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Sample records for acid groups neutralized

  1. Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

    PubMed

    Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Enriquez-Victorero, Carlos; Montero-Alejo, Ana Lilian; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

    2016-04-01

    Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions. PMID:26945637

  2. Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

    PubMed

    Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Enriquez-Victorero, Carlos; Montero-Alejo, Ana Lilian; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

    2016-04-01

    Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions.

  3. Capillary electrochromatography with polyacrylamide monolithic stationary phases having bonded dodecyl ligands and sulfonic acid groups: evaluation of column performance with alkyl phenyl ketones and neutral moderately polar pesticides.

    PubMed

    Zhang, M; El Rassi, Z

    2001-08-01

    In this report, we describe the preparation of porous polyacrylamide-based monolithic columns via vinyl polymerization. These monoliths possess in their structures bonded dodecyl ligands and sulfonic acid groups. While the sulfonic acid groups are meant to support the electroosmotic flow (EOF) necessary for moving the mobile phase through the monolithic capillary, the dodecyl ligands are introduced to provide the nonpolar sites for chromatographic retention. However, incorporating the sulfonic acid groups in the monoliths does not only support the EOF but also exhibit hydrophilic interaction with moderately polar compounds such as urea herbicides and carbamates insecticides. Consequently, mixed-mode (reversed-phase/normal phase) retention behavior is observed with neutral and moderately polar pesticides. The amount of sulfonic acid group in the monolith can be conveniently adjusted by changing the amount of vinylsulfonic acid added to the polymerization reaction. Optimum EOF velocity and adequate chromatographic retention are obtained when 15% vinylsulfonic acid is added to the reaction mixture. Under these conditions, rapid separation and high plate counts reaching greater than 400000 plates/m are readily obtained.

  4. Neutralization of rainwater acidity at Kanpur, India

    NASA Astrophysics Data System (ADS)

    Shukla, Sheo Prasad; Sharma, Mukesh

    2010-07-01

    Particulate matter (PM) levels show significant seasonal variability and this can influence the neutralization of rainwater acidity. Months were grouped in two periods: monsoon (July to October) and non-monsoon (November to June) for studying the seasonal variability in PM and rainwater composition. To clearly establish the cause effect relationship of acid rain neutralization, a two tier model was proposed involving source apportionment of particulates at two levels: (i) ambient air and (ii) rainwater particulate interaction. For modelling purpose, PM10 (n = 100), soil (n = 4) and rainwater (n = 83) samples were collected at Kanpur, India during 2000-2002. The collected samples were analysed for metals and water soluble ion composition to employ factor analysis for source identification. Knowledge of statistical correlation and chemistry fundamentals were combined to estimate the sources for acid rain neutralization. NH4+ was a dominating ion responsible for neutralizing the acidity of rainwater in monsoon period and Ca2+ was dominating in non-monsoon period. Components of secondary particles (SO42- and NO3-) showed affinity with NH4+, signifying the major role that ammonia can play if present in excess of stoichiometric requirements.

  5. Separation of Acids, Bases, and Neutral Compounds

    NASA Astrophysics Data System (ADS)

    Fujita, Megumi; Mah, Helen M.; Sgarbi, Paulo W. M.; Lall, Manjinder S.; Ly, Tai Wei; Browne, Lois M.

    2003-01-01

    Separation of Acids, Bases, and Neutral Compounds requires the following software, which is available for free download from the Internet: Netscape Navigator, version 4.75 or higher, or Microsoft Internet Explorer, version 5.0 or higher; Chime plug-in, version compatible with your OS and browser (available from MDL); and Flash player, version 5 or higher (available from Macromedia).

  6. Acid neutralization of precipitation in Northern China.

    PubMed

    Wang, Yuesi; Yu, Wenpeng; Pan, Yuepeng; Wu, Dan

    2012-02-01

    There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.

  7. Neutral Hydrogen in Local Group Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Grcevich, Jana

    The gas content of the faintest and lowest mass dwarf galaxies provide means to study the evolution of these unique objects. The evolutionary histories of low mass dwarf galaxies are interesting in their own right, but may also provide insight into fundamental cosmological problems. These include the nature of dark matter, the disagreement between the number of observed Local Group dwarf galaxies and that predicted by lambda cold dark matter models, and the discrepancy between the observed census of baryonic matter in the Milky Way's environment and theoretical predictions. This thesis explores these questions by studying the neutral hydrogen (HI) component of dwarf galaxies. First, limits on the HI mass of the ultra-faint dwarfs are presented, and the HI content of all Local Group dwarf galaxies is examined from an environmental standpoint. We find that those Local Group dwarfs within 270 kpc of a massive host galaxy are deficient in HI as compared to those at larger galactocentric distances. Ram-pressure arguments are invoked, which suggest halo densities greater than 2-3 x 10-4 cm-3 out to distances of at least 70 kpc, values which are consistent with theoretical models and suggest the halo may harbor a large fraction of the host galaxy's baryons. We also find that accounting for the incompleteness of the dwarf galaxy count, known dwarf galaxies whose gas has been removed could have provided at most 2.1 x 108 M⊙ of HI gas to the Milky Way. Second, we examine the possibility of discovering unknown gas-rich ultra-faint galaxies in the Local Group using HI. The GALFA-HI Survey catalog is searched for compact, isolated HI clouds which are most similar to the expected HI characteristics of low mass dwarf galaxies. Fifty-one Local Group dwarf galaxy candidates are identified through column density, brightness temperature, and kinematic selection criteria, and their properties are explored. Third, we present hydrodynamic simulations of dwarf galaxies experiencing a

  8. Amine bearing polymeric particles as acid neutralizers for engine oils

    SciTech Connect

    Theodore, A.N.; Chattha, M.S.

    1986-02-04

    This patent describes a lubricating oil composition consisting of a major proportion of a lubricating base oil and about 0.1 to 15 weight percent of an acid neutralizing additive which consists of polymer particles (a) bearing pendant amine groups, and (b) having a diameter of about 500 A and 10,000 A. The amine functional particles are formed by reacting polymer particles bearing pendant epoxide groups with a secondary amine in an amount so as to react essentially all of the epoxide groups on the epoxide bearing polymer particles with the secondary amine. The polymer particles bearing pendant epoxide groups are formed by the free radical addition polymerization of: (a) between about 50 and about 100 weight percent of an ethylenically unsaturated monomers bearing an epoxide group, and (b) 0 up to about 50 weight percent of other monoethylenically unsaturated monomers; in the presence of: (I) a non-polar organic liquid which is a solvent for the polymerizable monomers, but a non-solvent for the resultant polymer, and (II) polymeric dispersion stabilizer containing at least two segments, with one segment being solvated by the non-polar organic liquid and the second segment being of different polarity than the first segment and relatively insoluble in the non-polar organic liquid. The second segment of the stabilizer is chemically attached to the polymerized particle.

  9. Characteristics of neutralization of acids by newly isolated fungal cells.

    PubMed

    Shiomi, Naofumi; Yasuda, Takako; Inoue, Yoko; Kusumoto, Noriko; Iwasaki, Saori; Katsuda, Tomohisa; Katoh, Shigeo

    2004-01-01

    Soil microorganisms play an important role in maintaining soil pH at levels suitable for other soil organisms. To clarify the biological neutralization mechanism in soil, we isolated soil microorganisms showing a high ability to neutralize acids and studied their characteristics. From our taxonomic study, three isolated strains were identified as filamentous fungi, namely Mucor sp., Aspergillus fumigatus, and Aureobasidium pullulans. These strains could secrete basic materials, such as ammonia, for neutralization, grow in the medium at pH 4.0 and increase the pH of the medium to approximately 8.0. These microbial cells could neutralize not only nitric acid but also sulfuric and hydrochloric acids. The strains could also grow by utilizing nitric acid as a sole nitrogen source. In the soil containing these organisms, the pH was maintained in the neutral range by the buffering action of basic materials that they secrete. These results suggest that these fungal cells are useful for protecting the soil from acidification by acid rain.

  10. Microculture plaque neutralization test for California group arboviruses.

    PubMed

    Seawright, G L; Harding, G; Thomas, F C; Hanson, R P

    1974-11-01

    A microculture plaque neutralization test is described for California-group arboviruses that is as precise and quantitative as the standard test conducted in 60-mm petri dishes. It was shown that there was no significant between-panel or between-day variation in determinations and that a single pipette could be used for all serum-dilution levels within a titration without inoculum carry-over effect. The experimental protocol and statistical methods used produce 50% neutralization end points that meet the assumptions of parametric statistics. This permits the power and versatility of the analysis of variance to be exploited in testing for treatment effects in serological and immunological studies with viruses.

  11. Global Properties of Neutral Hydrogen in Compact Groups

    NASA Astrophysics Data System (ADS)

    Walker, Lisa May; Johnson, Kelsey E.; Gallagher, Sarah C.; Privon, George C.; Kepley, Amanda A.; Whelan, David G.; Desjardins, Tyler D.; Zabludoff, Ann I.

    2016-02-01

    Compact groups of galaxies provide a unique environment to study the evolution of galaxies amid frequent gravitational encounters. These nearby groups have conditions similar to those in the earlier universe when galaxies were assembled and give us the opportunity to witness hierarchical formation in progress. To understand how the compact group environment affects galaxy evolution, we examine the gas and dust in these groups. We present new single-dish GBT neutral hydrogen (H i) observations of 30 compact groups and define a new way to quantify the group H i content as the H i-to-stellar mass ratio of the group as a whole. We compare the H i content with mid-IR indicators of star formation and optical [g - r] color to search for correlations between group gas content and star formation activity of individual group members. Quiescent galaxies tend to live in H i-poor groups, and galaxies with active star formation are more commonly found in H i-rich groups. Intriguingly, we also find “rogue” galaxies whose star formation does not correlate with group H i content. In particular, we identify three galaxies (NGC 2968 in RSCG 34, KUG 1131+202A in RSCG 42, and NGC 4613 in RSCG 64) whose mid-IR activity is discrepant with the H i. We speculate that this mismatch between mid-IR activity and H i content is a consequence of strong interactions in this environment that can strip H i from galaxies and abruptly affect star formation. Ultimately, characterizing how and on what timescales the gas is processed in compact groups will help us understand the interstellar medium in complex, dense environments similar to the earlier universe.

  12. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic...

  13. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic...

  14. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic...

  15. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic...

  16. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic...

  17. Acid and neutral sphingomyelinases: roles and mechanisms of regulation.

    PubMed

    Marchesini, Norma; Hannun, Yusuf A

    2004-02-01

    Ceramide, an emerging bioactive lipid and second messenger, is mainly generated by hydrolysis of sphingomyelin through the action of sphingomyelinases. At least two sphingomyelinases, neutral and acid sphingomyelinases, are activated in response to many extracellular stimuli. Despite extensive studies, the precise cellular function of each of these sphingomyelinases in sphingomyelin turnover and in the regulation of ceramide-mediated responses is not well understood. Therefore, it is essential to elucidate the factors and mechanisms that control the activation of acid and neutral sphingomyelinases to understand their the roles in cell regulation. This review will focus on the molecular mechanisms that regulate these enzymes in vivo and in vitro, especially the roles of oxidants (glutathione, peroxide, nitric oxide), proteins (saposin, caveolin 1, caspases), and lipids (diacylglycerol, arachidonic acid, and ceramide).

  18. NEUTRALIZATION OF ACIDIC GROUND WATER NEAR GLOBE, ARIZONA.

    USGS Publications Warehouse

    Eychaner, James H.; Stollenwerk, Kenneth G.; ,

    1985-01-01

    Highly acidic contaminated water is moving through a shallow aquifer and interacting with streams near Globe, Arizona. Dissolved concentrations reach 3,000 mg/L iron, 150 mg/L copper, and 16,400 mg/L total dissloved solids; pH is as low as 3. 6. Samples from 16 PVC-cased observation wells include uncontaminated, contaminated, transition, and neutralized waters. Chemical reaction with sediments and mixing with uncontaminated water neutralizes the acidic water. The reactions form a transition zone where gypsum replaces calcite and most metals precipitate. Ferric hydroxide also precipitates if sufficient oxygen is available. Abundant gypsum crystals and ferric hydroxide coatings have been recovered from well cuttings. Large sulfate concentrations produce sulfate complexes with many metals that inhibit removal of metals from solution.

  19. Neutralization of Tumor Acidity Improves Antitumor Responses to Immunotherapy.

    PubMed

    Pilon-Thomas, Shari; Kodumudi, Krithika N; El-Kenawi, Asmaa E; Russell, Shonagh; Weber, Amy M; Luddy, Kimberly; Damaghi, Mehdi; Wojtkowiak, Jonathan W; Mulé, James J; Ibrahim-Hashim, Arig; Gillies, Robert J

    2016-03-15

    Cancer immunotherapies, such as immune checkpoint blockade or adoptive T-cell transfer, can lead to durable responses in the clinic, but response rates remain low due to undefined suppression mechanisms. Solid tumors are characterized by a highly acidic microenvironment that might blunt the effectiveness of antitumor immunity. In this study, we directly investigated the effects of tumor acidity on the efficacy of immunotherapy. An acidic pH environment blocked T-cell activation and limited glycolysis in vitro. IFNγ release blocked by acidic pH did not occur at the level of steady-state mRNA, implying that the effect of acidity was posttranslational. Acidification did not affect cytoplasmic pH, suggesting that signals transduced by external acidity were likely mediated by specific acid-sensing receptors, four of which are expressed by T cells. Notably, neutralizing tumor acidity with bicarbonate monotherapy impaired the growth of some cancer types in mice where it was associated with increased T-cell infiltration. Furthermore, combining bicarbonate therapy with anti-CTLA-4, anti-PD1, or adoptive T-cell transfer improved antitumor responses in multiple models, including cures in some subjects. Overall, our findings show how raising intratumoral pH through oral buffers therapy can improve responses to immunotherapy, with the potential for immediate clinical translation. PMID:26719539

  20. Neutralization of Tumor Acidity Improves Antitumor Responses to Immunotherapy.

    PubMed

    Pilon-Thomas, Shari; Kodumudi, Krithika N; El-Kenawi, Asmaa E; Russell, Shonagh; Weber, Amy M; Luddy, Kimberly; Damaghi, Mehdi; Wojtkowiak, Jonathan W; Mulé, James J; Ibrahim-Hashim, Arig; Gillies, Robert J

    2016-03-15

    Cancer immunotherapies, such as immune checkpoint blockade or adoptive T-cell transfer, can lead to durable responses in the clinic, but response rates remain low due to undefined suppression mechanisms. Solid tumors are characterized by a highly acidic microenvironment that might blunt the effectiveness of antitumor immunity. In this study, we directly investigated the effects of tumor acidity on the efficacy of immunotherapy. An acidic pH environment blocked T-cell activation and limited glycolysis in vitro. IFNγ release blocked by acidic pH did not occur at the level of steady-state mRNA, implying that the effect of acidity was posttranslational. Acidification did not affect cytoplasmic pH, suggesting that signals transduced by external acidity were likely mediated by specific acid-sensing receptors, four of which are expressed by T cells. Notably, neutralizing tumor acidity with bicarbonate monotherapy impaired the growth of some cancer types in mice where it was associated with increased T-cell infiltration. Furthermore, combining bicarbonate therapy with anti-CTLA-4, anti-PD1, or adoptive T-cell transfer improved antitumor responses in multiple models, including cures in some subjects. Overall, our findings show how raising intratumoral pH through oral buffers therapy can improve responses to immunotherapy, with the potential for immediate clinical translation.

  1. 40 CFR 417.30 - Applicability; description of the soap manufacturing by fatty acid neutralization subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... manufacturing by fatty acid neutralization subcategory. 417.30 Section 417.30 Protection of Environment... POINT SOURCE CATEGORY Soap Manufacturing by Fatty Acid Neutralization Subcategory § 417.30 Applicability; description of the soap manufacturing by fatty acid neutralization subcategory. The provisions of this...

  2. 40 CFR 417.30 - Applicability; description of the soap manufacturing by fatty acid neutralization subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... manufacturing by fatty acid neutralization subcategory. 417.30 Section 417.30 Protection of Environment... POINT SOURCE CATEGORY Soap Manufacturing by Fatty Acid Neutralization Subcategory § 417.30 Applicability; description of the soap manufacturing by fatty acid neutralization subcategory. The provisions of this...

  3. 40 CFR 417.30 - Applicability; description of the soap manufacturing by fatty acid neutralization subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... manufacturing by fatty acid neutralization subcategory. 417.30 Section 417.30 Protection of Environment... POINT SOURCE CATEGORY Soap Manufacturing by Fatty Acid Neutralization Subcategory § 417.30 Applicability; description of the soap manufacturing by fatty acid neutralization subcategory. The provisions of this...

  4. 40 CFR 417.30 - Applicability; description of the soap manufacturing by fatty acid neutralization subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... manufacturing by fatty acid neutralization subcategory. 417.30 Section 417.30 Protection of Environment... POINT SOURCE CATEGORY Soap Manufacturing by Fatty Acid Neutralization Subcategory § 417.30 Applicability; description of the soap manufacturing by fatty acid neutralization subcategory. The provisions of this...

  5. 40 CFR 417.30 - Applicability; description of the soap manufacturing by fatty acid neutralization subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... manufacturing by fatty acid neutralization subcategory. 417.30 Section 417.30 Protection of Environment... POINT SOURCE CATEGORY Soap Manufacturing by Fatty Acid Neutralization Subcategory § 417.30 Applicability; description of the soap manufacturing by fatty acid neutralization subcategory. The provisions of this...

  6. Usefulness of organic acid produced by Exiguobacterium sp. 12/1 on neutralization of alkaline wastewater.

    PubMed

    Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

    2012-01-01

    The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry.

  7. Vaccine-Induced Antibodies that Neutralize Group 1 and Group 2 Influenza A Viruses.

    PubMed

    Joyce, M Gordon; Wheatley, Adam K; Thomas, Paul V; Chuang, Gwo-Yu; Soto, Cinque; Bailer, Robert T; Druz, Aliaksandr; Georgiev, Ivelin S; Gillespie, Rebecca A; Kanekiyo, Masaru; Kong, Wing-Pui; Leung, Kwanyee; Narpala, Sandeep N; Prabhakaran, Madhu S; Yang, Eun Sung; Zhang, Baoshan; Zhang, Yi; Asokan, Mangaiarkarasi; Boyington, Jeffrey C; Bylund, Tatsiana; Darko, Sam; Lees, Christopher R; Ransier, Amy; Shen, Chen-Hsiang; Wang, Lingshu; Whittle, James R; Wu, Xueling; Yassine, Hadi M; Santos, Celia; Matsuoka, Yumiko; Tsybovsky, Yaroslav; Baxa, Ulrich; Mullikin, James C; Subbarao, Kanta; Douek, Daniel C; Graham, Barney S; Koup, Richard A; Ledgerwood, Julie E; Roederer, Mario; Shapiro, Lawrence; Kwong, Peter D; Mascola, John R; McDermott, Adrian B

    2016-07-28

    Antibodies capable of neutralizing divergent influenza A viruses could form the basis of a universal vaccine. Here, from subjects enrolled in an H5N1 DNA/MIV-prime-boost influenza vaccine trial, we sorted hemagglutinin cross-reactive memory B cells and identified three antibody classes, each capable of neutralizing diverse subtypes of group 1 and group 2 influenza A viruses. Co-crystal structures with hemagglutinin revealed that each class utilized characteristic germline genes and convergent sequence motifs to recognize overlapping epitopes in the hemagglutinin stem. All six analyzed subjects had sequences from at least one multidonor class, and-in half the subjects-multidonor-class sequences were recovered from >40% of cross-reactive B cells. By contrast, these multidonor-class sequences were rare in published antibody datasets. Vaccination with a divergent hemagglutinin can thus increase the frequency of B cells encoding broad influenza A-neutralizing antibodies. We propose the sequence signature-quantified prevalence of these B cells as a metric to guide universal influenza A immunization strategies.

  8. Vaccine-Induced Antibodies that Neutralize Group 1 and Group 2 Influenza A Viruses.

    PubMed

    Joyce, M Gordon; Wheatley, Adam K; Thomas, Paul V; Chuang, Gwo-Yu; Soto, Cinque; Bailer, Robert T; Druz, Aliaksandr; Georgiev, Ivelin S; Gillespie, Rebecca A; Kanekiyo, Masaru; Kong, Wing-Pui; Leung, Kwanyee; Narpala, Sandeep N; Prabhakaran, Madhu S; Yang, Eun Sung; Zhang, Baoshan; Zhang, Yi; Asokan, Mangaiarkarasi; Boyington, Jeffrey C; Bylund, Tatsiana; Darko, Sam; Lees, Christopher R; Ransier, Amy; Shen, Chen-Hsiang; Wang, Lingshu; Whittle, James R; Wu, Xueling; Yassine, Hadi M; Santos, Celia; Matsuoka, Yumiko; Tsybovsky, Yaroslav; Baxa, Ulrich; Mullikin, James C; Subbarao, Kanta; Douek, Daniel C; Graham, Barney S; Koup, Richard A; Ledgerwood, Julie E; Roederer, Mario; Shapiro, Lawrence; Kwong, Peter D; Mascola, John R; McDermott, Adrian B

    2016-07-28

    Antibodies capable of neutralizing divergent influenza A viruses could form the basis of a universal vaccine. Here, from subjects enrolled in an H5N1 DNA/MIV-prime-boost influenza vaccine trial, we sorted hemagglutinin cross-reactive memory B cells and identified three antibody classes, each capable of neutralizing diverse subtypes of group 1 and group 2 influenza A viruses. Co-crystal structures with hemagglutinin revealed that each class utilized characteristic germline genes and convergent sequence motifs to recognize overlapping epitopes in the hemagglutinin stem. All six analyzed subjects had sequences from at least one multidonor class, and-in half the subjects-multidonor-class sequences were recovered from >40% of cross-reactive B cells. By contrast, these multidonor-class sequences were rare in published antibody datasets. Vaccination with a divergent hemagglutinin can thus increase the frequency of B cells encoding broad influenza A-neutralizing antibodies. We propose the sequence signature-quantified prevalence of these B cells as a metric to guide universal influenza A immunization strategies. PMID:27453470

  9. Acid neutralization within limestone sand reactors receiving coal mine drainage

    USGS Publications Warehouse

    Watten, B.J.; Sibrell, P.L.; Schwartz, M.F.

    2005-01-01

    Pulsed bed treatment of acid mine drainage (AMD) uses CO2 to accelerate limestone dissolution and intermittent fluidization to abrade and carry away metal hydrolysis products. Tests conducted with a prototype of 60 L/min capacity showed effective removal of H+ acidity over the range 196-584 mg/L (CaCO3) while concurrently generating surplus acid neutralization capacity. Effluent alkalinity (mg/L CaCO3) rose with increases in CO2 (DC, mg/L) according to the model Alkalinity = 31.22 + 2.97(DC)0.5, where DC was varied from 11-726 mg/L. Altering fluidization and contraction periods from 30 s/30 s to 10 s/50 s did not influence alkalinity but did increase energy dissipation and bed expansion ratios. Field trials with three AMD sources demonstrated the process is capable of raising AMD pH above that required for hydrolysis and precipitation of Fe3+ and Al3+ but not Fe2+ and Mn2+. Numerical modeling showed CO2 requirements are reduced as AMD acidity increases and when DC is recycled from system effluent. ?? 2005 Elsevier Ltd. All rights reserved.

  10. Rheological evaluation of simulated neutralized current acid waste

    SciTech Connect

    Fow, C.L.; McCarthy, D.; Thornton, G.T.

    1986-06-01

    A byproduct of the Purex process is an aqueous waste stream that contains fission products. This waste stream, called current acid waste, is chemically neutralized and stored in double shell tanks on the Hanford Site. This neutralized current acid waste (NCAW) will be transported by pipe to B-Plant, a processing plant on the Hanford Site. Rheological and transport properties of NCAW slurry were evaluated. First, researchers conducted lab rheological evaluations of simulated NCAW. The results of these evaluations were then correlated with classical rheological models and scaled up to predict the performance that is likely to occur in the full-scale system. The NCAW in the tank will either be retrieved as is, i.e., no change in the concentration presently in the tank, or will be slightly concentrated before retrieval. Sluicing may be required to retrieve the solids. Three concentrations of simulated NCAW were evaluated that would simulate the different retrieval options: NCAW in the concentration that is presently in the tank; a slightly concentrated NCAW, called NCAW5.5; and equal parts of NCAW settled solids and water (simulating the sluicing stage), called NCAW1:1. The physical and rheological properties of three samples of each concentration at 25 and 100/sup 0/C were evaluated in the laboratory. The properties displayed by NCAW and NCAW5.5 at 25 and 100/sup 0/C allowed it to be classified as a pseudoplastic non-Newtonian fluid. NCAW1:1 at 25 and 100/sup 0/C displayed properties of a yield-pseudoplastic non-Newtonian fluid. The classical non-Newtonian models for pseudoplastic and yield-pseudoplastic fluids were used with the laboratory data to predict the full-scale pump-pipe network parameters.

  11. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. I. The model.

    PubMed

    Maurer, Patrick; Thomas, Vibin; Rivard, Ugo; Iftimie, Radu

    2010-07-28

    Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Bronsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa congruent with 1) as a model for excited-state HPTS( *) (pKa congruent with 1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

  12. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. I. The model

    NASA Astrophysics Data System (ADS)

    Maurer, Patrick; Thomas, Vibin; Rivard, Ugo; Iftimie, Radu

    2010-07-01

    Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Brønsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa≅1) as a model for excited-state HPTS∗ (pKa≅1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

  13. Comparison of Blood Loss between Neutral Drainage with Tranexamic Acid and Negative Pressure Drainage without Tranexamic Acid Following Primary Total Knee Arthroplasty

    PubMed Central

    Lee, Gwang Chul; Lee, Sang Hong; Pak, Chi-Hyoung; Park, Sang Ha; Jung, Sung

    2016-01-01

    Purpose There are many methods to reduce massive bleeding during total knee arthroplasty (TKA). In our study, tranexamic acid and neutral drainage were used to decrease total blood loss. Materials and Methods The study was performed on 97 TKA patients from March 2012 to January 2013. In the study group, tranexamic acid was administered and neutral drainage was applied. The study group had group I (unilateral, n=29) and group III (bilateral, n=17). The control group had group II (unilateral, n=35) and group IV (bilateral, n=16). Results In group I, the drainage volume on the 1st and 2nd postoperative days and the total drainage decreased with statistical significance (p<0.05). Between group III and group IV, group III had less drainage volume. In group III, the drainage volume on the 1st postoperative day and total drainage volume decreased statistically significantly (p<0.05). Between groups I and II, total blood loss showed no statistically significant difference, whereas between groups III and IV, the value was significantly different. Conclusions Intravenous administration of tranexamic acid with neutral drainage for 3 postoperative hours is a recommendable method because it can be helpful in reducing total blood loss in bilateral TKA. PMID:27595072

  14. Comparison of Blood Loss between Neutral Drainage with Tranexamic Acid and Negative Pressure Drainage without Tranexamic Acid Following Primary Total Knee Arthroplasty

    PubMed Central

    Lee, Gwang Chul; Lee, Sang Hong; Pak, Chi-Hyoung; Park, Sang Ha; Jung, Sung

    2016-01-01

    Purpose There are many methods to reduce massive bleeding during total knee arthroplasty (TKA). In our study, tranexamic acid and neutral drainage were used to decrease total blood loss. Materials and Methods The study was performed on 97 TKA patients from March 2012 to January 2013. In the study group, tranexamic acid was administered and neutral drainage was applied. The study group had group I (unilateral, n=29) and group III (bilateral, n=17). The control group had group II (unilateral, n=35) and group IV (bilateral, n=16). Results In group I, the drainage volume on the 1st and 2nd postoperative days and the total drainage decreased with statistical significance (p<0.05). Between group III and group IV, group III had less drainage volume. In group III, the drainage volume on the 1st postoperative day and total drainage volume decreased statistically significantly (p<0.05). Between groups I and II, total blood loss showed no statistically significant difference, whereas between groups III and IV, the value was significantly different. Conclusions Intravenous administration of tranexamic acid with neutral drainage for 3 postoperative hours is a recommendable method because it can be helpful in reducing total blood loss in bilateral TKA.

