drum storage safety risks

    SciTech Connect

    Conner, W.V.

    1994-06-17

    A study was conducted to determine if any potential safety problems exist in the residue drum backlog at the Rocky Flats Plant. Plutonium residues stored in 55-gallon drums were packaged for short-term storage until the residues could be processed for plutonium recovery. These residues have now been determined by the Department of Energy to be waste materials, and the residues will remain in storage until plans for disposal of the material can be developed. The packaging configurations which were safe for short-term storage may not be safe for long-term storage. Interviews with Rocky Flats personnel involved with packaging the residues reveal that more than one packaging configuration was used for some of the residues. A tabulation of packaging configurations was developed based on the information obtained from the interviews. A number of potential safety problems were identified during this study, including hydrogen generation from some residues and residue packaging materials, contamination containment loss, metal residue packaging container corrosion, and pyrophoric plutonium compound formation. Risk factors were developed for evaluating the risk potential of the various residue categories, and the residues in storage at Rocky Flats were ranked by risk potential. Preliminary drum head space gas sampling studies have demonstrated the potential for formation of flammable hydrogen-oxygen mixtures in some residue drums.

  8. Minimal residual disease analysis by eight-color flow cytometry in relapsed childhood acute lymphoblastic leukemia.

    PubMed

    Karawajew, Leonid; Dworzak, Michael; Ratei, Richard; Rhein, Peter; Gaipa, Giuseppe; Buldini, Barbara; Basso, Giuseppe; Hrusak, Ondrej; Ludwig, Wolf-Dieter; Henze, Günter; Seeger, Karl; von Stackelberg, Arend; Mejstrikova, Ester; Eckert, Cornelia

    2015-07-01

    Multiparametric flow cytometry is an alternative approach to the polymerase chain reaction method for evaluating minimal residual disease in treatment protocols for primary acute lymphoblastic leukemia. Given considerable differences between primary and relapsed acute lymphoblastic leukemia treatment regimens, flow cytometric assessment of minimal residual disease in relapsed leukemia requires an independent comprehensive investigation. In the present study we addressed evaluation of minimal residual disease by flow cytometry in the clinical trial for childhood relapsed acute lymphoblastic leukemia using eight-color flow cytometry. The major challenge of the study was to reliably identify low amounts of residual leukemic cells against the complex background of regeneration, characteristic of follow-up samples during relapse treatment. In a prospective study of 263 follow-up bone marrow samples from 122 patients with B-cell precursor acute lymphoblastic leukemia, we tested various B-cell markers, adapted the antibody panel to the treatment protocol, and evaluated its performance by a blinded parallel comparison with the polymerase chain reaction data. The resulting eight-color single-tube panel showed a consistently high overall concordance (P<0.001) and, under optimal conditions, sensitivity similar to that of the reference polymerase chain reaction method. Overall, evaluation of minimal residual disease by flow cytometry can be successfully integrated into the clinical management of relapsed childhood acute lymphoblastic leukemia either as complementary to the polymerase chain reaction or as an independent risk stratification tool. ALL-REZ BFM 2002 clinical trial information: NCT00114348.

  9. Occurence and implications of silicon nitride in enstatic chondrites

    NASA Technical Reports Server (NTRS)

    Alexander, C. M. O'D.; Swan, P.; Prombo, C. A.

    1994-01-01

    Silicon nitride Si3N4, has previously been observed to be a common constituent of acid residues of Qingzhen (EH3) and Indarch (EH4). Ion probe analysis of the Si, N and C isotopic compositions of individual Si3N4 grains from Qingzhen and Indarch acid residues suggest most, if not all, grains are Solar System in origin. A few grains have isotopically anomalous C but this is probably due to small presolar SiC grains adhering to them. In situ observations of the Si3N4 in Qingzhen show that it is only present within, and probably exsolved from, host phases which contain elemental Si in solid solution. Thermodynamic calculations suggest that the Si3N4 probably formed during metamorphism and not in the nebula. Thermodynamic calculations also show that sinoite (Si2N2O) and not Si3N4 should be the stable phase during metamorphism. It appears that kinetic factors must have inhibited the formation if sinoite in Qimgzhen and Indarch.

  10. PESTICIDE RESIDUE RECOVERIES FROM SURFACE WIPES

    EPA Science Inventory

    Human exposure is a consequence of pesticide use indoors with a primary source resulting from residue deposition on household surfaces. Accurate measurements of surface residues is essential for estimating exposure from different routes. Various procedures have been developed ...

  11. 48 CFR 970.5001 - Residual powers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 5 2010-10-01 2010-10-01 false Residual powers. 970.5001 Section 970.5001 Federal Acquisition Regulations System DEPARTMENT OF ENERGY AGENCY SUPPLEMENTARY....5001 Residual powers....

  12. 48 CFR 250.104 - Residual powers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false Residual powers. 250.104 Section 250.104 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS SYSTEM, DEPARTMENT... Contractual Actions 250.104 Residual powers....

  13. 48 CFR 970.5001 - Residual powers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 5 2012-10-01 2012-10-01 false Residual powers. 970.5001 Section 970.5001 Federal Acquisition Regulations System DEPARTMENT OF ENERGY AGENCY SUPPLEMENTARY....5001 Residual powers....

  14. 48 CFR 250.104 - Residual powers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 3 2011-10-01 2011-10-01 false Residual powers. 250.104 Section 250.104 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS SYSTEM, DEPARTMENT... Contractual Actions 250.104 Residual powers....

  15. 48 CFR 970.5001 - Residual powers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 5 2014-10-01 2014-10-01 false Residual powers. 970.5001 Section 970.5001 Federal Acquisition Regulations System DEPARTMENT OF ENERGY AGENCY SUPPLEMENTARY....5001 Residual powers....

  16. 48 CFR 1850.104 - Residual powers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 6 2014-10-01 2014-10-01 false Residual powers. 1850.104 Section 1850.104 Federal Acquisition Regulations System NATIONAL AERONAUTICS AND SPACE ADMINISTRATION... 1850.104 Residual powers....

  17. 48 CFR 1850.104 - Residual powers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 6 2013-10-01 2013-10-01 false Residual powers. 1850.104 Section 1850.104 Federal Acquisition Regulations System NATIONAL AERONAUTICS AND SPACE ADMINISTRATION... 1850.104 Residual powers....

  18. 48 CFR 1850.104 - Residual powers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 6 2012-10-01 2012-10-01 false Residual powers. 1850.104 Section 1850.104 Federal Acquisition Regulations System NATIONAL AERONAUTICS AND SPACE ADMINISTRATION... 1850.104 Residual powers....

  19. 48 CFR 250.104 - Residual powers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 3 2014-10-01 2014-10-01 false Residual powers. 250.104 Section 250.104 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS SYSTEM, DEPARTMENT... Contractual Actions 250.104 Residual powers....

  20. 48 CFR 970.5001 - Residual powers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 5 2013-10-01 2013-10-01 false Residual powers. 970.5001 Section 970.5001 Federal Acquisition Regulations System DEPARTMENT OF ENERGY AGENCY SUPPLEMENTARY....5001 Residual powers....

  1. 48 CFR 250.104 - Residual powers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 3 2012-10-01 2012-10-01 false Residual powers. 250.104 Section 250.104 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS SYSTEM, DEPARTMENT... Contractual Actions 250.104 Residual powers....

  2. 48 CFR 970.5001 - Residual powers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 5 2011-10-01 2011-10-01 false Residual powers. 970.5001 Section 970.5001 Federal Acquisition Regulations System DEPARTMENT OF ENERGY AGENCY SUPPLEMENTARY....5001 Residual powers....

  3. 48 CFR 250.104 - Residual powers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 3 2013-10-01 2013-10-01 false Residual powers. 250.104 Section 250.104 Federal Acquisition Regulations System DEFENSE ACQUISITION REGULATIONS SYSTEM, DEPARTMENT... Contractual Actions 250.104 Residual powers....

  4. Organochlorine residues in eggs of Alaskan seabirds

    USGS Publications Warehouse

    Ohlendorf, H.M.; Bartonek, J.C.; Divoky, G.J.; Klass, E.

    1982-01-01

    One egg from each of 440 clutches of eggs of 19 species of Alaskan seabirds collected in 1973-76 was analyzed for organochlorine residues. All eggs contained DDE; 98.9% contained PCB's; 84.3%, oxychlordane; and 82.7%, HCB. Endrin was found in only one egg, but DDD, DDT, dieldrin, heptachlor epoxide, mirex, cis-chlordane (or trans-nonachlor), cis-nonachlor, and toxaphene each occurred in at least 22% of the samples.Concentrations of organochlorines in the samples were generally low. Mean concentrations of eight compounds were highest in eggs of glaucous-winged gulls (Larus glaucescens) from three sites: DDE (5.16 ppm, wet weight), dieldrin (0.214 ppm), oxychlordane (0.251 ppm), and PCB's (3.55 ppm) in eggs from Bogoslof Island; heptachlor epoxide (0.037 ppm), cis-chlordane (0.075 ppm), and HCB (0.188 ppm) in eggs from Buldir Island; and cis-nonachlor (0.026 ppm) in eggs from the Semidi Islands. Highest concentrations of DDD (0.157 ppm), DDT (0.140 ppm), and toxaphene (0.101 ppm) were in eggs of fork-tailed storm-petrel (Oceanodroma furcata) from Buldir Island, and the highest concentration of mirex (0.044 ppm) was in fork-tailed storm-petrel eggs from the Barren Islands.Both frequency of occurrence and concentration of residues in the eggs differed geographically and by species, apparently reflecting non-uniform distribution of organochlorines in the environment, dissimilar feeding habits and migration patterns of the species, or metabolic differences among the species.The overall frequency of residue occurrence was highest in eggs from the Pribilof Islands, but only three species were represented in the samples collected there. Detectable residues also were more frequent in eggs from the Gulf of Alaska colonies than elsewhere, and the lowest frequency was in eggs from nesting colonies on or near the Seward Peninsula. Regionally, concentrations of DDE and PCB's were usually higher than average in eggs from the Gulf of Alaska and lower than average in eggs from the

  5. Inhibition of retrogressive reactions in coal/petroleum co-processing. Final technical report

    SciTech Connect

    Schobert, H.H.; Tomic, J.

    1993-05-25

    The objective of this study was to examine the processes in coal/petroleum coprocessing systems which led to coke formation. Specifically, the interactions between the petroleum residue and coal, leading to retrogressive products, were investigated. Five coals were reacted with five model compounds in order to investigate the coal conversions in a variety of solvents and to determine the role of the solvent in promoting or inhibiting coal conversion. The selected model compounds range from paraffinic to fully aromatic and were chosen as representative of types of compounds that are found in petroleum residua. Coprocessing experiments were conducted using the five coals and three petroleum residua. The effect of temperature on coal conversions was crucial. The coal conversions at 350 and 400{degree}C seem to be governed by the nature of the coal and to a lesser extent by the petroleum residua. Negative coal conversions were observed above 400{degree}C indicating that retrogressive processes had occurred. At temperatures higher than 400{degree}C, the petroleum residua undergo physical and chemical transformations and the influence of the petroleum residua on coal conversions is significant. The structural features of the residues indicated that the residues were predominately coal-derived. An overall increase in aromaticity was observed with increasing temperature which was also accompanied by loss of oxygen functional groups. The retrogressive reactions with non-caking coals involve carbonyl and carboxyl group leading to a final solid characterized by a cross-linked structure. In the case of caking coal, these reactions are governed by loss of aromatic oxygen groups and loss of alkyl groups.

  6. Theoretical analysis of physicochemical processes occurring during water treatment by ozone and ultraviolet radiation.

    PubMed

    Mishchuk, N A; Goncharuk, V V; Vakulenko, V F

    2008-06-22

    The paper presents a kinetic model developed for ozone dissolution in water and taking into account convective and diffusion processes occurring in the vicinity of floating bubbles that contain an ozone-air mixture. It was shown that the gradient of ozone concentration in a convective-diffusion layer and consequently the rate of ozone transfer from bubbles to the solution depended on the rate of ozone decomposition both in its reaction with organic admixtures and in the conditions of exposure to ultraviolet radiation. The obtained kinetic curves of destruction of organic compounds and changes of ozone concentration in water and ozone-air mixture are compared with experimental data for humic acids. The paper also analyzes additional factors affecting the kinetics of ozone dissolution and the rate of resultant reactions.

  7. Quasifission and fusion-fission in reactions with massive nuclei: Comparison of reactions leading to the Z=120 element

    SciTech Connect

    Nasirov, A. K.; Giardina, G.; Mandaglio, G.; Manganaro, M.; Hanappe, F.; Heinz, S.; Hofmann, S.; Muminov, A. I.; Scheid, W.

    2009-02-15

    The yields of evaporation residues, fusion-fission, and quasifission fragments in the {sup 48}Ca+{sup 144,154}Sm and {sup 16}O+{sup 186}W reactions are analyzed in the framework of the combined theoretical method based on the dinuclear system concept and advanced statistical model. The measured yields of evaporation residues for the {sup 48}Ca+{sup 154}Sm reaction can be well reproduced. The measured yields of fission fragments are decomposed into contributions coming from fusion-fission, quasifission, and fast-fission. The decrease in the measured yield of quasifission fragments in {sup 48}Ca+{sup 154}Sm at the large collision energies and the lack of quasifission fragments in the {sup 48}Ca+{sup 144}Sm reaction are explained by the overlap in mass angle distributions of the quasifission and fusion-fission fragments. The investigation of the optimal conditions for the synthesis of the new element Z=120 (A=302) show that the {sup 54}Cr+{sup 248}Cm reaction is preferable in comparison with the {sup 58}Fe+{sup 244}Pu and {sup 64}Ni+{sup 238}U reactions because the excitation function of the evaporation residues of the former reaction is some orders of magnitude larger than that for the last two reactions.

  8. Pesticide residues in foods imported into the United States.

    PubMed

    Wessel, J R; Yess, N J

    1991-01-01

    Interest in pesticide residues in foods has increased, and the issue of residues in imported foods has been raised as a potential public health problem. Three U.S. government agencies, EPA, FDA, and USDA, are responsible for regulating pesticides. EPA sets tolerances, and FDA and USDA enforce those tolerances. As part of its regulatory activities, FDA conducts a regulatory monitoring program that samples and analyzes each year approximately 20,000 food shipments, about 60% of which are imports. Samples of imported foods are collected at ports of entry, and are chosen on the basis of several factors rather than on a completely random basis. Raw agricultural products are emphasized. Most analyses are performed using MRMs, to make best use of FDA's resources. Using five MRMs, about half of the 300 pesticides with U.S. tolerances can be determined. Results from monitoring over the past several years have shown that nearly 60% of the imported foods sampled had no pesticide residues detected. Of those samples that were violative, 5% contained residues for which there was no U.S. tolerance, and less than 1% had over-tolerance residues. Examples are given of the various pesticide/commodity combinations that have been found to be violative. FDA is often criticized for the scope of its pesticide coverage, particularly with regard to imported foods. Some critics have promoted the idea of a 'circle of poison,' which is based on the premise that pesticides banned in the U.S. are exported and used on foods in foreign countries; then the food containing these residues is imported into the U.S. and consumed. However, FDA's testing of imported foods has shown that residues of EPA-banned pesticides are not occurring from currently purposeful uses. The violation rates for imports also have not been significantly different from those for domestic foods. This indicates that foreign producers, as well as domestic growers, generally use pesticides in a manner consistent with EPA

  9. On co-design of filter and fault estimator against randomly occurring nonlinearities and randomly occurring deception attacks

    NASA Astrophysics Data System (ADS)

    Hu, Jun; Liu, Steven; Ji, Donghai; Li, Shanqiang

    2016-07-01

    In this paper, the co-design problem of filter and fault estimator is studied for a class of time-varying non-linear stochastic systems subject to randomly occurring nonlinearities and randomly occurring deception attacks. Two mutually independent random variables obeying the Bernoulli distribution are employed to characterize the phenomena of the randomly occurring nonlinearities and randomly occurring deception attacks, respectively. By using the augmentation approach, the co-design problem of the robust filter and fault estimator is converted into the recursive filter design problem. A new compensation scheme is proposed such that, for both randomly occurring nonlinearities and randomly occurring deception attacks, an upper bound of the filtering error covariance is obtained and such an upper bound is minimized by properly designing the filter gain at each sampling instant. Moreover, the explicit form of the filter gain is given based on the solution to two Riccati-like difference equations. It is shown that the proposed co-design algorithm is of a recursive form that is suitable for online computation. Finally, a simulation example is given to illustrate the usefulness of the developed filtering approach.

  10. Transfer reactions with heavy elements

    SciTech Connect

    Hoffman, D.C.

    1986-04-01

    Transfer reactions for several transuranium elements are studied. (/sup 248/Cm, /sup 249/Bk, /sup 249/CF, /sup 254/Es), /sup 16,18/O, /sup 20,22/Ne, and /sup 40,48/Ca projectiles are used. The production of neutron-rich heavy actinides is enhanced by the use of neutron-rich projectiles /sup 18/O and /sup 22/Ne. The maxima of the isotopic distributions occur at only 2 to 3 mass numbers larger for /sup 48/Ca than for /sup 40/Ca reactions with /sup 248/Cm. The cross sections decrease rapidly with the number of nucleons transferred. The use of neutron-rich targets favors the production of neutron-rich isotopes. ''Cold'' heavy targets are produced. Comparisons with simple calculations of the product excitation energies assuming binary transfers indicate that the maxima of the isotopic distributions occur at the lightest product isotope for which the energy exceeds the reaction barrier. The cross sections for transfer of the same nucleon clusters appear to be comparable for a wide variety of systems. 23 refs., 4 figs., 4 tabs.

  11. Photosynthetic reaction centers in bacteria

    SciTech Connect

    Norris, J.R. Univ. of Chicago, IL ); Schiffer, M. )

    1990-07-30

    The photochemistry of photosynthesis begins in complexes called reaction centers. These have become model systems to study the fundamental process by which plants and bacteria convert and store solar energy as chemical free energy. In green plants, photosynthesis occurs in two systems, each of which contains a different reaction center, working in series. In one, known as photosystem 1, oxidized nicotinamide adenine dinucleotide phosphate (NADP[sup +]) is reduced to NADPH for use in a series of dark reactions called the Calvin cycle, named for Nobel Laureate Melvin Calvin, by which carbon dioxide is converted into useful fuels such as carbohydrates and sugars. In the other half of the photosynthetic machinery of green plants, called photosystem 2, water is oxidized to produce molecular oxygen. A different form of photosynthesis occurs in photosynthetic bacteria, which typically live at the bottom of ponds and feed on organic debris. Two main types of photosynthetic bacteria exist: purple and green. Neither type liberates oxygen from water. Instead, the bacteria feed on organic media or inorganic materials, such as sulfides, which are easier to reduce or oxidize than carbon dioxide or water. Perhaps in consequence, their photosynthetic machinery is simpler than that of green, oxygen-evolving plants and their primary photochemistry is better understood.

  12. 48 CFR 50.104 - Residual powers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Residual powers. 50.104... EXTRAORDINARY CONTRACTUAL ACTIONS AND THE SAFETY ACT Extraordinary Contractual Actions 50.104 Residual powers. This section prescribes standards and procedures for exercising residual powers under Pub. L....

  13. 9 CFR 311.39 - Biological residues.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Biological residues. 311.39 Section... Biological residues. Carcasses, organs, or other parts of carcasses of livestock shall be condemned if it is determined that they are adulterated because of the presence of any biological residues....

  14. 9 CFR 311.39 - Biological residues.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Biological residues. 311.39 Section... Biological residues. Carcasses, organs, or other parts of carcasses of livestock shall be condemned if it is determined that they are adulterated because of the presence of any biological residues....

  15. 9 CFR 311.39 - Biological residues.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Biological residues. 311.39 Section... Biological residues. Carcasses, organs, or other parts of carcasses of livestock shall be condemned if it is determined that they are adulterated because of the presence of any biological residues....

  16. 9 CFR 311.39 - Biological residues.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Biological residues. 311.39 Section... Biological residues. Carcasses, organs, or other parts of carcasses of livestock shall be condemned if it is determined that they are adulterated because of the presence of any biological residues....

  17. 48 CFR 50.104 - Residual powers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 1 2011-10-01 2011-10-01 false Residual powers. 50.104... EXTRAORDINARY CONTRACTUAL ACTIONS AND THE SAFETY ACT Extraordinary Contractual Actions 50.104 Residual powers. This section prescribes standards and procedures for exercising residual powers under Pub. L....

  18. 48 CFR 50.104 - Residual powers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 1 2012-10-01 2012-10-01 false Residual powers. 50.104... EXTRAORDINARY CONTRACTUAL ACTIONS AND THE SAFETY ACT Extraordinary Contractual Actions 50.104 Residual powers. This section prescribes standards and procedures for exercising residual powers under Pub. L....

  19. 48 CFR 50.104 - Residual powers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 1 2014-10-01 2014-10-01 false Residual powers. 50.104... EXTRAORDINARY CONTRACTUAL ACTIONS AND THE SAFETY ACT Extraordinary Contractual Actions 50.104 Residual powers. This section prescribes standards and procedures for exercising residual powers under Pub. L....

  20. 48 CFR 50.104 - Residual powers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 1 2013-10-01 2013-10-01 false Residual powers. 50.104... EXTRAORDINARY CONTRACTUAL ACTIONS AND THE SAFETY ACT Extraordinary Contractual Actions 50.104 Residual powers. This section prescribes standards and procedures for exercising residual powers under Pub. L....

  1. Soil nitrous oxide emissions following crop residue addition: a meta-analysis.

    PubMed

    Chen, Huaihai; Li, Xuechao; Hu, Feng; Shi, Wei

    2013-10-01

    Annual production of crop residues has reached nearly 4 billion metric tons globally. Retention of this large amount of residues on agricultural land can be beneficial to soil C sequestration. Such potential impacts, however, may be offset if residue retention substantially increases soil emissions of N(2)O, a potent greenhouse gas and ozone depletion substance. Residue effects on soil N(2)O emissions have gained considerable attention since early 1990s; yet, it is still a great challenge to predict the magnitude and direction of soil N(2)O emissions following residue amendment. Here, we used a meta-analysis to assess residue impacts on soil N(2)O emissions in relation to soil and residue attributes, i.e., soil pH, soil texture, soil water content, residue C and N input, and residue C : N ratio. Residue effects were negatively associated with C : N ratios, but generally residue amendment could not reduce soil N(2)O emissions, even for C : N ratios well above ca. 30, the threshold for net N immobilization. Residue effects were also comparable to, if not greater than, those of synthetic N fertilizers. In addition, residue effects on soil N(2)O emissions were positively related to the amounts of residue C input as well as residue effects on soil CO(2) respiration. Furthermore, most significant and stimulatory effects occurred at 60-90% soil water-filled pore space and soil pH 7.1-7.8. Stimulatory effects were also present for all soil textures except sand or clay content ≤10%. However, inhibitory effects were found for soils with >90% water-filled pore space. Altogether, our meta-analysis suggests that crop residues played roles beyond N supply for N(2)O production. Perhaps, by stimulating microbial respiration, crop residues enhanced oxygen depletion and therefore promoted anaerobic conditions for denitrification and N(2)O production. Our meta-analysis highlights the necessity to connect the quantity and quality of crop residues with soil properties for predicting

  2. MINIMAL RESIDUAL DISEASE IN ACUTE LYMPHOBLASTIC LEUKEMIA

    PubMed Central

    Campana, Dario

    2009-01-01

    In patients with acute lymphoblastic leukemia (ALL), monitoring of minimal residual disease (MRD) offers a way to precisely assess early treatment response and detect relapse. Established methods to study MRD are flow cytometric detection of abnormal immunophenotypes, polymerase chain reaction (PCR) amplification of antigen-receptor genes, and PCR amplification of fusion transcripts. The strong correlation between MRD levels and risk of relapse in childhood ALL is well established; studies in adult patients also support its prognostic value. Hence, results of MRD studies can be used to select treatment intensity and duration, and estimate the optimal timing for hematopoietic stem cell transplantation. Practical issues in the implementation of MRD assays in clinical studies include determining the most informative time point to study MRD, the levels of MRD that will trigger changes in treatment intensity, as well as the relative cost and informative power of different methodologies. The identification of new markers of leukemia and the use of increasingly refined assays should further facilitate routine monitoring of MRD and help clarifying the cellular and biologic features of leukemic cells that resist chemotherapy in vivo. PMID:19100372

  3. Lithium cell reactions

    NASA Astrophysics Data System (ADS)

    Clark, W.; Dampier, F.; Lombardi, A.; Cole, T.

    1983-12-01

    The objectives of this program were: (1) investigate reactions occurring in the Li/SOCl2 cell for a range of specified test conditions and (2) perform detailed analyses for impurities present in cell components, assess the impact of each impurity on cell performance and safety and recommend concentration limits for detrimental impurities. The products of the reduction of SOCl2 were investigated using linear sweep voltammetry (LSV) and constant current coulometry in dimethylformamide (DMF) supporting electrolyte. Voltammetric analysis after 50 to 100% of the SOCl2 had been reduced on platinum or glassy carbon cathodes showed no signs of significant quantities of unstable intermediates with lifetimes from 0.1 to 48 hours. Quantitative infrared spectroscopy demonstrated that substantial amounts of SO2 are absorbed on Shawinigan carbon from 1.8M LiAlCl4/SOCl2-SO solutions. Chemical analyses of the reagents and cell components used in Li/SOCl2 cell construction were carried out as well as cell discharge tests to determine the impact of key impurities on cell performance.

  4. Determination of Reaction Mechanisms Occurring at Fuel Cell Electrocatalysts Using Electrochemical Methods, Spectroelectrochemical Measurements and Analytical Techniques

    NASA Astrophysics Data System (ADS)

    Coutanceau, C.; Baranton, S.; Lamy, C.

    There is now a great interest in developing different kinds of fuel cells for several applications (stationary electric power plants, transportation, portable electronic devices). For many applications, hydrogen is the most convenient fuel, but it is not a primary fuel, so that it has to be produced from different sources: water, fossil fuels (natural gas, hydrocarbons, etc.), biomass resources, etc. When produced from fossil fuel and biomass resources, hydrogen gas contains a non negligible amount of CO, which acts as a poisoning species for platinum electrocatalysts. Other fuels, particularly alcohols, which are liquid under ambient temperature and pressure, are more convenient due to the easiness of their handling and distribution and high theoretical energy density (6 to 8 kWh kg-1, for methanol and ethanol, respectively). Direct Methanol Fuel Cells (DMFCs) and Direct Ethanol Fuel Cells (DEFCs) are based on the Proton Exchange Membrane Fuel Cell (PEMFC) system, in which hydrogen is replaced by the alcohol. Moreover, due to the presence of carbon monoxide, the issues for PEMFCs working with reformate gas are close to those met in Direct Alcohol Fuel Cells (DAFCs), where the dissociative adsorption of alcohol leads to the formation of adsorbed CO species.

  5. What should a radiation regulator do about naturally occurring radioactive material?

    PubMed

    Loy, J

    2015-06-01

    The standard regulatory framework of authorisation, review and assessment, inspection and enforcement, and regulation making is directed principally towards ensuring the regulatory control of planned exposure situations. Some mining and industrial activities involving exposures to naturally occurring radioactive material (NORM), such as uranium mining or the treatment and conditioning of NORM residues, may fit readily within this standard framework. In other cases, such as oil and gas exploration and production, the standard regulatory framework needs to be adjusted. For example, it is not sensible to require that an oil company seek a licence from the radiation regulator before drilling a well. The paper discusses other approaches that a regulator might take to assure protection and safety in such activities involving exposures to NORM, including the use of conditional exemptions from regulatory controls. It also suggests some areas where further guidance from the International Commission on Radiological Protection on application of the system of radiological protection to NORM would assist both regulators and operators.

  6. Arsenic poisoning in dairy cattle from naturally occurring arsenic pyrites.

    PubMed

    Hopkirk, R G

    1987-10-01

    An outbreak of arsenic poisoning occurred in which most of a 200 cow dairy herd were affected and six died. The source of the arsenic was naturally occurring arsenic pyrites from the Waiotapu Stream, near Rotorua. Arsenic levels in the nearby soil were as high as 6618 ppm. There was little evidence to suggest that treatment affected the course of the disease. Haematology was of little use in diagnosis, post-mortem signs were not always consistent and persistence of the element in the liver appeared short. Control of further outbreaks have been based on practical measures to minimise the intake of contaminated soil and free laying water by the stock. PMID:16031332

  7. Arsenic poisoning in dairy cattle from naturally occurring arsenic pyrites.

    PubMed

    Hopkirk, R G

    1987-10-01

    An outbreak of arsenic poisoning occurred in which most of a 200 cow dairy herd were affected and six died. The source of the arsenic was naturally occurring arsenic pyrites from the Waiotapu Stream, near Rotorua. Arsenic levels in the nearby soil were as high as 6618 ppm. There was little evidence to suggest that treatment affected the course of the disease. Haematology was of little use in diagnosis, post-mortem signs were not always consistent and persistence of the element in the liver appeared short. Control of further outbreaks have been based on practical measures to minimise the intake of contaminated soil and free laying water by the stock.

  8. Complexation Key to a pH Locked Redox Reaction

    ERIC Educational Resources Information Center

    Rizvi, Masood Ahmad; Dangat, Yuvraj; Shams, Tahir; Khan, Khaliquz Zaman

    2016-01-01

    An unfavorable pH can block a feasible electron transfer for a pH dependent redox reaction. In this experiment, a series of potentiometric titrations demonstrate the sequential loss in feasibility of iron(II) dichromate redox reaction over a pH range of 0-4. The pH at which this reaction failed to occur was termed as a pH locked reaction. The…

  9. Process to recycle shredder residue

    DOEpatents

    Jody, Bassam J.; Daniels, Edward J.; Bonsignore, Patrick V.

    2001-01-01

    A system and process for recycling shredder residue, in which separating any polyurethane foam materials are first separated. Then separate a fines fraction of less than about 1/4 inch leaving a plastics-rich fraction. Thereafter, the plastics rich fraction is sequentially contacted with a series of solvents beginning with one or more of hexane or an alcohol to remove automotive fluids; acetone to remove ABS; one or more of EDC, THF or a ketone having a boiling point of not greater than about 125.degree. C. to remove PVC; and one or more of xylene or toluene to remove polypropylene and polyethylene. The solvents are recovered and recycled.

  10. Automating a residual gas analyzer

    NASA Technical Reports Server (NTRS)

    Petrie, W. F.; Westfall, A. H.

    1982-01-01

    A residual gas analyzer (RGA), a device for measuring the amounts and species of various gases present in a vacuum system is discussed. In a recent update of the RGA, it was shown that the use of microprocessors could revolutionize data acquisition and data reduction. This revolution is exemplified by the Inficon 1Q200 RGA which was selected to meet the needs of this update. The Inficon RGA and the Zilog microcomputer were interfaced in order the receive and format the digital data from the RGA. This automated approach is discussed in detail.

  11. Different Structural Changes Occur in the Blue- and Green-Absorbing Proteorhodopsin During the Primary Photoreaction†

    PubMed Central

    Amsden, Jason J.; Kralj, Joel M.; Bergo, Vladislav B.; Spudich, Elena N.; Spudich, John L.; Rothschild, Kenneth J.

    2013-01-01

    We examine the structural changes during the primary photoreaction in blue-absorbing proteorhodopsin (BPR), a light-driven retinylidene proton pump, using low-temperature FTIR difference spectroscopy. Comparison of the light induced BPR difference spectrum recorded at 80 K to that of green-absorbing proteorhodopsin (GPR) reveals that there are several differences in the BPR and GPR primary photoreactions despite the similar structure of the retinal chromophore and all-trans → 13-cis isomerization. Strong bands near 1700 cm−1 assigned previously to a change in hydrogen bonding of Asn230 in GPR are still present in BPR but in addition bands in the same region are assigned on the basis of site-directed mutagenesis to changes occurring in Gln105. In the amide II region bands are assigned on the basis of total-N15 labeling to structural changes of the protein backbone, although no such bands were previously observed for GPR. A band at 3642 cm−1 in BPR, assigned to the OH stretching mode of a water molecule on the basis of H218O substitution, appears at a different frequency than a band at 3626 cm−1 previously assigned to a water molecule in GPR. However, the substitution of Gln105 for Leu105 in BPR leads to the appearance of both bands at 3642 and 3626 cm−1 indicating the waters assigned in BPR and GPR exist in separate distinct locations and can coexist in the GPR-like Q105L mutant of BPR. These results indicate that there exist significant differences in the conformational changes occurring in these two types proteorhodopsin during the initial photoreaction despite their similar chromophores structures, which might reflect a different arrangement of water in the active site as well as substitution of a hydrophilic for hydrophobic residue at residue 105. PMID:18842006

  12. Different structural changes occur in blue- and green-proteorhodopsins during the primary photoreaction.

    PubMed

    Amsden, Jason J; Kralj, Joel M; Bergo, Vladislav B; Spudich, Elena N; Spudich, John L; Rothschild, Kenneth J

    2008-11-01

    We examine the structural changes during the primary photoreaction in blue-absorbing proteorhodopsin (BPR), a light-driven retinylidene proton pump, using low-temperature FTIR difference spectroscopy. Comparison of the light-induced BPR difference spectrum recorded at 80 K to that of green-absorbing proteorhodopsin (GPR) reveals that there are several differences in the BPR and GPR primary photoreactions despite the similar structure of the retinal chromophore and all-trans --> 13-cis isomerization. Strong bands near 1700 cm(-1) assigned previously to a change in hydrogen bonding of Asn230 in GPR are still present in BPR. However, additional bands in the same region are assigned on the basis of site-directed mutagenesis to changes occurring in Gln105. In the amide II region, bands are assigned on the basis of total (15)N labeling to structural changes of the protein backbone, although no such bands were previously observed for GPR. A band at 3642 cm(-1) in BPR, assigned to the OH stretching mode of a water molecule on the basis of H2(18)O substitution, appears at a different frequency than a band at 3626 cm(-1) previously assigned to a water molecule in GPR. However, the substitution of Gln105 for Leu105 in BPR leads to the appearance of both bands at 3642 and 3626 cm(-1), indicating the waters assigned in BPR and GPR exist in separate distinct locations and can coexist in the GPR-like Q105L mutant of BPR. These results indicate that there exist significant differences in the conformational changes occurring in these two types proteorhodopsin during the initial photoreaction despite their similar chromophore structures, which might reflect a different arrangement of water in the active site as well as substitution of a hydrophilic for hydrophobic residue at residue 105. PMID:18842006

  13. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  14. Allergic reactions (image)

    MedlinePlus

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as by ... dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  15. Allergic reactions (image)

    MedlinePlus

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  16. Microfluidic chemical reaction circuits

    DOEpatents

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  17. Continuous detonation reaction engine

    NASA Technical Reports Server (NTRS)

    Lange, O. H.; Stein, R. J.; Tubbs, H. E.