  15. Identification of amino acid substitutions associated with neutralization phenotype in the human immunodeficiency virus type-1 subtype C gp120

    PubMed Central

    Kirchherr, Jennifer L; Hamilton, Jennifer; Lu, Xiaozhi; Gnanakaran, S; Muldoon, Mark; Daniels, Marcus; Kasongo, Webster; Chalwe, Victor; Mulenga, Chanda; Mwananyanda, Lawrence; Musonda, Rosemary M; Yuan, Xing; Montefiori, David C; Korber, Bette T; Haynes, Barton F; Gao, Feng

    2010-01-01

    Neutralizing antibodies (Nabs) are thought to play an important role in prevention and control of HIV-1 infection and should be targeted by an AIDS vaccine. It is critical to understand how HIV-1 induces Nabs by analyzing viral sequences in both tested viruses and sera. Neutralization susceptibility to antibodies in autologous and heterologous plasma was determined for multiple Envs (3–6) from each of 15 subtype C infected-individuals. Heterologous neutralization was divided into two distinct groups: plasma with strong, cross-reactive neutralization (N=9) and plasma with weak neutralization (N=6). Plasma with cross-reactive heterologous Nabs also more potently neutralized contemporaneous autologous viruses. Analysis of Env sequences in plasma from both groups revealed a three-amino acid substitution pattern in the V4 region that was associated with greater neutralization potency and breadth. Identification of such potential neutralization signatures may have important implications for the development of HIV-1 vaccines capable of inducing Nabs to subtype C HIV-1. PMID:21036380

  16. Big, strong, neutral, twisted, and chiral π acids.

    PubMed

    Zhao, Yingjie; Huang, Guangxi; Besnard, Celine; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2015-04-13

    General synthetic access to expanded π-acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion-π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron-withdrawing substituents decreases and the high π acidity needed for strong anion-π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion-π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from -3.96 to -4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X-ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation-π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches -4.45 eV, whereas two sulfone moieties give a value of -4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion-π interactions, these conceptually innovative π-acidic surfaces are also of interest as electron transporters in conductive materials.

  17. In Silico Classification of Proteins from Acidic and Neutral Cytoplasms

    PubMed Central

    Fang, Yaping; Middaugh, C. Russell; Fang, Jianwen

    2012-01-01

    Protein acidostability is a common problem in biopharmaceutical and other industries. However, it remains a great challenge to engineer proteins for enhanced acidostability because our knowledge of protein acidostabilization is still very limited. In this paper, we present a comparative study of proteins from bacteria with acidic (AP) and neutral cytoplasms (NP) using an integrated statistical and machine learning approach. We construct a set of 393 non-redundant AP-NP ortholog pairs and calculate a total of 889 sequence based features for these proteins. The pairwise alignments of these ortholog pairs are used to build a residue substitution propensity matrix between APs and NPs. We use Gini importance provided by the Random Forest algorithm to rank the relative importance of these features. A scoring function using the 10 most significant features is developed and optimized using a hill climbing algorithm. The accuracy of the score function is 86.01% in predicting AP-NP ortholog pairs and is 76.65% in predicting non-ortholog AP-NP pairs, suggesting that there are significant differences between APs and NPs which can be used to predict relative acidostability of proteins. The overall trends uncovered in the study can be used as general guidelines for designing acidostable proteins. To best of our knowledge, this work represents the first systematic comparative study of the acidostable proteins and their non-acidostable orthologs. PMID:23049817

  18. Poly(N-vinylimidazole) gels as insoluble buffers that neutralize acid solutions without dissolving.

    PubMed

    Horta, Arturo; Piérola, Inés F

    2009-04-01

    Typical buffers are solutions containing weak acids or bases. If these groups were anchored to insoluble gels, what would be their behavior? Simple thermodynamics is used to calculate the pH in two-phase systems that contain the weak acid or base fixed to only one of the phases and is absent in the other. The experimental reference of such systems are pH sensitive hydrogels and heterogeneous systems of biological interest. It is predicted that a basic hydrogel immersed in slightly acidic solutions should absorb the acid and leave the external solution exactly neutral (pH 7). This is in accordance with experimental results of cross-linked poly(N-vinylimidazole). The pH 7 cannot be obtained if the system were homogeneous; the confinement of the weak base inside the gel phase is a requisite for this neutral pH in the external solution. The solution inside the gel is regulated to a much higher pH, which has important implications in studies on chemical reactions and physical processes taking place inside a phase insoluble but in contact with a solution. PMID:19245223

  19. Metals in crayfish from neutralized acidic and non-acidic lakes

    SciTech Connect

    Bagatto, G.; Alikhan, M.A.

    1987-09-01

    Large amounts of acid forming SO/sub 2/, as well as Cu, Ni and other metals are being continuously released into the environment by mining and smelting activities at Sudbury, Ontario, Canada. Consequently, a number of lakes in this region has become both acid and metal stressed. The addition of basic calcium compounds to acidic ponds and lakes has long been recognized as beneficial, as it contributes to increased fish production and water quality. In addition to increases in pH and alkalinity, such additions may reduce water-dissolved metal concentrations, change water transparency and bring about alterations in species diversity. Neutralization experiments have shown that an increase in water alkalinity and DOC may reduce the acute toxicity of Cu to fish. However, the influence of water quality on metal availability and accumulation has received scant attention. Earlier work showed that tissue metal concentrations in crayfish were related to the distance from the emission site. The purpose of the present study is to compare concentrations of six metals in freshwater crayfish from a neutralized acidic lake and a closely situated non-acidic lake. Various tissue concentrations in crayfish are also examined to determine specific tissue sites for these accumulations.

  20. Star Formation as a Function of Neutral Hydrogen Gas Density in Local Group Galaxies

    NASA Astrophysics Data System (ADS)

    Carlson, Erika K.; Madore, Barry F.; Freedman, Wendy L.

    2016-06-01

    We present a study of the efficiency and timescales of star formation as a function of local neutral hydrogen gas density in four Local Group galaxies: M33, NGC 6822, the LMC, and the SMC. In this work, we conceptualize the process of star formation as a cycle of two major phases - (1) a gas dynamics phase in which neutral hydrogen gas coalesces into clouds, and (2) a stellar phase in which stars have formed and interrupt further gas coalescence during their active lifetimes. By examining the spatial distribution and number densities of stars on maps of neutral hydrogen, we estimate the timescale of the gas coalescence phase relative to the timescale of the stellar phase and infer an efficiency of star formation as a function of neutral hydrogen gas density. From these timescales and efficiencies, we will calculate star formation rates as a function of neutral hydrogen gas density in these galaxies.

  1. Brushing abrasion of luting cements under neutral and acidic conditions.

    PubMed

    Buchalla, W; Attin, T; Hellwig, E

    2000-01-01

    Four resin based materials (Compolute Aplicap, ESPE; Variolink Ultra, Vivadent; C&B Metabond, Parkell and Panavia 21, Kuraray), two carboxylate cements (Poly-F Plus, Dentsply DeTrey and Durelon Maxicap, ESPE), two glass-ionomer cements (Fuji I, GC and Ketac-Cem Aplicap, ESPE), one resin-modified glass ionomer cement (Vitremer, 3M) one polyacid-modified resin composite (Dyract Cem, Dentsply DeTrey) and one zinc phosphate cement (Harvard, Richter & Hoffmann) were investigated according to their brushing resistance after storage in neutral and acidic buffer solutions. For this purpose 24 cylindrical acrylic molds were each filled with the materials. After hardening, the samples were stored for seven days in 100% relative humidity and at 37 degrees C. Subsequently, they were ground flat and polished. Then each specimen was covered with an adhesive tape leaving a 4 mm wide window on the cement surface. Twelve samples of each material were stored for 24 hours in a buffer solution with a pH of 6.8. The remaining 12 samples were placed in a buffer with a pH of 3.0. All specimens were then subjected to a three media brushing abrasion (2,000 strokes) in an automatic brushing machine. Storage and brushing were performed three times. After 6,000 brushing strokes per specimen, the tape was removed. Brushing abrasion was measured with a computerized laser profilometer and statistically analyzed with ANOVA and Tukey's Standardized Range Test (p < or = 0.05). The highest brushing abrasion was found for the two carboxylate cements. The lowest brushing abrasion was found for one resin based material, Compolute Aplicap. With the exception of three resin-based materials, a lower pH led to a higher brushing abrasion.

  2. [Degradation kinetics of chlorogenic acid, cryptochlorogenic acid, and neochlorogenic acid at neutral and alkaline pH values].

    PubMed

    Zhu, Peng; Miao, Xiao-lei; Chen, Yong

    2016-01-01

    The degradation kinetics of chlorogenic acid (5-CQA), cryptochlorogenic acid (4-CQA), and neochlorogenic acid (3-CQA) in aqueous solution at 37 degrees C and different pH values (7.05, 7.96, 9.25) were investigated in the present work. The results indicated that 3-, 4- and 5-CQA tended to remain stable in acidic pH circumstance, and unstable in neutral and alkaline pH circumstance. With the increase of the alkalinity, the degradation of 3-, 4- and 5-CQA was increased leading to a less amount of total CQA and was satisfactorily described by the Weibull equation. Meanwhile, caffeic acid was not detected after the degradation of CQA. Moreover, the degradation of 3-CQA and 5-CQA tended to be converted to 4-CQA, and the degradation of 4-CQA tended to be converted to 3-CQA rather than 5-CQA. The comparison of the degradation kinetics parameters of 3-, 4- and 5-CQA at neutral and alkaline pH values showed that the orders of the rate constant (k) values were 4-CQA > 3-CQA > 5-CQA, while the orders of the degradation half life (t½) values were 4-CQA < 3-CQA < 5-CQA, indicating the orders of the stabilities of 3-, 4- and 5-CQA at 37 degrees C and neutral and alkaline pH values were 4-CQA < 3-CQA < 5-CQA. PMID:27405173

  3. Growth inhibition of Erwinia amylovora and related Erwinia species by neutralized short‑chain fatty acids.

    PubMed

    Konecki, Katrin; Gernold, Marina; Wensing, Annette; Geider, Klaus

    2013-11-01

    Short-chain fatty acids (SCFAs) are used to preserve food and could be a tool for control of fire blight caused by Erwinia amylovora on apple, pear and related rosaceous plants. Neutralized acids were added to buffered growth media at 0.5–75 mM and tested at pHs ranging from 6.8 to 5.5. Particularly at low pH, SCFAs with a chain length exceeding that of acetic acid such as propionic acid were effective growth inhibitors of E. amylovora possibly due to uptake of free acid and its intracellular accumulation. We also observed high inhibition with monochloroacetic acid. An E. billingiae strain was as sensitive to the acids as E. amylovora or E. tasmaniensis. Fire blight symptoms on pear slices were reduced when the slices were pretreated with neutralized propionic acid. Propionic acid is well water soluble and could be applied in orchards as a control agent for fire blight.

  4. On the neutralization of acid rock drainage by carbonate and silicate minerals

    NASA Astrophysics Data System (ADS)

    Sherlock, E. J.; Lawrence, R. W.; Poulin, R.

    1995-02-01

    The net result of acid-generating and-neutralizing reactions within mining wastes is termed acid rock drainage (ARD). The oxidation of sulfide minerals is the major contributor to acid generation. Dissolution and alteration of various minerals can contribute to the neutralization of acid. Definitions of alkalinity, acidity, and buffer capacity are reviewed, and a detailed discussion of the dissolution and neutralizing capacity of carbonate and silicate minerals related to equilibium conditions, dissolution mechanism, and kinetics is provided. Factors that determine neutralization rate by carbonate and silicate minerals include: pH, PCO 2, equilibrium conditions, temperature, mineral composition and structure, redox conditions, and the presence of “foreign” ions. Similar factors affect sulfide oxidation. Comparison of rates shows sulfides react fastest, followed by carbonates and silicates. The differences in the reaction mechanisms and kinetics of neutralization have important implications in the prediction, control, and regulation of ARD. Current static and kinetic prediction methods upon which mine permitting, ARD control, and mine closure plans are based do not consider sample mineralogy or the kinetics of the acid-generating and-neutralizing reactions. Erroneous test interpretations and predictions can result. The importance of considering mineralogy for site-specific interpretation is highlighted. Uncertainty in prediction leads to difficulties for the mine operator in developing satisfactory and cost-effective control and remediation measures. Thus, the application of regulations and guidelines for waste management planning need to beflexible.

  5. Effects of running the Bostom Marathon on plasma concentrations of large neutral amino acids

    NASA Technical Reports Server (NTRS)

    Conlay, L. A.; Wurtman, R. J.; Lopez G-Coviella, I.; Blusztajn, J. K.; Vacanti, C. A.; Logue, M.; During, M.; Caballero, B.; Maher, T. J.; Evoniuk, G.

    1989-01-01

    Plasma large neutral amino acid concentrations were measured in thirty-seven subjects before and after completing the Boston Marathon. Concentrations of tyrosine, phenylalanine, and methionine increased, as did their 'plasma ratios' (i.e., the ratio of each amino acid's concentration to the summed plasma concentrations of the other large neutral amino acids which compete with it for brain uptake). No changes were noted in the plasma concentrations of tryptophan, leucine, isoleucine, nor valine; however, the 'plasma ratios' of valine, leucine, and isoleucine all decreased. These changes in plasma amino acid patterns may influence neurotransmitter synthesis.

  6. Laboratory evaluation of limestone and lime neutralization of acidic uranium mill tailings solution. Progress report

    SciTech Connect

    Opitz, B.E.; Dodson, M.E.; Serne, R.J.

    1984-02-01

    Experiments were conducted to evaluate a two-step neutralization scheme for treatment of acidic uranium mill tailings solutions. Tailings solutions from the Lucky Mc Mill and Exxon Highland Mill, both in Wyoming, were neutralized with limestone, CaCO/sub 3/, to an intermediate pH of 4.0 or 5.0, followed by lime, Ca(OH)/sub 2/, neutralization to pH 7.3. The combination limestone/lime treatment methods, CaCO/sub 3/ neutralization to pH 4 followed by neutralization with Ca(OH)/sub 2/ to pH 7.3 resulted in the highest quality effluent solution with respect to EPA's water quality guidelines. The combination method is the most cost-effective treatment procedure tested in our studies. Neutralization experiments to evaluate the optimum solution pH for contaminant removal were performed on the same two tailings solutions using only lime Ca(OH)/sub 2/ as the neutralizing agent. The data indicate solution neutralization above pH 7.3 does not significantly increase removal of pH dependent contaminants from solution. Column leaching experiments were performed on the neutralized sludge material (the precipitated solid material which forms as the acidic tailings solutions are neutralized to pH 4 or above). The sludges were contacted with laboratory prepared synthetic ground water until several effluent pore volumes were collected. Effluent solutions were analyzed for macro ions, trace metals and radionuclides in an effort to evaluate the long term effectiveness of attenuating contaminants in sludges formed during solution neutralization. Neutralized sludge leaching experiments indicate that Ca, Na, Mg, Se, Cl, and SO/sub 4/ are the only constituents which show solution concentrations significantly higher than the synthetic ground water in the early pore volumes of long-term leaching studies.

  7. Production and transformation of dissolved neutral sugars and amino acids by bacteria in seawater

    NASA Astrophysics Data System (ADS)

    Jørgensen, L.; Lechtenfeld, O. J.; Benner, R.; Middelboe, M.; Stedmon, C. A.

    2014-10-01

    Dissolved organic matter (DOM) in the ocean consists of a heterogeneous mixture of molecules, most of which are of unknown origin. Neutral sugars and amino acids are among the few recognizable biomolecules in DOM, and the molecular composition of these biomolecules is shaped primarily by biological production and degradation processes. This study provides insight into the bioavailability of biomolecules as well as the chemical composition of DOM produced by bacteria. The molecular compositions of combined neutral sugars and amino acids were investigated in DOM produced by bacteria and in DOM remaining after 32 days of bacterial degradation. Results from bioassay incubations with natural seawater (sampled from water masses originating from the surface waters of the Arctic Ocean and the North Atlantic Ocean) and artificial seawater indicate that the molecular compositions following bacterial degradation are not strongly influenced by the initial substrate or bacterial community. The molecular composition of neutral sugars released by bacteria was characterized by a high glucose content (47 mol %) and heterogeneous contributions from other neutral sugars (3-14 mol %). DOM remaining after bacterial degradation was characterized by a high galactose content (33 mol %), followed by glucose (22 mol %) and the remaining neutral sugars (7-11 mol %). The ratio of D-amino acids to L-amino acids increased during the experiments as a response to bacterial degradation, and after 32 days, the D/L ratios of aspartic acid, glutamic acid, serine and alanine reached around 0.79, 0.32, 0.30 and 0.51 in all treatments, respectively. The striking similarity in neutral sugar and amino acid compositions between natural (representing marine semi-labile and refractory DOM) and artificial (representing bacterially produced DOM) seawater samples, suggests that microbes transform bioavailable neutral sugars and amino acids into a common, more persistent form.

  8. Bacterial production and transformation of dissolved neutral sugars and amino acids in seawater

    NASA Astrophysics Data System (ADS)

    Jørgensen, L.; Lechtenfeld, O.; Benner, R.; Middelboe, M.; Stedmon, C. A.

    2014-04-01

    Dissolved organic matter (DOM) in the ocean consists of a heterogeneous mixture of molecules, most of which are of unknown origin. Neutral sugars and amino acids are among the few recognizable biomolecules in DOM, and the molecular composition of these biomolecules is shaped primarily by biological production and degradation processes. This study provides insight into the bioavailability of biomolecules as well as the chemical composition of DOM produced by bacteria. The molecular compositions of neutral sugars and amino acids were investigated in DOM produced by bacteria and in DOM remaining after long-term bacterial degradation. Results from bioassay incubations (32 days) with natural and artificial seawater, indicate that the molecular compositions following bacterial degradation are not strongly influenced by the initial substrate or bacterial community. The molecular composition of neutral sugars released by bacteria was characterized by a high glucose content (47 mol%) and heterogeneous contributions from other neutral sugars (3-14 mol%). DOM remaining after bacterial degradation was characterized by a high galactose content (33 mol%), followed by glucose (22 mol%) and the remaining neutral sugars (7-11 mol%). The ratio of D-amino acids to L-amino acids increased during the experiments as a response to bacterial degradation, and after 32 days the D/L ratios of aspartic acid, glutamic acid, serine and alanine reached around 0.79, 0.32, 0.30 and 0.51 in all treatments, respectively. The striking similarity in neutral sugar and amino acid compositions between natural and artificial seawater samples, suggests that the microbial carbon pump also applies for neutral sugars and amino acids and that bacterially-produced biomolecules persist for long periods in the ocean.

  9. Reaction sequences in simulated neutralized current acid waste slurry during processing with formic acid

    SciTech Connect

    Smith, H.D.; Wiemers, K.D.; Langowski, M.H.; Powell, M.R.; Larson, D.E.

    1993-11-01

    The Hanford Waste Vitrification Plant (HWVP) is being designed for the Department of Energy to immobilize high-level and transuranic wastes as glass for permanent disposal. Pacific Northwest Laboratory is supporting the HWVP design activities by conducting laboratory-scale studies using a HWVP simulated waste slurry. Conditions which affect the slurry processing chemistry were evaluated in terms of offgas composition and peak generation rate and changes in slurry composition. A standard offgas profile defined in terms of three reaction phases, decomposition of H{sub 2}CO{sub 3}, destruction of NO{sub 2}{sup {minus}}, and production of H{sub 2} and NH{sub 3} was used as a baseline against which changes were evaluated. The test variables include nitrite concentration, acid neutralization capacity, temperature, and formic acid addition rate. Results to date indicate that pH is an important parameter influencing the N{sub 2}O/NO{sub x} generation ratio; nitrite can both inhibit and activate rhodium as a catalyst for formic acid decomposition to CO{sub 2} and H{sub 2}; and a separate reduced metal phase forms in the reducing environment. These data are being compiled to provide a basis for predicting the HWVP feed processing chemistry as a function of feed composition and operation variables, recommending criteria for chemical adjustments, and providing guidelines with respect to important control parameters to consider during routine and upset plant operation.

  10. Evaluation of the efficacy of Alka-Seltzer Effervescent in gastric acid neutralization.

    PubMed

    Chen, C T; Toung, T J; Haupt, H M; Hutchins, G M; Cameron, J L

    1984-03-01

    A commercially available antacid, a mixture of sodium and potassium bicarbonates and citric acid (Alka-Seltzer Effervescent), was evaluated experimentally and clinically for its efficacy in neutralizing 0.1 N HCl and gastric contents. In an in vitro titration study, Alka-Seltzer Effervescent buffered 5-30 times the volume of HCl with a pH between 1.0 and 2.0 to above a pH of 2.5. In an isolated canine pulmonary lobe model, aspiration of the antacid or acid-antacid mixture caused only a mild increase in lobe weight and did not increase intrapulmonary shunting. In the clinical study, when the antacid was given 5-40 min before administration of general anesthesia in a group of patients for emergency surgery, the pH of the gastric contents in each patient was increased to above 4.0. This contrasts with the control group of patients, which showed 50% (P less than 0.05) of the patients were at risk when no antacid was administered. Preoperative administration of Alka-Seltzer effectively increases the pH of the gastric contents in patients undergoing emergency surgery. PMID:6703349

  11. Combined use of chiral ionic liquid surfactants and neutral cyclodextrins: evaluation of ionic liquid head groups for enantioseparation of neutral compounds in capillary electrophoresis.

    PubMed

    Liu, Yijin; Shamsi, Shahab A

    2014-09-19

    Cyclodextrins (CDs) are most commonly used chiral selectors in capillary electrophoresis (CE). Although the use of neutral CDs and its derivatives have shown to resolve plethora of charged enantiomers, they cannot resolve neutral enantiomers. The use of ionic liquids (ILs) surfactants forming successful complex with CDs present itself an opportunity to resolve neutral enantiomers. In this work, the effect of IL head groups and their complexation ability with heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD) was studied for the separation of neutral enantiomers by CE. First, cationic IL type surfactants with different chiral head groups were synthesized. Physicochemical properties such as critical micelle concentration were determined by surface tension, whereas aggregation and polarity were determined by fluorescence spectroscopy. The complexation ability of ILs with TM-β-CD was characterized in the gas phase by CE-mass spectrometry. The influence of the type of ILs head group and its concentration on chiral resolution, resolution per unit time and selectivity were investigated for four structurally diverse neutral compounds. The binding constants of the neutral analytes to the IL-CD complex were estimated by y-reciprocal method. The hydrophobicity of the side chain of the IL head group displayed significant effect on the binding constants and enantioseparations.

  12. Classification of illicit heroin by UPLC-Q-TOF analysis of acidic and neutral manufacturing impurities.

    PubMed

    Liu, Cuimei; Hua, Zhendong; Bai, Yanping

    2015-12-01

    The illicit manufacture of heroin results in the formation of trace levels of acidic and neutral manufacturing impurities that provide valuable information about the manufacturing process used. In this work, a new ultra performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF) method; that features high resolution, mass accuracy and sensitivity for profiling neutral and acidic heroin manufacturing impurities was developed. After the UPLC-Q-TOF analysis, the retention times and m/z data pairs of acidic and neutral manufacturing impurities were detected, and 19 peaks were found to be evidently different between heroin samples from "Golden Triangle" and "Golden Crescent". Based on the data set of these 19 impurities in 150 authentic heroin samples, classification of heroin geographic origins was successfully achieved utilizing partial least squares discriminant analysis (PLS-DA). By analyzing another data set of 267 authentic heroin samples, the developed discrimiant model was validated and proved to be accurate and reliable.

  13. Eliciting neutralizing antibodies with gp120 outer domain constructs based on M-group consensus sequence.

    PubMed

    Qin, Yali; Banasik, Marisa; Kim, SoonJeung; Penn-Nicholson, Adam; Habte, Habtom H; LaBranche, Celia; Montefiori, David C; Wang, Chong; Cho, Michael W

    2014-08-01

    One strategy being evaluated for HIV-1 vaccine development is focusing immune responses towards neutralizing epitopes on the gp120 outer domain (OD) by removing the immunodominant, but non-neutralizing, inner domain. Previous OD constructs have not elicited strong neutralizing antibodies (nAbs). We constructed two immunogens, a monomeric gp120-OD and a trimeric gp120-OD×3, based on an M group consensus sequence (MCON6). Their biochemical and immunological properties were compared with intact gp120. Results indicated better preservation of critical neutralizing epitopes on gp120-OD×3. In contrast to previous studies, our immunogens induced potent, cross-reactive nAbs in rabbits. Although nAbs primarily targeted Tier 1 viruses, they exhibited significant breadth. Epitope mapping analyses indicated that nAbs primarily targeted conserved V3 loop elements. Although the potency and breadth of nAbs were similar for all three immunogens, nAb induction kinetics indicated that gp120-OD×3 was superior to gp120-OD, suggesting that gp120-OD×3 is a promising prototype for further gp120 OD-based immunogen development. PMID:25046154

  14. Eliciting Neutralizing Antibodies with gp120 Outer Domain Constructs Based on M-Group Consensus Sequence

    PubMed Central

    Qin, Yali; Banasik, Marisa; Kim, SoonJeung; Penn-Nicholson, Adam; Habte, Habtom H; Labranche, Celia; Montefiori, David C; Wang, Chong; Cho, Michael W

    2014-01-01

    One strategy being evaluated for HIV-1 vaccine development is focusing immune responses towards neutralizing epitopes on the gp120 outer domain (OD) by removing the immunodominant, but non-neutralizing, inner domain. Previous OD constructs have not elicited strong neutralizing antibodies (nAbs). We constructed two immunogens, a monomeric gp120-OD and a trimeric gp120-OD×3, based on an M group consensus sequence (MCON6). Their biochemical and immunological properties were compared with intact gp120. Results indicated better preservation of critical neutralizing epitopes on gp120-OD×3. In contrast to previous studies, our immunogens induced potent, cross-reactive nAbs in rabbits. Although nAbs primarily targeted Tier 1 viruses, they exhibited significant breadth. Epitope mapping analyses indicated that nAbs primarily targeted conserved V3 loop elements. Although the potency and breadth of nAbs were similar for all three immunogens, nAb induction kinetics indicated that gp120-OD×3 was superior to gp120-OD, suggesting that gp120-OD×3 is a promising prototype for further gp120 OD-based immunogen development. PMID:25046154

  15. Influences of acidic reaction and hydrolytic conditions on monosaccharide composition analysis of acidic, neutral and basic polysaccharides.

    PubMed

    Wang, Qing-Chi; Zhao, Xia; Pu, Jiang-Hua; Luan, Xiao-Hong

    2016-06-01

    Monosaccharide composition analysis is important for structural characterization of polysaccharides. To investigate the influences of acidic reaction and hydrolytic conditions on monosaccharide composition analysis of polysaccharides, we chose alginate, starch, chitosan and chondroitin sulfate as representative of acidic, neutral, basic and complex polysaccharides to compare the release degree of monosaccharides under different hydrolytic conditions. The hydrolysis stability of 10 monosaccharide standards was also explored. Results showed that the basic sugars were hard to release but stable, the acidic sugars (uronic acids) were easy to release but unstable, and the release and stability of neutral sugars were in between acidic and basic sugars. In addition, the hydrolysis process was applied to monosaccharide composition analysis of Hippocampus trimaculatus polysaccharide and the appropriate hydrolytic condition was accorded with that of the above four polysaccharides. Thus, different hydrolytic conditions should be used for the monosaccharide composition analysis of polysaccharides based on their structural characteristics. PMID:27083372

  16. Solvent systems combining neutral and acidic extractants for separating trivalent lanthanides from the transuranic elements.

    SciTech Connect

    Lumetta, G. J.; Gelis, A. V.; Vandegrift, G. F.; Chemical Sciences and Engineering Division; PNL

    2010-01-01

    This paper is a review of recent publications that have focused on combined extractant systems for separating trivalent actinides from the lanthanides. These mixed solvent systems combine an acidic extractant with a neutral extractant to achieve the actinide/lanthanide separation. Depending on the neutral extractant used, three categorizations of systems can be considered, including combinations of acidic extractants with 1 diamides, 2 carbamoylmethylphosphine oxides, and 3 polydentate nitrogen-donor ligands. This review of relevant publications indicates that, although there is significant potential for practical exploitation of mixed neutral/acidic extractant systems to achieve a single-step separation of trivalent actinides from acidic high-level waste solutions, the fundamental chemistry underlying these combined systems is not yet well understood. For example, although there is strong evidence suggesting that adducts form between the neutral and acidic extractants, the nature of these adducts generally is not known. Likewise, the structures of the mixed complexes formed between the metal ions and the two different extractants are not fully understood. Research into these basic phenomena likely will provide clues about how to design practical mixed-extractant systems that can be used to efficiently separate the transuranic elements from the lanthanides and other components of irradiated fuel.

  17. Groundwater leaching of neutralized and untreated acid-leached uranium-mill tailings

    SciTech Connect

    Gee, G.W.; Begej, C.W.; Campbell, A.C.; Sauter, N.N.; Opitz, B.E.; Sherwood, D.R.

    1981-01-01

    Tailings neutralization was examined to determine the effect of neutralization on contaminant release. Column leaching of acid extracted uranium mill tailings from Exxon Highland Mill, Wyoming, Pathfinder Gas Hills Mill, Wyoming, and the Dawn Midnite Mill, Washington, resulted in the flushing of high concentrations of salts in the first four pore volumes of leachate, followed by a steady decrease to the original groundwater salt concentrations. Neutralization decreased the concentration of salts and radionuclides leaching from the tailings and decreased the volume of solution required to return the solution to the groundwater pH and EC. Radium-226 and uranium-238 leached quickly from the tailings in the initial pore volumes of both neutralized and unneutralized tailings, and then decreased significantly. 6 figures, 5 tables.

  18. Single amino acid mutations in the capsid switch the neutralization phenotype of porcine circovirus 2.

    PubMed

    Saha, Dipongkor; Lefebvre, David J; Ooms, Karen; Huang, Liping; Delputte, Peter L; Van Doorsselaere, Jan; Nauwynck, Hans J

    2012-07-01

    Porcine circovirus 2 (PCV2) is the causative agent of porcine circovirus-associated diseases in pigs. Previously, it was demonstrated that mAbs 16G12, 38C1, 63H3 and 94H8 directed against the PCV2 capsid protein recognize PCV2 strains Stoon-1010 (PCV2a), 48285 (PCV2b), 1121 (PCV2a), 1147 (PCV2b) and II9F (PCV2b), but only neutralize Stoon-1010 and 48285. This points to the existence of two distinct PCV2 neutralization phenotypes: phenotype α (mAb recognition with neutralization; Stoon-1010 and 48285) and phenotype β (mAb recognition without neutralization; 1121, 1147 and II9F). In the present study, amino acids that are important in determining the neutralization phenotype were identified in the capsid. Mutation of T at position 190 to A in strain 48285 (phenotype α) resulted in a capsid resembling that of strain 1147 (phenotype β) and caused a loss of neutralization (switch from α to β). Mutations of P at position 151 to T and A at position 190 to T in strain II9F (phenotype β) resulted in a capsid resembling that of strain 48285 (phenotype α) and gave a gain of neutralization (switch from β to α). Mutations of T at position 131 to P and of E at position 191 to R in Stoon-1010 (phenotype α) changed the capsid into that of 1121 (phenotype β) and reduced neutralization (switch from α to β). This study demonstrated that single amino acid changes in the capsid result in a phenotypic switch from α to β or β to α.

  19. Circadian pattern of large neutral amino acids, glucose, insulin, and food intake in anorexia nervosa and bulimia nervosa.

    PubMed

    Schreiber, W; Schweiger, U; Werner, D; Brunner, G; Tuschl, R J; Laessle, R G; Krieg, J C; Fichter, M M; Pirke, K M

    1991-05-01

    Insulin, glucose, and large neutral amino acids (LNAA) were studied in 10 patients with anorexia nervosa, 13 patients with bulimia nervosa, and 15 healthy controls. Blood samples were collected at hourly intervals during the day and at two-hour intervals during the night over a 24-hour period. Ad libitum caloric and relative carbohydrate intake was significantly reduced in the anorectic and bulimic patients. Elevated concentrations of beta-hydroxybutyric acid (BHBA) were seen in the bulimic group, and low triiodothyronine (T3) concentrations in the anorectic group. Mean plasma glucose and insulin concentrations were significantly lowered in both groups. The tryptophan (Trp) to LNAA ratio was reduced in anorectic, but not in bulimic patients. These findings suggest that Trp influx into the brain is reduced in anorectic patients, possibly impairing central serotonergic function.

  20. Acid rain: neutralization within the hubbard brook ecosystem and regional implications.

    PubMed

    Johnson, N M

    1979-05-01

    The neutralization of strong acids from precipitation is largely accomplished (75 percent) in the soil zone by rapid reaction with basic aluminum salts and biologic matter. On a regional basis, acidified and aluminum-rich lakes and streams in New England are confined mainly to low-order watersheds.

  1. Neutralization and Acid Dissociation of Hydrogen Carbonate Ion: A Thermochemical Approach

    ERIC Educational Resources Information Center

    Koga, Nobuyoshi; Shigedomi, Kana; Kimura, Tomoyasu; Tatsuoka, Tomoyuki; Mishima, Saki

    2013-01-01

    A laboratory inquiry into the thermochemical relationships in the reaction between aqueous solutions of NaHCO[subscript 3] and NaOH is described. The enthalpy change for this reaction, delta[subscript r]H, and that for neutralization of strong acid and NaOH(aq), delta[subscript n]H, are determined calorimetrically; the explanation for the…

  2. Sulphuric acid and neutral cluster measerements with CI-APi-TOF

    NASA Astrophysics Data System (ADS)

    Jokinen, T.; Sipilä, M.; Junninen, H.; Ehn, M.; Hakala, J.; Lönn, G.; Petäjä, T.; Kulmala, M.; Worsnop, D. R.

    2012-04-01

    Sulphuric acid is a key compound in atmospheric nucleation (Sipilä et al., 2010) and in the atmosphere it is mainly produced photochemically via reaction of OH with SO2. The concentration of sulphuric acid is typically very low and rarely exceeds 108 molecules cm-3. The low concentrations set requirements for the detector used for quantitative measurements. A sensitive method measuring gas phase sulphuric acid was developed by Eisele and Tanner (1993). They used chemical ionization with nitrate ion, NO3-, and its clusters with HNO3, to selectively ionize sulphuric acid and detected it with a quadrupole mass spectrometer. We present a technique in which the atmospheric pressure chemical ionization (CI) inlet, with geometry similar to Eisele and Tanner (1993), is coupled with a high resolution atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF, Tofwerk Ag., Junninen et al., 2010). In the present setup the high resolution and mass range of the TOF allows separation and summing of different clusters. The advantage of this method is that it allows one to find neutral sulphuric acid containing clusters formed by nucleation in the atmosphere (Kuang et al., 2008) or in laboratory systems (Sipilä et al., 2010). The first ambient measurements using the CI-APi-TOF for sulphuric acid and neutral cluster detection are also presented. We found the CI-APi-TOF a highly stable and sensitive tool for molecular sulphuric acid detection. The limit of detection for sulphuric acid was 3•104 molecules cm-3 for two hour averaging. Signals from sulphuric acid clusters up to the tetramer were obtained but were found to result from naturally charged clusters formed by ion induced clustering in the atmosphere. Opposite to earlier studies with cluster mass spectrometers, we had no indication of neutral clusters. The reason is either less efficient charging of clusters in comparison to molecular sulphuric acid, or in low concentration of neutral clusters at our

  3. A comparison of neutralization efficiency of chemicals with respect to acidic Kopili River water

    NASA Astrophysics Data System (ADS)

    Kapil, Nibedita; Bhattacharyya, Krishna G.

    2016-02-01

    Among all the renewable sources of energy, hydropower is the most potential source which is economical, non-polluting and eco-friendly. The efficiency of hydropower plant in the long run depends on many factors like water and sediment quality. Erosive and corrosive wear of machine parts like turbine is a complex phenomenon. The problem becomes more acute if the hydroenvironment is acidic in nature. The wear and tear due to corrosion/erosion caused by acid mine drainage (AMD) from coal mines reduces the efficiency and the life of the equipments. In this work, neutralization of the acidic water of the Kopili River, Assam, India was investigated using a number of basic chemicals and quantitatively estimating their effectiveness and actual requirement. The acidic water of the river, used as the cooling water, has been found responsible for damaging the equipments of the Kopili Hydro Electric Power Project (KHEP), Assam/Meghalaya, India by reducing the life of all metallic parts through corrosion. In this work, use is made of a number of basic materials like calcium carbonate, calcium hydroxide, calcium oxide, sodium carbonate, sodium hydroxide, and ammonia to examine their neutralization efficiency with respect to the acidic water and it was found that quick lime or raw lime (CaO) has the highest neutralization capacity. Suggestions have been made for meeting the problem of acidity of the river water.

  4. Growth inhibition of Erwinia amylovora and related Erwinia species by neutralized short‑chain fatty acids.

    PubMed

    Konecki, Katrin; Gernold, Marina; Wensing, Annette; Geider, Klaus

    2013-11-01

    Short-chain fatty acids (SCFAs) are used to preserve food and could be a tool for control of fire blight caused by Erwinia amylovora on apple, pear and related rosaceous plants. Neutralized acids were added to buffered growth media at 0.5–75 mM and tested at pHs ranging from 6.8 to 5.5. Particularly at low pH, SCFAs with a chain length exceeding that of acetic acid such as propionic acid were effective growth inhibitors of E. amylovora possibly due to uptake of free acid and its intracellular accumulation. We also observed high inhibition with monochloroacetic acid. An E. billingiae strain was as sensitive to the acids as E. amylovora or E. tasmaniensis. Fire blight symptoms on pear slices were reduced when the slices were pretreated with neutralized propionic acid. Propionic acid is well water soluble and could be applied in orchards as a control agent for fire blight. PMID:24077735

  5. Metal Interactions with Microbial Biofilms in Acidic and Neutral pH Environments

    PubMed Central

    Ferris, F. G.; Schultze, S.; Witten, T. C.; Fyfe, W. S.; Beveridge, T. J.

    1989-01-01

    Microbial biofilms were grown on strips of epoxy-impregnated filter paper submerged at four sites in water contaminated with metals from mine wastes. At two sample stations, the water was acidic (pH 3.1); the other sites were in a lake restored to a near neutral pH level by application of a crushed limestone slurry. During a 17-week study period, planktonic bacterial counts increased from 101 to 103 CFU/ml at all sites. Biofilm counts increased rapidly over the first 5 weeks and then leveled to 104 CFU/cm2 in the neutral pH system and 103 CFU/cm2 at the acidic sites. In each case, the biofilms bound Mn, Fe, Ni, and Cu in excess of the amounts adsorbed by control strips covered with nylon filters (pore size, 0.22 μm) to exclude microbial growth; Co bound under neutral conditions but not under acidic conditions. Conditional adsorption capacity constants, obtained graphically from the data, showed that biofilm metal uptake at a neutral pH level was enhanced by up to 12 orders of magnitude over acidic conditions. Similarly, adsorption strength values were usually higher at elevated pH levels. In thin sections of the biofilms, encapsulated bacterial cells were commonly found enmeshed together in microcolonies. The extracellular polymers often contained iron oxide precipitates which generated weak electron diffraction patterns with characteristic reflections for ferrihydrite (Fe2O3 · H2O) at d equaling 0.15 and 0.25 nm. At neutral pH levels, these deposits incorporated trace amounts of Si and exhibited a granular morphology, whereas acicular crystalloids containing S developed under acidic conditions. Images PMID:16347914

  6. The role of the neutral amino acid transporter SNAT2 in cell volume regulation.

    PubMed

    Franchi-Gazzola, R; Dall'Asta, V; Sala, R; Visigalli, R; Bevilacqua, E; Gaccioli, F; Gazzola, G C; Bussolati, O

    2006-01-01

    Sodium-dependent neutral amino acid transporter-2 (SNAT2), the ubiquitous member of SLC38 family, accounts for the activity of transport system A for neutral amino acids in most mammalian tissues. As the transport process performed by SNAT2 is highly energized, system A substrates, such as glutamine, glycine, proline and alanine, reach high transmembrane gradients and constitute major components of the intracellular amino acid pool. Moreover, through a complex array of exchange fluxes, involving other amino acid transporters, and of metabolic reactions, such as the synthesis of glutamate from glutamine, SNAT2 activity influences the cell content of most amino acids, thus determining the overall size and the composition of the intracellular amino acid pool. As amino acids represent a large fraction of cell organic osmolytes, changes of SNAT2 activity are followed by modifications in both cell amino acids and cell volume. This mechanism is utilized by many cell types to perform an effective regulatory volume increase (RVI) upon hypertonic exposure. Under these conditions, the expression of SNAT2 gene is induced and newly synthesized SNAT2 proteins are preferentially targeted to the cell membrane, leading to a significant increase of system A transport Vmax. In cultured human fibroblasts incubated under hypertonic conditions, the specific silencing of SNAT2 expression, obtained with anti-SNAT2 siRNAs, prevents the increase in system A transport activity, hinders the expansion of intracellular amino acid pool, and significantly delays cell volume recovery. These results demonstrate the pivotal role played by SNAT2 induction in the short-term hypertonic RVI and suggest that neutral amino acids behave as compatible osmolytes in hypertonically stressed cells.

  7. Characterization and Diagnostic Value of Amino Acid Side Chain Neutral Losses Following Electron-Transfer Dissociation

    PubMed Central

    Xia, Qiangwei; Lee, M. Violet; Rose, Christopher M.; Marsh, Alyce J.; Hubler, Shane L.; Wenger, Craig D.; Coon, Joshua J.

    2011-01-01

    Using a large set of high mass accuracy and resolution ETD tandem mass spectra, we characterized ETD-induced neutral losses. From these data we deduced the chemical formula for 20 of these losses. Many of them have been previously observed in electron-capture dissociation (ECD) spectra, such as losses of the side chains of arginine, aspartic acid, glutamic acid, glutamine, asparagine, leucine, histidine, and carbamidomethylated cysteine residues. With this information, we examined the diagnostic value of these amino acid-specific losses. Among 1285 peptide–spectrum matches, 92.5% have agreement between neutral loss-derived peptide amino acid composition and the peptide sequences. Moreover, we show that peptides can be uniquely identified by using only the accurate precursor mass and amino acid composition based on neutral losses; the median number of sequence candidates from an accurate mass query is reduced from 21 to 8 by adding side chain loss information. Besides increasing confidence in peptide identification, our findings suggest the potential use of these diagnostic losses in ETD spectra to improve false discovery rate estimation and to enhance the performance of scoring functions in database search algorithms. PMID:21472585

  8. Characterization and Diagnostic Value of Amino Acid Side Chain Neutral Losses Following Electron-Transfer Dissociation

    NASA Astrophysics Data System (ADS)

    Xia, Qiangwei; Lee, M. Violet; Rose, Christopher M.; Marsh, Alyce J.; Hubler, Shane L.; Wenger, Craig D.; Coon, Joshua J.

    2011-02-01

    Using a large set of high mass accuracy and resolution ETD tandem mass spectra, we characterized ETD-induced neutral losses. From these data we deduced the chemical formula for 20 of these losses. Many of them have been previously observed in electron-capture dissociation (ECD) spectra, such as losses of the side chains of arginine, aspartic acid, glutamic acid, glutamine, asparagine, leucine, histidine, and carbamidomethylated cysteine residues. With this information, we examined the diagnostic value of these amino acid-specific losses. Among 1285 peptide-spectrum matches, 92.5% have agreement between neutral loss-derived peptide amino acid composition and the peptide sequences. Moreover, we show that peptides can be uniquely identified by using only the accurate precursor mass and amino acid composition based on neutral losses; the median number of sequence candidates from an accurate mass query is reduced from 21 to 8 by adding side chain loss information. Besides increasing confidence in peptide identification, our findings suggest the potential use of these diagnostic losses in ETD spectra to improve false discovery rate estimation and to enhance the performance of scoring functions in database search algorithms.

  9. Beta-galactosidase and selective neutrality. [amino acid composition of proteins

    NASA Technical Reports Server (NTRS)

    Holmquist, R.

    1979-01-01

    Three hypotheses to explain the amino acid composition of proteins are inconsistent (about 10 to the minus 9th) with the experimental data for beta-galactosidase from Escherichia coli. The exceptional length of this protein, 1021 residues, permits rigorous tests of these hypotheses without complication from statistical artifacts. Either this protein is not at compositional equilibrium, which is unlikely from knowledge about other proteins, or the evolution of this protein and its coding gene have not been selectively neutral. However, the composition of approximately 60% of the molecule is consistent with either a selectively neutral or nonneutral evolutionary process.

  10. Column leaching test to evaluate the use of alkaline industrial wastes to neutralize acid mine tailings

    SciTech Connect

    Doye, I.; Duchesne, J.

    2005-08-01

    Acid mine drainage is a serious environmental problem caused by the oxidation of sulfide minerals that releases highly acidic, sulfate, and metals-rich drainage. In this study, alkaline industrial wastes were mixed with acid mine tailings in order to obtain neutral conditions. A series of column leaching tests were performed to evaluate the behavior of reactive mine tailings amended with alkaline-additions under dynamic conditions. Column tests were conducted of oxidized mine tailings combined with cement kiln dust, red mud bauxite, and mixtures of cement kiln dust with red mud bauxite. The pH results show the addition of 10% of alkaline materials permits the maintenance of near neutral conditions. In the presence of 10% alkaline material, the concentration of toxic metals such as Al, Cu, Fe, Zn are significantly reduced as well as the number of viable cells (Thiobacillus ferrooxidans) compared to control samples.

  11. Neutralization of the antimicrobial effect of glyphosate by humic acid in vitro.

    PubMed

    Shehata, Awad A; Kühnert, Manfred; Haufe, Svent; Krüger, Monika

    2014-06-01

    In the present study, the neutralization ability of the antimicrobial effect of glyphosate by different humic acids was investigated. The minimal inhibitory concentrations of glyphosate for different bacteria such as Bacillus badius, Bifidobacterium adolescentis, Escherichia coli, E. coli 1917 strain Nissle, Enterococcus faecalis, Enterococcus faecium, Salmonella enteritidis and Salmonella typhimurium were determined in the presence or absence of different concentrations of humic acid (0.25, 0.5 and 1.0 mg mL(-1)). Our findings indicated that humic acids inhibited the antimicrobial effect of glyphosate on different bacteria. This information can help overcome the negative impact of glyphosate residues in feed and water. PMID:24268342

  12. Fecal free and conjugated bile acids and neutral sterols in vegetarians, omnivores, and patients with colorectal cancer.

    PubMed

    Korpela, J T; Adlercreutz, H; Turunen, M J

    1988-04-01

    Increased excretion and intestinal bacterial metabolism of bile acids and neutral sterols have been suggested to be associated with an increased risk of colorectal cancer. We determined fecal neutral sterol and bile acid profiles by new capillary column gas-liquid chromatographic methods in 18 patients with colorectal cancer, 10 omnivores, and 10 vegetarians. The methods also determine concentrations of esterified neutral sterols and saponifiable bile acids formed by intestinal bacterial action. Patients with colorectal cancer had the highest concentrations of neutral animal sterols, the lowest degree of esterification of neutral sterols, the lowest relative amount of saponifiable bile acids, and the highest concentrations of unconjugated primary bile acids. These differences were statistically significant (p less than 0.05) and more profound when the patients were compared with vegetarians than with omnivores. Since epidemiologic studies suggest that vegetarians have a lower risk of colorectal cancer than omnivores, these differences are discussed as possible risk factors for colorectal cancer.

  13. Inhibition of succinic acid production in metabolically engineered Escherichia coli by neutralizing agent, organic acids, and osmolarity.

    PubMed

    Andersson, Christian; Helmerius, Jonas; Hodge, David; Berglund, Kris A; Rova, Ulrika

    2009-01-01

    The economical viability of biochemical succinic acid production is a result of many processing parameters including final succinic acid concentration, recovery of succinate, and the volumetric productivity. Maintaining volumetric productivities >2.5 g L(-1) h(-1) is important if production of succinic acid from renewable resources should be competitive. In this work, the effects of organic acids, osmolarity, and neutralizing agent (NH4OH, KOH, NaOH, K2CO3, and Na2CO3), and Na2CO3) on the fermentative succinic acid production by Escherichia coli AFP184 were investigated. The highest concentration of succinic acid, 77 g L(-1), was obtained with Na2CO3. In general, irrespective of the base used, succinic acid productivity per viable cell was significantly reduced as the concentration of the produced acid increased. Increased osmolarity resulting from base addition during succinate production only marginally affected the productivity per viable cell. Addition of the osmoprotectant glycine betaine to cultures resulted in an increased aerobic growth rate and anaerobic glucose consumption rate, but decreased succinic acid yield. When using NH4OH productivity completely ceased at a succinic acid concentration of approximately 40 g L(-1). Volumetric productivities remained at 2.5 g L(-1) h(-1) for up to 10 h longer when K- or Na-bases where used instead of NH4OH. The decrease in cellular succinic acid productivity observed during the anaerobic phase was found to be due to increased organic acid concentrations rather than medium osmolarity.

  14. Magnesium hydroxide as the neutralizing agent for radioactive hydrochloric acid solutions

    SciTech Connect

    Palmer, M.J.; Fife, K.W.

    1995-10-01

    The current technology at Los Alamos for removing actinides from acidic chloride waste streams is precipitation with approximately 10 M potassium hydroxide. Although successful, there are many inherent drawbacks to this precipitation technique which will be detailed in this paper. Magnesium hydroxide (K{sub sp} = 1.3 x 10{sup -11}) has limited solubility in water and as a result of the common ion effect, cannot generate a filtrate with a pH greater than 9. At a pH of 9, calcium (K{sub sp} = 5.5 x 10{sup -6}) will not coprecipitate as the hydroxide. This is an important factor since many acidic chloride feeds to hydroxide precipitation contain significant amounts of calcium. In addition, neutralization with Mg(OH){sub 2} produces a more filterable precipitate because neutralization occurs as the Mg(OH){sub 2} is dissolved by the acid rather than as a result of the much faster liquid/liquid reaction of KOH with the waste acid. This slower solid/liquid reaction allows time for crystal growth to occur and produces more easily filterable precipitates. On the other hand, neutralization of spent acid with strong KOH that yields numerous hydroxide ions in solution almost instantaneously forming a much larger volume of small crystallites that result in gelatinous, slow-filtering precipitates. Magnesium hydroxide also offers a safety advantage. Although mildly irritating, it is a weak base and safe and easy to handle. From a waste minimization perspective, Mg(OH){sub 2} offers many advantages. First, the magnesium hydroxide is added as a solid. This step eliminates the diluent water used in KOH neutralizations. Secondly, because the particle size of the precipitate is larger, more actinides are caught on the filter paper resulting in a smaller amount of actinide being transferred to the TA-50 Liquid Waste Treatment Facility. Third, the amount of solids that must be reprocessed is significantly smaller resulting in less waste generation from the downstream processes.

  15. Increased adhesion between neutral lipid bilayers: interbilayer bridges formed by tannic acid.

    PubMed

    Simon, S A; Disalvo, E A; Gawrisch, K; Borovyagin, V; Toone, E; Schiffman, S S; Needham, D; McIntosh, T J

    1994-06-01

    Tannic acid (TA) is a naturally occurring polyphenolic compound that aggregates membranes and neutral phosolipid vesicles and precipitates many proteins. This study analyzes TA binding to lipid membranes and the ensuing aggregation. The optical density of dispersions of phosphatidylcholine (PC) vesicles increased upon the addition of TA and electron micrographs showed that TA caused the vesicles to aggregate and form stacks of tightly packed disks. Solution calorimetry showed that TA bound to PC bilayers with a molar binding enthalpy of -8.3 kcal/mol and zeta potential measurements revealed that TA imparted a small negative charge to PC vesicles. Monolayer studies showed that TA bound to PC with a dissociation constant of 1.5 microM and reduced the dipole potential by up to 250 mV. Both the increase in optical density and decrease in dipole potential produced by TA could be reversed by the addition of polyvinylpyrrolidone, a compound that chelates TA by providing H-bond acceptor groups. NMR, micropipette aspiration, and x-ray diffraction experiments showed that TA incorporated into liquid crystalline PC membranes, increasing the area per lipid molecule and decreasing the bilayer thickness by 2 to 4%. 2H-NMR quadrupole splitting measurements also showed that TA associated with a PC molecule for times much less than 10(-4) s. In gel phase bilayers, TA caused the hydrocarbon chains from apposing monolayers to fully interdigitate. X-ray diffraction measurements of both gel and liquid crystalline dispersions showed that TA, at a critical concentration of about 1 mM, reduced the fluid spacing between adjacent bilayers by 8-10 A. These data place severe constraints on how TA can pack between adjacent bilayers and cause vesicles to adhere. We conclude that TA promotes vesicle aggregation by reducing the fluid spacing between bilayers by the formation of transient interbilayer bridges by inserting its digallic acid residues into the interfacial regions of adjacent bilayers

  16. V1/V2 Neutralizing Epitope is Conserved in Divergent Non-M Groups of HIV-1

    PubMed Central

    Morgand, Marion; Bouvin-Pley, Mélanie; Plantier, Jean-Christophe; Moreau, Alain; Alessandri, Elodie; Simon, François; Pace, Craig S.; Pancera, Marie; Ho, David D.; Poignard, Pascal; Bjorkman, Pamela J.; Mouquet, Hugo; Nussenzweig, Michel C.; Kwong, Peter D.; Baty, Daniel; Chames, Patrick; Braibant, Martine

    2016-01-01

    Background: Highly potent broadly neutralizing monoclonal antibodies (bNAbs) have been obtained from individuals infected by HIV-1 group M variants. We analyzed the cross-group neutralization potency of these bNAbs toward non-M primary isolates (PI). Material and Methods: The sensitivity to neutralization was analyzed in a neutralization assay using TZM-bl cells. Twenty-three bNAbs were used, including reagents targeting the CD4-binding site, the N160 glycan-V1/V2 site, the N332 glycan-V3 site, the membrane proximal external region of gp41, and complex epitopes spanning both env subunits. Two bispecific antibodies that combine the inhibitory activity of an anti-CD4 with that of PG9 or PG16 bNAbs were included in the study (PG9-iMab and PG16-iMab). Results: Cross-group neutralization was observed only with the bNAbs targeting the N160 glycan-V1/V2 site. Four group O PIs, 1 group N PI, and the group P PI were neutralized by PG9 and/or PG16 or PGT145 at low concentrations (0.04–9.39 μg/mL). None of the non-M PIs was neutralized by the bNAbs targeting other regions at the highest concentration tested, except 10E8 that neutralized weakly 2 group N PIs and 35O22 that neutralized 1 group O PI. The bispecific bNAbs neutralized very efficiently all the non-M PIs with IC50 below 1 μg/mL, except 2 group O strains. Conclusion: The N160 glycan-V1/V2 site is the most conserved neutralizing site within the 4 groups of HIV-1. This makes it an interesting target for the development of HIV vaccine immunogens. The corresponding bNAbs may be useful for immunotherapeutic strategies in patients infected by non-M variants. PMID:26413851

  17. Chapter A6. Section 6.6. Alkalinity and Acid Neutralizing Capacity

    USGS Publications Warehouse

    Rounds, Stewart A.; Wilde, Franceska D.

    2002-01-01

    Alkalinity (determined on a filtered sample) and Acid Neutralizing Capacity (ANC) (determined on a whole-water sample) are measures of the ability of a water sample to neutralize strong acid. Alkalinity and ANC provide information on the suitability of water for uses such as irrigation, determining the efficiency of wastewater processes, determining the presence of contamination by anthropogenic wastes, and maintaining ecosystem health. In addition, alkalinity is used to gain insights on the chemical evolution of an aqueous system. This section of the National Field Manual (NFM) describes the USGS field protocols for alkalinity/ANC determination using either the inflection-point or Gran function plot methods, including calculation of carbonate species, and provides guidance on equipment selection.

  18. Stemflow acid neutralization capacity in a broadleaved deciduous forest: the role of edge effects.

    PubMed

    Shiklomanov, Alexey N; Levia, Delphis F

    2014-10-01

    Atmospheric deposition is an important pathway for moisture, nutrient, and pollutant exchange among the atmosphere, forest, and soils. Previous work has shown the importance of proximity to the forest edge to chemical fluxes in throughfall, but far less research has considered stemflow. This study examined the difference in acid neutralization capacity (ANC) of stemflow of nineteen Liriodendron tulipifera L. (yellow poplar) trees between the forest edge and interior in a rural area of northeastern Maryland. We measured ANC directly via potentiometric titration. Stemflow from trees at the forest edge was found to have significantly higher and more variable pH and ANC than in the forest interior (p < 0.01). No mathematical trend between ANC and distance to the forest edge was observed, indicating the importance of individual tree characteristics in stemflow production and chemistry. These results reaffirm the importance of stemflow for acid neutralization by deciduous tree species.

  19. Hydrodynamic Instabilities Driven by Acid-base Neutralization Reaction in Immiscible System

    NASA Astrophysics Data System (ADS)

    Asad, Ahmed; Yang, Ya-hui; Chai, Chuan; Wu, Jiang-tao

    2010-10-01

    The hydrodynamic instabilities driven by an acid-base neutralization reaction, in contact along a plane interface, placed in a Hele-Shaw cell under the gravitational field are reported. The system consists of the heavier aqueous tetramethyle-ammonium hydroxide below the lighter layer of organic phase with propionic acid as reacting specie. The effect of chemical composition on hydrodynamic instabilities during interfacial mass transfer accompanied by a neutralization reaction is investigated. Depending on the initial concentration of the reacting species, Marangoni convection in the form of roll cells or trains of waves is observed. Mach-Zehnder interferometer is used to measure the change in base concentration at the time of instability formation. The results show that the instabilities resulted from the convection flow are more efficient to the mechanism of mass transfer and can drastically alter pattern formation in the system.

  20. Stemflow acid neutralization capacity in a broadleaved deciduous forest: the role of edge effects.

    PubMed

    Shiklomanov, Alexey N; Levia, Delphis F

    2014-10-01

    Atmospheric deposition is an important pathway for moisture, nutrient, and pollutant exchange among the atmosphere, forest, and soils. Previous work has shown the importance of proximity to the forest edge to chemical fluxes in throughfall, but far less research has considered stemflow. This study examined the difference in acid neutralization capacity (ANC) of stemflow of nineteen Liriodendron tulipifera L. (yellow poplar) trees between the forest edge and interior in a rural area of northeastern Maryland. We measured ANC directly via potentiometric titration. Stemflow from trees at the forest edge was found to have significantly higher and more variable pH and ANC than in the forest interior (p < 0.01). No mathematical trend between ANC and distance to the forest edge was observed, indicating the importance of individual tree characteristics in stemflow production and chemistry. These results reaffirm the importance of stemflow for acid neutralization by deciduous tree species. PMID:25005886

  1. The amino acid residues at 102 and 104 in GP5 of porcine reproductive and respiratory syndrome virus regulate viral neutralization susceptibility to the porcine serum neutralizing antibody.