    1968-01-01

    Reaction engine operates on the principles of a controlled condensed detonation rather than on the principles of gas expansion. The detonation results in reaction products that are expelled at a much higher velocity.

  18. Fiber-optic polymer residue monitor

    SciTech Connect

    Pfeifer, K.B.; Jarecki, R.L. Jr.; Dalton, T.J.

    1998-10-01

    Semiconductor processing tools that use a plasma to etch polysilicon or oxides produce residue polymers that build up on the exposed surfaces of the processing chamber. These residues are generally stressed and with time can cause flaking onto wafers resulting in yield loss. Currently, residue buildup is not monitored, and chambers are cleaned at regular intervals resulting in excess downtime for the tool. In addition, knowledge of the residue buildup rate and index of refraction is useful in determining the state of health of the chamber process. The authors have developed a novel optical fiber-based robust sensor that allows measurement of the residue polymer buildup while not affecting the plasma process.

  19. Managing residual limb hyperhidrosis in wounded warriors.

    PubMed

    Pace, Sarah; Kentosh, Joshua

    2016-06-01

    Residual limb dermatologic problems are a common concern among young active traumatic amputee patients who strive to maintain an active lifestyle. Hyperhidrosis of residual limbs is a recognized inciting factor that often contributes to residual limb dermatoses and is driven by the design of the prosthetic liner covering the residual limb. Treatment of hyperhidrosis in this population presents a unique challenge. Several accepted treatments of hyperhidrosis can offer some relief but have been limited by lack of results or side-effect profiles. Microwave thermal ablation has presented an enticing potential for residual limb hyperhidrosis. PMID:27416083

  20. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  1. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  2. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  3. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  4. [Toxicological evaluation of pesticide and chemical residues in control of biological processes in vegetables under glass and plastics].

    PubMed

    Goedicke, H J

    1988-01-01

    The cultivation of vegetables under glass and plastics is one of the most intensive application fields of pesticides and chemicals for regulation of biological processes. Therefore it may potentially occur a relatively high residues contamination of the crops. The author reveals in a survey the residue situation of usual insecticides, acaricides, fungicides, and chemicals for regulation of biological processes on tomatoes, cucumbers, and lettuce in comparison with the maximum residue limit after cold fogging application. The residues of benomyl, carbendazim, and ethylen-bis-dithiocarbamate are detailed discussed in the light of the latest toxicological findings. The results the residues of 11 agents on the crops show that after the corresponding preharvest interval the residues constitute 1.7-78% of the maximum residue limit. The conclusion is drawn that the cold fogging application of the agents under glass and plastics does not result in food hygienic toxicological problems. PMID:3068546

  5. Measurement of Residual Flexibility for Substructures Having Prominent Flexible Interfaces

    NASA Technical Reports Server (NTRS)

    Tinker, Michael L.; Bookout, Paul S.

    1994-01-01

    Verification of a dynamic model of a constrained structure requires a modal survey test of the physical structure and subsequent modification of the model to obtain the best agreement possible with test data. Constrained-boundary or fixed-base testing has historically been the most common approach for verifying constrained mathematical models, since the boundary conditions of the test article are designed to match the actual constraints in service. However, there are difficulties involved with fixed-base testing, in some cases making the approach impractical. It is not possible to conduct a truly fixed-base test due to coupling between the test article and the fixture. In addition, it is often difficult to accurately simulate the actual boundary constraints, and the cost of designing and constructing the fixture may be prohibitive. For use when fixed-base testing proves impractical or undesirable, alternate free-boundary test methods have been investigated, including the residual flexibility technique. The residual flexibility approach has been treated analytically in considerable detail and has had limited frequency response measurements for the method. This concern is well-justified for a number of reasons. First, residual flexibilities are very small numbers, typically on the order of 1.0E-6 in/lb for translational diagonal terms, and orders of magnitude smaller for off-diagonal values. This poses difficulty in obtaining accurate and noise-free measurements, especially for points removed from the excitation source. A second difficulty encountered in residual measurements lies in obtaining a clean residual function in the process of subtracting synthesized modal data from a measured response function. Inaccuracies occur since modes are not subtracted exactly, but only to the accuracy of the curve fits for each mode; these errors are compounded with increasing distance from the excitation point. In this paper, the residual flexibility method is applied to a simple

  6. Social and Economic Polarization: Is It Occurring among Blacks?

    ERIC Educational Resources Information Center

    Farley, Reynolds; Bianchi, Suzanne M.

    An emerging hypothesis about black progress since the civil rights movement in the United States postulates that economic polarization is occurring in the black community. This hypothesis, which incorporates conflicting earlier theories of declining versus persistent racial differences, suggests that talented and well-educated blacks are competing…

  7. Naturally occurring fatty acids: source, chemistry and uses

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Natural occurring fatty acids are a large and complex class of compounds found in plants and animals. Fatty acids are abundant and of interest because of their renewability, biodegradability, biocompatibility, low cost, and fascinating chemistry. Of the many fatty acids, only 20-25 of them are widel...

  8. Integrative Priming Occurs Rapidly and Uncontrollably during Lexical Processing

    ERIC Educational Resources Information Center

    Estes, Zachary; Jones, Lara L.

    2009-01-01

    Lexical priming, whereby a prime word facilitates recognition of a related target word (e.g., "nurse" [right arrrow] "doctor"), is typically attributed to association strength, semantic similarity, or compound familiarity. Here, the authors demonstrate a novel type of lexical priming that occurs among unassociated, dissimilar, and unfamiliar…

  9. URBAN STORMWATER TRACING WITH THE NATURALLY OCCURRING DEUTERIUM ISOTOPE

    EPA Science Inventory

    Measurements of the naturally-occurring deuterium isotope assist the tracing of water components during wet-weather flows in an urban watershed. A transect of installations in the vadose and saturated zones was completed in the vicinity of a small stream and storm sewer. High-r...

  10. 33 CFR 330.3 - Activities occurring before certain dates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... waters of the United States outside the limits of navigable waters of the United States that occurred before the phase-in dates which extended Section 404 jurisdiction to all waters of the United States. The phase-in dates were: After July 25, 1975, discharges into navigable waters......

  11. 33 CFR 330.3 - Activities occurring before certain dates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... waters of the United States outside the limits of navigable waters of the United States that occurred before the phase-in dates which extended Section 404 jurisdiction to all waters of the United States. The phase-in dates were: After July 25, 1975, discharges into navigable waters......

  12. 33 CFR 330.3 - Activities occurring before certain dates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... waters of the United States outside the limits of navigable waters of the United States that occurred before the phase-in dates which extended Section 404 jurisdiction to all waters of the United States. The phase-in dates were: After July 25, 1975, discharges into navigable waters......

  13. 33 CFR 330.3 - Activities occurring before certain dates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... waters of the United States outside the limits of navigable waters of the United States that occurred before the phase-in dates which extended Section 404 jurisdiction to all waters of the United States. The phase-in dates were: After July 25, 1975, discharges into navigable waters......

  14. RUN OUTS OCCUR WHEN IRON HAS UNSEATED MOLDING SAND AND ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    RUN OUTS OCCUR WHEN IRON HAS UNSEATED MOLDING SAND AND RUN OUT OF THE MOLD UNDER POURING JACKETS AND SPILLS ONTO THE MOLDING PLATFORM. WORKERS GENERALLY WAIT SEVERAL MINUTES FOR THE IRON TO SOLIDIFY AND, WHILE IT IS STILL RED-HOT, REMOVE IT FROM THE PLATFORM AND SCRAP THE MOLD. - Southern Ductile Casting Company, Centerville Foundry, 101 Airport Road, Centreville, Bibb County, AL

  15. Catalytic diastereoselective petasis reactions.

    PubMed

    Muncipinto, Giovanni; Moquist, Philip N; Schreiber, Stuart L; Schaus, Scott E

    2011-08-22

    Multicomponent Petasis reactions: the first diastereoselective Petasis reaction catalyzed by chiral biphenols that enables the synthesis of syn and anti β-amino alcohols in pure form has been developed. The reaction exploits a multicomponent approach that involves boronates, α-hydroxy aldehydes, and amines. PMID:21751322

  16. Programmability of Chemical Reaction Networks

    NASA Astrophysics Data System (ADS)

    Cook, Matthew; Soloveichik, David; Winfree, Erik; Bruck, Jehoshua

    Motivated by the intriguing complexity of biochemical circuitry within individual cells we study Stochastic Chemical Reaction Networks (SCRNs), a formal model that considers a set of chemical reactions acting on a finite number of molecules in a well-stirred solution according to standard chemical kinetics equations. SCRNs have been widely used for describing naturally occurring (bio)chemical systems, and with the advent of synthetic biology they become a promising language for the design of artificial biochemical circuits. Our interest here is the computational power of SCRNs and how they relate to more conventional models of computation. We survey known connections and give new connections between SCRNs and Boolean Logic Circuits, Vector Addition Systems, Petri nets, Gate Implementability, Primitive Recursive Functions, Register Machines, Fractran, and Turing Machines. A theme to these investigations is the thin line between decidable and undecidable questions about SCRN behavior.

  17. Prebiotic condensation reactions using cyanamide

    NASA Technical Reports Server (NTRS)

    Sherwood, E.; Nooner, D. W.; Eichberg, J.; Epps, D. E.; Oro, J.

    1978-01-01

    Condensation reactions in cyanamide, 4-amino-5-imidazole-carboxamide and cyanamide, imidazole systems under dehydrating conditions at moderate temperatures (60 to 100 deg C) were investigated. The cyanamide, imidazole system was used for synthesis of palmitoylglycerols from ammonium palmitate and glycerol. With the addition of deoxythymidine to the former system, P1, P2-dideoxythymidine 5 prime-phosphate was obtained; the same cyanamide, 4-amino-5-imidazole-carboxamide system was used to synthesize deoxythymidine oligonucleotides using deoxythymidine 5 prime-phosphate and deoxythymidine 5 prime-triphosphate, and peptides using glycine, phenylalanine or isoleucine with adenosine 5 prime-triphosphate. The pH requirements for these reactions make their prebiotic significance questionable; however, it is conceivable that they could occur in stable pockets of low interlayer acidity in a clay such as montmorillonite.

  18. Modelling reaction kinetics inside cells

    PubMed Central

    Grima, Ramon; Schnell, Santiago

    2009-01-01

    In the past decade, advances in molecular biology such as the development of non-invasive single molecule imaging techniques have given us a window into the intricate biochemical activities that occur inside cells. In this article we review four distinct theoretical and simulation frameworks: (1) non-spatial and deterministic, (2) spatial and deterministic, (3) non-spatial and stochastic and (4) spatial and stochastic. Each framework can be suited to modelling and interpreting intracellular reaction kinetics. By estimating the fundamental length scales, one can roughly determine which models are best suited for the particular reaction pathway under study. We discuss differences in prediction between the four modelling methodologies. In particular we show that taking into account noise and space does not simply add quantitative predictive accuracy but may also lead to qualitatively different physiological predictions, unaccounted for by classical deterministic models. PMID:18793122

  19. Level Densities of Residual Nuclei from particle evaporation of {sup 64}Cu

    SciTech Connect

    Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J.

    2009-07-06

    The reactions of {sup 6}Li on {sup 58}Fe and {sup 7}Li on {sup 57}Fe have been studied at beam energy 15 MeV. These two reactions produce the same compound nucleus, {sup 64}Cu. The neutron, proton, and alpha spectra were measured at backward angles. The data obtained have been compared with Hauser Fesh-bach model calculations. The level density parameters of the residual nuclei have been obtained from the particle evaporation spectra.

  20. Evidence for pervasive melt-rock reaction within the uppermost mantle at Hess Deep

    NASA Astrophysics Data System (ADS)

    Shejwalkar, A. S.; Coogan, L. A.

    2015-12-01

    A suite of spinel harzburgites from ODP Site 895 at Hess Deep have been analysed for the major and trace element compositions of the major mineral phases and of the bulk rock to investigate the effect of melt rock reaction on mineral and bulk rock geochemistry. The harzburgites are at the depleted end of the global array of abyssal peridotite compositions in terms of moderately incompatible elements such as Al2O3, CaO, V and Sc. The whole-rock HREE abundances can be modeled as the residues of 15-25% near fractional melting of DMM however the LREE have much higher concentrations than predicted by this model and the samples show a significant positive Eu anomaly. The data can be fit well by a model of near-fractional melting followed by 0.5 to 2% precipitation of plagioclase that has a trace element composition in equilibrium with MORB. Plagioclase impregnation is common in the mantle section drilled at Site 895 although plagioclase is not observed petrographically in the samples studied here. The rocks are 20-70% altered and we hypothesize that plagioclase was entirely replaced during this alteration. The LREE-enrichment, relative to a melting residue, observed in the bulk-rock is not observed in clinopyroxene compositions. One explanation for this could be that the rocks were relatively cool when plagioclase impregnation occurred meaning diffusion was inefficient at modifying the clinopyroxene compositions [e.g. 1]. Whether melt-rock reaction occurs on- or off-axis is currently being investigated. Refs: [1] Niu, 2004. Journal of Petrology. Volume 45 (12), 2423-2458.

  1. Mineralogical Characteristics of Carbonate Rock-Hosted Naturally Occurring Asbestos

    NASA Astrophysics Data System (ADS)

    Shin, E.; Roh, Y.

    2012-12-01

    Naturally Occurring Asbestos (NOA) occurs in rocks and soils as a result of natural weathering and human activities. The parent rocks of asbestos have been associated with ultramafic and mafic rocks, and carbonate rock. The previous studies on naturally occurring asbestos were mainly limited to ultramafic and mafic rock-hosted asbestos and studies on carbonate rock-hosted asbestos are relatively rare in South Korea. Therefore, this study was aimed to characterize mineralogy of carbonate rock-hosted NOA at Muju and Jangsu, Jeonbuk province and Seosan and Asan, Chungnam province. The rock types at the four sites are consisting mainly of Precambrian metasedimentary rock. XRD and PLM analyses showed fibrous minerals in the sites were tremolite and actinolite of acicular and columnar forms. SEM-EDS analyses showed that asbestiform tremolite and actinolite had various ratios of length and diameters over 12:1, and needle and columnar forms. A columnar forms of tremolite and actinolite were showed small acicular at the edge of the particle. Its main chemical compositions are mainly Si, O, Mg, Ca, which were identical to tremolite. Actinolite contains Fe in addition to Si, O, Mg, Ca. EPMA analyses of asbestos occurred at Muju indicated that chemical composition are 55% SiO2, 23.2% MgO, 13.1 % CaO, and 0.61 % FeO and the chemical formula calculated as (K0.01Na0.01)Ca2.01(Mg4.94Fe0.05) (Al0.004Si7.98)O22(OH)2, which is close to ideal tremolite. In addition to tremolite, actinolite was also occurred at Seosan, Chungnam. XRD analyses showed that antigorite was existed at Muju, but PLM and SEM analyses showed the antigorite was platy structure, not asbestiform. These results indicate that asbestiform tremolite and actinolite with acicular forms contains in carbonate rocks at Muju and Jangsu, Jeonbuk and Seosan and Asan, Chungnam province South Korea.

  2. Allergic reactions to insect stings and bites.

    PubMed

    Moffitt, John E

    2003-11-01

    Insect stings are an important cause of anaphylaxis. Anaphylaxis can also occur from insect bites but is less common. Insect venoms contain several well-characterized allergens that can trigger anaphylactic reactions. Effective methods to diagnose insect sting allergy and assess risk of future sting reactions have been developed. Management strategies using insect avoidance measures, self-injectable epinephrine, and allergen immunotherapy are very effective in reducing insect-allergic patients' risk of reaction from future stings. Diagnostic and management strategies for patients allergic to insect bites are less developed.

  3. RESIDUAL STRESSES IN 3013 CONTAINERS

    SciTech Connect

    Mickalonis, J.; Dunn, K.

    2009-11-10

    The DOE Complex is packaging plutonium-bearing materials for storage and eventual disposition or disposal. The materials are handled according to the DOE-STD-3013 which outlines general requirements for stabilization, packaging and long-term storage. The storage vessels for the plutonium-bearing materials are termed 3013 containers. Stress corrosion cracking has been identified as a potential container degradation mode and this work determined that the residual stresses in the containers are sufficient to support such cracking. Sections of the 3013 outer, inner, and convenience containers, in both the as-fabricated condition and the closure welded condition, were evaluated per ASTM standard G-36. The standard requires exposure to a boiling magnesium chloride solution, which is an aggressive testing solution. Tests in a less aggressive 40% calcium chloride solution were also conducted. These tests were used to reveal the relative stress corrosion cracking susceptibility of the as fabricated 3013 containers. Significant cracking was observed in all containers in areas near welds and transitions in the container diameter. Stress corrosion cracks developed in both the lid and the body of gas tungsten arc welded and laser closure welded containers. The development of stress corrosion cracks in the as-fabricated and in the closure welded container samples demonstrates that the residual stresses in the 3013 containers are sufficient to support stress corrosion cracking if the environmental conditions inside the containers do not preclude the cracking process.