    PubMed

    Fan, Baochao; Liu, Xing; Bai, Juan; Zhang, Tingjie; Zhang, Qiaoya; Jiang, Ping

    2015-06-01

    Porcine reproductive and respiratory syndrome virus (PRRSV) is mainly responsible for the heavy economic losses in pig industry in the world. A number of neutralizing epitopes have been identified in the viral structural proteins GP3, GP4, GP5 and M. In this study, the important amino acid (aa) residues of HP-PRRSV strain BB affecting neutralization susceptibility of antibody were examined using resistant strains generated under neutralizing antibody (NAb) pressure in MARC-145 cells, reverse genetic technique and virus neutralization assay. HP-PRRSV strain BB was passaged under the pressure of porcine NAb serum in vitro. A resistant strain BB34s with 102 and 104 aa substitutions in GP5, which have been predicted to be the positive sites for pressure selection (Delisle et al., 2012), was cloned and identified. To determine the effect of the two aa residues on neutralization, eight recombinant PRRSV strains were generated, and neutralization assay results confirmed that the aa residues 102 and 104 in GP5 played an important role in NAbs against HP-PRRSV in MARC-145 cells and porcine alveolar macrophages. Alignment of GP5 sequences revealed that the variant aa residues at 102 and 104 were frequent among type 2 PRRSV strains. It may be helpful for understanding the mechanism regulating the neutralization susceptibility of PRRSV to the NAbs and monitoring the antigen variant strains in the field.

  2. Classification of illicit heroin by UPLC-Q-TOF analysis of acidic and neutral manufacturing impurities.

    PubMed

    Liu, Cuimei; Hua, Zhendong; Bai, Yanping

    2015-12-01

    The illicit manufacture of heroin results in the formation of trace levels of acidic and neutral manufacturing impurities that provide valuable information about the manufacturing process used. In this work, a new ultra performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF) method; that features high resolution, mass accuracy and sensitivity for profiling neutral and acidic heroin manufacturing impurities was developed. After the UPLC-Q-TOF analysis, the retention times and m/z data pairs of acidic and neutral manufacturing impurities were detected, and 19 peaks were found to be evidently different between heroin samples from "Golden Triangle" and "Golden Crescent". Based on the data set of these 19 impurities in 150 authentic heroin samples, classification of heroin geographic origins was successfully achieved utilizing partial least squares discriminant analysis (PLS-DA). By analyzing another data set of 267 authentic heroin samples, the developed discrimiant model was validated and proved to be accurate and reliable. PMID:26364155

  3. Global molecular identification from graphs. Neutral and ionized main-group diatomic molecules.

    PubMed

    James, Bryan; Caviness, Ken; Geach, Jonathan; Walters, Chris; Hefferlin, Ray

    2002-01-01

    Diophantine equations and inequalities are presented for main-group closed-shell diatomic molecules. Specifying various bond types (covalent, dative, ionic, van der Waals) and multiplicities, it becomes possible to identify all possible molecules. While many of the identified species are probably unstable under normal conditions, they are interesting and present a challenge for computational or experimental analysis. Ionized molecules with net charges of -1, 1, and 2 are also identified. The analysis applies to molecules with atoms from periods 2 and 3 but can be generalized by substituting isovalent atoms. When closed-shell neutral diatomics are positioned in the chemical space (with axes enumerating the numbers of valence electrons of the free atoms), it is seen that they lie on a few parallel isoelectronic series.

  4. Cellular distribution of the neutral amino acid transporter subtype ASCT2 in mouse brain.

    PubMed

    Gliddon, Catherine M; Shao, Zongjun; LeMaistre, Jillian L; Anderson, Christopher M

    2009-01-01

    ASCT2 is an ASC (alanine-, serine-, cysteine-preferring) neutral amino acid exchanger that may regulate CNS function by transporting amino acid substrates including L-serine, L-cysteine, L-glutamine, L-glutamate and D-serine. Despite the potentially important role of ASCT2 in influencing metabolic and signaling functions of these amino acids in brain, there has been little description of its distribution in brain tissue. We employed a commercially available human ASCT2 antibody in immunohistochemistry studies in adult mouse brain and found a wide regional distribution for ASCT2 that was limited to dendrites labeled by anti-microtubule-associated protein-2 in cortex, hippocampus and striatum. No ASCT2 immunoreactivity was observed in areas labeled by antibodies against a neuronal cell body marker (NeuN), or either of the astrocyte markers, glial fibrillary acidic protein or S100beta. In cerebellum both Purkinje cell bodies and dendrites were positive for ASCT2 immunoreactivity. In support of a dendritic localization for ASCT2 in cortex, low affinity (K(T) > 1 mM), Na(+)-dependent D-serine and L-glutamine uptake characteristic of ASCT2-mediated transport was observed in P2 synaptosomal preparations. These results suggest that ASCT2 may be an important neuronal neutral amino acid transporter and highlight a discrepancy between findings of astrocyte ASCT2 function in tissue culture and brain in situ.

  5. Characterization of Acid-neutralizing Basic Monomers in Co-solvent Systems by NMR

    PubMed Central

    Laurence, Jennifer S.; Nelson, Benjamin N.; Ye, Qiang; Park, Jonggu; Spencer, Paulette

    2014-01-01

    Metabolic activity of the oral microbiota leads to acidification of the microenvironment and promotes demineralization of tooth structure at the margin of composite restorations. The pathogenic impact of the biofilm at the margin of the composite restoration could be reduced by engineering novel dentin adhesives that neutralize the acidic micro-environment. Integrating basic moieties into methacrylate derivatives has the potential to buffer against acid-induced degradation, and we are investigating basic monomers for this purpose. These monomers must be compatible with existing formulations, which are hydrophobic and marginally miscible with water. As such, cosolvent systems may be required to enable analysis of monomer function and chemical properties. Here we present an approach for examining the neutralizing capacity of basic methacrylate monomers in a water/ethanol co-solvent system using NMR spectroscopy. NMR is an excellent tool for monitoring the impact of co-solvent effects on pKa and buffering capacity of basic monomers because chemical shift is extremely sensitive to small changes that most other methods cannot detect. Because lactic acid (LA) is produced by oral bacteria and is prevalent in this microenvironment, LA was used to analyze the effectiveness of basic monomers to neutralize acid. The 13C chemical shift of the carbonyl in lactic acid was monitored as a function of ethanol and monomer concentration and each was correlated with pH to determine the functional buffering range. This study shows that the buffering capacity of even very poorly water-soluble monomers can be analyzed using NMR. PMID:25400302

  6. Stream chemistry in the eastern United States. 2. Current sources of acidity in acidic and low acid-neutralizing-capacity streams

    SciTech Connect

    Herlihy, A.T.; Kaufmann, P.R.; Mitch, M.E.

    1991-01-01

    The authors examined anion composition in National Stream Survey (NSS) data in order to evaluate the most probable sources of current acidity in acidic and low acid neutralizing capacity (ANC) streams in the eastern United States. Acidic streams that had almost no organic influence (less than 10% of total anions) and sulfate and nitrate concentrations indicative of evaporative concentration of atmospheric deposition were classified as acidic due to acidic deposition. These acidic streams were located in small forested watersheds in the Mid-Atlantic Highlands (an estimated 1950 km of stream length) and in the Mid-Atlantic Coastal Plain (1250 km). Acidic streams affected primarily by acidic deposition but also influenced by naturally occurring organic anions accounted for another 1180 km of acidic stream length and were located in the New Jersey Pine Barrens, plateau tops in the Mid-Atlantic and Southeast Highlands, and the Florida Panhandle. The total length of streams acidic due to acid mine drainage in the NSS (4590 km) was about the same as the total length of acidic streams likely affected by acidic deposition (4380 km). Acidic streams whose acid anion composition was dominated by organics were located in Florida and the Mid-Atlantic Coastal Plain. In Florida, most of the acidic streams were organic dominated, whereas about half of the streams in the Mid-Atlantic Coastal Plain were organic dominated. Organic-dominated acidic streams were not observed in the Mid-Atlantic and Southeast Highlands.

  7. Stream chemistry in the eastern United States, 2, Current sources of acidity in acidic and low acid-neutralizing capacity streams

    NASA Astrophysics Data System (ADS)

    Herlihy, Alan T.; Kaufmann, Philip R.; Mitch, Mark E.

    1991-04-01

    We examined anion composition in National Stream Survey (NSS) data in order to evaluate the most probable sources of current acidity in acidic and low acid-neutralizing capacity (ANC) streams in the eastern United States. Acidic streams that had almost no organic influence (less than 10% of total anions) and sulfate and nitrate concentrations indicative of evaporative concentration of atmospheric deposition were classified as acidic due to acidic deposition. These acidic streams were located in small (<30 km2) forested watersheds in the Mid-Atlantic Highlands (an estimated 1950 km of stream length) and in the Mid-Atlantic Coastal Plain (1250 km). Acidic streams affected primarily by acidic deposition but also influenced by naturally occurring organic anions accounted for another 1180 km of acidic stream length and were located in the New Jersey Pine Barrens, plateau tops in the Mid-Atlantic and Southeast Highlands, and the Florida Panhandle. The total length of streams acidic due to acid mine drainage in the NSS (4590 km) was about the same as the total length of acidic streams likely affected by acidic deposition (4380 km). Acidic streams whose acid anion composition was dominated by organics were located in Florida and the Mid-Atlantic Coastal Plain. In Florida, most of the acidic streams were organic dominated, whereas about half of the streams in the Mid-Atlantic Coastal Plain were organic dominated. Organic-dominated acidic streams were not observed in the Mid-Atlantic and Southeast Highlands.

  8. Behavior of Neutral Hydrogen in the NGC 877/6 Galaxy Group

    NASA Astrophysics Data System (ADS)

    Manning Hall, Porter; Minchin, Robert F.; Taylor, Rhys

    2015-01-01

    We observed a 5 square degree area centered on -02:17:31, 14:32:00 at 21-cm as part of the Arecibo Galaxy Environment Survey (AGES) with the NGC 877/6 galaxy group at a velocity of 4000 km/s as the primary target. Our observations covered the redshift range -5,000 < cz < 20,000 km/s allowing for a large volume in front and behind the complex to be analyzed. The NGC 877/6 group contains 8 galaxies inside a common HI envelope with a total neutral hydrogen mass of LogMHI = 10.73. HI is detected outside of the optically-identified galaxies and there are a number of tidal features within the complex. These include AGC 749170, a possible tidal remnant identified by ALFALFA and whose detection we confirm here. Another, smaller group associated with UGC 1742 (LogMHI = 9.95; cz = 6900 km/s) was identified as showing signs of galaxy interaction as well as the possibility of a tidal formation not catalogued in NED as a galaxy. Of the 44 HI sources identified in the data cube, 12 (27%) were not previously recorded in the NED database as galaxies. We will continue our analysis with data from the Mock spectrometers which will extend the redshift range to 45000 km/s.

  9. Neutral molecular cluster formation of sulfuric acid-dimethylamine observed in real time under atmospheric conditions.

    PubMed

    Kürten, Andreas; Jokinen, Tuija; Simon, Mario; Sipilä, Mikko; Sarnela, Nina; Junninen, Heikki; Adamov, Alexey; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Hutterli, Manuel; Kangasluoma, Juha; Kirkby, Jasper; Laaksonen, Ari; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Schobesberger, Siegfried; Seinfeld, John H; Steiner, Gerhard; Tomé, António; Tröstl, Jasmin; Winkler, Paul M; Williamson, Christina; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Kenneth S; Kulmala, Markku; Worsnop, Douglas R; Curtius, Joachim

    2014-10-21

    For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.

  10. Two groups challenge US acid rain efforts

    SciTech Connect

    Not Available

    1987-11-01

    In its report, Acid Rain Invades Our National Parks, the National Parks and Conservation Association (NPCA) says acid rain is being detected at all 27 national park monitoring sites. In 1980, 87 national parks expressed concern in a NPCA survey over acid rain. Repolled in 1986, more than half of the respondents reported that no research on acid rain was under way. The NPCA report concludes that the alarm that was sounded in 1980 fell largely on deaf ears, and calls for the structural and scientific reorganization of the National Park Service. The National Audubon Society shares NPCA's dissatisfaction with federal efforts to tackle the problem of acid rain and has taken testing into its own hands. Through its Citizens Acid Rain Monitoring Network, Audubon volunteers have collected readings of acidity at 64 monitoring stations in 31 states since July.

  11. MALDI mechanism of dihydroxybenzoic acid isomers: desorption of neutral matrix and analyte.

    PubMed

    Liang, Chi Wei; Lee, Chih Hao; Lin, Yu-Jiun; Lee, Yuan Tseh; Ni, Chi Kung

    2013-05-01

    Angular resolved velocity distributions of laser desorbed neutral matrices (dihydroxybenzoic acids, DHB) and analytes (tryptophan) embedded in these matrices were investigated at 322 nm by a modified crossed molecular beam apparatus. Desorbed ions generated from MALDI were measured by a time-of-flight mass spectrometer. Desorptions of neutral matrix and analyte from 2,3-DHB, 2,4-DHB, 2,5-DHB, 2,6-DHB, and 3,5--DHB at 322 nm have similar properties, but the ion intensities are in the order 2,3DHB ≅ 2,6-DHB > 2,5-DHB ≅ 2,4-DHB > 3,5-DHB. It indicates that the combination of various parameters related to neutral species, including absorption coefficient, sublimation energy, contact of analyte and matrix in crystal, and plume dynamics of desorbed species are not crucial in the determination of MALDI process for DHB isomers. The difference of matrix activity of DHB isomers at this wavelength must result from the other properties, like the excited state lifetime, proton affinity, gas-phase basicity, acidity, ionization energy, or the other properties related to the primary reactions in ion generation.

  12. Electroactive self-doped poly(amic acid) with oligoaniline and sulfonic acid groups: synthesis and electrochemical properties.

    PubMed

    Chi, Maoqiang; Wang, Shutao; Liang, Yuan; Chao, Danming; Wang, Ce

    2014-06-01

    A novel poly(amic acid) with pendant aniline tetramer and sulfonic acid groups (ESPAA) was synthesized by ternary polymerization and characterized by Fourier-transform infrared spectra, ((1))H NMR and gel permeation chromatography. The polymer showed good thermal stability and excellent solubility in the common organic solvents. The electrochemical properties were investigated carefully on a CHI 660A Electrochemical Workstation. The polymer displayed good electroactivity in acid, neutral and even in alkaline solutions (pH=1-10) due to the self-doping effect between aniline tetramer and sulfonic/carboxylic acid groups. It also exhibited satisfactory electrochromic performance with high contrast value, acceptable coloration efficiency and fast switching time in the range of pH=1-9.

  13. Gas-phase structures and thermochemistry of neutral histidine and its conjugated acid and base.

    PubMed

    Riffet, Vanessa; Bouchoux, Guy

    2013-04-28

    Extensive exploration of the conformational space of neutral, protonated and deprotonated histidine has been conducted at the G4MP2 level. Theoretical protonation and deprotonation thermochemistry as well as heats of formation of gaseous histidine and its ionized forms have been calculated at the G4 level considering either the most stable conformers or an equilibrium population of conformers at 298 K. These theoretical results were compared to evaluated experimental determinations. Recommended proton affinity and protonation entropy deduced from these comparisons are PA(His) = 980 kJ mol(-1) and ΔpS(His) ∼ 0 J mol(-1) K(-1), thus leading to a gas-phase basicity value of GB(His) = 947.5 kJ mol(-1). Similarly, gas phase acidity parameters are ΔacidH(o)(His) = 1373 kJ mol(-1), ΔacidS(His) ∼ 10 J mol(-1) K(-1) and ΔacidG(o)(His) = 1343 kJ mol(-1). Computed G4 heats of formation values are equal to -290, 265 and -451 kJ mol(-1) for gaseous neutral histidine and its protonated and deprotonated forms, respectively. The present computational data correct, and complete, previous thermochemical parameter estimates proposed for gas-phase histidine and its acido-basic properties.

  14. Inflammatory responses to neutral fat and fatty acids in multiple organs in a rat model of fat embolism syndrome.

    PubMed

    Takada, Meri; Chiba, Shoetsu; Nagai, Tomonori; Takeshita, Hiroshi; Kanno, Sanae; Ikawa, Toru; Sakamoto, Kana; Sagi, Morihisa; Ichiba, Kazue; Mukai, Toshiji

    2015-09-01

    Fat embolism syndrome (FES) is a common complication of long bone fractures. FES is rare but with significant morbidity and occasional fatalities. Studies of animal models of FES are numerous; however, few studies compare inflammatory reactions in multiple organs. The present study investigated the effect of neutral fat and fatty acids, which cause changes in multiple organs and induce FES. Using rats we evaluated the ratio of lung-to-body weight and conducted histological analyses and quantitative analysis of inflammatory cytokine mRNAs in the lungs following intravenous administration of neutral fat or fatty acids. Neutral fat increased the ratio of lung-to-body weight, and neutral fat formed emboli in lung capillaries. The levels of interleukin-1 beta (IL-1β), IL-6 and tumor necrosis factor-alpha (TNF-α) in the lungs increased after injection of neutral fat and oleic acid. Analysis of the histologic changes revealed that the highest numbers of fat droplets, occluding the capillaries of the lungs, kidney, heart, and brain formed 12h after the injection of neutral fat and fat droplets gradually diminished 48h later. Fat droplets were not detected in any organs after the injection of oleic acid. IL-1β and TNF-α levels in the lungs were elevated 9-24h after the injection of neutral fat, although IL-6 levels peaked at 6h. After injection of oleic acid, peak levels of IL-1β, IL-6, and TNF-α were detected at 6h, and IL-6 again increased in all organs and plasma at 15h. Neutral fat, but not fatty acids, formed emboli in the capillaries of multiple organs. These findings suggest that neutral fat increased inflammatory cytokine levels by forming emboli in organ capillaries, particularly in the lungs, while oleic acid augmented inflammatory cytokine levels by stimulating endothelial cells of multiple organs.

  15. Impaired Nutrient Signaling and Body Weight Control in a Na+ Neutral Amino Acid Cotransporter (Slc6a19)-deficient Mouse*

    PubMed Central

    Bröer, Angelika; Juelich, Torsten; Vanslambrouck, Jessica M.; Tietze, Nadine; Solomon, Peter S.; Holst, Jeff; Bailey, Charles G.; Rasko, John E. J.; Bröer, Stefan

    2011-01-01

    Amino acid uptake in the intestine and kidney is mediated by a variety of amino acid transporters. To understand the role of epithelial neutral amino acid uptake in whole body homeostasis, we analyzed mice lacking the apical broad-spectrum neutral (0) amino acid transporter B0AT1 (Slc6a19). A general neutral aminoaciduria was observed similar to human Hartnup disorder which is caused by mutations in SLC6A19. Na+-dependent uptake of neutral amino acids into the intestine and renal brush-border membrane vesicles was abolished. No compensatory increase of peptide transport or other neutral amino acid transporters was detected. Mice lacking B0AT1 showed a reduced body weight. When adapted to a standard 20% protein diet, B0AT1-deficient mice lost body weight rapidly on diets containing 6 or 40% protein. Secretion of insulin in response to food ingestion after fasting was blunted. In the intestine, amino acid signaling to the mammalian target of rapamycin (mTOR) pathway was reduced, whereas the GCN2/ATF4 stress response pathway was activated, indicating amino acid deprivation in epithelial cells. The results demonstrate that epithelial amino acid uptake is essential for optimal growth and body weight regulation. PMID:21636576

  16. Lipase catalyzed synthesis of neutral glycerides rich in micronutrients from rice bran oil fatty acid distillate.

    PubMed

    Nandi, Sumit; Gangopadhyay, Sarbani; Ghosh, Santinath

    2008-01-01

    Neutral glycerides with micronutrients like sterols, tocopherols and squalene may be prepared from cheap raw material like rice bran oil fatty acid distillate (RBO FAD). RBO FAD is an important byproduct of vegetable oil refining industries in the physical refining process. Glycerides like triacylglycerols (TAG), diacylglycerols (DAG) and monoacylglycerols (MAG) containing significant amounts of unsaponifiable matter like sterols, tocopherols and hydrocarbons (mainly squalene) may certainly be considered as novel functional food ingredients. Fatty acids present in RBO FAD were esterified with glycerol of varying amount (1:0.33, 1:0.5, 1:1 and 1:1.5 of FAD : glycerol ratio) for 8 h using non-specific enzyme NS 40013 (Candida antartica). After esterification the product mixture containing mono, di- and triglycerides was purified by molecular distillation to remove excess free fatty acids and also other volatile undesirable components. The purified product containing sterols, tocopherols and squalene can be utilized in various food formulations. PMID:18838832

  17. Lipase catalyzed synthesis of neutral glycerides rich in micronutrients from rice bran oil fatty acid distillate.

    PubMed

    Nandi, Sumit; Gangopadhyay, Sarbani; Ghosh, Santinath

    2008-01-01

    Neutral glycerides with micronutrients like sterols, tocopherols and squalene may be prepared from cheap raw material like rice bran oil fatty acid distillate (RBO FAD). RBO FAD is an important byproduct of vegetable oil refining industries in the physical refining process. Glycerides like triacylglycerols (TAG), diacylglycerols (DAG) and monoacylglycerols (MAG) containing significant amounts of unsaponifiable matter like sterols, tocopherols and hydrocarbons (mainly squalene) may certainly be considered as novel functional food ingredients. Fatty acids present in RBO FAD were esterified with glycerol of varying amount (1:0.33, 1:0.5, 1:1 and 1:1.5 of FAD : glycerol ratio) for 8 h using non-specific enzyme NS 40013 (Candida antartica). After esterification the product mixture containing mono, di- and triglycerides was purified by molecular distillation to remove excess free fatty acids and also other volatile undesirable components. The purified product containing sterols, tocopherols and squalene can be utilized in various food formulations.

  18. Equivalence-point electromigration acid-base titration via moving neutralization boundary electrophoresis.

    PubMed

    Yang, Qing; Fan, Liu-Yin; Huang, Shan-Sheng; Zhang, Wei; Cao, Cheng-Xi

    2011-04-01

    In this paper, we developed a novel method of acid-base titration, viz. the electromigration acid-base titration (EABT), via a moving neutralization boundary (MNR). With HCl and NaOH as the model strong acid and base, respectively, we conducted the experiments on the EABT via the method of moving neutralization boundary for the first time. The experiments revealed that (i) the concentration of agarose gel, the voltage used and the content of background electrolyte (KCl) had evident influence on the boundary movement; (ii) the movement length was a function of the running time under the constant acid and base concentrations; and (iii) there was a good linearity between the length and natural logarithmic concentration of HCl under the optimized conditions, and the linearity could be used to detect the concentration of acid. The experiments further manifested that (i) the RSD values of intra-day and inter-day runs were less than 1.59 and 3.76%, respectively, indicating similar precision and stability in capillary electrophoresis or HPLC; (ii) the indicators with different pK(a) values had no obvious effect on EABT, distinguishing strong influence on the judgment of equivalence-point titration in the classic one; and (iii) the constant equivalence-point titration always existed in the EABT, rather than the classic volumetric analysis. Additionally, the EABT could be put to good use for the determination of actual acid concentrations. The experimental results achieved herein showed a new general guidance for the development of classic volumetric analysis and element (e.g. nitrogen) content analysis in protein chemistry.

  19. Spectral investigation and theoretical study of zwitterionic and neutral forms of quinolinic acid

    NASA Astrophysics Data System (ADS)

    Karabacak, M.; Sinha, L.; Prasad, O.; Bilgili, S.; Sachan, Alok K.; Asiri, A. M.; Atac, A.

    2015-09-01

    In this study, molecular structure and vibrational analysis of quinolinic acid (2,3-pyridinedicarboxylic acid), in zwitterionic and neutral forms, were presented using FT-IR, FT-Raman, NMR, UV experimental techniques and quantum chemical calculations. FT-IR and FT-Raman spectra of 2,3-pyridinedicarboxylic acid (2,3-PDCA) in the solid phase were recorded in the region 4000-400 cm-1 and 3500-0 cm-1, respectively. The geometrical parameters and energies were obtained for zwitter and neutral forms by using density functional theory (DFT) at B3LYP/6-311++G(d,p) level of theory. 3D potential energy scan was performed by varying the selected dihedral angles using M06-2X and B3LYP functionals at 6-31G(d) level of theory and thus the most stable conformer of the title compound was determined. The most stable conformer was further optimized at higher level and vibrational wavenumbers were calculated. Theoretical vibrational assignment of 2,3-PDCA, using percentage potential energy distribution (PED) was done with MOLVIB program. 13C and 1H NMR spectra were recorded in DMSO. Chemical shifts were calculated at the same level of theory. The UV absorption spectra of the studied compound in ethanol and water were recorded in the range of 200-400 nm. The optimized geometric parameters were compared with experimental data.

  20. Stemflow Acid Neutralization Capacity in a Broadleaved Deciduous Forest: The Role of Edge Effects

    NASA Astrophysics Data System (ADS)

    Levia, D. F., Jr.; Shiklomanov, A.

    2014-12-01

    The fragmentation of forests is occurring at an accelerated rate in parts of the United States. Forest fragmentation creates edge habitat that affects the biogeochemistry of forests. Atmospheric deposition is known to increase at the forest edge in comparison to the forest interior. Past research has demonstrated the critical role of edge effects on throughfall chemistry but no known work has examined the relationship between stemflow chemistry and edge effects. To fill this data gap, we quantified the stemflow acid neutralization capacity (ANC) of nineteen Liriodendron tulipifera L. (yellow poplar) trees between forest edge and interior locations in the Piedmont of the mid-Atlantic USA. ANC was measured directly by potentiometric titration. Both stemflow pH and ANC were higher for L. tulipifera trees on the forest edge as opposed to those in interior locations (p < 0.01), although marked variability was observed among individual trees. It is critical to note that the ANC of stemflow of edge trees is almost certainly contextual, depending on geographic locality. This is to say that stemflow from edge trees may neutralize acid inputs in some locations (as in our case) but lead to enhanced acidification of aqueous inputs to forest soils in other locales where the dry deposition of acid anions is high. The experimental results have ramifications for forest management schema seeking to increase or decrease the extent of edge habitat in forest fragments.

  1. Identification of neutral and acidic deoxyribonuclease activities in Tetrahymena thermophila life stages.

    PubMed

    Aslan, Erhan; Arslanyolu, Muhittin

    2015-04-01

    Deoxyribonucleases (DNases) play a major role in apoptotic DNA fragmentation/degradation, and apoptotic-like DNA degradation is also observed during conjugation of the ciliate Tetrahymena thermophila; however, the characteristics of neutral and acidic DNases are still undefined in its life stages. Here, we report the biochemical characterization of DNase activities displayed in three different Tetrahymena life stages in a comparative manner. Maximum DNase activity of Tetrahymena was observed under acidic conditions, indicating that Tetrahymena has strong DNase II-like activities. Zymography revealed that Tetrahymena has at least five distinct DNase activity bands at 28, 32, 33.8, 35.5, and 69-kDa, and that the activities at 32 and 33.8-kDa were also secreted into starvation buffer. Cofactor analysis demonstrated that Mg(2+) exerted inhibitory effects on neutral DNase activities. Unexpectedly, Mg(2+) and Ca(2+) had favorable effects on acidic DNase activities. The DNase activity profile of conjugating Tetrahymena cells revealed that the 32 and 33.8-kDa activities at pH 5.0 increased from 14 to 18 h of conjugation, corresponding to the final resorption of the old macronucleus by lysosomal enzymes during programmed nuclear death (PND). Overall, we found that Tetrahymena DNases exhibit different biochemical properties and a possible involvement of DNase II-like activities in PND.

  2. Acid mine drainage treatment using by-products from quicklime manufacturing as neutralization chemicals.

    PubMed

    Tolonen, Emma-Tuulia; Sarpola, Arja; Hu, Tao; Rämö, Jaakko; Lassi, Ulla

    2014-12-01

    The aim of this research was to investigate whether by-products from quicklime manufacturing could be used instead of commercial quicklime (CaO) or hydrated lime (Ca(OH)2), which are traditionally used as neutralization chemicals in acid mine drainage treatment. Four by-products were studied and the results were compared with quicklime and hydrated lime. The studied by-products were partly burnt lime stored outdoors, partly burnt lime stored in a silo, kiln dust and a mixture of partly burnt lime stored outdoors and dolomite. Present application options for these by-products are limited and they are largely considered waste. Chemical precipitation experiments were performed with the jar test. All the studied by-products removed over 99% of Al, As, Cd, Co, Cu, Fe, Mn, Ni, Zn and approximately 60% of sulphate from acid mine drainage. However, the neutralization capacity of the by-products and thus the amount of by-product needed as well as the amount of sludge produced varied. The results indicated that two out of the four studied by-products could be used as an alternative to quicklime or hydrated lime for acid mine drainage treatment. PMID:25193795

  3. Hydrobiogeochemical interactions in 'anoxic' limestone drains for neutralization of acidic mine drainage

    USGS Publications Warehouse

    Robbins, E.I.; Cravotta, C.A.; Savela, C.E.; Nord, G.L.