  4. South Polar Residual Ice Cap

    NASA Technical Reports Server (NTRS)

    1990-01-01

    This mosaic is composed of 18 Viking Orbiter images (6 each in red, green, and violet filters), acquired on September 28, 1977, during revolution 407 of Viking Orbiter 2. The south pole is located just off the lower left edge of the polar cap, and the 0 degree longitude meridian extends toward the top of the mosaic. The large crater near the right edge (named 'South') is about 100 km in diameter. These images were acquired during southern summer on Mars (Ls = 341 degrees); the sub-solar declination was 8 degrees S., and the south polar cap was nearing its final stage of retreat just prior to vernal equinox. The south residual cap is approximately 400 km across, and the exposed surface is thought to consist dominantly of carbon-dioxide frost. This is in contrast to the water-ice surface of the north polar residual cap. It is likely that water ice is present in layers that underlie the south polar cap and that comprise the surrounding layered terrains. Near the top of this image, irregular pits with sharp-rimmed cliffs appear 'etched', presumably by wind. A series of rugged mountains (extending toward the upper right corner of the image) are of unknown origin.

  5. Cold vacuum drying residual free water test description

    SciTech Connect

    Pajunen, A.L.

    1997-12-23

    Residual free water expected to remain in a Multi-Canister Overpack (MCO) after processing in the Cold Vacuum Drying (CVD) Facility is investigated based on three alternative models of fuel crevices. Tests and operating conditions for the CVD process are defined based on the analysis of these models. The models consider water pockets constrained by cladding defects, water constrained in a pore or crack by flow through a porous bed, and water constrained in pores by diffusion. An analysis of comparative reaction rate constraints is also presented indicating that a pressure rise test can be used to show MCO`s will be thermally stable at operating temperatures up to 75 C.

  6. DNA and Protein Requirements for Substrate Conformational Changes Necessary for Human Flap Endonuclease-1-catalyzed Reaction.

    PubMed

    Algasaier, Sana I; Exell, Jack C; Bennet, Ian A; Thompson, Mark J; Gotham, Victoria J B; Shaw, Steven J; Craggs, Timothy D; Finger, L David; Grasby, Jane A

    2016-04-01

    Human flap endonuclease-1 (hFEN1) catalyzes the essential removal of single-stranded flaps arising at DNA junctions during replication and repair processes. hFEN1 biological function must be precisely controlled, and consequently, the protein relies on a combination of protein and substrate conformational changes as a prerequisite for reaction. These include substrate bending at the duplex-duplex junction and transfer of unpaired reacting duplex end into the active site. When present, 5'-flaps are thought to thread under the helical cap, limiting reaction to flaps with free 5'-terminiin vivo Here we monitored DNA bending by FRET and DNA unpairing using 2-aminopurine exciton pair CD to determine the DNA and protein requirements for these substrate conformational changes. Binding of DNA to hFEN1 in a bent conformation occurred independently of 5'-flap accommodation and did not require active site metal ions or the presence of conserved active site residues. More stringent requirements exist for transfer of the substrate to the active site. Placement of the scissile phosphate diester in the active site required the presence of divalent metal ions, a free 5'-flap (if present), a Watson-Crick base pair at the terminus of the reacting duplex, and the intact secondary structure of the enzyme helical cap. Optimal positioning of the scissile phosphate additionally required active site conserved residues Tyr(40), Asp(181), and Arg(100)and a reacting duplex 5'-phosphate. These studies suggest a FEN1 reaction mechanism where junctions are bound and 5'-flaps are threaded (when present), and finally the substrate is transferred onto active site metals initiating cleavage.

  7. DNA and Protein Requirements for Substrate Conformational Changes Necessary for Human Flap Endonuclease-1-catalyzed Reaction*

    PubMed Central

    Algasaier, Sana I.; Exell, Jack C.; Bennet, Ian A.; Thompson, Mark J.; Gotham, Victoria J. B.; Shaw, Steven J.; Craggs, Timothy D.; Finger, L. David; Grasby, Jane A.

    2016-01-01

    Human flap endonuclease-1 (hFEN1) catalyzes the essential removal of single-stranded flaps arising at DNA junctions during replication and repair processes. hFEN1 biological function must be precisely controlled, and consequently, the protein relies on a combination of protein and substrate conformational changes as a prerequisite for reaction. These include substrate bending at the duplex-duplex junction and transfer of unpaired reacting duplex end into the active site. When present, 5′-flaps are thought to thread under the helical cap, limiting reaction to flaps with free 5′-termini in vivo. Here we monitored DNA bending by FRET and DNA unpairing using 2-aminopurine exciton pair CD to determine the DNA and protein requirements for these substrate conformational changes. Binding of DNA to hFEN1 in a bent conformation occurred independently of 5′-flap accommodation and did not require active site metal ions or the presence of conserved active site residues. More stringent requirements exist for transfer of the substrate to the active site. Placement of the scissile phosphate diester in the active site required the presence of divalent metal ions, a free 5′-flap (if present), a Watson-Crick base pair at the terminus of the reacting duplex, and the intact secondary structure of the enzyme helical cap. Optimal positioning of the scissile phosphate additionally required active site conserved residues Tyr40, Asp181, and Arg100 and a reacting duplex 5′-phosphate. These studies suggest a FEN1 reaction mechanism where junctions are bound and 5′-flaps are threaded (when present), and finally the substrate is transferred onto active site metals initiating cleavage. PMID:26884332

  8. Modeling the oxidation of methionine residues by peroxides in proteins.

    PubMed

    Chennamsetty, Naresh; Quan, Yong; Nashine, Vishal; Sadineni, Vikram; Lyngberg, Olav; Krystek, Stanley

    2015-04-01

    We report the use of molecular modeling to predict the oxidation propensity of methionine residues in proteins. Oxidation of methionine to the sulfoxide form is one of the major degradation pathways for therapeutic proteins. Oxidation can occur during production, formulation, or storage of pharmaceuticals and it often reduces or eliminates biological activity. We use a molecular model based on atomistic simulations called 2-shell water coordination number to predict the oxidation rates for several model proteins and therapeutic candidates. In addition, we implement models that are based on static and simulation average of the solvent-accessible area (SAA) for either the side chain or the sulfur atom in the methionine residue. We then compare the results from the different models against the experimentally measured relative rates of methionine oxidation. We find that both the 2-shell model and the simulation-averaged SAA models are accurate in predicting the oxidation propensity of methionine residues for the proteins tested. We also find the appropriate parameter ranges where the models are most accurate. These models have significant predictive power and can be used to enable further protein engineering or to guide formulation approaches in stabilizing the unstable methionine residues.

  9. Ruminal Methanogen Community in Dairy Cows Fed Agricultural Residues of Corn Stover, Rapeseed, and Cottonseed Meals.

    PubMed

    Wang, Pengpeng; Zhao, Shengguo; Wang, Xingwen; Zhang, Yangdong; Zheng, Nan; Wang, Jiaqi

    2016-07-13

    The purpose was to reveal changes in the methanogen community in the rumen of dairy cows fed agricultural residues of corn stover, rapeseed, and cottonseed meals, compared with alfalfa hay or soybean meal. Analysis was based on cloning and sequencing the methyl coenzyme M reductase α-subunit gene of ruminal methanogens. Results revealed that predicted methane production was increased while population of ruminal methanogens was not significantly affected when cows were fed diets containing various amounts of agricultural residues. Richness and diversity of methanogen community were markedly increased by addition of agricultural residues. The dominant ruminal methanogens shared by all experimental groups belonged to rumen cluster C, accounting for 71% of total, followed by the order Methanobacteriales (29%). Alterations of ruminal methanogen community and prevalence of particular species occurred in response to fed agricultural residue rations, suggesting the possibility of regulating target methanogens to control methane production by dairy cows fed agricultural residues. PMID:27322573

  10. Carbonylation of myofibrillar proteins through the maillard pathway: effect of reducing sugars and reaction temperature.

    PubMed

    Villaverde, Adriana; Estévez, Mario

    2013-03-27

    Carbonylation is recognized as one of the most remarkable chemical modifications in oxidized proteins and is generally ascribed to the direct attack of free radicals to basic amino acid residues. The purpose of this work was to investigate the formation of specific carbonyls, α-aminoadipic and γ-glutamic semialdehydes (AAS and GGS, respectively), in myofibrillar proteins (MP) through a Maillard-type pathway in the presence of reducing sugars. The present study confirmed the concurrent formation of protein carbonyls and advanced glycation end-products (AGEs) during incubation (80 °C/48 h) of MP (4 mg/mL) in the presence of reducing sugars (0.5 M). Copper irons (10 μM) were found to promote the formation of protein carbonyls, and a specific inhibitor of the Maillard reaction (0.02 M pyridoxamine) blocked the carbonylation process which emphasize the occurrence of a Maillard-type pathway. The Maillard-mediated carbonylation occurred in a range of reducing sugars (0.02-0.5 M) and reaction temperatures (4-110 °C) compatible with food systems. Upcoming studies on this topic may contribute further to shed light on the complex interactions between protein oxidation and the Maillard reaction and the impact of the protein damage on food quality and human health.

  11. Forgiveness, retaliation and paranoid reactions.

    PubMed

    Hunter, R C

    1978-04-01

    It has been suggested that clinical states from grudgingness and habitual bitterness through to delusions of persecution are best resolved by forgiving. The process of forgiving requires that previously unacknowledged impulses, particularly aggressive ones, are accepted in oneself and others. If the therapist is aware of this, he can, in the transference, reinforce the patient's good introjects by providing a non-judgemental, acceptant model for the patient and thereby facilitate the adoption of the forgiving attitude. Sometimes habitual forgiving can occur as a reaction formation, and should be dealt with as such.

  12. Histidine residues in the peptide D-Lys(6)-GnRH: potential for copolymerization in polymeric nanoparticles.

    PubMed

    Kafka, Alexandra P; Kleffmann, Torsten; Rades, Thomas; McDowell, Arlene

    2009-01-01

    Poly(ethylcyanoacrylate) (PECA) nanoparticles containing the bioactive d-Lys(6)-GnRH were manufactured by an in situ interfacial polymerization process using a w/o-microemulsion template containing the peptide in the dispersed aqueous pseudophase of the microemulsion. Polymeric nanoparticles were characterized using PCS, RP-HPLC (bulk level) and MALDI TOF mass spectrometry (molecular level). The peptide d-Lys(6)-GnRH was reactive with the alkylcyanoacrylate monomer, resulting in some of the peptide copolymerizing with the monomer. MALDI TOF/TOF (tandem) analysis revealed that the histidine residue in position 2 of d-Lys(6)-GnRH interacts covalently in the polymerization process. A reaction mechanism for this nucleophilic interference is suggested. The copolymerization reaction appeared to occur within seconds after the addition of the monomer to the microemulsion. The surface charge of resulting nanoparticles was less negative (-3 mV) compared with the zeta potential of empty nanoparticles (-27.5 mV). The copolymerization yielded high entrapment rates of 95 +/- 4% of peptide, but showed limited release ( approximately 11%) of free peptide over 5 days. A separate experiment demonstrated that the addition of d-Lys(6)-GnRH to preformed empty PECA nanoparticles (ex situ) also yielded fractions of copolymerized peptide suggesting a certain proportion of polymer remains available for copolymerization possibly through an unzipping depolymerization/repolymerization process. Therefore, the reactivity of histidine residues in bioactives needs to be considered whenever using the bioactive in situ or ex situ with polymeric PECA nanoparticles.

  13. Reproduction, growth, and tissue residues of deer fed dieldrin

    USGS Publications Warehouse

    Murphy, D.A.; Korschgen, L.J.

    1970-01-01

    Feeding tests were conducted from January, 1966, to January, 1969, to ascertain the effects of daily ingestions of sublethal amounts of dieldrin on white-tailed deer (Odocoileus virginianus). Groups of deer on 0 ppm dieldrin (controls), 5 ppm, and 25 ppm dieldrin were maintained at these respective levels, as were their progeny. Treated food was readily accepted. Dieldrin intoxication was not observed, and 9 of 10 animals of each group survived 3 years of treatment. No differences in conception or in utero mortality were found between groups. Fawns from dieldrin-fed does were smaller at birth and greater post-partum mortality occurred. Fertility of male progeny was not affected. Growth was slower and remained reduced in dieldrin-treated females which were immature when the study began. Hematologic values and serum protein concentrations were not significantly (P > 0.05) related to treatment. Liver/body weight ratios were significantly (P < 0.05) larger for the 25-ppm-dieldrin group. Pituitary glands were smaller and thyroids were larger in dieldrin-fed deer. Weight gains of fawns were significantly (P < 0.05) reduced 2 of 3 years in dieldrin-treated groups. Placental transfer of dieldrin occurred. Whole milk from does fed 25 ppm dieldrin contained residues of 17 ppm. Residue levels in brain, liver, and thigh muscle tissues showed no evidence of increasing with length of treatment, but showed definite relationships to levels of dieldrin in daily diets. Nursing fawns had higher residues in brain tissues than did older deer on 5 ppm a d 25 ppm dieldrin. Highest brain residues (12.60 and 12.10 ppm, wet weight) occurred in fawns only a few days of age at death. Equilibrium between ingestion and storage or excretion of dieldrin occurred prior to 200 days and continued until nearly 1,100 days. There was no evidence of a sharp decline in residues after a long period of continued dosage. Daily ingestion of 100 and 200 ppm of dieldrin proved fatal to yearling male deer at 27

  14. Dicofol and DDT residues in lizard carcasses and bird eggs from Texas, Florida, and California

    USGS Publications Warehouse

    Clark, D.R.; Flickinger, Edward L.; White, D.H.; Hothem, R.L.; Belisle, A.A.

    1995-01-01

    Relatively high dicofol residues occured in some lizards in Texas citrus orchards in early summer when female lizards were producing eggs. The data from bird eggs were too few for conclusions, but to detect peak residue loads, future dicofol studies should concentrate on predaceous bird species likely to feed within the treated agricultural habitats, and collecting of eggs for analysis should begin within days after spray application.

  15. Issues related to regulatory control of naturally occurring radioactive materials

    SciTech Connect

    Chen, S.Y.

    1997-04-01

    Nearly 80% of human radiation exposure is from naturally occurring radioactive materials (NORM). While exposure from man-made sources of radiation has been well regulated, no consistent regulatory controls exist for NORM. Because elevated radiation levels have resulted from NORM enhancement activities such as occur in the petroleum, fertilizer, mining, and processing industries, some form of regulatory control is in order. In the US, regulation of NORM by federal agencies such as the Nuclear Regulatory Commission or the Environmental Protection Agency is not anticipated in the near future because there are no authorizing federal statutes. Important issues for addressing the control of NORM include source characterization and generation, radiation protection concerns, waste management and disposition, and the regulatory framework.

  16. Stress fractures of the second metatarsal base occur in nondancers.

    PubMed

    Chuckpaiwong, Bavornrit; Cook, Chad; Nunley, James A

    2007-08-01

    Stress fractures of the base of the second metatarsal are common in ballet dancers and essentially are unreported in nondancers. We presumed base of the second metatarsal stress fractures in nondancers occur in a wide variety of individuals regardless of demographics, are highly associated with athletic activities, and have specific examination findings and poor clinical outcomes. Using a retrospective chart review, we identified 12 stress fractures at the base of the second metatarsal (nine patients) in nondancers. Our review suggests second metatarsal base stress fractures occur in nondancers in a diverse population, and nonoperative treatment provides limited success. Advanced radiographic study, specifically MRI, is useful to assist the early diagnosis and prognostication. All of the stress fractures were treated nonoperatively; six fractures (50%) developed nonunion and five underwent subsequent surgery. The surgery for nonunion provided successful outcomes; however, risk factors such as low bone mass and comorbidities may have played important roles in the prognosis.

  17. The Natural Occurring Compounds Targeting Endoplasmic Reticulum Stress.

    PubMed

    Liu, Hai; Yang, Jianqiong; Li, Linfu; Shi, Weimei; Yuan, Xiaoliang; Wu, Longhuo

    2016-01-01

    ER stress has been implicated in pathophysiological development of many diseases. Persistent overwhelming stimuli trigger ER stress to initiate apoptosis, autophagy, and cell death. IRE1-JNK and eIF2α-CHOP signaling pathways are the two important players of ER stress, which is also modulated by ROS production, calcium disturbance, and inflammatory factors. ER stress has been developed as a novel strategy for diseases management. Recently, a vast of research focuses on the natural occurring compounds targeting ER stress, which results in medical benefits to human diseases. These small reported molecules mainly include polyphenols, alkaloids, and saponins. Many of them have been developed for use in clinical applications. To better understand the pharmacological mechanism of these molecules in ER stress in diseases, efforts have been made to discover and deliver medical merits. In this paper, we will summarize the natural occurring compounds targeting ER stress. PMID:27563337

  18. The Natural Occurring Compounds Targeting Endoplasmic Reticulum Stress

    PubMed Central

    Liu, Hai; Yang, Jianqiong; Li, Linfu; Shi, Weimei

    2016-01-01

    ER stress has been implicated in pathophysiological development of many diseases. Persistent overwhelming stimuli trigger ER stress to initiate apoptosis, autophagy, and cell death. IRE1-JNK and eIF2α-CHOP signaling pathways are the two important players of ER stress, which is also modulated by ROS production, calcium disturbance, and inflammatory factors. ER stress has been developed as a novel strategy for diseases management. Recently, a vast of research focuses on the natural occurring compounds targeting ER stress, which results in medical benefits to human diseases. These small reported molecules mainly include polyphenols, alkaloids, and saponins. Many of them have been developed for use in clinical applications. To better understand the pharmacological mechanism of these molecules in ER stress in diseases, efforts have been made to discover and deliver medical merits. In this paper, we will summarize the natural occurring compounds targeting ER stress. PMID:27563337

  19. Naturally occurring iridoids and secoiridoids. An updated review, part 4.

    PubMed

    Dinda, Biswanath; Debnath, Sudhan; Banik, Rajarshi

    2011-01-01

    A compilation of new naturally occurring iridoids and secoiridoids including their glycosides, esters, aglycones, derivatives and dimers reported during mid 2008-2010 is provided with available physical and spectral data: mp, [α](D), UV, IR, circular dichroism (CD), (1)H- and (13)C-NMR as well as natural source with family and references. The important bioactivity of new and known iridoids and secoiridoids reported during this period is also highlighted.

  20. Analytical evaluation of integrals occurring in bound-free transitions

    SciTech Connect

    Burlon, R.; Leone, C.; Basile, S.; Trombetta, F.; Ferrante, G.

    1988-01-15

    A class of three-dimensional integrals on spatial coordinates of the type occurring in treatments of multiphoton ionization of atoms and of other bound-free transitions is evaluated in closed form for both hydrogenic and Slater-type wave functions. The reported method of evaluation is illustrated with a number of examples, including the multiphoton ionization of hydrogen by a very intense laser field, when the ejected electrons have absorbed more photons than the minimum required to reach the continuum.

  1. Sensory-motor transformations for speech occur bilaterally.

    PubMed

    Cogan, Gregory B; Thesen, Thomas; Carlson, Chad; Doyle, Werner; Devinsky, Orrin; Pesaran, Bijan

    2014-03-01

    Historically, the study of speech processing has emphasized a strong link between auditory perceptual input and motor production output. A kind of 'parity' is essential, as both perception- and production-based representations must form a unified interface to facilitate access to higher-order language processes such as syntax and semantics, believed to be computed in the dominant, typically left hemisphere. Although various theories have been proposed to unite perception and production, the underlying neural mechanisms are unclear. Early models of speech and language processing proposed that perceptual processing occurred in the left posterior superior temporal gyrus (Wernicke's area) and motor production processes occurred in the left inferior frontal gyrus (Broca's area). Sensory activity was proposed to link to production activity through connecting fibre tracts, forming the left lateralized speech sensory-motor system. Although recent evidence indicates that speech perception occurs bilaterally, prevailing models maintain that the speech sensory-motor system is left lateralized and facilitates the transformation from sensory-based auditory representations to motor-based production representations. However, evidence for the lateralized computation of sensory-motor speech transformations is indirect and primarily comes from stroke patients that have speech repetition deficits (conduction aphasia) and studies using covert speech and haemodynamic functional imaging. Whether the speech sensory-motor system is lateralized, like higher-order language processes, or bilateral, like speech perception, is controversial. Here we use direct neural recordings in subjects performing sensory-motor tasks involving overt speech production to show that sensory-motor transformations occur bilaterally. We demonstrate that electrodes over bilateral inferior frontal, inferior parietal, superior temporal, premotor and somatosensory cortices exhibit robust sensory-motor neural

  2. Occurence of ore metals in some terrestrial geothermal systems

    SciTech Connect

    Browne, P.

    1984-02-01

    Drilling programs and the study of active geothermal systems have shown that the reservoir rocks in many fields contain minor quantities of base and precious metals. Commonly, base-metal sulfides occur in the subsurface but, where present, Au, Ag, Hg, As, Tl and Sb rich precipitates deposit near, or at, the surface. Although in some fields (Geysers, Larderello, Tongonan) some of the ore minerals (and others) are relict, there is evidence that they are now depositing in a few systems. Recent work on active hydrothermal systems in New Zealand shows that: (1) Sphalerite, galena, chalcopyrite (forming veins and disseminated discrete crystals) plus rare pentlandite, cobaltite and arsenopyrite, occur at Broadlands, NZ. Rare quantities of base-metal sulfides also occur in cores and cuttings from the geothermal fields of Waiotapu, Kawerau, Tauhara, and Ngawha. Further, Kakimoto (1983) has identified cassiterite, native silver, and trace gold in cores from Tauhara, in the south-eastern part of the Wairakei field. Bore temperatures at the depths from which these minerals were recovered are mostly between 220/sup 0/ and 300/sup 0/C, but at Broadlands are locally as low as 120/sup 0/C. The host rocks are Quaternary calc-alkali, silicic lavas and pyroclastic rocks, andesites, dacite and deep Mesozoic greywackes and argillites; however, there is no obvious relationship between mineralization and stratigraphy, permeability or well output. The deposition of amorphous precious metal precipitates (Au, Ag, Hg, As, Sb, Tl) from hot springs and well discharges has taken place at Broadlands, Waiotapu and Rotokawa; it also occurs at Kawerau. Water discharging from Frying Pan Lake, Waimangu, is presently depositing siliceous sinter containing up to 4.1% tungsten.

  3. Sensory-motor transformations for speech occur bilaterally.

    PubMed

    Cogan, Gregory B; Thesen, Thomas; Carlson, Chad; Doyle, Werner; Devinsky, Orrin; Pesaran, Bijan

    2014-03-01

    Historically, the study of speech processing has emphasized a strong link between auditory perceptual input and motor production output. A kind of 'parity' is essential, as both perception- and production-based representations must form a unified interface to facilitate access to higher-order language processes such as syntax and semantics, believed to be computed in the dominant, typically left hemisphere. Although various theories have been proposed to unite perception and production, the underlying neural mechanisms are unclear. Early models of speech and language processing proposed that perceptual processing occurred in the left posterior superior temporal gyrus (Wernicke's area) and motor production processes occurred in the left inferior frontal gyrus (Broca's area). Sensory activity was proposed to link to production activity through connecting fibre tracts, forming the left lateralized speech sensory-motor system. Although recent evidence indicates that speech perception occurs bilaterally, prevailing models maintain that the speech sensory-motor system is left lateralized and facilitates the transformation from sensory-based auditory representations to motor-based production representations. However, evidence for the lateralized computation of sensory-motor speech transformations is indirect and primarily comes from stroke patients that have speech repetition deficits (conduction aphasia) and studies using covert speech and haemodynamic functional imaging. Whether the speech sensory-motor system is lateralized, like higher-order language processes, or bilateral, like speech perception, is controversial. Here we use direct neural recordings in subjects performing sensory-motor tasks involving overt speech production to show that sensory-motor transformations occur bilaterally. We demonstrate that electrodes over bilateral inferior frontal, inferior parietal, superior temporal, premotor and somatosensory cortices exhibit robust sensory-motor neural

  4. Breast carcinomas occurring in young women (< 35 years) are different.

    PubMed Central

    Walker, R. A.; Lees, E.; Webb, M. B.; Dearing, S. J.

    1996-01-01

    One hundred and sixty-three breast carcinomas occurring in women aged between 26 and 44 years were examined for pathological features, oestrogen and progesterone receptor status, proliferation as determined by Ki-67 labelling and the presence of c-erbB-2 and p53 protein, and were compared with a control group of carcinomas from women in the 50-67 years age group. Carcinomas occurring in women aged under 35 years had a significantly high incidence of being poorly differentiated and of having high proliferation rates. This group also had a significantly high incidence of p53 protein staining. Carcinomas in the under 30 years age group had a lower incidence of oestrogen and progesterone receptor positivity. No differences were found in c-erbB-2-positive staining between the groups. Infiltrating lobular carcinomas were only identified in women aged 40 years and over. There was a higher incidence of a family history in the 35-44 years age group (18%) than in the under 35 years age group (11%). Breast carcinomas occurring in women aged under 35 years are more aggressive. An important finding is the high incidence of p53 positivity, which may indicate genetic instability. Images Figure 1 PMID:8956795

  5. Where and when does reconnection occur in the tail?

    NASA Astrophysics Data System (ADS)

    McPherron, Robert L.

    2016-05-01

    We comment on the question of when and where reconnection begins in the tail and how it is related to the onset of auroral expansion. This question was addressed in a workshop dedicated to Unsolved Problems in Magnetospheric Physics held in Scarborough, UK, in September 2015. The answer is that it typically occurs first in the midtail a little beyond 20 Re somewhat before midnight about 55 min after a southward turning of the solar wind magnetic field. It appears to be a consequence of plasma sheet thinning down to the scale of an ion gyroradius. The onset of the activation and expansion of auroral activity and accompanying magnetic signatures typically occur within 1 or 2 min of the appearance of signatures of midtail reconnection. The unanswered question is which comes first and whether reconnection is the cause of the auroral expansion. We point out that older observations clearly established that plasmoids (flux ropes) are released from near 20 Re within a few minutes of the usual signatures of expansion onset. This is only possible if reconnection occurs close to the Earth. More detailed observations with modern spacecraft have led to the development of new explanations for the cause of the substorm expansion that appear to neglect older observations. We conclude that it is essential to carefully define the various terms used in the study of substorms and to develop quantitative methods that enable statistical studies of the various processes associated with auroral expansion onset.

  6. Pathologic features of naturally occurring juvenile polyarteritis in beagle dogs.

    PubMed

    Snyder, P W; Kazacos, E A; Scott-Moncrieff, J C; HogenEsch, H; Carlton, W W; Glickman, L T; Felsburg, P J

    1995-07-01

    Eighteen young Beagle dogs (eight males and 10 females), ages 6-40 months, with canine juvenile polyarteritis syndrome (CJPS), a naturally occurring vasculitis and perivasculitis of unknown etiology, were necropsied, and their tissues were examined by histopathologic and histochemical methods. The condition is characterized by recurring episodes of an acute onset of fever (> 40 C) and neck pain that persist for 3-7 days. The major histopathologic alterations were a systemic vasculitis and perivasculitis. During the febrile, painful period of CJPS, the vascular lesions ranged from a histiocytic-lymphocytic periarterial infiltration to transmural arterial inflammation with concomitant fibrinoid necrosis and vascular thrombosis. Massive periarterial accumulations of inflammatory cells were common and often extended into adjacent tissues. The small- to medium-sized muscular arteries of the heart, cranial mediastinum, and cervical spinal meninges were consistently involved. Vasculitis occasionally occurred in other organ systems. The vascular lesions in dogs examined during clinically normal periods consisted of intimal and medial fibrosis, ruptured elastic laminae, and mild perivasculitis; these lesions were probably related to previous episodes of vasculitis. Eight dogs that had experienced repeated acute episodes also developed splenic, hepatic, and renal amyloidosis. The clinical signs, laboratory abnormalities, and the vascular lesions suggest that the condition may be immune-system mediated. CJPS may serve as a naturally occurring animal model of human immune-system-mediated vasculitides such as polyarteritis nodosa, infantile polyarteritis, and Kawasaki disease.

  7. Skin picking disorder with co-occurring body dysmorphic disorder.

    PubMed

    Grant, Jon E; Redden, Sarah A; Leppink, Eric W; Odlaug, Brian L

    2015-09-01

    There is clinical overlap between skin picking disorder (SPD) and body dysmorphic disorder (BDD), but little research has examined clinical and cognitive correlates of the two disorders when they co-occur. Of 55 participants with SPD recruited for a neurocognitive study and two pharmacological studies, 16 (29.1%) had co-occurring BDD. SPD participants with and without BDD were compared to each other and to 40 healthy volunteers on measures of symptom severity, social functioning, and cognitive assessments using the Stop-signal task (assessing response impulsivity) and the Intra-dimensional/Extra-dimensional Set Shift task (assessing cognitive flexibility). Individuals with SPD and BDD exhibited significantly worse picking, significantly worse overall psychosocial functioning, and significantly greater dysfunction on aspects of cognitive flexibility. These results indicate that when SPD co-occurs with BDD unique clinical and cognitive aspects of SPD may be more pronounced. Future work should explore possible subgroups in SPD and whether these predict different treatment outcomes. PMID:26070103

  8. Removal of element mercury by medicine residue derived biochars in presence of various gas compositions.

    PubMed

    Li, Guoliang; Shen, Boxiong; Li, Yongwang; Zhao, Bin; Wang, Fumei; He, Chuan; Wang, Yinyin; Zhang, Min

    2015-11-15

    Pyrolyzed biochars from an industrial medicinal residue waste were modified by microwave activation and NH4Cl impregnation. Mercury adsorption of different modified biochars was investigated in a quartz fixed-bed reactor. The results indicated that both physisorption and chemisorption of Hg(0) occurred on the surface of M6WN5 which was modified both microwave and 5wt.% NH4Cl loading, and exothermic chemisorption process was a dominant route for Hg(0) removal. Microwave activation improved pore properties and NH4Cl impregnation introduced good active sites for biochars. The presence of NO and O2 increased Hg(0) adsorption whereas H2O inhibited Hg(0) adsorption greatly. A converse effect of SO2 was observed on Hg(0) removal, namely, low concentration of SO2 promoted Hg(0) removal obviously whereas high concentration of SO2 suppressed Hg(0) removal. The Hg(0) removal by M6WN5 was mainly due to the reaction of the C−Cl with Hg(0) to form HgCl2, and the active state of C−Cl(*) groups might be an intermediate group in this process. Thermodynamic analysis showed that mercury adsorption by the biochars was exothermic process and apparent adsorption energy was 43.3 kJ/mol in the range of chemisorption. In spite of low specific surface area, M6WN5 proved to be a promising Hg(0) sorbent in flue gas when compared with other sorbents.

  9. Flux melting of residual peridotite and formation of highly refractory peridotites and boninites in the northern Oman mantle section

    NASA Astrophysics Data System (ADS)

    Takazawa, E.; Kanke, N.; Nomoto, Y.; Fujii, S.

    2013-12-01

    Highly refractory peridotites often occur in the mantle section of the northern Oman ophiolite. These peridotites are generally considered as residues after extraction of boninitic melt from residual harzburgite by flux melting (Arai et al., 2006; Tamura et al., 2006; Kanke and Takazawa, 2013; Nomoto and Takazawa, 2013). The distribution of highly refractory peridotite is variable in the Oman mantle section depending on the scale and magnitude of hydrous melting of residual peridotites. In this study, we summarize the diversity of the occurrence of highly refractory peridotites in the northern Oman ophiolite and discuss the factors that control them. In the Fizh mantle section the range of spinel Cr# (=Cr/[Cr+Al] atomic ratio) in harzburgite gradually changes from the southern part (Cr# 0.43-0.67) to the northern part (Cr# 0.22-0.78). This corresponds to the compositional variation along paleo-ridge segment. In the northern part where paleo-ridge segment end was located, fertile peridotite such as lherzolite and highly refractory harzburgite in which the Cr# of spinel exceeds 0.7 closely occur together. The highly refractory harzburgites are distributed as a belt in the direction of NW-SE (highly refractory zone, hereafter). Moreover, spinel Cr# of dunites in the Fizh block also show a large range from 0.45 to 0.8 and frequency becomes the highest by 0.65-0.7. Spinel Cr# of harzburgite in the Salahi mantle section ranges in 0.48-0.70 and Fo content of olivine ranges in 90.1-92.2 except for the ultramafic complex. It occurs in the southwest part of the Salahi block and is composed of highly refractory large-scale massive dunite (spinel Cr# 0.7-0.84) associated with minor amounts of harzburgite (spinel Cr# 0.63-0.72) and pyroxenites. During oceanic thrusting of the Oman ophiolite hydrous fluids infiltrated from the base of the ophiolite caused flux melting of harzburgite forming dunite channels. It is thought that fluid infiltration within dunite channels may have

  10. Biomass-based polyols through oxypropylation reaction.

    PubMed

    Aniceto, José P S; Portugal, Inês; Silva, Carlos M

    2012-08-01

    Biomass residues are a potential renewable source for the sustainable production of chemicals, materials, fuels, and energy embodying the so-called biorefinery concept. In this context, agro-forestry and agro-food industry by-products have attracted considerable interest of researchers in academia and industry as a renewable source of polymeric materials. The research developed to date on the valorization of biomass residues by converting them into polyols through oxypropylation is the subject of this review. These bio-based polyols exhibit properties similar to their petrochemical counterparts and, as such, can be used with economical advantage in the production of polyurethanes. The operating conditions of the oxypropylation reaction depend on the biomass and on the desired polyol properties. The discussion of their influence and the economic viability of the process are also presented. PMID:22807440

  11. Biological activity of some naturally occurring resins, gums and pigments against in vitro LDL oxidation.

    PubMed

    Andrikopoulos, Nikolaos K; Kaliora, Andriana C; Assimopoulou, Andreana N; Papapeorgiou, Vassilios P

    2003-05-01

    Naturally occurring gums and resins with beneficial pharmaceutical and nutraceutical properties were tested for their possible protective effect against copper-induced LDL oxidation in vitro. Chiosmastic gum (CMG) (Pistacia lentiscus var. Chia resin) was the most effective in protecting human LDL from oxidation. The minimum and maximum doses for the saturation phenomena of inhibition of LDL oxidation were 2.5 mg and 50 mg CMG (75.3% and 99.9%, respectively). The methanol/water extract of CMG was the most effective compared with other solvent combinations. CMG when fractionated in order to determine a structure-activity relationship showed that the total mastic essential oil, collofonium-like residue and acidic fractions of CMG exhibited a high protective activity ranging from 65.0% to 77.8%. The other natural gums and resins (CMG resin 'liquid collection', P. terebinthus var. Chia resin, dammar resin, acacia gum, tragacanth gum, storax gum) also tested as above, showed 27.0%-78.8% of the maximum LDL protection. The other naturally occurring substances, i.e. triterpenes (amyrin, oleanolic acid, ursolic acid, lupeol, 18-a-glycyrrhetinic acid) and hydroxynaphthoquinones (naphthazarin, shikonin and alkannin) showed 53.5%-78.8% and 27.0%-64.1% LDL protective activity, respectively. The combination effects (68.7%-76.2% LDL protection) of ursolic-, oleanolic- and ursodeoxycholic- acids were almost equal to the effect (75.3%) of the CMG extract in comparable doses. PMID:12748987

  12. Antibody-mediated neutralization of Ebola virus can occur by two distinct mechanisms

    SciTech Connect

    Shedlock, Devon J.; Bailey, Michael A.; Popernack, Paul M.; Cunningham, James M.; Burton, Dennis R.; Sullivan, Nancy J.