    1999-01-01

    Processes affecting neutralization of acidic coal mine drainage were evaluated within 'anoxic' limestone drains (ALDs). Influents had pH???3.5 and dissolved oxygen <2 mg/l. Even though effluents were near neutral (pH 6 and alkalinity acidity), two of the four ALDs were failing due to clogging. Mineral-saturation indices indicated the potential for dissolution of calcite and gypsum, and precipitation of Al3+ and Fe3+ compounds. Cleavage mounts of calcite and gypsum that were suspended within the ALDs and later examined microscopically showed dissolution features despite coatings by numerous bacteria, biofilms, and Fe-Al-Si precipitates. In the drain exhibiting the greatest flow reduction, Al-hydroxysulfates had accumulated on limestone surfaces and calcite etch points, thus causing the decline in transmissivity and dissolution. Therefore, where Al loadings are high and flow rates are low, a pre-treatment step is indicated to promote Al removal before diverting acidic mine water into alkalinity-producing materials. ?? 1998 Elsevier Science Ltd.

  4. 2-Pyridinyl-N-(2,4-difluorobenzyl)aminoethyl Group As Thermocontrolled Implement for Protection of Carboxylic Acids.

    PubMed

    Brzezinska, Jolanta; Witkowska, Agnieszka; Bałabańska, Sandra; Chmielewski, Marcin K

    2016-07-01

    A thermolabile protecting group strategy for carboxylic acids is expanded. Thermosensitive esters are readily prepared using a known procedure, and their stability under neutral condition is investigated. Effective thermolytic deprotection initiated only by temperature for different carboxylic acids is demonstrated, and the compatibility of a thermolytic protecting group with acidic and basic protecting groups in an orthogonal protection strategy is also presented. This study showed interesting correlations between the pKa of acids and the deprotection rate of their well-protected moieties.

  5. Observation of neutral sulfuric acid-amine containing clusters in laboratory and ambient measurements

    SciTech Connect

    Kuang C.; Zhao, J.; Smith, J. N.; Eisele, F. L.; Chen, M.; McMurry, P. H.

    2011-11-02

    Recent ab initio calculations showed that amines can enhance atmospheric sulfuric acid-water nucleation more effectively than ammonia, and this prediction has been substantiated in laboratory measurements. Laboratory studies have also shown that amines can effectively displace ammonia in several types of ammonium clusters. However, the roles of amines in cluster formation and growth at a microscopic molecular scale (from molecular sizes up to 2 nm) have not yet been well understood. Processes that must be understood include the incorporation of amines into sulfuric acid clusters and the formation of organic salts in freshly nucleated particles, which contributes significantly to particle growth rates. We report the first laboratory and ambient measurements of neutral sulfuric acid-amine clusters using the Cluster CIMS, a recently-developed mass spectrometer designed for measuring neutral clusters formed in the atmosphere during nucleation. An experimental technique, which we refer to as Semi-Ambient Signal Amplification (SASA), was employed. Sulfuric acid was added to ambient air, and the concentrations and composition of clusters in this mixture were analyzed by the Cluster CIMS. This experimental approach led to significantly higher cluster concentrations than are normally found in ambient air, thereby increasing signal-to-noise levels and allowing us to study reactions between gas phase species in ambient air and sulfuric acid containing clusters. Mass peaks corresponding to clusters containing four H{sub 2}SO{sub 4} molecules and one amine molecule were clearly observed, with the most abundant sulfuric acid-amine clusters being those containing a C2- or C4-amine (i.e. amines with masses of 45 and 73 amu). Evidence for C3- and C5-amines (i.e. amines with masses of 59 and 87 amu) was also found, but their correlation with sulfuric acid tetramer was not as strong as was observed for the C2- and C4-amines. The formation mechanisms for those sulfuric acid

  6. Content and Vacuole/Extravacuole Distribution of Neutral Sugars, Free Amino Acids, and Anthocyanin in Protoplasts 1

    PubMed Central

    Wagner, George J.

    1979-01-01

    Neutral sugar, free amino acid, and anthocyanin levels and vacuole/extravacuole distribution were determined for Hippeastrum and Tulipa petal and Tulipa leaf protoplasts. Glucose and fructose, the predominant neutral monosaccharides observed, were primarily vacuolar in location. Glutamine, the predominant free amino acid found, was primarily extravacuolar. γ-Methyleneglutamate was identified as a major constituent of Tulipa protoplasts. Qualitative characterization of Hippeastrum petal and vacuole organic acids indicated the presence of oxalic, malic, citric, and isocitric acids. Data are presented which indicate that vacuoles obtained by gentle osmotic shock of protoplasts in dibasic phosphate have good purity and retain their contents. Images PMID:16660921

  7. Acute effects of aspartame on large neutral amino acids and monoamines in rat brain.

    PubMed

    Fernstrom, J D; Fernstrom, M H; Gillis, M A

    1983-04-01

    The dipeptide aspartame (APM; aspartylphenylalanine methylester), an artificial sweetener, was studied in vivo for its ability to influence brain levels of the large neutral amino acids and the rates of hydroxylation of the aromatic amino acids. The administration by gavage of APM (200 mg/kg) caused large increments in blood and brain levels of phenylalanine and tyrosine by 60 minutes. Brain tryptophan level was occasionally reduced significantly, but the brain levels of the branched-chain amino acids were always unaffected. Smaller doses (50, 100 mg/kg) also raised blood and brain tyrosine and phenylalanine, but did not reduce brain tryptophan levels. At the highest dose (200 mg/kg), APM gavage caused an insignificant increase in dopa accumulation (after NSD-1015), and a modest reduction in 5-hydroxytryptophan accumulation. No changes in the brain levels of serotonin, 5-hydroxyindoleacetic acid, dopamine, dihydroxyphenylacetic acid, homovanillic acid, or norepinephrine were produced by APM administration (200 mg/kg). These results thus indicate that APM, even when administered in amounts that cause large increments in brain tyrosine and phenylalanine, produce minimal effects on the rates of formation of monoamine transmitters.

  8. Crystallogenesis of bacteriophage P22 tail accessory factor gp26 at acidic and neutral pH

    SciTech Connect

    Cingolani, Gino Andrews, Dewan; Casjens, Sherwood

    2006-05-01

    The crystallogenesis of bacteriophage P22 tail-fiber gp26 is described. To study possible pH-induced conformational changes in gp26 structure, native trimeric gp26 has been crystallized at acidic pH (4.6) and a chimera of gp26 fused to maltose-binding protein (MBP-gp26) has been crystallized at neutral and alkaline pH (7-10). Gp26 is one of three phage P22-encoded tail accessory factors essential for stabilization of viral DNA within the mature capsid. In solution, gp26 exists as an extended triple-stranded coiled-coil protein which shares profound structural similarities with class I viral membrane-fusion protein. In the cryo-EM reconstruction of P22 tail extracted from mature virions, gp26 forms an ∼220 Å extended needle structure emanating from the neck of the tail, which is likely to be brought into contact with the cell’s outer membrane when the viral DNA-injection process is initiated. To shed light on the potential role of gp26 in cell-wall penetration and DNA injection, gp26 has been crystallized at acidic, neutral and alkaline pH. Crystals of native gp26 grown at pH 4.6 diffract X-rays to 2.0 Å resolution and belong to space group P2{sub 1}, with a dimer of trimeric gp26 molecules in the asymmetric unit. To study potential pH-induced conformational changes in the gp26 structure, a chimera of gp26 fused to maltose-binding protein (MBP-gp26) was generated. Hexagonal crystals of MBP-gp26 were obtained at neutral and alkaline pH using the high-throughput crystallization robot at the Hauptman–Woodward Medical Research Institute, Buffalo, NY, USA. These crystals diffract X-rays to beyond 2.0 Å resolution. Structural analysis of gp26 crystallized at acidic, neutral and alkaline pH is in progress.

  9. Neutral Hydrogen Clouds Near Early-Type Dwarf Galaxies of the Local Group

    NASA Astrophysics Data System (ADS)

    Bouchard, Antoine; Carignan, Claude; Staveley-Smith, Lister

    2006-06-01

    Parkes neutral hydrogen 21 cm line (H I) observations of the surroundings of nine early-type Local Group dwarfs are presented. We detected numerous H I clouds in the general direction of those dwarfs, and these clouds are often offset from the optical center of the galaxies. Although all the observed dwarfs, except Antlia, occupy phase-space regions where the high-velocity cloud (HVC) density is well above average, the measured offsets are smaller than one would expect from a fully random cloud distribution. Possible association is detected for 11 of the 16 investigated clouds, while for two galaxies, Sextans and Leo I, no H I was detected. The galaxies in which H I clouds were found not to coincide with the optical yet have a significant probability of being associated are the Sculptor dwarf, Tucana, LGS 3, Cetus, and Fornax. If the clouds are indeed associated, these galaxies have H I masses of MHI=2×105, 2×106, 7×105, 7×105, and 1×105 Msolar, respectively. However, neither ram pressure nor tidal stripping can easily explain the offsets. In some cases, large offsets are found where ram pressure should be the least effective.

  10. The evolution of a mining lake - From acidity to natural neutralization.

    PubMed

    Sienkiewicz, Elwira; Gąsiorowski, Michał

    2016-07-01

    Along the border of Poland and Germany (central Europe), many of the post-mining lakes have formed "an anthropogenic lake district". This study presents the evolution of a mining lake ecosystem (TR-33) based on subfossil phyto- and zooplankton, isotopic data (δ(13)C, δ(15)N), elemental analyses of organic carbon and nitrogen (C/N ratio and TOC) and sedimentological analyses. Recently, lake TR-33 became completely neutralized from acidification and an increase in eutrophication began a few years ago. However, the lake has never been neutralized by humans; only natural processes have influenced the present water quality. From the beginning of the existence of the lake (1920s) to the present, we can distinguish four stages of lake development: 1) very shallow reservoir without typical lake sediments but with a sand layer containing fine lignite particles and very poor diatom and cladoceran communities; 2) very acidic, deeper water body with increasing frequencies of phyto- and zooplankton; 3) transitional period (rebuilding communities of diatoms and Cladocera), meaning a deep lake with benthic and planktonic fauna and flora with wide ecological tolerances; and 4) a shift to circumneutral conditions with an essential increase in planktonic taxa that prefer more fertile waters (eutrophication). In the case of lake TR-33, this process of natural neutralization lasted approximately 23years.

  11. Alteration of the phospho- or neutral lipid content and fatty acid composition in Listeria monocytogenes due to acid adaptation mechanisms for hydrochloric, acetic and lactic acids at pH 5.5 or benzoic acid at neutral pH.

    PubMed

    Mastronicolis, Sofia K; Berberi, Anita; Diakogiannis, Ioannis; Petrova, Evanthia; Kiaki, Irene; Baltzi, Triantafillia; Xenikakis, Polydoros

    2010-10-01

    This study provides a first approach to observe the effects on Listeria monocytogenes of cellular exposure to acid stress at low or neutral pH, notably how phospho- or neutral lipids are involved in this mechanism, besides the fatty acid profile alteration. A thorough investigation of the composition of polar and neutral lipids from L. monocytogenes grown at pH 5.5 in presence of hydrochloric, acetic and lactic acids, or at neutral pH 7.3 in presence of benzoic acid, is described relative to cells grown in acid-free medium. The results showed that only low pH values enhance the antimicrobial activity of an acid. We suggest that, irrespective of pH, the acid adaptation response will lead to a similar alteration in fatty acid composition [decreasing the ratio of branched chain/saturated straight fatty acids of total lipids], mainly originating from the neutral lipid class of adapted cultures. Acid adaptation in L. monocytogenes was correlated with a decrease in total lipid phosphorus and, with the exception of cells adapted to benzoic acid, this change in the amount of phosphorus reflected a higher content of the neutral lipid class. Upon acetic or benzoic acid stress the lipid phosphorus proportion was analysed in the main phospholipids present: cardiolipin, phosphatidylglycerol, phosphoaminolipid and phosphatidylinositol. Interestingly only benzoic acid had a dramatic effect on the relative quantities of these four phospholipids.

  12. Revisiting the Kinetics and Mechanism of the Tetrathionate-Hypochlorous Acid Reaction in Nearly Neutral Medium

    NASA Astrophysics Data System (ADS)

    Varga, Dénes; Horváth, Attila K.

    2009-11-01

    The tetrathionate-hypochlorous acid reaction has been investigated in nearly neutral medium at I = 0.5 M ionic strength and T = 25.0 ± 0.1 °C in dihydrogen-phosphate-hydrogen-phosphate buffer by UV-vis spectrophotometry. In excess of hypochlorous acid, the stoichiometry was found to be S4O62- + 7HOCl + 3H2O → 4SO42- + 7Cl- + 13H+, but in excess of tetrathionate colloidal sulfur precipitates. On the basis of the simultaneous evaluation of the kinetic curves, a nine-step kinetic model with four fitted and five fixed rate coefficients is proposed. Analogous oxidation reactions of tetrathionate are also compared and discussed.

  13. Preliminary observations of lung injury produced by instillation of HF in acidic and neutral buffer

    SciTech Connect

    Brainard, J.R.; Kinkead, S.A.; Kober, E.M.; Sebring, R.J.; Stavert, D.M.; Lehnert, B.E.

    1990-01-01

    Perfluoroisobutylene (PFIB) is an extremely toxic organofluoride that can be produced during pyrolysis of tetrafluoroethylene polymers, including Teflon{reg sign}. Inhalation of PFIB at very low concentrations causes acute lung injury, the hallmark of which is pulmonary edema. Several lines of evidence have suggested that hydrolysis of PFIB and resulting production of hydrofluoric acid may be responsible for pulmonary damage. In order to investigate the potential involvement of hydrofluoric acid in producing lung injury and its relationship to the mechanism of fluorocarbon toxicity, we have compared the pulmonary injury produced by PFIB, by dissociated (H{sup +} and F{sup {minus}}), and by undissociated (HF) hydrofluoric acid in the deep lung. By delivering hydrofluoric acid by intratracheal instillation in neutral buffer, we demonstrate that F{sup {minus}} produces no significant pulmonary injury as assessed by increased in lung weight and ultrastructural changes. Similarly, instillation of acid buffer alone demonstrated that H{sup +} did not produce detectable lung injury. Instillation of HF produced changes in lung weight and ultrastructure similar to those observed in PFIB-treated rats. However, the ultrastructural studies show that in contrast to inhalation of PFIB, which produces both endothelial and epithelial cell damage, instillation of HF appears to exert its injurious effects only upon epithelial cells. 9 refs., 1 fig.

  14. Chemical composition of rainwater and the acid neutralizing effect at Beijing and Chizhou city, China

    NASA Astrophysics Data System (ADS)

    Xu, Zhifang; Wu, Yao; Liu, Wen-Jing; Liang, Chong-Shan; Ji, Jianpeng; Zhao, Tong; Zhang, Xuan

    2015-10-01

    The chemical compositions were measured in rainwater samples collected during 2011-2012 from two representative cities, Beijing in north China and Chizhou city in south China. The rainwater was highly acidic with a volume-weighted mean (VWM) pH of 4.56, ranging from 3.77 to 5.67, and about 94% of the samples had pH below 5.0 in Chizhou. The pH values of rainwater in Beijing ranged from 3.78 to 6.62, with a VWM value of 4.85. The predominant ions in the precipitation were SO42 -, Ca2 + and NH4+ at both sites. The VWM concentrations of ions in rainwater were higher in Beijing, and the SO42 - concentration of rainwater in Beijing was about twice that in Chizhou. However, due to the weaker neutralization of acidity, the rainwater from Chizhou had relatively low pH values. According to the results of linear regression analysis, the percentage of the potential acidity counteracted by Ca2 + and NH4+ was higher in rainwater in Beijing (90.7%) than that in Chizhou (70.8%). Using Na as an indicator of marine origin, and Al for the terrestrial inputs, the proportions of sea salt and terrestrial elements were estimated from elemental ratios. More than 98% of SO42 - and Ca2 + in rainwater samples are non-sea-salt origin at both sites. Coal combustion may be the main source of SO42 -, and local and remote soil dust may be an important source of Ca2 + in Beijing rainwater. The high concentrations of alkaline ions (Ca2 + and NH4+) have played an important role to neutralize the acidity of rainwater in Beijing.

  15. On-line assessment of mixing in an acid waste neutralization system

    SciTech Connect

    Brown, N.E.; Resnick, P.J.; Bickel, T.C.

    1990-01-01

    The acid was neutralization system at Sandia National Laboratories treats process waste water from the Microelectronics Development Laboratory (MDL). The system consists of two 9,500 liter stirred tank reactors in series with an approximate feed rate of 3.17 L/s. The tanks are equipped with 320 W mixers with single impellers. pH sensors in each tank control acid and caustic delivery pumps. Sporadic excursions outside the required range of pH 5 to 11 were observed. Tracer experiments using methylene blue dye were performed during normal MDL operations to assess mixing in the individual reactors and the system. Tracers were injected as instantaneous pulses into the reactors and time dependent concentrations were measured in the effluent. Dimensionless exit age distributions were obtained which were similar to distributions for continuous stirred tank reactors (CSTR). These age distributions were extended to predict fluoride concentrations. The data indicate a separate fluoride collection system will be required to meet local environmental safety and health (ES H) regulations. Results from these tracer experiments have lead to cost effective design improvements in our neutralization system. 4 refs., 8 figs., 1 tab.

  16. Neutral loss of isocyanic acid in peptide CID spectra: a novel diagnostic marker for mass spectrometric identification of protein citrullination.

    PubMed

    Hao, Gang; Wang, Danchen; Gu, Jane; Shen, Qiuying; Gross, Steven S; Wang, Yanming

    2009-04-01

    Protein citrullination is emerging as an important signaling mechanism that modulates a variety of biological processes. This protein modification constitutes only a 1 Da mass shift, and can be readily confused with other common protein modifications that yield an identical mass shift. In an attempt to develop a robust methodology for detection of protein citrullination sites, we analyzed synthetic citrulline-containing peptides by electrospray ionization tandem mass spectrometry. Collision-induced dissociation (CID) spectra revealed abundant neutral loss of 43 Da from citrullinated peptide precursor ions, which was reconciled by elimination of the HNCO moiety (isocyanic acid) from the citrulline ureido group. The elimination occurs readily in multiple charge states of precursor ions and also in b and y ions. HNCO loss in CID spectra provides a novel diagnostic marker for citrullination, and its utility was demonstrated by the discovery of Arg197 as the specific site of citrullination on nucleophosmin upon peptidylarginine deiminase 4 treatment. PMID:19200748

  17. G glycoprotein amino acid residues required for human monoclonal antibody RAB1 neutralization are conserved in rabies virus street isolates.

    PubMed

    Wang, Yang; Rowley, Kirk J; Booth, Brian J; Sloan, Susan E; Ambrosino, Donna M; Babcock, Gregory J

    2011-08-01

    Replacement of polyclonal anti-rabies immunoglobulin (RIG) used in rabies post-exposure prophylaxis (PEP) with a monoclonal antibody will eliminate cost and availability constraints that currently exist using RIG in the developing world. The human monoclonal antibody RAB1 has been shown to neutralize all rabies street isolates tested; however for the laboratory-adapted fixed strain, CVS-11, mutation in the G glycoprotein of amino acid 336 from asparagine (N) to aspartic acid (D) resulted in resistance to neutralization. Interestingly, this same mutation in the G glycoprotein of a second laboratory-adapted fixed strain (ERA) did not confer resistance to RAB1 neutralization. Using cell surface staining and lentivirus pseudotyped with rabies virus G glycoprotein (RABVpp), we identified an amino acid alteration in CVS-11 (K346), not present in ERA (R346), which was required in combination with D336 to confer resistance to RAB1. A complete analysis of G glycoprotein sequences from GenBank demonstrated that no identified rabies isolates contain the necessary combination of G glycoprotein mutations for resistance to RAB1 neutralization, consistent with the broad neutralization of RAB1 observed in direct viral neutralization experiments with street isolates. All combinations of amino acids 336 and 346 reported in the sequence database were engineered into the ERA G glycoprotein and RAB1 was able to neutralize RABVpp bearing ERA G glycoprotein containing all known combinations at these critical residues. These data demonstrate that RAB1 has the capacity to neutralize all identified rabies isolates and a minimum of two distinct mutations in the G glycoprotein are required for abrogation of RAB1 neutralization.

  18. Stream chemistry in the eastern United States. 2. Current sources of acidity in acidic and low acid-neutralizing capacity streams

    SciTech Connect

    Herlihy, A.T.; Kaufmann, P.R.; Mitch, M.E. )

    1991-04-01

    The authors examined anion composition in National Stream Survey (NSS) data in order to evaluate the most probably sources of current acidity in acidic and low acid-neutralizing capacity (ANC) streams in the eastern US. Acidic streams that had almost no organic influence (less than 10% of total anions) and sulfate and nitrate concentrations indicative of evaporative concentration of atmospheric deposition were classified as acidic due to acidic deposition. These acidic streams were located in small (<30 km{sup 2}) forested watersheds in the Mid-Atlantic Highlands (an estimated 1,950 km of stream length) and in the Mid-Atlantic Coastal Plain (1,250 km). Acidic streams affected primarily by acidic deposition but also influenced by naturally occurring organic anions accounted for another 1,180 km of acidic stream length, and were located in the New Jersey Pine Barrens, plateau tops in the Mid-Atlantic and Southeast Highlands, and the Florida Panhandle. The total length of streams acidic due to acid mine drainage in the NSS (4,590 km) was about the same as the total length of acidic streams likely affected by acidic deposition (4,380 km). Acidic streams whose acid anion composition was dominated by organics were located in Florida and the Mid-Atlantic Coastal Plain. In Florida, most of the acidic streams were organic dominated, whereas about half of the streams in the Mid-Atlantic Coastal Plain were organic dominated. Organic-dominated acidic streams were not observed in the Mid-Atlantic and Southeast Highlands.

  19. Overproduction and secretion of free fatty acids through disrupted neutral lipid recycle in Saccharomyces cerevisiae.

    PubMed

    Leber, Christopher; Polson, Brian; Fernandez-Moya, Ruben; Da Silva, Nancy A

    2015-03-01

    The production of fuels and chemicals from biorenewable resources is important to alleviate the environmental concerns, costs, and foreign dependency associated with the use of petroleum feedstock. Fatty acids are attractive biomolecules due to the flexibility of their iterative biosynthetic pathway, high energy content, and suitability for conversion into other secondary chemicals. Free fatty acids (FFAs) that can be secreted from the cell are particularly appealing due to their lower harvest costs and straightforward conversion into a broad range of biofuel and biochemical products. Saccharomyces cerevisiae was engineered to overproduce extracellular FFAs by targeting three native intracellular processes. β-oxidation was disrupted by gene knockouts in FAA2, PXA1 and POX1, increasing intracellular fatty acids levels up to 55%. Disruptions in the acyl-CoA synthetase genes FAA1, FAA4 and FAT1 allowed the extracellular detection of free fatty acids up to 490mg/L. Combining these two disrupted pathways, a sextuple mutant (Δfaa1 Δfaa4 Δfat1 Δfaa2 Δpxa1 Δpox1) was able to produce 1.3g/L extracellular free fatty acids. Further diversion of carbon flux into neutral lipid droplet formation was investigated by the overexpression of DGA1 or ARE1 and by the co-overexpression of a compatible lipase, TGL1, TGL3 or TGL5. The sextuple mutant overexpressing the diacylglycerol acyltransferase, DGA1, and the triacylglycerol lipase, TGL3, yielded 2.2g/L extracellular free fatty acids. This novel combination of pathway interventions led to 4.2-fold higher extracellular free fatty acid levels than previously reported for S. cerevisiae.

  20. High-mobility group box 1 protein (HMGB1) neutralization ameliorates experimental autoimmune encephalomyelitis.

    PubMed

    Robinson, Andrew P; Caldis, Matthew W; Harp, Christopher T; Goings, Gwendolyn E; Miller, Stephen D

    2013-06-01

    Multiple sclerosis (MS) is an autoimmune, demyelinating disease and as such, the gold standard of treatment is to selectively suppress the pathogenic autoimmune response without compromising the entire arm of the adaptive immune response. One target of this strategy lying upstream of the pathologic adaptive immune response is the local, innate immune signaling that initiates and drives autoimmunity and sterile injury. High-mobility group box 1 protein (HMGB1) is a ubiquitous nuclear protein that when released from necrotic cells, such as damaged oligodendrocytes in MS lesions, drives pro-inflammatory responses. Here we demonstrate that HMGB1 drives neuroinflammatory responses in experimental autoimmune encephalomyelitis (EAE), a murine model for MS, and that inhibition of HMGB1 signaling ameliorates disease. Specifically i.v. injection of an HMGB1 neutralizing antibody in the C57BL/6 model of chronic EAE or SJL/J model of relapsing-remitting EAE ameliorated clinical disease prophylactically or during ongoing disease, blocked T cell infiltration of the central nervous system, and inhibited systemic CD4(+) T cell responses to myelin epitopes. Additionally, lymphocytes from EAE mice restimulated in vitro in the presence of recombinant HMGB1 exhibited increased proliferation and pro-inflammatory cytokine production, an effect that was blocked by anti-HMGB1 antibody. Similarly recombinant HMGB1 promoted proliferation and pro-inflammatory cytokine production of human peripheral blood mononuclear cells stimulated in vitro, and anti-HMGB1 antibody blocked this effect. These findings indicate that HMGB1 contributes to neuroinflammatory responses that drive EAE pathogenesis and that HMGB1 blockade may be a novel means to selectively disrupt the pro-inflammatory loop that drives MS autoimmunity.

  1. Theoretical models of mercury dissolution from dental amalgams in neutral and acidic flows

    NASA Astrophysics Data System (ADS)

    Keanini, Russell G.; Ferracane, Jack L.; Okabe, Toru

    2001-06-01

    This article reports an experimental and theoretical investigation of mercury dissolution from dental amalgams immersed in neutral (noncorrosive) and acidic (corrosive) flows. Atomic absorption spectrophotometric measurements of Hg loss indicate that in neutral flow, surface oxide films formed in air prior to immersion persist and effectively suppress significant mercury release. In acidic (pH 1) flows, by contrast, oxide films are unstable and dissolve; depending on the amalgam’s material composition, particularly its copper content, two distinct mercury release mechanisms are initiated. In low copper amalgam, high initial mercury release rates are observed and appear to reflect preferential mercury dissolution from unstable Sn8Hg ( γ 2) grains within the amalgam matrix. In high copper amalgam, mercury release rates are initially low, but increase with time. Microscopic examination suggests that this feature reflects corrosion of copper from grains of Cu6Sn5 ( η') and consequent exposure of Ag2Hg3 ( γ 1) grains; the latter serve as internal mercury release sites and become more numerous as corrosion proceeds. Three theoretical models are proposed in order to explain observed dissolution characteristics. Model I, applicable to high and low copper amalgams in neutral flow, assumes that mercury dissolution is mediated by solid diffusion within the amalgam, and that a thin oxide film persists on the amalgam’s surface and lumps diffusive in-film transport into an effective convective boundary condition. Model II, applicable to low copper amalgam in acidic flow, assumes that the amalgam’s external oxide film dissolves on a short time scale relative to the experimental observation period; it neglects corrosive suppression of mercury transport. Model III, applicable to high copper amalgam in acidic flow, assumes that internal mercury release sites are created by corrosion of copper in η' grains and that corrosion proceeds via an oxidation-reduction reaction

  2. Reactivity of alanylalanine diastereoisomers in neutral and acid aqueous solutions: a versatile stereoselectivity.

    PubMed

    Plasson, Raphaël; Tsuji, Maika; Kamata, Masazumi; Asakura, Kouichi

    2011-10-01

    A good comprehension of the reactivity of peptides in aqueous solution is fundamental in prebiotic chemistry, namely for understanding their stability and behavior in primitive oceans. Relying on the stereoselectivity of the involved reactions, there is a huge interest in amino acid derivatives for explaining the spontaneous emergence of homochirality on primitive Earth. The corresponding kinetic and thermodynamic parameters are however still poorly known in the literature. We studied the reactivity of alanylalanine in acidic to neutral conditions as a model system. The hydrolysis into amino acids, the epimerization of the N-terminal residue, and the cyclization into diketopiperazine could be successfully identified and studied. This kinetic investigation highlighted interesting behaviors. Complex mechanisms were observed in very acidic conditions. The relative kinetic stability of the diastereoisomers of the dipeptide is highly dependent of the pH, with the possibility to dynamically destabilize the thermodynamically more stable diastereoisomers. The existence of the cyclization of dipeptides adds complexity to the system. On one hand it brings additional stereoselectivities; on the other hand fast racemization of heterochiral dipeptides is obtained.