    2010-06-05

    Human Ebola virus causes severe hemorrhagic fever disease with high mortality and there is no vaccine or treatment. Antibodies in survivors occur early, are sustained, and can delay infection when transferred into nonhuman primates. Monoclonal antibodies (mAbs) from survivors exhibit potent neutralizing activity in vitro and are protective in rodents. To better understand targets and mechanisms of neutralization, we investigated a panel of mAbs shown previously to react with the envelope glycoprotein (GP). While one non-neutralizing mAb recognized a GP epitope in the nonessential mucin-like domain, the rest were specific for GP1, were neutralizing, and could be further distinguished by reactivity with secreted GP. We show that survivor antibodies, human KZ52 and monkey JP3K11, were specific for conformation-dependent epitopes comprising residues in GP1 and GP2 and that neutralization occurred by two distinct mechanisms; KZ52 inhibited cathepsin cleavage of GP whereas JP3K11 recognized the cleaved, fusion-active form of GP.

  13. Internal Modification of U2 Small Nuclear (Snrna) Occurs in Nucleoli of Xenopus Oocytes

    PubMed Central

    Yu, Yi-Tao; Shu, Mei-Di; Narayanan, Aarthi; Terns, Rebecca M.; Terns, Michael P.; Steitz, Joan A.

    2001-01-01

    U2 small nuclear (sn)RNA contains a large number of posttranscriptionally modified nucleotides, including a 5′ trimethylated guanosine cap, 13 pseudouridines, and 10 2′-O-methylated residues. Using Xenopus oocytes, we demonstrated previously that at least some of these modified nucleotides are essential for biogenesis of a functional snRNP. Here we address the subcellular site of U2 internal modification. Upon injection into the cytoplasm of oocytes, G-capped U2 that is transported to the nucleus becomes modified, whereas A-capped U2 that remains in the cytoplasm is not modified. Furthermore, by injecting U2 RNA into isolated nuclei or enucleated oocytes, we observe that U2 internal modifications occur exclusively in the nucleus. Analysis of the intranuclear localization of fluorescently labeled RNAs shows that injected wild-type U2 becomes localized to nucleoli and Cajal bodies. Both internal modification and nucleolar localization of U2 are dependent on the Sm binding site. An Sm-mutant U2 is targeted only to Cajal bodies. The Sm binding site can be replaced by a nucleolar localization signal derived from small nucleolar RNAs (the box C/D motif), resulting in rescue of internal modification as well as nucleolar localization. Analysis of additional chimeric U2 RNAs reveals a correlation between internal modification and nucleolar localization. Together, our results suggest that U2 internal modification occurs within the nucleolus. PMID:11257127

  14. Direct Reactions with MoNA-LISA

    NASA Astrophysics Data System (ADS)

    Kuchera, Anthony

    2016-03-01

    Nuclear reactions can be used to probe the structure of nuclei. Direct reactions, which take place on short time scales, are well-suited for experiments with beams of short-lived nuclei. One such reaction is nucleon knockout where a proton or neutron is removed from the incoming beam from the interaction with a target. Single nucleon knockout reactions have been used to study the single-particle nature of nuclear wave functions. A recent experiment at the National Superconducting Cyclotron Laboratory was performed to measure cross sections from single nucleon knockout reactions for several p-shell nuclei. Detection of the residual nucleus in coincidence with any gamma rays emitted from the target allowed cross sections to ground and excited states to be measured. Together with input from reaction theory, ab initio structure theories can be tested. Simultaneously the accuracy of knockout reaction models can be validated by detecting the knocked out neutron with the Modular Neutron Array and Large multi-Institutional Scintillator Array (MoNA-LISA). Preliminary results from this experiment will be shown. Knockout reactions can also be used to populate nuclei which are neutron unbound, thus emit neutrons nearly instantaneously. The structure of these nuclei, therefore, cannot be probed with gamma ray spectroscopy. However, with large neutron detectors like MoNA-LISA the properties of these short-lived nuclei are able to be measured. Recent results using MoNA-LISA to study the structure of neutron-rich nuclei will be presented. The author would like to acknowledge support from the NNSA and NSF.

  15. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

    ERIC Educational Resources Information Center

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  16. Non-equilibrium effects in high temperature chemical reactions

    NASA Technical Reports Server (NTRS)

    Johnson, Richard E.

    1987-01-01

    Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

  17. Facile synthesis and antibacterial activity of naturally occurring 5-methoxyfuroflavone.

    PubMed

    Alam, Mohammad Sayed; Lee, Dong-Ung

    2010-12-01

    A convenient synthesis of 5-methoxyfuroflavone (6, pongaglabol methyl ether), a constituent of some Pongamia or Millettia genus, was achieved by starting from 2,4-dihydroxy-6-methoxyacetophenone via a chalcone precursor, followed by treatment with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). This five-step reaction (total yield: 21.6%) is more facile with that of previously utilized procedures using each different starting material. Antibacterial activities of the above compound and its precursor chalcones, which also belongs to the class of furoflavonoids, were tested by the disc diffusion method against Shigella dysenteriae, Salmonella typhi, Streptococcus-β-haemolyticus, and Staphylococcus aureus. 5-Methoxyfuroflavone showed moderate bactericidal activity against all tested bacterial strains, whereas its corresponding chalcone compound revealed a selective activity. PMID:21139271

  18. Leaching Properties of Naturally Occurring Heavy Metals from Soils

    NASA Astrophysics Data System (ADS)

    Zhang, M.; Hoshino, M.; Yoshikawa, M.; Hara, J.; Sugita, H.

    2014-12-01

    The major threats to human health from heavy metals are associated with exposure to arsenic, lead, cadmium, chromium, mercury, as well as some other elements. The effects of such heavy metals on human health have been extensively studied and reviewed by international organizations such as WHO. Due to their toxicity, heavy metal contaminations have been regulated by national environmental standards in many countries, and/or laws such as the Soil Contamination Countermeasures Act in Japan. Leaching of naturally occurring heavy metals from the soils, especially those around abandoned metal mines into surrounding water systems, either groundwater or surface water systems, is one of the major pathways of exposure. Therefore, understanding the leaching properties of toxic heavy metals from naturally polluted soils is of fundamentally importance for effectively managing abandoned metal mines, excavated rocks discharged from infrastructure constructions such as tunneling, and/or selecting a pertinent countermeasure against pollution when it is necessary. In this study, soil samples taken from the surroundings of abandoned metal mines in different regions in Japan were collected and analyzed. The samples contained multiple heavy metals such as lead, arsenic and chromium. Standard leaching test and sequential leaching test considering different forms of contaminants, such as trivalent and pentavalent arsenics, and trivalent and hexavalent chromiums, together with standard test for evaluating total concentration, X-ray Fluorescence Analysis (XRF), X-ray diffraction analysis (XRD) and Cation Exchange Capacity (CEC) tests were performed. In addition, sequential leaching tests were performed to evaluate long-term leaching properties of lead from representative samples. This presentation introduces the details of the above experimental study, discusses the relationships among leaching properties and chemical and mineral compositions, indicates the difficulties associated with

  19. Frog Virus 3 DNA Replication Occurs in Two Stages

    PubMed Central

    Goorha, R.

    1982-01-01

    Viral DNA synthesis in frog virus 3 (FV3)-infected cells occurs both in the nucleus and in the cytoplasm (Goorha et al., Virology 84:32-51, 1978). Relationships between viral DNA molecules synthesized in these two compartments and their role in the virus replication were examined. The data presented here suggest that (i) FV3 DNA replicated in two stages and (ii) nucleus and cytoplasm were the sites of stages 1 and 2 of DNA replication, respectively. Stages 1 and 2 were further distinguished by their temporal appearance during infection and by the sizes of the replicating DNA as determined by sedimentation in neutral sucrose gradients. In stage 1, replicating molecules, between the size of unit and twice the unit length, were produced early in infection (2 h postinfection). In contrast, stage 2 of DNA replication occurred only after 3 h postinfection, and replicating molecules were large concatemers. Results of pulse-chase experiments showed that the concatemeric DNA served as the precursor for the production of mature FV3 DNA. Denaturation of concatemeric DNA with alkali or digestion with S1 nuclease reduced it to less than genome size molecules, indicating the presence of extensive single-stranded regions. Analysis of replicating DNA by equilibrium centrifugation in CsCl gradients after a pulse-chase suggested that these single-stranded regions were subsequently repaired. Based on these and previous data, a scheme of FV3 replication is presented. According to this scheme, FV3 utilizes the nucleus for early transcription and stage 1 of DNA replication. The viral DNA is then transported to the cytoplasm, where it participates in stage 2 DNA replication to form a concatemeric replication complex. The processing of concatemers to produce mature viral DNA and virus assembly also occurs in the cytoplasm. This mode of replication is strikingly different from any other known DNA virus. PMID:7109033

  20. Immune Responses in Broiler Chicks Fed Propolis Extraction Residue-supplemented Diets

    PubMed Central

    Eyng, C.; Murakami, A. E.; Santos, T. C.; Silveira, T. G. V.; Pedroso, R. B.; Lourenço, D. A. L.

    2015-01-01

    This study was conducted to evaluate the effect of inclusion of propolis extraction residue in the feed of broilers from 1 to 21 d of age on phagocytic activity of macrophages, cutaneous basophil hypersensitivity response to phytohemagglutinin, antibody production against Newcastle disease, lymphoid organ weight and hematological profile and to determine the optimal level of inclusion. 120 chicks, reared in metabolism cages until 21 days of age, were distributed in a completely randomized design, with five treatments (0%, 1%, 2%, 3%, and 4% of propolis residue) and six replications. The relative weight of thymus and monocyte percentage were affected by propolis residue, with a quadratic response (p<0.05) and lowest values estimated at 2.38% and 2.49%, respectively. Changes in relative weight of cloacal bursa and spleen, percentage of lymphocyte, heterophil, basophil, eosinophil, and heterophil:lymphocyte ratio, antibody production against Newcastle disease, phagocytic activity of macrophages and the average number of phagocytosed erythrocytes were not observed. The nitric oxide production with regard to positive control (macrophages+erythrocytes) decreased linearly (p<0.05) with increased doses of propolis residue. The remaining variables of nitric oxide production (negative control – macrophages, and difference between the controls) were not affected by propolis residue. The cutaneous basophil hypersensitivity response to phytohemagglutinin as determined by the increase in interdigital skin thickness exhibited a quadratic response (p<0.05), which predicted a lower reaction response at a dose of 2.60% of propolis residue and highest reaction response after 43.05 hours of phytohemagglutinin injection. The inclusion of 1% to 4% of propolis extraction residue in broiler diets from 1 to 21 days of age was not able to improve the immune parameters, despite the modest changes in the relative weight in thymus, blood monocyte percentage, nitric oxide concentration, and

  1. Immune Responses in Broiler Chicks Fed Propolis Extraction Residue-supplemented Diets.

    PubMed

    Eyng, C; Murakami, A E; Santos, T C; Silveira, T G V; Pedroso, R B; Lourenço, D A L

    2015-01-01

    This study was conducted to evaluate the effect of inclusion of propolis extraction residue in the feed of broilers from 1 to 21 d of age on phagocytic activity of macrophages, cutaneous basophil hypersensitivity response to phytohemagglutinin, antibody production against Newcastle disease, lymphoid organ weight and hematological profile and to determine the optimal level of inclusion. 120 chicks, reared in metabolism cages until 21 days of age, were distributed in a completely randomized design, with five treatments (0%, 1%, 2%, 3%, and 4% of propolis residue) and six replications. The relative weight of thymus and monocyte percentage were affected by propolis residue, with a quadratic response (p<0.05) and lowest values estimated at 2.38% and 2.49%, respectively. Changes in relative weight of cloacal bursa and spleen, percentage of lymphocyte, heterophil, basophil, eosinophil, and heterophil:lymphocyte ratio, antibody production against Newcastle disease, phagocytic activity of macrophages and the average number of phagocytosed erythrocytes were not observed. The nitric oxide production with regard to positive control (macrophages+erythrocytes) decreased linearly (p<0.05) with increased doses of propolis residue. The remaining variables of nitric oxide production (negative control - macrophages, and difference between the controls) were not affected by propolis residue. The cutaneous basophil hypersensitivity response to phytohemagglutinin as determined by the increase in interdigital skin thickness exhibited a quadratic response (p<0.05), which predicted a lower reaction response at a dose of 2.60% of propolis residue and highest reaction response after 43.05 hours of phytohemagglutinin injection. The inclusion of 1% to 4% of propolis extraction residue in broiler diets from 1 to 21 days of age was not able to improve the immune parameters, despite the modest changes in the relative weight in thymus, blood monocyte percentage, nitric oxide concentration, and

  2. Myelodysplastic Syndrome Occurring in a Patient with Gorlin Syndrome.

    PubMed

    Mull, Jamie L; Madden, Lisa M; Bayliss, Susan J

    2016-07-01

    We report a case of myelodysplastic syndrome (MDS) occurring in an African American boy with Gorlin syndrome with a novel PTCH1 mutation. Before developing MDS, the patient had been treated with chemotherapy and radiation for a medulloblastoma. He received a bone marrow transplant for the MDS and eventually died of treatment complications. Secondary hematologic malignancies are a known complication of certain chemotherapeutics, although whether a patient with Gorlin syndrome has a greater propensity for the development of such malignancies is unclear. PMID:27241746

  3. An Update on Antitumor Activity of Naturally Occurring Chalcones

    PubMed Central

    Zhang, En-Hui; Wang, Ru-Feng; Guo, Shu-Zhen; Liu, Bin

    2013-01-01

    Chalcones, which have characteristic 1,3-diaryl-2-propen-1-one skeleton, are mainly produced in roots, rhizomes, heartwood, leaves, and seeds of genera Angelica, Sophora, Glycyrrhiza, Humulus, Scutellaria, Parartocarpus, Ficus, Dorstenia, Morus, Artocarpus, and so forth. They have become of interest in the research and development of natural antitumor agents over the past decades due to their broad range of mechanisms including anti-initiation, induction of apoptosis, antiproliferation, antimetastasis, antiangiogenesis, and so forth. This review summarizes the studies on the antitumor activity of naturally occurring chalcones and their underlying mechanisms in detail during the past decades. PMID:23690855

  4. Synthetic muscle promoters: activities exceeding naturally occurring regulatory sequences

    NASA Technical Reports Server (NTRS)

    Li, X.; Eastman, E. M.; Schwartz, R. J.; Draghia-Akli, R.

    1999-01-01

    Relatively low levels of expression from naturally occurring promoters have limited the use of muscle as a gene therapy target. Myogenic restricted gene promoters display complex organization usually involving combinations of several myogenic regulatory elements. By random assembly of E-box, MEF-2, TEF-1, and SRE sites into synthetic promoter recombinant libraries, and screening of hundreds of individual clones for transcriptional activity in vitro and in vivo, several artificial promoters were isolated whose transcriptional potencies greatly exceed those of natural myogenic and viral gene promoters.

  5. Transmission of Naturally Occurring Lymphoma in Macaque Monkeys

    NASA Astrophysics Data System (ADS)

    Hunt, Ronald D.; Blake, Beverly J.; Chalifoux, Laura V.; Sehgal, Prabhat K.; King, Norval W.; Letvin, Norman L.

    1983-08-01

    Spontaneously occurring rhesus monkey lymphomas were transmitted into healthy rhesus monkeys by using tumor cell suspensions. The naturally arising tumors included an immunoblastic sarcoma and an undifferentiated lymphoma. Recipient animals developed undifferentiated lymphomas, poorly differentiated lymphomas, or parenchymal lymphoproliferative abnormalities suggestive of early lesions of lymphoma. Some of these animals developed such opportunistic infections as cytomegalovirus hepatitis and cryptosporidiosis. They also showed evidence of an abnormal circulating peripheral blood mononuclear cell. These findings, all characteristic of the acquired immune deficiency syndrome (AIDS) of macaques, suggest a link between these transmissible lymphomas and AIDS in macaque monkeys.

  6. Naturally occurring crystalline phases: analogues for radioactive waste forms

    SciTech Connect

    Haaker, R.F.; Ewing, R.C.

    1981-01-01

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included.

  7. Pseudo-Kaposi sarcoma (acroangiodermatitis): occurring after bullous erysipelas.

    PubMed

    Kutlubay, Zekayi; Yardimci, Gürkan; Engin, Burhan; Demirkesen, Cuyan; Aydin, Övgü; Khatib, Rashid; Tuzun, Yalçın

    2015-05-01

    Pseudo-Kaposi sarcoma is a benign reactive vascular proliferative disorder, which can be seen at any age. It occurs when the chronic venous pressure changes result in vascular proliferation in the upper and mid dermis. This disease is divided into two subtypes: the most frequent subtype is the Mali type and seen in early ages. The Mali type is seen in chronic venous insufficiency and in those patients with arteriovenous shunts. The rare subtype is the Stewart-Bluefarb type. This disease must be distinguished from Kaposi sarcoma because of their clinical resemblance. Herein, we present a patient with pseudo-Kaposi sarcoma, which developed after bullous erysipelas.

  8. Photoprotective substance occurs primarily in outer layers of fish skin

    USGS Publications Warehouse

    Fabacher, D.L.; Little, E.E.

    1998-01-01

    Methanol extracts of dorsal skin layers, eyes, gills, and livers from ultraviolet-B (UVB) radiation-sensitive and UVB-tolerant species of freshwater fish were examined for a substance that appears to be photoprotective. Significantly larger amounts of this substance were found in extracts of outer dorsal skin layers from both UVB-sensitive and UVB-tolerant fish when compared with extracts of inner dorsal skin layers. This substance occurred in minor amounts or was not detected in eye, gill, and liver extracts. The apparent primary function of this substance in fish is to protect the cells in outer dorsal skin layers from harmful levels of UVB radiation.

  9. An update on antitumor activity of naturally occurring chalcones.

    PubMed

    Zhang, En-Hui; Wang, Ru-Feng; Guo, Shu-Zhen; Liu, Bin

    2013-01-01

    Chalcones, which have characteristic 1,3-diaryl-2-propen-1-one skeleton, are mainly produced in roots, rhizomes, heartwood, leaves, and seeds of genera Angelica, Sophora, Glycyrrhiza, Humulus, Scutellaria, Parartocarpus, Ficus, Dorstenia, Morus, Artocarpus, and so forth. They have become of interest in the research and development of natural antitumor agents over the past decades due to their broad range of mechanisms including anti-initiation, induction of apoptosis, antiproliferation, antimetastasis, antiangiogenesis, and so forth. This review summarizes the studies on the antitumor activity of naturally occurring chalcones and their underlying mechanisms in detail during the past decades.

  10. H-2Dd exploits a four residue peptide binding motif

    PubMed Central

    1993-01-01

    We have characterized the amino acid sequences of over 20 endogenous peptides bound by a soluble analog of H-2Dd, H-2Dds. Synthetic analogs corresponding to self, viral, tumor, or motif peptides were then tested for their ability to bind to H-2Dd by serologic epitope induction assays using both purified soluble protein and cell surface H-2Dd. The dominant primary sequence motif included glycine at position 2, proline at position 3, and a hydrophobic COOH terminus: leucine, isoleucine, or phenylalanine at position 9 or 10. Ancillary support for high affinity binding was contributed by a positively charged residue at position 5. Three-dimensional computer models of H-2Dds/peptide complexes, based on the crystallographic structure of the human HLA-B27/peptide complex, showed that the basic residue at position 5 was in position to form a salt bridge with aspartic acid at position 156, a polymorphic residue of the H-2Dd heavy (H) chain. Analysis of 28 such models, including 17 based on nonamer self-peptides, revealed considerable variation in the structure of the major histocompatibility complex (MHC) surrounding peptide residue 1, depending on the size and charge of the side chain. Interactions between the side chains of peptide residues 5 and 7, and 6 and 8 commonly occurred. Those peptide positions with limited sequence variability and least solvent accessibility may satisfy structural requirements for high affinity binding of the peptide to the MHC class I H chain, whereas the highly variable positions of the peptide (such as positions 4, 6, and 8) may contribute more to the T cell epitopes. PMID:8245770

  11. Application of organic geochemistry to coastal tar residues from Central California

    USGS Publications Warehouse

    Kvenvolden, K.A.; Rosenbauer, R.J.; Hostettler, F.D.; Lorenson, T.D.

    2000-01-01

    Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy (13C-enriched) carbon isotopic compositions spanning a narrow range (??13C = -22.2 to -23.4???), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.

  12. Stabilization of geothermal residues by encapsulation in portland cement-based composites

    SciTech Connect

    Webster, R.P.; Kukacka, L.E.

    1988-05-01

    Presented are the results from a laboratory test program conducted to identify and evaluate materials for converting hazardous geothermal residues to a non-hazardous and potentially usable form. Results indicate that the residues can be effectively incorporated, as a fine aggregate, into portland cement-based composites. Five geothermal residues obtained from sites in the Salton Sea area of California were evaluated. Three of these were classified as hazardous. After mixing with cement, the leach rates were all well below specified levels. Although structural-grade composites were produced, gradual reductions in properties with time up to 1 yr were noted. This indicates ongoing chemical reactions between the cement paste and the constituents of the residues. Further research is necessary before the composites could be considered for use in structural applications. 3 refs., 8 tabs.

  13. Patents for ELISA tests to detect antibiotic residues in foods of animal origin.

    PubMed

    Reig, Milagro; Toldrá, Fidel

    2011-05-01

    The use of antibiotics in the European Union was banned since the 1(st) of January 2006. At present, and even though such ban, residues of drugs used in animal therapy or, illegally, as growth promoters might be found in food. Such residues may cause adverse health effects on consumers like allergic reactions in sensitive individuals develop transmissible antimicrobial resistance in food microflora, and have technological implications in the manufacture of fermented products. This is the reason why to check food for the presence of antibiotics residues is still necessary. ELISA test constitutes an attractive screening technique due to its simplicity, large number of samples per kit and possibility of automation. The aim of this manuscript is to provide a review of the numerous patents and applications for the analysis of antibiotic residues in foods. PMID:21428870

  14. Patents for ELISA tests to detect antibiotic residues in foods of animal origin.

    PubMed

    Reig, Milagro; Toldrá, Fidel

    2011-05-01

    The use of antibiotics in the European Union was banned since the 1(st) of January 2006. At present, and even though such ban, residues of drugs used in animal therapy or, illegally, as growth promoters might be found in food. Such residues may cause adverse health effects on consumers like allergic reactions in sensitive individuals develop transmissible antimicrobial resistance in food microflora, and have technological implications in the manufacture of fermented products. This is the reason why to check food for the presence of antibiotics residues is still necessary. ELISA test constitutes an attractive screening technique due to its simplicity, large number of samples per kit and possibility of automation. The aim of this manuscript is to provide a review of the numerous patents and applications for the analysis of antibiotic residues in foods.

  15. Noncanonical reactions of flavoenzymes.

    PubMed

    Sobrado, Pablo

    2012-01-01

    Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a "molecular scaffold" in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  16. Anaphylactic reactions to cinoxacin.

    PubMed Central

    Stricker, B. H.; Slagboom, G.; Demaeseneer, R.; Slootmaekers, V.; Thijs, I.; Olsson, S.

    1988-01-01

    During 1981 to mid-1988 three cases of anaphylactic shock after treatment with the quinolone derivative cinoxacin were reviewed by the Netherlands Centre for Monitoring of Adverse Reactions to Drugs and 17 cases of an anaphylactic type of reaction notified to the World Health Organisation Collaborating Centre for International Drug Monitoring. In five out of six patients for whom data were available the reaction began shortly after taking a single capsule of a second or next course of treatment. Cinoxacin is related to nalidixic acid, and one patient previously treated with that agent subsequently had an anaphylactoid reaction to cinoxacin and later developed a skin reaction to nalidixic acid. There were no deaths, and patients treated as an emergency with plasma expanders or with adrenaline and corticosteroids generally recovered promptly and uneventfully. In view of the potentially fatal consequences of anaphylactic reactions to cinoxacin and other quinolones doctors should take care when prescribing these drugs. PMID:3147004

  17. Reaction spreading on graphs

    NASA Astrophysics Data System (ADS)

    Burioni, Raffaella; Chibbaro, Sergio; Vergni, Davide; Vulpiani, Angelo

    2012-11-01

    We study reaction-diffusion processes on graphs through an extension of the standard reaction-diffusion equation starting from first principles. We focus on reaction spreading, i.e., on the time evolution of the reaction product M(t). At variance with pure diffusive processes, characterized by the spectral dimension ds, the important quantity for reaction spreading is found to be the connectivity dimension dl. Numerical data, in agreement with analytical estimates based on the features of n independent random walkers on the graph, show that M(t)˜tdl. In the case of Erdös-Renyi random graphs, the reaction product is characterized by an exponential growth M(t)˜eαt with α proportional to ln, where is the average degree of the graph.

  18. Studies Of Residual Flexibility And Vibration Testing

    NASA Technical Reports Server (NTRS)

    Admire, John R.; Tinker, Michael L.; Bookout, Paul S.; Ivey, Edward W.

    1995-01-01

    Collection of reports presents theoretical and experimental studies in which concept of residual flexibility applied to modal vibration testing and verification of mathematical models of vibrations of flexible structure constrained by another structure. "Residual flexibility" denotes that part of interface flexibility due to mode shapes out of frequency range of test. Studies directed toward assessing residual-flexibility approach as substitute for fixed-base vibrational testing of payloads installed in spacecraft.

  19. Residual stresses in polymer matrix composite laminates

    NASA Technical Reports Server (NTRS)

    Hahn, H. T.

    1976-01-01

    Residual stresses in composites are induced during fabrication and by environmental exposure. The theory formulated can describe the shrinkage commonly observed after a thermal expansion test. Comparison between the analysis and experimental data for laminates of various material systems indicates that the residual stress-free temperature can be lower than the curing temperature, depending on the curing process. Effects of residual stresses on ply failure including the acoustic emission characteristics are discussed.

  20. Optical systolic array processor using residue arithmetic

    NASA Technical Reports Server (NTRS)

    Jackson, J.; Casasent, D.

    1983-01-01

    The use of residue arithmetic to increase the accuracy and reduce the dynamic range requirements of optical matrix-vector processors is evaluated. It is determined that matrix-vector operations and iterative algorithms can be performed totally in residue notation. A new parallel residue quantizer circuit is developed which significantly improves the performance of the systolic array feedback processor. Results are presented of a computer simulation of this system used to solve a set of three simultaneous equations.

  1. Effect of kinetics on residue curve maps for reactive distillation

    SciTech Connect

    Venimadhavan, G.; Buzad, G.; Doherty, M.F.; Malone, M.F. . Dept. of Chemical Engineering)

    1994-11-01

    A class of models is derived for studying the effects of chemical kinetics on residue curve maps for reactive distillation. Activity-based rate and phase equilibrium expressions provide an accurate and thermodynamically consistent description of composition changes in nonideal, reacting vapor-liquid mixtures. For certain strategies of operation, which dictate the rate of product removal, the model equations are nonautonomous, leading to unusual dynamic behavior. However, for a certain special product removal policy, the effects of kinetics can be described by a single parameter, the Damkoehler number, which measures the rate of reaction relative to product removal. For small values of the Damkoehler number, the nonreactive simple distillation residue curve map is recovered and the singular points are the pure components and azeotropes in the nonreactive mixture. A bifurcation analysis shows the deformation and, in some cases, the disappearance of these singular points as the Damkoehler number is increased until the equilibrium reactive residue curve map is recovered at large values. A model problem for the reactive distillation of methyl tert-butyl ether from isobutene and methanol is solved.

  2. Studies on residue-free decontaminants for chemical warfare agents.

    PubMed

    Wagner, George W

    2015-03-17

    Residue-free decontaminants based on hydrogen peroxide, which decomposes to water and oxygen in the environment, are examined as decontaminants for chemical warfare agents (CWA). For the apparent special case of CWA on concrete, H2O2 alone, without any additives, effectively decontaminates S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), pinacolyl methylphosphorofluoridate (GD), and bis(2-choroethyl) sulfide (HD) in a process thought to involve H2O2 activation by surface-bound carbonates/bicarbonates (known H2O2 activators for CWA decontamination). A plethora of products are formed during the H2O2 decontamination of HD on concrete, and these are characterized by comparison to synthesized authentic compounds. As a potential residue-free decontaminant for surfaces other than concrete (or those lacking adsorbed carbonate/bicarbonate) H2O2 activation for CWA decontamination is feasible using residue-free NH3 and CO2 as demonstrated by reaction studies for VX, GD, and HD in homogeneous solution. Although H2O2/NH3/CO2 ("HPAC") decontaminants are active for CWA decontamination in solution, they require testing on actual surfaces of interest to assess their true efficacy for surface decontamination.

  3. Studies on residue-free decontaminants for chemical warfare agents.

    PubMed

    Wagner, George W

    2015-03-17

    Residue-free decontaminants based on hydrogen peroxide, which decomposes to water and oxygen in the environment, are examined as decontaminants for chemical warfare agents (CWA). For the apparent special case of CWA on concrete, H2O2 alone, without any additives, effectively decontaminates S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), pinacolyl methylphosphorofluoridate (GD), and bis(2-choroethyl) sulfide (HD) in a process thought to involve H2O2 activation by surface-bound carbonates/bicarbonates (known H2O2 activators for CWA decontamination). A plethora of products are formed during the H2O2 decontamination of HD on concrete, and these are characterized by comparison to synthesized authentic compounds. As a potential residue-free decontaminant for surfaces other than concrete (or those lacking adsorbed carbonate/bicarbonate) H2O2 activation for CWA decontamination is feasible using residue-free NH3 and CO2 as demonstrated by reaction studies for VX, GD, and HD in homogeneous solution. Although H2O2/NH3/CO2 ("HPAC") decontaminants are active for CWA decontamination in solution, they require testing on actual surfaces of interest to assess their true efficacy for surface decontamination. PMID:25710477

  4. Establishing optimal quantitative-polymerase chain reaction assays for routine diagnosis and tracking of minimal residual disease in JAK2-V617F-associated myeloproliferative neoplasms: a joint European LeukemiaNet/MPN&MPNr-EuroNet (COST action BM0902) study

    PubMed Central

    Jovanovic, J V; Ivey, A; Vannucchi, A M; Lippert, E; Oppliger Leibundgut, E; Cassinat, B; Pallisgaard, N; Maroc, N; Hermouet, S; Nickless, G; Guglielmelli, P; van der Reijden, B A; Jansen, J H; Alpermann, T; Schnittger, S; Bench, A; Tobal, K; Wilkins, B; Cuthill, K; McLornan, D; Yeoman, K; Akiki, S; Bryon, J; Jeffries, S; Jones, A; Percy, M J; Schwemmers, S; Gruender, A; Kelley, T W; Reading, S; Pancrazzi, A; McMullin, M F; Pahl, H L; Cross, N C P; Harrison, C N; Prchal, J T; Chomienne, C; Kiladjian, J J; Barbui, T; Grimwade, D

    2013-01-01

    Reliable detection of JAK2-V617F is critical for accurate diagnosis of myeloproliferative neoplasms (MPNs); in addition, sensitive mutation-specific assays can be applied to monitor disease response. However, there has been no consistent approach to JAK2-V617F detection, with assays varying markedly in performance, affecting clinical utility. Therefore, we established a network of 12 laboratories from seven countries to systematically evaluate nine different DNA-based quantitative PCR (qPCR) assays, including those in widespread clinical use. Seven quality control rounds involving over 21 500 qPCR reactions were undertaken using centrally distributed cell line dilutions and plasmid controls. The two best-performing assays were tested on normal blood samples (n=100) to evaluate assay specificity, followed by analysis of serial samples from 28 patients transplanted for JAK2-V617F-positive disease. The most sensitive assay, which performed consistently across a range of qPCR platforms, predicted outcome following transplant, with the mutant allele detected a median of 22 weeks (range 6–85 weeks) before relapse. Four of seven patients achieved molecular remission following donor lymphocyte infusion, indicative of a graft vs MPN effect. This study has established a robust, reliable assay for sensitive JAK2-V617F detection, suitable for assessing response in clinical trials, predicting outcome and guiding management of patients undergoing allogeneic transplant. PMID:23860450

  5. Establishing optimal quantitative-polymerase chain reaction assays for routine diagnosis and tracking of minimal residual disease in JAK2-V617F-associated myeloproliferative neoplasms: a joint European LeukemiaNet/MPN&MPNr-EuroNet (COST action BM0902) study.