  3. Reactivity of Alanylalanine Diastereoisomers in Neutral and Acid Aqueous Solutions: a Versatile Stereoselectivity

    NASA Astrophysics Data System (ADS)

    Plasson, Raphaël; Tsuji, Maika; Kamata, Masazumi; Asakura, Kouichi

    2011-10-01

    A good comprehension of the reactivity of peptides in aqueous solution is fundamental in prebiotic chemistry, namely for understanding their stability and behavior in primitive oceans. Relying on the stereoselectivity of the involved reactions, there is a huge interest in amino acid derivatives for explaining the spontaneous emergence of homochirality on primitive Earth. The corresponding kinetic and thermodynamic parameters are however still poorly known in the literature. We studied the reactivity of alanylalanine in acidic to neutral conditions as a model system. The hydrolysis into amino acids, the epimerization of the N-terminal residue, and the cyclization into diketopiperazine could be successfully identified and studied. This kinetic investigation highlighted interesting behaviors. Complex mechanisms were observed in very acidic conditions. The relative kinetic stability of the diastereoisomers of the dipeptide is highly dependent of the pH, with the possibility to dynamically destabilize the thermodynamically more stable diastereoisomers. The existence of the cyclization of dipeptides adds complexity to the system. On one hand it brings additional stereoselectivities; on the other hand fast racemization of heterochiral dipeptides is obtained.

  4. Magnetic properties, acid neutralization capacity, and net acid production of rocks in the Animas River Watershed Silverton, Colorado

    USGS Publications Warehouse

    McCafferty, Anne E.; Yager, Douglas B.; Horton, Radley M.; Diehl, Sharon F.

    2006-01-01

    Federal land managers along with local stakeholders in the Upper Animas River watershed near Silverton, Colorado are actively designing and implementing mine waste remediation projects to mitigate the effects of acid mine drainage from several abandoned hard rock metal mines and mills. Local source rocks with high acid neutralization capacity (ANC) within the watershed are of interest to land managers for use in these remediation projects. A suite of representative samples was collected from propylitic to weakly sericitic-altered volcanic and plutonic rocks exposed in outcrops throughout the watershed. Acid-base accounting laboratory methods coupled with mineralogic and geochemical characterization provide insight into lithologies that have a range of ANC and net acid production (NAP). Petrophysical lab determinations of magnetic susceptibility converted to estimates for percent magnetite show correlation with the environmental properties of ANC and NAP for many of the lithologies. A goal of our study is to interpret watershed-scale airborne magnetic data for regional mapping of rocks that have varying degrees of ANC and NAP. Results of our preliminary work are presented here.

  5. New laboratory atomic data for neutral, singly and doubly ionised iron group elements for astrophysics applications

    NASA Astrophysics Data System (ADS)

    Pickering, Juliet C.; Nave, Gillian; Liggins, Florence; Clear, Christian; Ruffoni, Matthew; Sansonetti, Craig

    2015-08-01

    We present new laboratory spectroscopic measurements to produce atomic data for astrophysically important species: neutral, singly and doubly ionised iron group elements.We use high resolution Fourier Transform Spectrometry (FTS) (resolving power up to 2x106 at 200nm) to measure atomic spectra, giving accurate line wavelengths (to a few parts in 108), atomic energy levels, hyperfine structure splitting and log gfs (accurate to a few %) (Ruffoni et al this meeting). These data are vital for astrophysical spectral analyses for: line identification, spectrum synthesis, elemental abundance determinations [eg 1], and disentangling of blends etc. It is not possible to theoretically calculate these atomic data to the accuracy needed for modern astrophysics applications.At Imperial College we have a unique visible-VUV FT spectrometer with short wavelength cut-off of 135nm. We supplement FTS data at shorter wavelengths with spectra recorded on the NIST 10.7m grating spectrograph (with phosphor image or photographic plates) and at longer wavelengths in the IR we use the NIST IR FT spectrometer.An elemental spectrum may contain thousands of spectral lines from the IR to VUV. We use these wavelengths to correct known atomic energy levels, and search for new atomic levels. The result is a classified linelist and accurate atomic energy levels.We present progress on iron group element atomic energy levels and wavelengths for V I and V II [2,3], Co III [4], Cr I, Mn I and Mn II, and Ni II.This work is supported by STFC(UK), The Leverhulme Trust, The Royal Society and NASA.References[1] Bergemann M, Pickering JC & Gehren T,“NLTE analysis of Co I/Co II lines in spectra of cool stars with new laboratory hyperfine splitting constants",MNRAS 401(2) 1334 (2010)[2] Thorne AP, Pickering JC & Semeniuk J,“The spectrum and term analysis of V II”, ApJS 207,13 (2013)[3] Thorne AP, Pickering JC & Semeniuk J,“The spectrum and term analysis of V I",ApJS 192,11 (2011)[4] Smillie DG

  6. Neutral and acidic products derived from hydroxyl radical-induced oxidation of arabinotriose assessed by electrospray ionisation mass spectrometry.

    PubMed

    Moreira, Ana S P; da Costa, Elisabete V; Evtuguin, Dmitry V; Coimbra, Manuel A; Nunes, Fernando M; Domingues, M Rosário M

    2014-04-01

    The oxidation of α-(1 → 5)-L-arabinotriose (Ara3), an oligosaccharide structurally related to side chains of coffee arabinogalactans, was studied in reaction with hydroxyl radicals generated under conditions of Fenton reaction (Fe(2+)/H2O2). The acidic and neutral oxidation products were separated by ligand exchange/size-exclusion chromatography, subsequently identified by electrospray ionisation mass spectrometry (ESI-MS) and structurally characterised by tandem MS (ESI-MS/MS). In acidic fraction were identified several oxidation products containing an acidic residue at the corresponding reducing end of Ara3, namely arabinonic acid, and erythronic, glyceric and glycolic acids formed by oxidative scission of the furanose ring. In neutral fractions were identified derivatives containing keto, hydroxy and hydroperoxy moieties, as well as derivatives resulting from the ring scission at the reducing end of Ara3. In both acidic and neutral fractions, beyond the trisaccharide derivatives, the corresponding di- and monosaccharide derivatives were identified indicating the occurrence of oxidative depolymerisation. The structural characterisation of these oxidation products by ESI-MS/MS allowed the differentiation of isobaric and isomeric species of acidic and neutral character. The species identified in this study may help in detection of roasting products associated with the free radical-mediated oxidation of coffee arabinogalactans.

  7. Prevalence of Neutralizing Antibodies to Japanese Encephalitis Virus among High-Risk Age Groups in South Korea, 2010.

    PubMed

    Lee, Eun Ju; Cha, Go-Woon; Ju, Young Ran; Han, Myung Guk; Lee, Won-Ja; Jeong, Young Eui

    2016-01-01

    After an extensive vaccination policy, Japanese encephalitis (JE) was nearly eliminated since the mid-1980s in South Korea. Vaccination in children shifted the affected age of JE patients from children to adults. However, an abrupt increase in JE cases occurred in 2010, and this trend has continued. The present study aimed to investigate the prevalence of neutralizing antibodies to the JE virus (JEV) among high-risk age groups (≥40 years) in South Korea. A plaque reduction neutralization test was conducted to evaluate the prevalence of neutralizing antibodies to JEV in 945 subjects within four age groups (30-39, 40-49, 50-59, and 60-69 years) in 10 provinces. Of the 945 enrolled subjects, 927 (98.1%) exhibited antibodies against JEV. No significant differences were found in the prevalence of neutralizing antibodies according to sex, age, or occupation. However, there were significant differences in the plaque reduction rate according to age and occupation; oldest age group had a higher reduction rate, and subjects who were employed in agriculture or forestry also had a higher value than the other occupations. We also found that three provinces (Gangwon, Jeonnam, and Gyeongnam) had a relatively lower plaque reduction rate than the other locations. In addition, enzyme-linked immunosorbent assays were conducted to determine recent viral infections and 12 (1.3%) subjects were found to have been recently infected by the virus [corrected]. In conclusion, the present study clearly indicated that the prevalence of neutralizing antibodies has been maintained at very high levels among adult age groups owing to vaccination or natural infections, or both. In the future, serosurveillance should be conducted periodically using more representative samples to better understand the population-level immunity to JE in South Korea.

  8. Neutral Hydrogen in the Local Group and around the Milky Way

    NASA Astrophysics Data System (ADS)

    Wolfe, Spencer A.

    Galaxies in our universe must acquire fresh gas to continue forming new stars. A likely source of this material may be the gas that resides between galaxies. We do not, however, have a clear understanding of the specifics, such as its distribution. The first claimed detection of this "cosmic web" of material directly in emission was published a decade ago using the Westerbork Synthesis Radio Telescope in the Netherlands while surveying neutral hydrogen in the Local Group of galaxies. Later evidence, in the form of stellar surveys and test particle simulations, showed that a tidal origin of the gas was another possibility. More recent survey work of the Local Group, specifically between the galaxies M31 and M33, motivated us to map a section of the Westerbork emission using the Robert C . Byrd Green Bank Telescope (GBT). Our survey covers a 12 square degree area between M31 and M33, in which we reach 21 cm column density sensitivities of 1017.2 cm-2 after 400 hours of observations. These observations provide more than a factor of five better spatial resolution, and better than a factor of three in velocity resolution. Not only do we confirm the emission seen in the Westerbork data, we find that the hydrogen gas is composed of clouds a few kiloparsecs across, with properties suggesting they are a unique population to the Local Group. We conclude that the clouds are likely transient condensations from an intergalactic filament of gas, although a tidal feature cannot currently be ruled out. We also conducted GBT pointings to the northwest of M31 to search for the extended emission seen in the Westerbork data as well. What detections we find appear to be more related to the high velocity cloud population of M31. We are continuing to map other regions around M31 to search for more diffuse emission. We also present southern sky maps of the high velocity and intermediate velocity clouds around our own Milky Way, using 21 cm survey data from the Parkes telescope in

  9. Seasonal variations in acid-neutralizing capacity in 13 northeast United States headwater streams

    NASA Astrophysics Data System (ADS)

    Dewalle, David R.; Davies, Trevor D.

    1997-04-01

    Variations in acid-neutralizing capacity (ANC) in 13 streams in the Adirondack, Catskill, and Northern Appalachian Plateau regions of the northeast United States were related to discharge, time of year, and seasonal variations in cation and anion concentrations using periodic regression analysis, ANC varied significantly with both discharge and time of year in 12 streams. Generation of ANC seasonal variations, being dependent upon the precise timing and magnitude of seasonal variations in cation and anion concentrations, was unique to each stream. Greatest seasonal ANC variations occurred in streams where seasonal variations in major anion and cation concentrations were completely out of phase. Maximum errors that could occur because of extrapolation of ANC data from one time of year to another were equal to or greater than maximum errors due to extrapolation of ANC from one discharge to another.

  10. RESULTS OF THE 2H EVAPORATOR ACID CLEANING AND IN-POT NEUTRALIZATION

    SciTech Connect

    Wilmarth, B; Phillip Norris, P; Terry Allen, T

    2007-05-29

    The estimated 200 gallons of sodium aluminosilicate scale (NAS) present in the 242-16H Evaporator pot prior to chemical cleaning was subjected to four batches of 1.5 M (9 wt%) nitric acid. Each batch was neutralized with 19 M (50 wt %) sodium hydroxide (caustic) before transfer to Tank 38. The chemical cleaning process began on November 20, 2006, and was terminated on December 10, 2006. An inspection of the pot's interior was performed and based on data gathered during that inspection; the current volume of scale in the pot is conservatively estimated to be 36.3 gallons, which is well below the 200 gallon limit specified in the Technical Safety Requirements. In addition, the performance during all aspects of cleaning agreed well with the flowsheet developed at the bench and pilot scale. There were some lessons learned during the cleaning outage and are detailed in appendices of this report.

  11. Transuranic removal from neutralized current acid waste with pneumatic hydropulse filtration

    SciTech Connect

    Simmons, F.M.

    1988-06-01

    Neutralized current acid waste (NCAW) is generated by the solvent extraction portion of the PUREX process. It contains <20% solids by volume, and is currently stored in underground tanks at Hanford. These solids contain the transuranic (TRU) elements and most of the fission products and will be converted to glass for permanent disposal. Because of the high cost of vitrification and repository disposal, there is a large economic incentive to minimize volume. Separation of the solids from the supernatant liquor provides a more concentrated high-level waste stream for vitrification, thereby reducing the cost. Removal of the solids will also provide an approximately TRU-free supernatant liquor which can be disposed of as grout in near-surface facilities. Allowing the solids to settle, then decanting (settle/decant) and filtering the supernatant are the principal unit operations used for TRU removal. 3 figs.

  12. Group Members' Self-Monitoring as a Possible Neutralizer of Leadership.

    ERIC Educational Resources Information Center

    Anderson, Lynn R.; Tolson, Jerry

    1989-01-01

    Responses from 195 staff nurses indicated that impact of leader's behavior was neutralized among low self-monitoring nurses, but intensified among high self-monitors. Correlations between staff nurses' job performance and their ratings of head nurses' leadership behaviors were not significant for low self-monitoring nurses but were significant for…

  13. Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

    PubMed

    Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

    2014-12-01

    We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

  14. Insight into acid-base nucleation experiments by comparison of the chemical composition of positive, negative, and neutral clusters.

    PubMed

    Bianchi, Federico; Praplan, Arnaud P; Sarnela, Nina; Dommen, Josef; Kürten, Andreas; Ortega, Ismael K; Schobesberger, Siegfried; Junninen, Heikki; Simon, Mario; Tröstl, Jasmin; Jokinen, Tuija; Sipilä, Mikko; Adamov, Alexey; Amorim, Antonio; Almeida, Joao; Breitenlechner, Martin; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Kangasluoma, Juha; Keskinen, Helmi; Kim, Jaeseok; Kirkby, Jasper; Laaksonen, Ari; Lawler, Michael J; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Tomé, António; Virtanen, Annele; Viisanen, Yrjö; Williamson, Christina; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Curtius, Joachim; Kulmala, Markku; Worsnop, Douglas R; Donahue, Neil M; Baltensperger, Urs

    2014-12-01

    We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision. PMID:25406110

  15. Alkaline, acid, and neutral phosphatase activities are induced during development in Myxococcus xanthus.

    PubMed Central

    Weinberg, R A; Zusman, D R

    1990-01-01

    One of the signals that has been reported to be important in stimulating fruiting body formation of Myxococcus xanthus is starvation for phosphate. We therefore chose to study phosphatase activity during M. xanthus development. Many phosphatases can cleave the substrate p-nitrophenol phosphate. Using this substrate in buffers at various pHs, we obtained a profile of phosphatase activities during development and germination of M. xanthus. These experiments indicated that there are five patterns of phosphatase activity in M. xanthus: two vegetative and three developmental. The two uniquely vegetative activities have pH optima at 7.2 and 8.5. Both require magnesium and both are inhibited by the reducing agent dithiothreitol. The developmental (spores) patterns of activity have pH optima of 5.2, 7.2, and 8.5. All three activities are Mg independent. Only the alkaline phosphatase activity is inhibited by dithiothreitol. The acid phosphatase activity is induced very early in development, within the first 2 to 4 h. Both the neutral and alkaline phosphatase Mg-independent activities are induced much later, about the time that myxospores become evident (24 to 30 h). The three activities are greatly diminished upon germination; however, the kinetics of loss differ for all three. The acid phosphatase activity declines very rapidly, the neutral activity begins to decline only after spores begin to convert to rods, and the alkaline phosphatase activity remains high until the time the cells begin to divide. All three developmental activities were measured in the developmental signalling mutants carrying asg, csg, and dsg. The pattern of expression obtained in the mutants was consistent with that of other developmentally regulated genes which exhibit similar patterns of expression during development. The ease with which phosphatases can be assayed should make the activities described in this report useful biochemical markers of stages of both fruiting body formation and

  16. The glutamate and neutral amino acid transporter family: physiological and pharmacological implications.

    PubMed

    Kanai, Yoshikatsu; Hediger, Matthias A

    2003-10-31

    The solute carrier family 1 (SLC1) is composed of five high affinity glutamate transporters, which exhibit the properties of the previously described system XAG-, as well as two Na+-dependent neutral amino acid transporters with characteristics of the so-called "ASC" (alanine, serine and cysteine). The SLC1 family members are structurally similar, with almost identical hydropathy profiles and predicted membrane topologies. The transporters have eight transmembrane domains and a structure reminiscent of a pore loop between the seventh and eighth domains [Neuron 21 (1998) 623]. However, each of these transporters exhibits distinct functional properties. Glutamate transporters mediate transport of L-Glu, L-Asp and D-Asp, accompanied by the cotransport of 3 Na+ and one 1 H+, and the countertransport of 1 K+, whereas ASC transporters mediate Na+-dependent exchange of small neutral amino acids such as Ala, Ser, Cys and Thr. Given the high concentrating capacity provided by the unique ion coupling pattern of glutamate transporters, they play crucial roles in protecting neurons against glutamate excitotoxicity in the central nervous system (CNS). The regulation and manipulation of their function is a critical issue in the pathogenesis and treatment of CNS disorders involving glutamate excitotoxicity. Loss of function of the glial glutamate transporter GLT1 (SLC1A2) has been implicated in the pathogenesis of amyotrophic lateral sclerosis (ALS), resulting in damage of adjacent motor neurons. The importance of glial glutamate transporters in protecting neurons from extracellular glutamate was further demonstrated in studies of the slc1A2 glutamate transporter knockout mouse. The findings suggest that therapeutic upregulation of GLT1 may be beneficial in a variety of pathological conditions. Selective inhibition of the neuronal glutamate transporter EAAC1 (SLC1A1) but not the glial glutamate transporters may be of therapeutic interest, allowing blockage of glutamate exit from

  17. Factors affecting acid neutralizing capacity in the Adirondack region of New York: a solute mass balance approach.

    PubMed

    Ito, Mari; Mitchell, Myron J; Driscoll, Charles T; Roy, Karen M

    2005-06-01

    High rates of acidic deposition in the Adirondack region of New York have accelerated acidification of soils and surface waters. Annual input-output budgets for major solutes and acid-neutralizing capacity (ANC) were estimated for 43 drainage lake-watersheds in the Adirondacks from 1998 to 2000. Sulfate was the predominant anion on an equivalent basis in both precipitation and drainage export. Calcium ion had the largest cation drainage export, followed by Mg2+. While these watersheds showed net nitrogen (N) retention, the drainage losses of SO4(2-), Cl-, base cations, and ANC exceeded their respective inputs from precipitation. Land cover (forest type and wetlands) affected the export of SO4(2-), N solutes, and dissolved organic carbon (DOC). The relationships of solute export with elevation (negative for base cations and Cl-, positive for NO3- and H+) suggest the importance of the concomitant changes of biotic and abiotic watershed characteristics associated with elevational gradients. The surface water ANC increased with the sum of base cations and was greatest in the lakes with watersheds characterized by thick deposits of glacial till. The surface water ANC was also higher in the lake-watersheds with lower DOC export. Some variation in lake ANC was associated with variability in acidic deposition. Using a classification system previously developed for Adirondack lakes on the basis primarily of surficial geology, lake-watersheds were grouped into five classes. The calculated ANC fluxes based on the major sinks and sources of ANC were comparable with measured ANC for the thick-till (I) and the medium-till lake-watersheds with low DOC (II). The calculated ANC was overestimated for the medium-till with high DOC (III) and the thin-till with high DOC (V) lake-watersheds, suggesting the importance of naturally occurring organic acids as an ANC sink, which was not included in the calculations. The lower calculated estimates than the measured ANC for the thin-till lake

  18. COMBINING NEUTRAL AND ACIDIC EXTRACTANTS FOR RECOVERING TRANSURANIC ELEMENTS FROM NUCLEAR FUEL

    SciTech Connect

    Lumetta, Gregg J.; Neiner, Doinita; Sinkov, Sergey I.; Carter, Jennifer C.; Braley, Jenifer C.; Latesky, Stanley; Gelis, Artem V.; Tkac, Peter; Vandegrift, George F.

    2011-10-03

    We have been investigating a solvent extraction system that combines a neutral extractant--octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO)--with an acidic extractant--bis(2-ethylhexyl)phosphoric acid (HDEHP)--to form a single process solvent for separating Am and Cm from the other components of irradiated nuclear fuel. It was originally hypothesized that the extraction chemistry of CMPO would dominate under conditions of high acidity (> 1 M HNO3), resulting in co-extraction of the transuranic and lanthanide elements into the organic phase. Contacting the loaded solvent with a solution of diethylenetriaminepentaacetate (DTPA) buffered with lactic or citric acid at pH {approx}3 to 4 would result in a condition in which the HDEHP chemistry dominates. Although the data somewhat support this hypothesis, it is clear that there are interactions between the two extractants such that they do not act independently in the extraction and stripping regimes. We report here studies directed at determining the nature and extent of interaction between CMPO and HDEHP, the synergistic behavior of CMPO and HDEHP in the extraction of americium and neodymium, and progress towards determining the thermodynamics of this extraction system. Neodymium and americium behave similarly in the combined solvent system, with a significant synergy between CMPO and HDEHP in the extraction of both of these trivalent elements from lactate-buffered DTPA solutions. In contrast, a much weaker synergistic behaviour is observed for europium. Thus, investigations into the fundamental chemistry involved in this system have focused on the neodymium extraction. The extraction of neodymium has been systematically investigated, individually varying the HDEHP concentration, the CMPO concentration, or the aqueous phase composition. Thermodynamic modeling of the neodymium extraction system has been initiated. Interactions between CMPO and HDEHP in the organic phase must be taken into account in

  19. Amino acids from the late Precambrian Thule group, Greenland.

    PubMed

    Akiyama, M; Shimoyama, A; Ponnamperuma, C

    1982-06-01

    Amino acids were recovered at concentration level of 10-9 M/g from the interior of chert and dolomite of the Late Precambrian Thule Group. Examination of the stability of amino acids in chert under dry-heating conditions suggests that these amino acids have been preserved with a predominance of L-enantiomers in the precambrian chert. Enantiomer analysis of amino acids in dolomite showed a thermal effect resulting from a late precambrian igneous intrusion. This evidence indicates that the amino acids isolated from the Thule samples were chemical fossils and not recent contaminants.

  20. General Chemistry Students' Conceptual Understanding and Language Fluency: Acid-Base Neutralization and Conductometry

    ERIC Educational Resources Information Center

    Nyachwaya, James M.

    2016-01-01

    The objective of this study was to examine college general chemistry students' conceptual understanding and language fluency in the context of the topic of acids and bases. 115 students worked in groups of 2-4 to complete an activity on conductometry, where they were given a scenario in which a titration of sodium hydroxide solution and dilute…

  1. Effect of acidity and elevated PCO2 on acid. Neutralization within pulsed limestone bed reactors receiving coal mine drainage

    USGS Publications Warehouse

    Watten, B.J.; Sibrell, P.L.; Schwartz, M.F.

    2004-01-01

    Limestone has potential for reducing reagent costs and sludge volume associated with the treatment of acid mine drainage (AMD), but its use has been restricted by slow dissolution rates and sensitivity to scale forming reactions that retard transport of H+ at the solid-liquid interface. We evaluated a pulsed limestone bed (PLB) remediation process designed to circumvent these problems through use of intermittently fluidized beds of granular limestone and elevated carbon dioxide pressure. PLB limestone dissolution (LD, mg/L), and effluent alkalinity (Alk, mg/L) were correlated with reactor pressure (PCO2, kPa), influent acidity (Acy, mg/L) and reactor bed height (H, cm) using a prototype capable of processing 10 L/min. The PLB process effectively neutralized sulfuric acid acidity over the range of 6-1033 mg/L (as CaCO3) while generating high concentrations of alkalinity (36-1086 mg/L) despite a hydraulic residence time of just 4.2-5.0 min. Alk and LD (mg/L CaCO3) rose with increases in influent acidity and PCO2 (p < 0.001) according to the models: Alk = 58 + 38.4 (PCO2)0.5 + 0.080 (Acy) - 0.0059(PCO2) 0.5 (Acy); LD = 55 + 38.3 (PCO2)0.5 + 1.08 (Acy) - 0.0059 (PCO2)0.5 (Acy). Alkalinity decreased at an increasing rate with reductions in H over the range of 27.3-77.5 cm (p < 0.001). Carbon dioxide requirements (Q(avg)CO2, L/min) increased with PCO2 (p < 0.001) following the model Q(avg)CO2 = 0.858 (PCO2)0.620, resulting in a greater degree of pH buffering (depression) within the reactors, a rise in limestone solubility and an increase in limestone dissolution related to carbonic acid attack. Corresponding elevated concentrations of effluent alkalinity allow for sidestream treatment with blending. Numerical modeling demonstrated that carbon dioxide requirements are reduced as influent acidity rises and when carbon dioxide is recovered from system effluent and recycled. Field trials demonstrated that the PLB process is capable of raising the pH of AMD above that

  2. Amino acid sequence of rabbit kidney neutral endopeptidase 24.11 (enkephalinase) deduced from a complementary DNA.

    PubMed Central

    Devault, A; Lazure, C; Nault, C; Le Moual, H; Seidah, N G; Chrétien, M; Kahn, P; Powell, J; Mallet, J; Beaumont, A

    1987-01-01

    Neutral endopeptidase (EC 3.4.24.11) is a major constituent of kidney brush border membranes. It is also present in the brain where it has been shown to be involved in the inactivation of opioid peptides, methionine- and leucine-enkephalins. For this reason this enzyme is often called 'enkephalinase'. In order to characterize the primary structure of the enzyme, oligonucleotide probes were designed from partial amino acid sequences and used to isolate clones from kidney cDNA libraries. Sequencing of the cDNA inserts revealed the complete primary structure of the enzyme. Neutral endopeptidase consists of 750 amino acids. It contains a short N-terminal cytoplasmic domain (27 amino acids), a single membrane-spanning segment (23 amino acids) and an extracellular domain that comprises most of the protein mass. The comparison of the primary structure of neutral endopeptidase with that of thermolysin, a bacterial Zn-metallopeptidase, indicates that most of the amino acid residues involved in Zn coordination and catalytic activity in thermolysin are found within highly honmologous sequences in neutral endopeptidase. Images Fig. 1. Fig. 3. PMID:2440677

  3. Effect of neutralized solid waste generated in lime neutralization on the ferrous ion bio-oxidation process during acid mine drainage treatment.

    PubMed

    Liu, Fenwu; Zhou, Jun; Zhou, Lixiang; Zhang, Shasha; Liu, Lanlan; Wang, Ming

    2015-12-15

    Bio-oxidation of ferrous ions prior to lime neutralization exhibits great potential for acid mine drainage (AMD) treatment, while slow ferrous ion bio-oxidation or total iron precipitation is a bottleneck in this process. In this study, neutralized solid waste (NSW) harvested in an AMD lime neutralization procedure was added as a crystal seed in AMD for iron oxyhydroxysulfate bio-synthesis. The effect of this waste on ferrous ion oxidation efficiency, total iron precipitation efficiency, and iron oxyhydroxysulfate minerals yield during ferrous ion bio-oxidation by Acidithiobacillus ferrooxidans was investigated. Ferrous ion oxidation efficiency was greatly improved by adding NSW. After 72 h incubation, total iron precipitation efficiency in treatment with 24 g/L of NSW was 1.74-1.03 times higher than in treatment with 0-12 g/L of NSW. Compared with the conventional treatment system without added NSW, the iron oxyhydroxysulfate minerals yield was increased by approximately 21.2-80.9% when 3-24 g/L of NSW were added. Aside from NSW, jarosite and schwertmannite were the main precipitates during ferrous ion bio-oxidation with NSW addition. NSW can thus serve as the crystal seed for iron oxyhydroxysulfate mineral bio-synthesis in AMD, and improve ferrous ion oxidation and total iron precipitation efficiency significantly.