    PubMed

    Jovanovic, J V; Ivey, A; Vannucchi, A M; Lippert, E; Oppliger Leibundgut, E; Cassinat, B; Pallisgaard, N; Maroc, N; Hermouet, S; Nickless, G; Guglielmelli, P; van der Reijden, B A; Jansen, J H; Alpermann, T; Schnittger, S; Bench, A; Tobal, K; Wilkins, B; Cuthill, K; McLornan, D; Yeoman, K; Akiki, S; Bryon, J; Jeffries, S; Jones, A; Percy, M J; Schwemmers, S; Gruender, A; Kelley, T W; Reading, S; Pancrazzi, A; McMullin, M F; Pahl, H L; Cross, N C P; Harrison, C N; Prchal, J T; Chomienne, C; Kiladjian, J J; Barbui, T; Grimwade, D

    2013-10-01

    Reliable detection of JAK2-V617F is critical for accurate diagnosis of myeloproliferative neoplasms (MPNs); in addition, sensitive mutation-specific assays can be applied to monitor disease response. However, there has been no consistent approach to JAK2-V617F detection, with assays varying markedly in performance, affecting clinical utility. Therefore, we established a network of 12 laboratories from seven countries to systematically evaluate nine different DNA-based quantitative PCR (qPCR) assays, including those in widespread clinical use. Seven quality control rounds involving over 21,500 qPCR reactions were undertaken using centrally distributed cell line dilutions and plasmid controls. The two best-performing assays were tested on normal blood samples (n=100) to evaluate assay specificity, followed by analysis of serial samples from 28 patients transplanted for JAK2-V617F-positive disease. The most sensitive assay, which performed consistently across a range of qPCR platforms, predicted outcome following transplant, with the mutant allele detected a median of 22 weeks (range 6-85 weeks) before relapse. Four of seven patients achieved molecular remission following donor lymphocyte infusion, indicative of a graft vs MPN effect. This study has established a robust, reliable assay for sensitive JAK2-V617F detection, suitable for assessing response in clinical trials, predicting outcome and guiding management of patients undergoing allogeneic transplant. PMID:23860450

  6. Reaction profiles in porous electrodes. Final report

    SciTech Connect

    Katan, T.; Carlen, P.J.

    1985-05-01

    An experimental program was conducted to ascertain causes of alkaline zinc electrode shape change and to determine the development of reaction profiles within the pores of porous zinc electrodes. Various analog electrochemical cells were operated to isolate and evaluate the individual processes occurring during charge and discharge. It was found that both edge effects and osmosis can be responsible for the shape change phenomenon.

  7. Nuclear reaction studies

    SciTech Connect

    Alexander, J.M.; Lacey, R.A.

    1994-11-01

    Research focused on the statistical and dynamical properties of ``hot`` nuclei formed in symmetric heavy-ion reactions. Theses included ``flow`` measurements and the mechanism for multifragment disassembly. Model calculations are being performed for the reactions C+C, Ne+Al, Ar+Sc, Kr+Nb, and Xe+La. It is planned to study {sup 40}Ar reactions from 27 to 115 MeV/nucleon. 2 figs., 41 refs.

  8. Immune reaction to propanidid.

    PubMed

    Christmas, D

    1984-05-01

    An adverse reaction to the intravenous anaesthetic agent propanidid is described in which the main features were hypotension, facial erythema, and abdominal pain. Changes in serum complement levels and differential white cell counts indicate that this was an immune reaction mediated by the classical complement pathway. The immune reaction apparently involved antibodies other than those of the IgE (reagin) class, and circumstantial evidence suggests that it was specific to propanidid rather than to the entire formulation or to Cremophor EL.

  9. Enzymatic reaction paths as determined by transition path sampling

    NASA Astrophysics Data System (ADS)

    Masterson, Jean Emily

    Enzymes are biological catalysts capable of enhancing the rates of chemical reactions by many orders of magnitude as compared to solution chemistry. Since the catalytic power of enzymes routinely exceeds that of the best artificial catalysts available, there is much interest in understanding the complete nature of chemical barrier crossing in enzymatic reactions. Two specific questions pertaining to the source of enzymatic rate enhancements are investigated in this work. The first is the issue of how fast protein motions of an enzyme contribute to chemical barrier crossing. Our group has previously identified sub-picosecond protein motions, termed promoting vibrations (PVs), that dynamically modulate chemical transformation in several enzymes. In the case of human heart lactate dehydrogenase (hhLDH), prior studies have shown that a specific axis of residues undergoes a compressional fluctuation towards the active site, decreasing a hydride and a proton donor--acceptor distance on a sub-picosecond timescale to promote particle transfer. To more thoroughly understand the contribution of this dynamic motion to the enzymatic reaction coordinate of hhLDH, we conducted transition path sampling (TPS) using four versions of the enzymatic system: a wild type enzyme with natural isotopic abundance; a heavy enzyme where all the carbons, nitrogens, and non-exchangeable hydrogens were replaced with heavy isotopes; and two versions of the enzyme with mutations in the axis of PV residues. We generated four separate ensembles of reaction paths and analyzed each in terms of the reaction mechanism, time of barrier crossing, dynamics of the PV, and residues involved in the enzymatic reaction coordinate. We found that heavy isotopic substitution of hhLDH altered the sub-picosecond dynamics of the PV, changed the favored reaction mechanism, dramatically increased the time of barrier crossing, but did not have an effect on the specific residues involved in the PV. In the mutant systems

  10. Residues of profenofos in spring onion.

    PubMed

    Talebi, K; Ghassami, M R

    2004-01-01

    Profenofos is one of the commonly used insecticides in the control of Trips tabaci on spring onion in Iran. Residues of profenofos in spring onion were determined in two different fields under the same conditions. In the first field, onion plants were sprayed with profenofos (40EC) at the rate of 1000 g/ha. Spraying was repeated 2 weeks later. In the second field one spraying was preformed at the same rate. Spring onionwere sampled at different time intervals and analyzed for profenofos residues using a GC equipped with NPD detector. In the first field's samples, the residues were 0.097 and 0.025 mg/kg at 2 and 6 days after spraying, respectively. The residues declined to 0.002 mg/kg on the day twelve. Two days after the second spraying the residues was 0.27 mg/kg, which reduced to 0.032 on the day sixth. However the residues were not detectable 32 days after the second spraying. In the second field, residue levels were 0.193 and 0.043 mg/kg at 2 and 6 days after spraying. Residues, which found after 32 days, were less than 0.001 mg/kg. The rate of residue decay in the first field was higher than the second field. PMID:15756871

  11. Methods of separating particulate residue streams

    DOEpatents

    Hoskinson, Reed L.; Kenney, Kevin L.; Wright, Christopher T.; Hess, J. Richard

    2011-04-05

    A particulate residue separator and a method for separating a particulate residue stream may include an air plenum borne by a harvesting device, and have a first, intake end and a second, exhaust end; first and second particulate residue air streams that are formed by the harvesting device and that travel, at least in part, along the air plenum and in a direction of the second, exhaust end; and a baffle assembly that is located in partially occluding relation relative to the air plenum and that substantially separates the first and second particulate residue air streams.

  12. Naturally occurring organic osmolytes: from cell physiology to disease prevention.

    PubMed

    Khan, Shagufta H; Ahmad, Nihal; Ahmad, Faizan; Kumar, Raj

    2010-12-01

    Osmolytes are naturally occurring organic compounds, which represent different chemical classes including amino acids, methylamines, and polyols. By accumulating high concentrations of osmolytes, organisms adapt to perturbations that can cause structural changes in their cellular proteins. Osmolytes shift equilibrium toward natively-folded conformations by raising the free energy of the unfolded state. As osmolytes predominantly affect the protein backbone, the balance between osmolyte-backbone interactions and amino acid side chain-solvent interactions determines protein folding. Abnormal cell volume regulation significantly contributes to the pathophysiology of several disorders, and cells respond to these changes by importing, exporting, or synthesizing osmolytes to maintain volume homeostasis. In recent years, it has become quite evident that cells regulate many biological processes such as protein folding, protein disaggregation, and protein-protein interactions via accumulation of specific osmolytes. Many genetic diseases are attributed to the problems associated with protein misfolding/aggregation, and it has been shown that certain osmolytes can protect these proteins from misfolding. Thus, osmolytes can be utilized as therapeutic targets for such diseases. In this review article, we discuss the role of naturally occurring osmolytes in protein stability, underlying mechanisms, and their potential use as therapeutic molecules. PMID:21190292

  13. Daily intakes of naturally occurring radioisotopes in typical Korean foods.

    PubMed

    Choi, Min-Seok; Lin, Xiu-Jing; Lee, Sun Ah; Kim, Wan; Kang, Hee-Dong; Doh, Sih-Hong; Kim, Do-Sung; Lee, Dong-Myung

    2008-08-01

    The concentrations of naturally occurring radioisotopes ((232)Th, (228)Th, (230)Th, (228)Ra, (226)Ra, and (40)K) in typical Korean foods were evaluated. The daily intakes of these radioisotopes were calculated by comparing concentrations in typical Korean foods and the daily consumption rates of these foods. Daily intakes were as follows: (232)Th, 0.00-0.23; (228)Th, 0.00-2.04; (230)Th, 0.00-0.26; (228)Ra, 0.02-2.73; (226)Ra, 0.01-4.37 mBq/day; and (40)K, 0.01-5.71 Bq/day. The total daily intake of the naturally occurring radioisotopes measured in this study from food was 39.46 Bq/day. The total annual internal dose resulting from ingestion of radioisotopes in food was 109.83 muSv/y, and the radioisotope with the highest daily intake was (40)K. These values were same level compiled in other countries.

  14. Aggregatibacter actinomycetemcomitans leukotoxin cytotoxicity occurs through bilayer destabilization

    PubMed Central

    Brown, Angela C.; Boesze-Battaglia, Kathleen; Du, Yurong; Stefano, Frank P.; Kieba, Irene R.; Epand, Raquel F.; Kakalis, Lazaros; Yeagle, Philip L.; Epand, Richard M.; Lally, Edward T.

    2012-01-01

    Summary The Gram-negative bacterium, Aggregatibacter actinomycetemcomitans, is a common inhabitant of the human upper aerodigestive tract. The organism produces an RTX (Repeats in ToXin) toxin (LtxA) that kills human white blood cells. LtxA is believed to be a membrane-damaging toxin, but details of the cell surface interaction for this and several other RTX toxins have yet to be elucidated. Initial morphological studies suggested that LtxA was bending the target cell membrane. Because the ability of a membrane to bend is a function of its lipid composition, we assessed the proficiency of LtxA to release of a fluorescent dye from a panel of liposomes composed of various lipids. Liposomes composed of lipids that form nonlamellar phases were susceptible to LtxA-induced damage while liposomes composed of lipids that do not form non-bilayer structures were not. Differential scanning calorimetry demonstrated that the toxin decreased the temperature at which the lipid transitions from a bilayer to a nonlamellar phase, while 31P nuclear magnetic resonance studies showed that the LtxA-induced transition from a bilayer to an inverted hexagonal phase occurs through the formation of an isotropic intermediate phase. These results indicate that LtxA cytotoxicity occurs through a process of membrane destabilization. PMID:22309134

  15. Macaques Exhibit a Naturally-Occurring Depression Similar to Humans

    PubMed Central

    Xu, Fan; Wu, Qingyuan; Xie, Liang; Gong, Wei; Zhang, Jianguo; Zheng, Peng; Zhou, Qinmin; Ji, Yongjia; Wang, Tao; Li, Xin; Fang, Liang; Li, Qi; Yang, Deyu; Li, Juan; Melgiri, Narayan D.; Shively, Carol; Xie, Peng

    2015-01-01

    Rodent models have dominated preclinical investigations into the mechanisms of depression. However, these models-which rely on subjecting individual rodents to physical stressors - do not realistically resemble the etiopathological development of depression, which occurs naturally in a social context. A non-human primate model that better reflects the social ethological aspects of depression would be more advantageous to investigating pathophysiological mechanisms and developing antidepressant therapeutics. Here, we describe and model a naturally-occurring depressive state in a non-human primate species, the cynomolgus monkey (Macaca fascicularis), in a realistic social ethological context and associate the depressed behavioral phenotype with significant serum metabolic perturbations. One to two subjects per stable social colony (17–22 subjects) manifested a depressive phenotype that may be attributed to psychosocial stress. In accordance with rodent and human studies, the serum metabolic phenotype of depressed and healthy subjects significantly differed, supporting the model's face validity. However, application of the fast-acting antidepressant ketamine failed to demonstrate predictive validity. This study proposes a non-human primate depression model in a realistic social ethological context that can better approximate the psychosocial stressors underlying depression. PMID:25783476

  16. On the mechanical friction losses occurring in automotive differential gearboxes.

    PubMed

    Antoni, Grégory

    2014-01-01

    In the automobile industry, the mechanical losses resulting from friction are largely responsible for various kinds of surface damage, such as the scuffing occurring in some mechanical assemblies. These scuffing processes seem to be due to a local loss of lubrication between certain mechanical elements of the same assembly, leading to a sharp increase in the friction, which can lead to a surface and volume damage in some of them, and even can cause, in the worst case, the whole destruction of the mechanical system if it has continued to operate. Predicting and checking the occurrence of this kind of undesirable phenomena, especially in some principal systems of the vehicle, represents nowadays, a crucial challenge in terms of automobile reliability and safety. This study focuses on the mechanical friction losses liable to occur in differential automobile gearboxes, which can lead in the long term to the scuffing of these mechanical systems. The friction losses involved were modeled, using a simple analytical approach, which is presented and discussed.

  17. Effects of later-occurring nonlinguistic sounds on speech categorization.

    PubMed

    Wade, Travis; Holt, Lori L

    2005-09-01

    Nonspeech stimuli influence phonetic categorization, but effects observed so far have been limited to precursors' influence on perception of following speech. However, both preceding and following speech affect phonetic categorization. This asymmetry raises questions about whether general auditory processes play a role in context-dependent speech perception. This study tested whether the asymmetry stems from methodological issues or genuine mechanistic limitations. To determine whether and how backward effects of nonspeech context on speech may occur, one experiment examined perception of CVC words with [ga]-[da] series onsets followed by one of two possible embedded tones and one of two possible final consonants. When the tone was separated from the target onset by 100 ms, contrastive effects of tone frequency similar to those of previous studies were observed; however, when the tone was moved closer to the target segment assimilative effects were observed. In another experiment, contrastive effects of a following tone were observed in both CVC words and CV nonwords, although the size of the effects depended on syllable structure. Results are discussed with respect to contrastive mechanisms not speech-specific but operating at a relatively high level, taking into account spectrotemporal patterns occurring over extended periods before and after target events. PMID:16240828

  18. Economic losses occurring due to brucellosis in Indian livestock populations.

    PubMed

    Singh, B B; Dhand, N K; Gill, J P S

    2015-05-01

    Brucellosis is a serious public health issue in India. Estimation of economic losses occurring due to brucellosis is required to help formulate prevention and control strategies, but has not been done in India. We estimated economic losses due to brucellosis by sourcing prevalence data from epidemiological surveys conducted in India. Data for livestock populations were obtained from official records. Probability distributions were used for many of the input parameters to account for uncertainty and variability. The analysis revealed that brucellosis in livestock is responsible for a median loss of US $ 3.4 billion (5th-95th percentile 2.8-4.2 billion). The disease in cattle and buffalo accounted for 95.6% of the total losses occurring due to brucellosis in livestock populations. The disease is responsible for a loss of US $ 6.8 per cattle, US$18.2 per buffalo, US $ 0.7 per sheep, US $ 0.5 per goat and US $ 0.6 per pig. These losses are additional to the economic and social consequences of the disease in humans. The results suggest that the disease causes significant economic losses in the country and should be controlled on a priority basis.

  19. Predictors, treatment, and outcomes of STEMI occurring in hospitalized patients.

    PubMed

    Dai, Xuming; Kaul, Prashant; Smith, Sidney C; Stouffer, George A

    2016-03-01

    ST-segment elevation myocardial infarction (STEMI) is most commonly caused by an acute thrombotic occlusion of a coronary artery. For patients in whom the onset of STEMI occurs outside of hospital (outpatient STEMI), early reperfusion therapy with either fibrinolysis or primary percutaneous coronary intervention reduces complications and improves survival, compared with delayed reperfusion. STEMI systems of care are defined as integrated groups of separate entities focused on reperfusion therapy for STEMI, generally including emergency medical services, emergency medicine, cardiology, nursing, and hospital administration. These systems of care have been successful at reducing total ischaemia time and outpatient STEMI mortality. By contrast, much less is known about STEMI that occurs in hospitalized patients (inpatient STEMI), which has unique clinical features and much worse outcomes than outpatient STEMI. Inpatient STEMI is associated with older age, a higher female:male ratio, and more comorbidities than outpatient STEMI. Delays in diagnosis and infrequent use of reperfusion therapy probably also contribute to unfavourable outcomes for inpatient STEMI.

  20. Beauveria caledonica is a naturally occurring pathogen of forest beetles.

    PubMed

    Glare, Travis R; Reay, Stephen D; Nelson, Tracey L; Moore, Roger

    2008-03-01

    In New Zealand, two introduced scolytid beetles, Hylastes ater and Hylurgus ligniperda (Curculionidae: Scolytinae) are pests in pine plantations. Investigation of the naturally occurring pathogens of these exotic pests revealed that both are attacked by Beauveria caledonica, a species originally isolated and described from soil in Scotland. The isolates in New Zealand were identical in morphology and conserved DNA region (rDNA, elongation factor alpha) sequence to isolates held in the USDA-ARS insect pathogens culture collection. In bioassay, the B. caledonica isolates were highly pathogenic to adults of H. ligniperda and larvae of Tenebrio molitor. Sporulation was observed on cadavers, confirming the species can utilise the cadavers. As both species were likely to have been introduced to New Zealand from Europe, a search was made for B. caledonica in the northern UK and Ireland. The fungus was found as a naturally-occurring pathogen of the weevil pest, Hylobius abietis (Curculionidae: Scolytinae), developing in spruce and other beetles in forests in both regions. PMID:18308525