  4. Neutralizing Aspartate 83 Modifies Substrate Translocation of Excitatory Amino Acid Transporter 3 (EAAT3) Glutamate Transporters*

    PubMed Central

    Hotzy, Jasmin; Machtens, Jan-Philipp; Fahlke, Christoph

    2012-01-01

    Excitatory amino acid transporters (EAATs) terminate glutamatergic synaptic transmission by removing glutamate from the synaptic cleft into neuronal and glial cells. EAATs are not only secondary active glutamate transporters but also function as anion channels. Gating of EAAT anion channels is tightly coupled to transitions within the glutamate uptake cycle, resulting in Na+- and glutamate-dependent anion currents. A point mutation neutralizing a conserved aspartic acid within the intracellular loop close to the end of transmembrane domain 2 was recently shown to modify the substrate dependence of EAAT anion currents. To distinguish whether this mutation affects transitions within the uptake cycle or directly modifies the opening/closing of the anion channel, we used voltage clamp fluorometry. Using three different sites for fluorophore attachment, V120C, M205C, and A430C, we observed time-, voltage-, and substrate-dependent alterations of EAAT3 fluorescence intensities. The voltage and substrate dependence of fluorescence intensities can be described by a 15-state model of the transport cycle in which several states are connected to branching anion channel states. D83A-mediated changes of fluorescence intensities, anion currents, and secondary active transport can be explained by exclusive modifications of substrate translocation rates. In contrast, sole modification of anion channel opening and closing is insufficient to account for all experimental data. We conclude that D83A has direct effects on the glutamate transport cycle and that these effects result in changed anion channel function. PMID:22532568

  5. Large neutral amino acids: dietary effects on brain neurochemistry and function.

    PubMed

    Fernstrom, John D

    2013-09-01

    The ingestion of large neutral amino acids (LNAA), notably tryptophan, tyrosine and the branched-chain amino acids (BCAA), modifies tryptophan and tyrosine uptake into brain and their conversion to serotonin and catecholamines, respectively. The particular effect reflects the competitive nature of the transporter for LNAA at the blood-brain barrier. For example, raising blood tryptophan or tyrosine levels raises their uptake into brain, while raising blood BCAA levels lowers tryptophan and tyrosine uptake; serotonin and catecholamine synthesis in brain parallel the tryptophan and tyrosine changes. By changing blood LNAA levels, the ingestion of particular proteins causes surprisingly large variations in brain tryptophan uptake and serotonin synthesis, with minimal effects on tyrosine uptake and catecholamine synthesis. Such variations elicit predictable effects on mood, cognition and hormone secretion (prolactin, cortisol). The ingestion of mixtures of LNAA, particularly BCAA, lowers brain tryptophan uptake and serotonin synthesis. Though argued to improve physical performance by reducing serotonin function, such effects are generally considered modest at best. However, BCAA ingestion also lowers tyrosine uptake, and dopamine synthesis in brain. Increasing dopamine function in brain improves performance, suggesting that BCAA may fail to increase performance because dopamine is reduced. Conceivably, BCAA administered with tyrosine could prevent the decline in dopamine, while still eliciting a drop in serotonin. Such an LNAA mixture might thus prove an effective enhancer of physical performance. The thoughtful development and application of dietary proteins and LNAA mixtures may thus produce treatments with predictable and useful functional effects.

  6. A facile nanoaggregation strategy for oral delivery of hydrophobic drugs by utilizing acid base neutralization reactions

    NASA Astrophysics Data System (ADS)

    Chen, Huabing; Wan, Jiangling; Wang, Yirui; Mou, Dongsheng; Liu, Hongbin; Xu, Huibi; Yang, Xiangliang

    2008-09-01

    Nanonization strategies have been used to enhance the oral availability of numerous drugs that are poorly soluble in water. Exploring a facile nanonization strategy with highly practical potential is an attractive focus. Here, we report a novel facile nanoaggregation strategy for constructing drug nanoparticles of poorly soluble drugs with pH-dependent solubility by utilizing acid-base neutralization in aqueous solution, thus facilitating the exploration of nanonization in oral delivery for general applicability. We demonstrate that hydrophobic itraconazole dissolved in acid solution formed a growing core and aggregated into nanoparticles in the presence of stabilizers. The nanoparticles, with an average diameter of 279.3 nm and polydispersity index of 0.116, showed a higher dissolution rate when compared with the marketed formulation; the average dissolution was about 91.3%. The in vivo pharmacokinetic studies revealed that the nanoparticles had a rapid absorption and enhanced oral availability. The diet state also showed insignificant impact on the absorption of itraconazole from nanoparticles. This nanoaggregation strategy is a promising nanonization method with a facile process and avoidance of toxic organic solvents for oral delivery of poorly soluble drugs with pH-dependent solubility and reveals a highly practical potential in the pharmaceutical and chemical industries.

  7. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  8. An Introductory Laboratory Exercise for Acids and Bases.

    ERIC Educational Resources Information Center

    Miller, Richard; Silberman, Robert

    1986-01-01

    Discusses an acid-base neutralization exercise requiring groups of students to determine: (1) combinations of solutions giving neutralization; (2) grouping solutions as acids or bases; and (3) ranking groups in order of concentration. (JM)

  9. Distinct Plasma Profile of Polar Neutral Amino Acids, Leucine, and Glutamate in Children with Autism Spectrum Disorders

    ERIC Educational Resources Information Center

    Tirouvanziam, Rabindra; Obukhanych, Tetyana V.; Laval, Julie; Aronov, Pavel A.; Libove, Robin; Banerjee, Arpita Goswami; Parker, Karen J.; O'Hara, Ruth; Herzenberg, Leonard A.; Herzenberg, Leonore A.; Hardan, Antonio Y.

    2012-01-01

    The goal of this investigation was to examine plasma amino acid (AA) levels in children with Autism Spectrum Disorders (ASD, N = 27) and neuro-typically developing controls (N = 20). We observed reduced plasma levels of most polar neutral AA and leucine in children with ASD. This AA profile conferred significant post hoc power for discriminating…

  10. Development and Implementation of a Simple, Engaging Acid Rain Neutralization Experiment and Corresponding Animated Instructional Video for Introductory Chemistry Students

    ERIC Educational Resources Information Center

    Rand, Danielle; Yennie, Craig J.; Lynch, Patrick; Lowry, Gregory; Budarz, James; Zhu, Wenlei; Wang, Li-Qiong

    2016-01-01

    Here we describe an acid rain neutralization laboratory experiment and its corresponding instructional video. This experiment has been developed and implemented for use in the teaching laboratory of a large introductory chemistry course at Brown University. It provides a contextually relevant example to introduce beginner-level students with…

  11. Analysis of Physical Science Textbooks for Conceptual Frameworks on Acids, Bases and Neutralization: Implications for Students' Conceptual Understanding.

    ERIC Educational Resources Information Center

    Erduran, Sibel

    Eight physical science textbooks were analyzed for coverage on acids, bases, and neutralization. At the level of the text, clarity and coherence of statements were investigated. The conceptual framework for this topic was represented in a concept map which was used as a coding tool for tracing concepts and links present in textbooks. Cognitive…

  12. Lactic acid production from lime-treated wheat straw by Bacillus coagulans: neutralization of acid by fed-batch addition of alkaline substrate

    PubMed Central

    Maas, Ronald H. W.; Bakker, Robert R.; Jansen, Mickel L. A.; Visser, Diana; de Jong, Ed; Eggink, Gerrit

    2008-01-01

    Conventional processes for lignocellulose-to-organic acid conversion requires pretreatment, enzymatic hydrolysis, and microbial fermentation. In this study, lime-treated wheat straw was hydrolyzed and fermented simultaneously to lactic acid by an enzyme preparation and Bacillus coagulans DSM 2314. Decrease in pH because of lactic acid formation was partially adjusted by automatic addition of the alkaline substrate. After 55 h of incubation, the polymeric glucan, xylan, and arabinan present in the lime-treated straw were hydrolyzed for 55%, 75%, and 80%, respectively. Lactic acid (40.7 g/l) indicated a fermentation efficiency of 81% and a chiral l(+)-lactic acid purity of 97.2%. In total, 711 g lactic acid was produced out of 2,706 g lime-treated straw, representing 43% of the overall theoretical maximum yield. Approximately half of the lactic acid produced was neutralized by fed-batch feeding of lime-treated straw, whereas the remaining half was neutralized during the batch phase with a Ca(OH)2 suspension. Of the lime added during the pretreatment of straw, 61% was used for the neutralization of lactic acid. This is the first demonstration of a process having a combined alkaline pretreatment of lignocellulosic biomass and pH control in fermentation resulting in a significant saving of lime consumption and avoiding the necessity to recycle lime. PMID:18247027

  13. Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions

    SciTech Connect

    Pearson, C.D.; Green, J.D.

    1993-01-01

    Acid and base fractions from petroleum vacuum resids with no detectable (by visible spectrophotometry) quantities of porphyrinic Ni or V complexes were hydrotreated under various conditions to determine if significant amounts of porphyrinic metals were released, via disassociation or other means, upon hydrotreating. No significant quantities were observed, thereby indicating that nonporphyrinic metals were not simply associated, complexed or otherwise masked (in terms of visible spectrophotometric response) porphyrinic metal complexes. However, it is possible that hydrotreating was simply not effective in breaking up these associates and/or that some porphyrinic forms of metal were in fact released but were rapidly destroyed by hydrotreating. In addition, three liquid chromatographic (LC) separation methods were sequentially applied to Cerro Negro (Orinoco belt Venezuelan heavy crude) >700{degree}C resid in an effort to separate and concentrate the metal complexes present. Nonaqueous ion exchange chromatography was used initially to separate the resid into acid, base and neutral types. Two concentrates containing 19,500 and 13,500 ppm total V, or an estimated 19 and 13 wt % V-containing compounds respectively, were obtained. The degree of enrichment of Ni compounds obtained was significantly lower. By visible spectrophotometry, using vanadyl etioporphyrin as a standard, each of the concentrates contained near a 1:1 ratio of porphyrinic:nonporphyrinic V complexes. Analogous separation behavior for porphyrinic versus nonporphyrinic metal forms was observed throughout much of the work, thereby suggesting that a comparable diversity of structures existed within each general class of metal compounds. The generally wide dispersion of both Ni and V over the LC separation scheme suggests a structural variety of metal complexes that is comparable to that observed for other heteroatoms (N, S, O) in petroleum.

  14. Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions

    SciTech Connect

    Pearson, C.D.; Green, J.D.

    1993-01-01

    Acid and base fractions from petroleum vacuum resids with no detectable (by visible spectrophotometry) quantities of porphyrinic Ni or V complexes were hydrotreated under various conditions to determine if significant amounts of porphyrinic metals were released, via disassociation or other means, upon hydrotreating. No significant quantities were observed, thereby indicating that nonporphyrinic metals were not simply associated, complexed or otherwise masked (in terms of visible spectrophotometric response) porphyrinic metal complexes. However, it is possible that hydrotreating was simply not effective in breaking up these associates and/or that some porphyrinic forms of metal were in fact released but were rapidly destroyed by hydrotreating. In addition, three liquid chromatographic (LC) separation methods were sequentially applied to Cerro Negro (Orinoco belt Venezuelan heavy crude) >700[degree]C resid in an effort to separate and concentrate the metal complexes present. Nonaqueous ion exchange chromatography was used initially to separate the resid into acid, base and neutral types. Two concentrates containing 19,500 and 13,500 ppm total V, or an estimated 19 and 13 wt % V-containing compounds respectively, were obtained. The degree of enrichment of Ni compounds obtained was significantly lower. By visible spectrophotometry, using vanadyl etioporphyrin as a standard, each of the concentrates contained near a 1:1 ratio of porphyrinic:nonporphyrinic V complexes. Analogous separation behavior for porphyrinic versus nonporphyrinic metal forms was observed throughout much of the work, thereby suggesting that a comparable diversity of structures existed within each general class of metal compounds. The generally wide dispersion of both Ni and V over the LC separation scheme suggests a structural variety of metal complexes that is comparable to that observed for other heteroatoms (N, S, O) in petroleum.

  15. Cross-Linking Poly(lactic acid) Film Surface by Neutral Hyperthermal Hydrogen Molecule Bombardment.

    PubMed

    Du, Wangli; Shao, Hong; He, Zhoukun; Tang, Changyu; Liu, Yu; Shen, Tao; Zhu, Yan; Lau, Woon-ming; Hui, David

    2015-12-16

    Constructing a dense cross-linking layer on a polymer film surface is a good way to improve the water resistance of poly(lactic acid) (PLA). However, conventional plasma treatments have failed to achieve the aim as a result of the unavoidable surface damage arising from the charged species caused by the uncontrolled high energy coming from colliding ions and electrons. In this work, we report a modified plasma method called hyperthermal hydrogen-induced cross-linking (HHIC) technology to construct a dense cross-linking layer on PLA film surfaces. This method produces energy-controlled neutral hyperthermal hydrogen, which selectively cleaves C-H bonds by molecule collision from the PLA film without breaking other bonds (e.g., C-C bonds in the polymer backbone), and results in subsequent cross-linking of the carbon radicals generated from the organic molecules. The formation of a dense cross-linking layer can serve as a barrier layer to significantly improve both the hydrophobicity and water vapor barrier property of the PLA film. Because of the advantage of selective cleavage of C-H bonds by HHIC treatment, the original physical properties (e.g., mechanical strength and light transmittance) of the PLA films are well-preserved. PMID:26594874

  16. Neutral and acidic milk oligosaccharides of the striped skunk (Mephitidae: Mephitis mephitis).

    PubMed

    Taufik, Epi; Sekii, Nobuhiro; Senda, Akitsugu; Fukuda, Kenji; Saito, Tadao; Eisert, Regina; Oftedal, Olav T; Urashima, Tadasu

    2013-07-01

    The biological significance of the tremendous variation in proportions of oligosaccharides and lactose among mammalian milks is poorly understood. We investigated milk oligosaccharides of the striped skunk (Mephitis mephitis) and compared these results to other species of the clade Mustelida. Individual oligosaccharides were identified by proton nuclear magnetic resonance spectroscopy. In the striped skunk, six oligosaccharides were identified: isoglobotriose, 2'-fucosyllactose, A-tetrasaccharide, Galili pentasaccharide, 3'-sialyllactose and monosialyl monogalactosyl lacto-N-neohexaose. Four of these have been found in related Mustelida and the other two in more distantly related carnivorans. The neutral and acidic oligosaccharides derive from three core structures: lactose (Gal(β1-4)Glc), lacto-N-neotetraose (Gal(β1-4)GlcNAc(β1-3)Gal(β1-4)Glc) and lacto-N-neohexaose (Gal(β1-4)GlcNAc(β1-3)[Gal(β1-4)GlcNAc(β1-6)]Gal(β1-4)Glc). PMID:23607515

  17. Microemulsion electrokinetic chromatography as a suitable tool for lipophilicity determination of acidic, neutral, and basic compounds.

    PubMed

    Subirats, Xavier; Yuan, Hui-Ping; Chaves, Verónica; Marzal, Núria; Rosés, Martí

    2016-07-01

    In the present work, several MEEKC systems are studied to assess their suitability for lipophilicity determination of acidic, neutral, and basic compounds. Thus, several microemulsion compositions over a wide range of pH values (from 2.0 to 12.0), containing heptane, 1-butanol and different types and amounts of surfactant (SDS or sodium cholate: from 1.3 to 3.3%) are characterized using Abraham's solvation model. The addition of acetonitrile (up to 10%) is also studied, since it increases the resolution of the technique for the most lipophilic compounds. The system coefficients obtained are very similar to those of the 1-octanol/water, used as the reference lipophilicity index, allowing simple and linear correlations between the 1-octanol/water partition values (log Po/w ) and MEEKC mass distribution ratios (log kMEEKC ). Variations in the microemulsion composition (aqueous buffer, surfactant, concentration of ACN) did not significantly affect the similarity of the MEEKC systems to log Po/w partition.

  18. Cross-Linking Poly(lactic acid) Film Surface by Neutral Hyperthermal Hydrogen Molecule Bombardment.

    PubMed

    Du, Wangli; Shao, Hong; He, Zhoukun; Tang, Changyu; Liu, Yu; Shen, Tao; Zhu, Yan; Lau, Woon-ming; Hui, David

    2015-12-16

    Constructing a dense cross-linking layer on a polymer film surface is a good way to improve the water resistance of poly(lactic acid) (PLA). However, conventional plasma treatments have failed to achieve the aim as a result of the unavoidable surface damage arising from the charged species caused by the uncontrolled high energy coming from colliding ions and electrons. In this work, we report a modified plasma method called hyperthermal hydrogen-induced cross-linking (HHIC) technology to construct a dense cross-linking layer on PLA film surfaces. This method produces energy-controlled neutral hyperthermal hydrogen, which selectively cleaves C-H bonds by molecule collision from the PLA film without breaking other bonds (e.g., C-C bonds in the polymer backbone), and results in subsequent cross-linking of the carbon radicals generated from the organic molecules. The formation of a dense cross-linking layer can serve as a barrier layer to significantly improve both the hydrophobicity and water vapor barrier property of the PLA film. Because of the advantage of selective cleavage of C-H bonds by HHIC treatment, the original physical properties (e.g., mechanical strength and light transmittance) of the PLA films are well-preserved.

  19. Microemulsion electrokinetic chromatography as a suitable tool for lipophilicity determination of acidic, neutral, and basic compounds.

    PubMed

    Subirats, Xavier; Yuan, Hui-Ping; Chaves, Verónica; Marzal, Núria; Rosés, Martí

    2016-07-01

    In the present work, several MEEKC systems are studied to assess their suitability for lipophilicity determination of acidic, neutral, and basic compounds. Thus, several microemulsion compositions over a wide range of pH values (from 2.0 to 12.0), containing heptane, 1-butanol and different types and amounts of surfactant (SDS or sodium cholate: from 1.3 to 3.3%) are characterized using Abraham's solvation model. The addition of acetonitrile (up to 10%) is also studied, since it increases the resolution of the technique for the most lipophilic compounds. The system coefficients obtained are very similar to those of the 1-octanol/water, used as the reference lipophilicity index, allowing simple and linear correlations between the 1-octanol/water partition values (log Po/w ) and MEEKC mass distribution ratios (log kMEEKC ). Variations in the microemulsion composition (aqueous buffer, surfactant, concentration of ACN) did not significantly affect the similarity of the MEEKC systems to log Po/w partition. PMID:27126602

  20. Investigation of metal ion extraction and aggregate formation combining acidic and neutral organophosphorous reagents

    SciTech Connect

    Braatz, A.D.; Nilsson, M.; Ellis, R.; Antonio, M.

    2013-07-01

    In the present study, we investigate how varying mixtures of tri-n-butyl phosphate (TBP) and dibutyl phosphate (HDBP) results in enhanced extraction of lanthanum(III), La{sup 3+}, and dysprosium(III), Dy{sup 3+}. Water and metal ion extraction were carefully monitored as a function of TBP:HDBP mole ratio.In addition to these techniques, EXAFS was used to determine the coordination environment of the metal ion in this system. To produce the necessary signal, a concentration of 1.25*10{sup -3} M La{sup 3+} and Dy{sup 3+} was used. Although previous studies of synergistic extraction of metal cations using combinations of neutral and acidic reagents explain the enhanced extraction by increased dehydration of the metal ion and the formation of mixed extractant complexes, our evidence for the increased water extraction coupled with the aggregate formation suggests a reverse micellar aspect to synergism in the system containing TBP and HDBP. It is quite possible that both of these phenomena contribute to our system behavior. The EXAFS data shows that, based on coordination numbers alone, several possible structures may exist. From this study, we cannot provide a definitive answer as to the nature of extraction in this system or the exact complex formed during extraction.

  1. Neutral and acidic milk oligosaccharides of the striped skunk (Mephitidae: Mephitis mephitis).

    PubMed

    Taufik, Epi; Sekii, Nobuhiro; Senda, Akitsugu; Fukuda, Kenji; Saito, Tadao; Eisert, Regina; Oftedal, Olav T; Urashima, Tadasu

    2013-07-01

    The biological significance of the tremendous variation in proportions of oligosaccharides and lactose among mammalian milks is poorly understood. We investigated milk oligosaccharides of the striped skunk (Mephitis mephitis) and compared these results to other species of the clade Mustelida. Individual oligosaccharides were identified by proton nuclear magnetic resonance spectroscopy. In the striped skunk, six oligosaccharides were identified: isoglobotriose, 2'-fucosyllactose, A-tetrasaccharide, Galili pentasaccharide, 3'-sialyllactose and monosialyl monogalactosyl lacto-N-neohexaose. Four of these have been found in related Mustelida and the other two in more distantly related carnivorans. The neutral and acidic oligosaccharides derive from three core structures: lactose (Gal(β1-4)Glc), lacto-N-neotetraose (Gal(β1-4)GlcNAc(β1-3)Gal(β1-4)Glc) and lacto-N-neohexaose (Gal(β1-4)GlcNAc(β1-3)[Gal(β1-4)GlcNAc(β1-6)]Gal(β1-4)Glc).

  2. Distributions of 12 elements on 64 absorbers from simulated Hanford Neutralized Current Acid Waste (NCAW)

    SciTech Connect

    Svitra, Z.V.; Bowen, S.M.; Marsh, S.F.

    1994-12-01

    As part of the Hanford Tank Waste Remediation System program at Los Alamos, we evaluated 64 commercially available or experimental absorber materials for their ability to remove hazardous components from high-level waste. These absorbers included cation and anion exchange resins, inorganic exchangers, composite absorbers, and a series of liquid extractants sorbed on porous support-beads. We tested these absorbers with a solution that simulates Hanford neutralized current acid waste (NCAW) (pH 14.2). To this simulant solution we added the appropriate radionuclides and used gamma spectrometry to measure fission products (Cs, Sr, Tc, and Y) and matrix elements (Cr, Co, Fe, Mn, Ni, V, Zn, and Zr). For each of 768 element/absorber combinations, we measured distribution coefficients for dynamic contact periods of 30 min, 2 h, and 6 h to obtain information about sorption kinetics. On the basis of these 2304 measured distribution coefficients, we determined that many of the tested absorbers may be suitable for processing NCAW solutions.

  3. Self-assembled ternary complexes of neutral liposomes, deoxyribonucleic acid, and bivalent metal cations. Promising vectors for gene transfer?

    NASA Astrophysics Data System (ADS)

    Bruni, P.; Pisani, M.; Amici, A.; Marchini, C.; Montani, M.; Francescangeli, O.

    2006-02-01

    By means of synchrotron x-ray diffraction we demonstrate the self-assembled formation of the neutral ternary dioleoyl-phosphatidylcholine-deoxyribonucleic acid (plasmid)-Me2+ (Me=Ca and Mn) complexes in the liquid-crystalline Lα phase. We also report an attempt of an in vitro transfection on mouse fibroplast NIH 3T3 cell lines, which shows the capability of these complexes to transfect DNA. Based on the reported results, efficient encapsulation of DNA plasmids in these ternary neutral complexes may represent an important alternative to current systemic gene approaches.

  4. A practical application of Driscoll's equation for predicting the acid-neutralizing capacity in acidic natural waters equilibria with the mineral phase gibbsite.

    PubMed

    Bi, S P; An, S Q; Liu, F

    2001-05-01

    A practical application of Driscoll's equation for predicting the acid-neutralizing capacity (ANC) in acidic waters equilibria with the mineral phase gibbsite is reported in this paper. Theoretical predication values of ANC are compared with the experimental data obtained from different literatures. The effect of aluminum (Al) on the value of ANC is investigated. It indicates that Al plays an important role in regulating the buffering effects in acidic natural waters. Failure to consider Al in acidic waters may bias assessment results in certain situations so as to overestimate the ANC values in response to increase in atmospheric deposition.

  5. Cross-neutralization study of seven California group (Bunyaviridae) strains in homoiothermous (PS) and poikilothermous (XTC-2) vertebrate cells.

    PubMed

    Hubálek, Z; Chanas, A C; Johnson, B K; Simpson, D I

    1979-02-01

    Antigenic relationships among seven California group strains were studied by a plaque-reduction neutralization test (PRNT). Cross-reactions occurred in most cases but three subgroups were noted: (1) the major serogroup contained the viruses of California encephalitis, LaCrosse, Snowshoe Hare and Trahyna (including the Lumbo strain) whereas (2) Jamestown Canyon and (3) Trivittatus viruses were distinct. There was no significant difference between the PRNT results in mammalian (PS) cells incubated at 37 degrees C and amphibian (XTC-2) cells incubated at 28 degrees C. Trivittatus virus failed to produce plaques in XTC-2 cells.

  6. Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids.

    PubMed

    Banerjee, Amit; Senthilkumar, Soundararasu; Baskaran, Sundarababu

    2016-01-18

    Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3 -NaIO4 -mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues.

  7. High yields of fatty acid and neutral lipid production from cassava bagasse hydrolysate (CBH) by heterotrophic Chlorella protothecoides.

    PubMed

    Chen, Junhui; Liu, Xiaoguang; Wei, Dong; Chen, Gu

    2015-09-01

    The fermentation process for high yields of fatty acid and neutral lipid production from cassava bagasse hydrolysate (CBH) was developed by heterotrophic Chlorella protothecoides. An efficient single-step enzymatic hydrolysis of cassava bagasse (CB) by cellulase was firstly developed to produce >30 g/L of reducing sugars. The concentrated CBH was subsequently applied in a batch culture, producing 7.9 g/L of dry biomass with yield of 0.44 g/g reducing sugar and 34.3 wt% of fatty acids and 48.6 wt% of neutral lipids. Furthermore, fed-batch fermentation using CBH achieved higher yields of fatty acids (41.0 wt% and a titer of 5.83 g/L) and neutral lipids (58.4 wt% and yield of 0.22 g/g reducing sugar). Additionally, the fatty acid profile analysis showed that the intercellular lipid was suitable to prepare high-quality biodiesel. This study demonstrated the feasibility of using CBH as low-cost feedstock to produce crude algal oil for sustainable biodiesel production.

  8. Characterization of a Broadly Neutralizing Monoclonal Antibody That Targets the Fusion Domain of Group 2 Influenza A Virus Hemagglutinin

    PubMed Central

    Tan, Gene S.; Lee, Peter S.; Hoffman, Ryan M. B.; Mazel-Sanchez, Beryl; Krammer, Florian; Leon, Paul E.; Ward, Andrew B.; Wilson, Ian A.

    2014-01-01

    ABSTRACT Due to continuous changes to its antigenic regions, influenza viruses can evade immune detection and cause a significant amount of morbidity and mortality around the world. Influenza vaccinations can protect against disease but must be annually reformulated to match the current circulating strains. In the development of a broad-spectrum influenza vaccine, the elucidation of conserved epitopes is paramount. To this end, we designed an immunization strategy in mice to boost the humoral response against conserved regions of the hemagglutinin (HA) glycoprotein. Of note, generation and identification of broadly neutralizing antibodies that target group 2 HAs are rare and thus far have yielded only a few monoclonal antibodies (MAbs). Here, we demonstrate that mouse MAb 9H10 has broad and potent in vitro neutralizing activity against H3 and H10 group 2 influenza A subtypes. In the mouse model, MAb 9H10 protects mice against two divergent mouse-adapted H3N2 strains, in both pre- and postexposure administration regimens. In vitro and cell-free assays suggest that MAb 9H10 inhibits viral replication by blocking HA-dependent fusion of the viral and endosomal membranes early in the replication cycle and by disrupting viral particle egress in the late stage of infection. Interestingly, electron microscopy reconstructions of MAb 9H10 bound to the HA reveal that it binds a similar binding footprint to MAbs CR8020 and CR8043. IMPORTANCE The influenza hemagglutinin is the major antigenic target of the humoral immune response. However, due to continuous antigenic changes that occur on the surface of this glycoprotein, influenza viruses can escape the immune system and cause significant disease to the host. Toward the development of broad-spectrum therapeutics and vaccines against influenza virus, elucidation of conserved regions of influenza viruses is crucial. Thus, defining these types of epitopes through the generation and characterization of broadly neutralizing

  9. Fourier Transform Infrared Spectroscopy Demonstrates The Reactivity Of The Protonated Carboxyl Group Of The Acid Salt Of Calcium Bilirubinate.

    NASA Astrophysics Data System (ADS)

    Soloway, R. D.; Wu, J.-G.; Xu, D.-F.; Zhang, Y.-F.; Martini, D. K.; Hong, N.-K.; Crowther, R. S.

    1989-12-01

    Calcium bilirubinate is a major salt in pigment gallstones. Bilirubin IX (H2BR) is a tetrapyrrole with 1 propionic acid side chain on both the B and C rings. A striking feature is the strong intramolecular hydrogen bonding of both carboxyl groups as determined by x-ray diffraction. This greatly reduces aqueous solubility. Much less is known about the structure of the salts of calcium bilirubinate since single crystals have not been formed. One or both carboxyl groups of bilirubin may coordinate with calcium in stone, forming the acid or neutral salt.

  10. Virucidal effect of acidic electrolyzed water and neutral electrolyzed water on avian influenza viruses.

    PubMed

    Tamaki, Shio; Bui, Vuong N; Ngo, Lai H; Ogawa, Haruko; Imai, Kunitoshi

    2014-03-01

    The virucidal effects of two types of electrolyzed water, acidic electrolyzed water (AEW) and neutral electrolyzed water (NEW), on avian influenza viruses were studied. Virus titers of the highly pathogenic H5N1 virus and the low-pathogenic H9N2 virus irreversibly decreased by >5-log at 1 min after the viruses were mixed with NEW containing ≥43 ppm free available chlorine (FAC), but not with NEW containing <17 ppm FAC. The minimum concentration of FAC for a virucidal effect of NEW was estimated at around 40 ppm. In contrast, the virus titers decreased by >5 log at 1 min after the viruses were mixed with AEW, in which the concentration of the FAC ranged from 72 to 0 ppm. Thus, the virucidal effect of AEW did not depend on the presence of FAC. Reverse transcription polymerase chain reaction amplified fragments of the M and NP genes, but not the complete M gene, from RNA extracted from the AEW-inactivated virus. Moderate morphological changes were found under the electron microscope, although no changes were observed in the electrophoresed proteins of the AEW-inactivated virus. No viral genes were amplified from the RNA extracted from the NEW-inactivated virus, regardless of the length of the targeted genes. No viral particles were detected under the electron microscope and no viral proteins were detected by electrophoresis for the NEW-inactivated virus. Thus, this study demonstrated potent virucidal effects of AEW and NEW and differences in the virucidal mechanism of the two types of electrolyzed water.

  11. Neutral sphingomyelinase-2, acid sphingomyelinase, and ceramide levels in COPD patients compared to controls

    PubMed Central

    Lea, Simon R; Metcalfe, Hannah J; Plumb, Jonathan; Beerli, Christian; Poll, Chris; Singh, Dave; Abbott-Banner, Katharine H

    2016-01-01

    Background Increased pulmonary ceramide levels are suggested to play a causative role in lung diseases including COPD. Neutral sphingomyelinase-2 (nSMase-2) and acid SMase (aSMase), which hydrolyze sphingomyelin to produce ceramide, are activated by a range of cellular stresses, including inflammatory cytokines and pathogens, but notably cigarette smoke appears to only activate nSMase-2. Our primary objective was to investigate nSMase-2 and aSMase protein localization and quantification in lung tissue from nonsmokers (NS), smokers (S), and COPD patients. In addition, various ceramide species (C16, C18, and C20) were measured in alveolar macrophages from COPD patients versus controls. Materials and methods Patients undergoing surgical resection for suspected or confirmed lung cancer were recruited, and nSMase-2 and aSMase protein was investigated in different areas of lung tissue (small airways, alveolar walls, subepithelium, and alveolar macrophages) by immunohistochemistry. Ceramide species were measured in alveolar macrophages from COPD patients and controls by mass spectrometry. Results nSMase-2 and aSMase were detected in the majority of small airways. There was a significant increase in nSMase-2 immunoreactivity in alveolar macrophages from COPD patients (54%) compared with NS (31.7%) (P<0.05), and in aSMase immunoreactivity in COPD (68.2%) and S (69.5%) alveolar macrophages compared with NS (52.4%) (P<0.05). aSMase labeling was also increased in the subepithelium and alveolar walls of S compared with NS. Ceramide (C20) was significantly increased in alveolar macrophages from COPD patients compared with controls. Conclusion nSMase-2 and aSMase are both increased in COPD alveolar macrophages at the protein level; this may contribute toward the elevated ceramide (C20) detected in alveolar macrophages from COPD patients. PMID:27660431

  12. Neutral sphingomyelinase-2, acid sphingomyelinase, and ceramide levels in COPD patients compared to controls

    PubMed Central

    Lea, Simon R; Metcalfe, Hannah J; Plumb, Jonathan; Beerli, Christian; Poll, Chris; Singh, Dave; Abbott-Banner, Katharine H

    2016-01-01

    Background Increased pulmonary ceramide levels are suggested to play a causative role in lung diseases including COPD. Neutral sphingomyelinase-2 (nSMase-2) and acid SMase (aSMase), which hydrolyze sphingomyelin to produce ceramide, are activated by a range of cellular stresses, including inflammatory cytokines and pathogens, but notably cigarette smoke appears to only activate nSMase-2. Our primary objective was to investigate nSMase-2 and aSMase protein localization and quantification in lung tissue from nonsmokers (NS), smokers (S), and COPD patients. In addition, various ceramide species (C16, C18, and C20) were measured in alveolar macrophages from COPD patients versus controls. Materials and methods Patients undergoing surgical resection for suspected or confirmed lung cancer were recruited, and nSMase-2 and aSMase protein was investigated in different areas of lung tissue (small airways, alveolar walls, subepithelium, and alveolar macrophages) by immunohistochemistry. Ceramide species were measured in alveolar macrophages from COPD patients and controls by mass spectrometry. Results nSMase-2 and aSMase were detected in the majority of small airways. There was a significant increase in nSMase-2 immunoreactivity in alveolar macrophages from COPD patients (54%) compared with NS (31.7%) (P<0.05), and in aSMase immunoreactivity in COPD (68.2%) and S (69.5%) alveolar macrophages compared with NS (52.4%) (P<0.05). aSMase labeling was also increased in the subepithelium and alveolar walls of S compared with NS. Ceramide (C20) was significantly increased in alveolar macrophages from COPD patients compared with controls. Conclusion nSMase-2 and aSMase are both increased in COPD alveolar macrophages at the protein level; this may contribute toward the elevated ceramide (C20) detected in alveolar macrophages from COPD patients.

  13. The crystallinity of calcium phosphate powders influenced by the conditions of neutralized procedure with citric acid additions

    SciTech Connect

    Li Chengfeng

    2009-05-06

    Calcium phosphate powders with nano-sized crystallinity were synthesized by neutralization using calcium hydroxide and orthophosphoric acid with the assistance of citric acid. The influence of processing parameters, such as free or additive citric acid, synthetic temperature and ripening time, on the crystallinity of hydroxyapatite were investigated. The results of X-ray diffraction and microstructure observations showed that the crystallinity and morphology of nano-sized hydroxyapatite particles were influenced by the presence or absence of citric acid. It was found that the crystallinities and crystallite sizes of hydroxyapatite powders prepared with the additive citric acid increased with increasing synthetic temperature and ripening time. Especially, the crystallinities of (h k 0) planes were raised and more homogeneously grown particles were obtained with increasing synthetic temperature.

  14. Cysteamine-induced inhibition of acid neutralization and the increase in hydrogen ion back-diffusion in duodenal mucosa

    SciTech Connect

    Ohe, K.; Okada, Y.; Fujiwara, T.; Inoue, M.; Miyoshi, A.

    1982-03-01

    To investigate the possible impairment of defensive mechanisms in cysteamine-induced duodenal ulceration, the effect of cysteamine on the neutralization of acid by the duodenum and the back-diffusion of hydrogen ions into the duodenal mucosa has been studied. The results obtained were as follows. (1) The intraduodenal pH started to decrease between 3 and 4 hr after cysteamine injection. (2) By perfusion of the duodenal loop excluding the opening of bile and pancreatic ducts, the amount of hydrogen ions (H+) neutralized was found to be significantly lower in cysteamine-treated animals than in the controls. (3) the back-diffusion of luminal H+ into the duodenal mucosa, estimated by measuring the H+ disappearance from the test solution including 100 mM HCl, was significantly increased by cysteamine. From these findings, it has been concluded that cysteamine reduces the resistance of duodenal mucosa to acid coming from the stomach.

  15. Structural and thermotropic properties of calcium-dimyristoylphosphatidic acid complexes at acidic and neutral pH conditions.

    PubMed Central

    Takahashi, H.; Yasue, T.; Ohki, K.; Hatta, I.

    1995-01-01

    Two kinds of calcium-dimyristoylphosphatidic acid (DMPA) complexes at acidic and neutral pH conditions were prepared in the following ways. The complex at pH 4 was obtained by adding Ca2+ to DMPA dispersion in pure water. On the other hand, the complex at pH 7.4 was obtained by adding Ca2+ to DMPA dispersion in the presence of NaOH. The stoichiometries of Ca2+ ion to DMPA molecule are 0.5-0.67 and approximately 1 for the complexes at pH 4 and 7.4, respectively. Static x-ray diffraction shows that the hydrocarbon chains of the Ca(2+)-DMPA complex at pH 4 at 20 degrees C are more tightly packed than those of the complex at pH 7.4 at 20 degrees C. Furthermore, the complex at pH 4 at 20 degrees C gives rise to several reflections that might be related to the ordered arrangement of the Ca2+ ions. These results indicate that the structure of the complex at pH 4 is crystalline-like. In the differential scanning calorimetry (DSC) thermogram, the complex at pH 7.4 undergoes no phase transition in a temperature range between 30 and 80 degrees C. On the other hand, in the DSC thermogram for the complex at pH 4, a peak appears at 65.8 degrees C in the first heating scan. In the successive second heating scan, a transition peak appears at 63.5 degrees C. In connection with the DSC results, the structural changes associated with these phase transitions were studied with temperature-scan x-ray diffraction. In the first heating scan, although a peak appears at 65.80C in the DSC thermogram, the hydrocarbon chain packing gradually converts from an orthorhombic lattice to a hexagonal lattice near 52 degree C, and successively the chain melting phase transition occurs near 670C. In the second heating scan, the hydrocarbon chains are packed in a hexagonal lattice over the whole temperature range and the chain melting phase transition occurs near 63.5 degree C. Therefore,the Ca2+-DMPA complex at pH 4 has a metastable state. The metastable state transforms to a stable state by

  16. Comparative study of cadmium and lead accumulations in Cambarus bartoni (Fab. ) (Decapoda, Crustacea) from an acidic and a neutral lake

    SciTech Connect

    Keenan, S.; Alikhan, M.A. )

    1991-07-01

    The purpose of the study reported in this paper was to compare concentrations of lead and cadmium in the sediment and water, as well as in the crayfish, Cambarus Bartoni (Fab.) (Decapoda - Crustacea) trapped from an acidic and a neutral lake in the Sudbury district of Northeastern Ontario. Hepatopancreatic, alimentary canal, tail muscles and exoskeletal concentrations in the crayfish are also examined to determine specific tissue sites for these accumulations.

  17. Neutral loss analysis of amino acids by desorption electrospray ionization using an unmodified tandem quadrupole mass spectrometer.

    PubMed

    Corso, Gaetano; Paglia, Giuseppe; Garofalo, Daniela; D'Apolito, Oceania

    2007-01-01

    A new method to analyze free amino acids using desorption electrospray ionization (DESI) has been implemented. The method is based on the neutral loss mode determination of underivatized amino acids using a tandem quadrupole mass spectrometer equipped with an unmodified atmospheric interface. Qualitative and quantitative optimization of DESI parameters, including ESI voltage, solvent flow rate, angle of collection and incidence, gas flow and temperatures, was performed for amino acids detection. The parameters for DESI analysis were evaluated using a mixture of valine, leucine, methionine, phenylalanine and tyrosine standards. A few microliters of this mixture were deposited on a slide, dried and analyzed at a flow rate of 2 microL/min. The optimal ionization response was obtained using laboratory glass slides and an equivalent solution of water/methanol doped with 2% of formic acid. The method specificity was evaluated by comparing product ion spectra and neutral loss analysis of amino acids obtained either by DESI or by electrospray ionization flow injection analysis (ESI-FIA). To evaluate the quantitative response on amino acids analyzed by DESI, calibration curves were performed on amino acid standard solutions spiked with a fixed amount of labelled amino acids. The method was also employed to analyze free amino acids from blood spots, after a rapid solvent extraction without other sample pretreatment, from positive and negative subjects. The method enables one to analyze biological samples and to discriminate healthy subjects from patients affected by inherited metabolic diseases. The intrinsic high-throughput analysis of DESI represents an opportunity, because of its potential application in clinical chemistry, for the expanded screening of some inborn errors of metabolism.

  18. Toxic effects of Al-based coagulants on Brassica chinensis and Raphanus sativus growing in acid and neutral conditions.

    PubMed

    Zhang, Kaisong; Zhou, Qixing

    2005-04-01

    The ecotoxicological effects of aluminum (Al)-based coagulants are of concern because of their wide-ranging applications in wastewater treatment and water purification. As important Al-based coagulants, AlCl(3) and PAC (polyaluminum-chloride) were selected as examples to examine the toxic effects on representative vegetables including the cabbage Brassica chinensis and the radish Raphanus sativus over a range of exposure concentrations in neutral (pH 7.00) and acidic (pH 4.00) conditions, using seed germination and root elongation in the early-growth stage as indicators of toxicity. The results showed that root elongation of the two vegetables was a more sensitive indicator than was seed germination for evaluating the toxicity of Al. As a single influencing factor, H(+) had no significant direct effects on root elongation of Brassica chinensis and Raphanus sativus under the experimental conditions. The toxicity of Al played the main role in inhibiting root elongation and seed germination and was strongly related to changes in pH. There was a markedly positive relationship between the inhibitory rate of root elongation, seed germination, and the concentration of Al at pH 4.00 (p < 0.01). The toxic effect of AlCl(3) on Brassica chinensis was less with a neutral pH than at pH 4.00, but Raphanus sativus was more susceptible to AlCl(3) toxicity at a neutral pH than at pH 4.00. Both Raphanus sativus and Brassica chinensis had a more toxic response to a low concentration (<64 mg . L(-1)) of PAC in a neutral condition than in an acidic condition. Undoubtedly, the Al toxicity caused by Al-based coagulants at a neutral pH is relevant when treatment solids are used in agriculture.

  19. Evidence for inhibition of exodus of small neutral amino acids from non-brain tissues in hyperphenylalaninaemic rats.

    PubMed

    de Cespedes, C; Thoene, J G; Lowler, K; Christensen, H N

    1989-01-01

    The mechanism of the depletion of several plasma amino acids in PKU has remained unexplained. In the present study, a statistically significant decrease in the plasma concentration of several amino acids was observed 2 h after the intraperitoneal injection of Phe to weanling rats. The pattern was very similar to the one observed in PKU patients. Statistically significant increases in the distribution ratios liver/plasma and, mainly, muscle/plasma ratios accompanied in most of the cases the corresponding decreases in plasma concentrations. Equimolar injection under the same conditions of the non-insulinogenic transport system L analogue, the a(+/-) isomer of the 2-aminonorbornane-2-carboxylic acid, produced, in a parallel effect to Phe, statistically significant increases in the distribution ratios of Ala and Gly, and probably of Pro in muscle, as well as of Ala in liver. These results seem to indicate that the high intracellular Phe attained inhibits the exodus of small neutral amino acids through system L, causing their depletion in plasma and ultimately in the brain. This effect may be additive to the inhibition by Phe of the entry of bulky neutral amino acids at the level of the blood-brain barrier. Further study is needed to assess the relevance of these effects to PKU.

  20. Sensitive 21cm Observations of Neutral Hydrogen in the Local Group near M31

    NASA Astrophysics Data System (ADS)

    Wolfe, Spencer A.; Lockman, Felix J.; Pisano, D. J.

    2016-01-01

    Very sensitive 21 cm H i measurements have been made at several locations around the Local Group galaxy M31 using the Green Bank Telescope at an angular resolution of 9.‧1, with a 5σ detection level of NH i = 3.9 × 1017 cm-2 for a 30 km s-1 line. Most of the H i in a 12 square-degree area almost equidistant between M31 and M33 is contained in nine discrete clouds that have a typical size of a few kpc and a H i mass of 105M⊙. Their velocities in the Local Group Standard of Rest lie between -100 and +40 km s-1, comparable to the systemic velocities of M31 and M33. The clouds appear to be isolated kinematically and spatially from each other. The total H i mass of all nine clouds is 1.4 × 106M⊙ for an adopted distance of 800 kpc, with perhaps another 0.2 × 106M⊙ in smaller clouds or more diffuse emission. The H i mass of each cloud is typically three orders of magnitude less than the dynamical (virial) mass needed to bind the cloud gravitationally. Although they have the size and H i mass of dwarf galaxies, the clouds are unlikely to be part of the satellite system of the Local Group, as they lack stars. To the north of M31, sensitive H i measurements on a coarse grid find emission that may be associated with an extension of the M31 high-velocity cloud (HVC) population to projected distances of ˜100 kpc. An extension of the M31 HVC population at a similar distance to the southeast, toward M33, is not observed.

  1. Gallic Acid as a Complexing Agent for Copper Chemical Mechanical Polishing Slurries at Neutral pH

    NASA Astrophysics Data System (ADS)

    Kim, Yung Jun; Kang, Min Cheol; Kwon, Oh Joong; Kim, Jae Jeong

    2011-05-01

    Gallic acid was investigated as a new complexing agent for copper (Cu) chemical mechanical polishing slurries at neutral pH. Addition of 0.03 M gallic acid and 1.12 M H2O2 at pH 7 resulted in a Cu removal rate of 560.73±17.49 nm/min, and the ratio of the Cu removal rate to the Cu dissolution rate was 14.8. Addition of gallic acid improved the slurry performance compared to glycine addition. X-ray photoelectron spectroscopy analysis and contact angle measurements showed that addition of gallic acid enhanced the Cu polishing behavior by suppressing the formation of surface Cu oxide.

  2. Incorporation of alpha-Ketoglutaric Acid as a Fixed Bed Scrubber Media for the Neutralization of Hydrazine Family Hypergolic Fuels

    NASA Technical Reports Server (NTRS)

    DeVor, R. W.; Santiago-Maldonado, E.; Parkerson, J. K.

    2010-01-01

    A candidate scrubber media, alpha-ketoglutaric acid (aKGA) adsorbed onto a silica-based substrate was examined as a potential alternative to the hydrazine-family hypergolic fuel neutralization techniques currently utilized at NASA/Kennedy Space Center (KSC). Helvenson et. al. has indicated that aKGA will react with hydrazines to produce non-hazardous, possibly biodegradable products. Furthermore, the authors have previously tested and demonstrated the use of aKGA aqueous solutions as a replacement neutralizing agent for citric acid, which is currently used as a scrubbing agent in liquid scrubbers at KSC. Specific properties examined include reaction efficiency, the loading capacity of aKGA onto various silica substrates, and the comparison of aKGA media performance to that of the citric acid vapor scrubber systems at KSC and a commercial vapor scrubber media. Preliminary investigations showed hydrophobic aerogel particles to be an ideal substrate for the deposition of the aKGA. Current studies have shown that the laboratory produced aKGA-Aerogel absorbent media are more efficient and cost effective than a commercially available fixed bed scrubber media, although much less cost effective than liquid-based citric acid scrubbers (although possibly safer and less labor intensive). A comparison of all three alternative scrubber technologies (liquid aKGA, solid-phase aKGA, and commercially available sorbent materials) is given considering both hypergolic neutralization capabilities and relative costs (as compared to the current citric acid scrubbing technology in use at NASA/KSC).

  3. Typing of Blood-Group Antigens on Neutral Oligosaccharides by Negative-Ion Electrospray Ionization Tandem Mass Spectrometry

    PubMed Central

    Zhang, Hongtao; Zhang, Shuang; Tao, Guanjun; Zhang, Yibing; Mulloy, Barbara; Zhan, Xiaobei; Chai, Wengang

    2013-01-01

    Blood-group antigens, such as those containing fucose and bearing the ABO(H)- and Lewis-type determinants expressed on the carbohydrate chains of glycoproteins and glycolipids, and also on unconjugated free oligosaccharides in human milk and other secretions, are associated with various biological functions. We have previously shown the utility of negative-ion electrospay ionization tandem mass spectrometry with collision-induced dissociation (ESI-CID-MS/MS) for typing of Lewis (Le) determinants, e.g. Lea, Lex, Leb, and Ley on neutral and sialylated oligosaccharide chains. In the present report we extended the strategy to characterization of blood-group A-, B- and H-determinants on type 1 and type 2, and also on type 4 globoside chains to provide a high sensitivity method for typing of all the major blood-group antigens, including the A, B, H, Lea, Lex, Leb, and Ley determinants, present in oligosaccharides. Using the principles established we identified two minor unknown oligosaccharide components present in the products of enzymatic synthesis by bacterial fermentation. We also demonstrated that the unique fragmentations derived from the D- and 0,2A-type cleavages observed in ESI-CID-MS/MS, which are important for assigning blood-group and chain types, only occur under the negative-ion conditions for reducing sugars but not for reduced alditols or under positive-ion conditions. PMID:23692402

  4. Mutation and gene transfer of neutral amino acid transport System L genes in mammalian cells

    SciTech Connect

    El-Gewely, M.R.; Collarini, E.J.; Campbell, G.S.; Oxender, D.L.

    1987-05-01

    The authors are attempting to clone the genes coding for amino acid transport System L. Chinese hamster ovary (CHO) cell mutants that are temperature sensitive in their leucyl-tRNA synthetase show temperature-dependent regulation of System L. Temperature resistant mutants isolated from these cells have constitutively derepressed System L activity. Somatic cell fusion studies using these mutants have suggested that a trans-acting element controls regulation of System L. Mutants with reduced transport activity were isolated by a TH-suicide selection. The growth of these mutant cells is limited by the transport defect. CHO mutants were transformed with a human cosmid library, followed by selection at high temperatures and low leucine concentrations. Some transformants have increased levels of System L activity, suggesting that human genes coding for leucine transport have been incorporated into the CHO genome. Human sequences were rescued by a lambda in vitro packaging system. These sequences hybridize to vector and total human DNA. Experiments are being done to confirm that these sequences indeed code for transport System L. They are also attempting to label membrane components of amino acid transporters by group-specific modifying reagents.

  5. Single particle and pair dynamics in water-formic acid mixtures containing ionic and neutral solutes: nonideality in dynamical properties.

    PubMed

    Gupta, Rini; Chandra, Amalendu

    2008-05-14

    A series of molecular dynamics simulations of water-formic acid mixtures containing either an ionic solute or a neutral hydrophobic solute has been performed to study the extent of nonideality in the dynamics of these solutes for varying composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to show nonideal behavior with variation of composition, and similar nonideality is also observed for the diffusion and orientational relaxation of solvent molecules in these mixtures. The diffusion coefficient of a neutral hydrophobic solute, however, decreases monotonically with increase in water concentration. We have also investigated some of the pair dynamical properties such as water-water and water-formic acid hydrogen bond relaxation and residence dynamics of water molecules in water and formic acid hydration shells. The lifetimes of water-water hydrogen bonds are found to be longer than those between formic acid carbonyl oxygen-water hydrogen bonds, whereas the lifetimes of formic acid hydroxyl hydrogen-water hydrogen bonds are longer than those of water-water hydrogen bonds. In general, the hydrogen bond lifetimes for both water-water and water-formic acid hydrogen bonds are found to decrease with increase in water concentration. Residence times of water molecules also show the same trend with increase in formic acid concentration. Interestingly, these pair dynamical properties show a monotonic dependence on composition without any maximum or minimum and behave almost ideally with respect to changes in the composition of the mixtures. The present calculations are performed with fixed-charge nonpolarizable models of the solvent and solute molecules without taking into account many-body polarization effects in an explicit manner. PMID:18532825

  6. Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

    1995-01-01

    An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

  7. Luminescence properties of compounds of europium(III) with quinaldic acid and phosphor-containing neutral ligands

    NASA Astrophysics Data System (ADS)

    Kalinovskaya, I. V.

    2016-06-01

    Luminescent complex mixed-ligand compounds of europium(III) with quinaldic acid and phosphor- containing neutral ligands have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the obtained complex mixed-ligand compounds of europium( III) have been studied. It is shown that, during thermolysis, a water molecule and neutral ligand are detached in two stages with endothermic effects. It is established that quinaldinate ion is coordinated to europium(III) ion in a bidentate fashion. The Stark structure of the 5 D 0-7 F j ( j = 0, 1, 2) transitions in low-temperature luminescence spectra of complex compounds of europium(III) has been analyzed.

  8. Structural characterization of neutral oligosaccharides with blood-group A and H activity isolated from bovine submaxillary mucin.

    PubMed Central

    Savage, A V; D'Arcy, S M; Donoghue, C M

    1991-01-01

    In this study we investigated the structures of 11 neutral oligosaccharides released from bovine submaxillary mucin by alkaline borohydride treatment and isolated by h.p.l.c. One hexa-, one penta-, three tetra-, four tri- and two di-saccharides containing core types 1, 2, 3 or 4 were obtained. We report their structures, determined by a combination of one- and two-dimensional 1H n.m.r. spectroscopy at 270 MHz and methylation analysis involving g.l.c.-m.s., along with their approximate molar ratios. Only three of these oligosaccharides have previously been reported in this source. Of the new oligosaccharides, one contains the blood-group-A antigenic determinant, two contain the blood-group-H type 2 determinant, while another contains the blood-group-H type 3 determinant. The oligosaccharide GlcNAc beta (1----6)[GlcNAc beta (1----3)]GalNAcol, although previously found as a core structure, has been isolated here as a novel trisaccharide. PMID:1718265

  9. Acid-neutralizing potential of minerals in intrusive rocks of the Boulder batholith in northern Jefferson County, Montana

    USGS Publications Warehouse

    Desborough, George A.; Briggs, Paul H.; Mazza, Nilah; Driscoll, Rhonda

    1998-01-01

    Experimental studies show that fresh granitic rocks of the Boulder batholith in the Boulder River headwaters near Basin, Montana have significant acid-neutralizing potential and are capable of neutralizing acidic water derived from metal-mining related wastes or mine workings. Laboratory studies show that in addition to the acidneutralizing potential (ANP) of minor amounts of calcite in these rocks, biotite, tremolite, and feldspars will contribute significantly to long-term ANP. We produced 0.45 micrometer-filtered acidic (pH = 2.95) leachate for use in these ANP experiments by exposing metal-mining related wastes to deionized water in a waste:leachate ratio of 1:20. We then exposed these leachates to finely-ground and sized fractions of batholith rocks, and some of their mineral fractions for extended and repeated periods, for which results are reported here. The intent was to understand what reactions of metal-rich acidic water and fresh igneous rocks would produce. The reactions between the acidic leachates and the bulk rocks and mineral fractions are complex. Factors such as precipitation of phases like Fe-hydroxides and Alhydroxides and the balance between dissolved cations and anions that are sulfate dominated complicate analysis of the results. Research by others of acid neutralization by biotite and tremolite attributed a rise in pH to proton (H+) adsorption in sites vacated by K, Mg, and Ca. Destruction of the silicate framework and liberation of associated structural hydroxyl ions may contribute to ANP. Studies by others have indicated that the conversion of biotite to a vermiculite-type structure by removal of K at a pH of 4 consumes about six protons for every mole of biotite, but at a pH of 3 there is pronounced dissolution of the tetrahedral lattice. The ANP of fresh granitic rocks is much higher than anticipated. The three bulk Boulder igneous rock samples studied have minimum ANP equivalent to about 10-14 weight percent calcite. This ANP is in

  10. Synthesis and characterization of higher amino acid Schiff bases, as monosodium salts and neutral forms. Investigation of the intramolecular hydrogen bonding in all Schiff bases, antibacterial and antifungal activities of neutral forms

    NASA Astrophysics Data System (ADS)

    Güngör, Özlem; Gürkan, Perihan

    2014-09-01

    Schiff bases derived from 5-nitro-salicylaldehyde and 4-aminobutyric acid, 5-aminopentanoic acid and 6-aminohexanoic acid were synthesized both as monosodium salts (1a-3a) and neutral forms (1b-3b). The monosodium-Schiff bases were characterized by elemental analysis, 1H/13C NMR, IR, powder XRD, UV-vis spectra and conductivity measurements. The neutral-Schiff bases were characterized by elemental analysis, 1H/13C NMR, 2D NMR (HMQC), mass, IR, powder XRD, UV-vis spectra and conductivity measurements. The intramolecular hydrogen bonding and related tautomeric equilibria in all the Schiff bases were studied by UV-vis and 1H NMR spectra in solution. Additionally, the neutral-Schiff bases were screened against Staphylococcus aureus-EB18, S. aureus-ATCC 25923, Escherichia coli-ATCC 11230, Candida albicans-M3 and C. albicans-ATCC 16231.

  11. Acid mine drainage neutralization in a pilot sequencing batch reactor using limestone from a paper and pulp industry.

    PubMed

    Vadapalli, V R K; Zvimba, J N; Mathye, M; Fischer, H; Bologo, L

    2015-01-01

    This study investigated the implications of using two grades of limestone from a paper and pulp industry for neutralization of acid mine drainage (AMD) in a pilot sequencing batch reactor (SBR). In this regard, two grades of calcium carbonate were used to neutralize AMD in a SBR with a hydraulic retention time (including settling) of 100 min and a sludge retention time of 360 min, by simultaneously monitoring the Fe(II) removal kinetics and overall assessment of the AMD after treatment. The Fe(II) kinetics removal and overall AMD treatment were observed to be highly dependent on the limestone grade used, with Fe(II) completely removed to levels lower than 50 mg/L in cycle 1 after 30 min using high quality or pure paper and pulp limestone. On the contrary, the other grade limestone, namely waste limestone, could only achieve a similar Fe(II) removal efficiency after four cycles. It was also noticed that suspended solids concentration plays a significant role in Fe(II) removal kinetics. In this regard, using pure limestone from the paper and pulp industry will have advantages compared with waste limestone for AMD neutralization. It has significant process impacts for the SBR configuration as it allows one cycle treatment resulting in a significant reduction of the feed stock, with subsequent generation of less sludge during AMD neutralization. However, the use of waste calcium carbonate from the paper and pulp industry as a feed stock during AMD neutralization can achieve significant cost savings as it is cheaper than the pure limestone and can achieve the same removal efficiency after four cycles.

  12. Three amino acid residues in the envelope of human immunodeficiency virus type 1 CRF07_BC regulate viral neutralization susceptibility to the human monoclonal neutralizing antibody IgG1b12.

    PubMed

    Nie, Jianhui; Zhao, Juan; Chen, Qingqing; Huang, Weijin; Wang, Youchun

    2014-10-01

    The CD4 binding site (CD4bs) of envelope glycoprotein (Env) is an important conserved target for anti-human immunodeficiency virus type 1 (HIV-1) neutralizing antibodies. Neutralizing monoclonal antibodies IgG1 b12 (b12) could recognize conformational epitopes that overlap the CD4bs of Env. Different virus strains, even derived from the same individual, showed distinct neutralization susceptibility to b12. We examined the key amino acid residues affecting b12 neutralization susceptibility using single genome amplification and pseudovirus neutralization assay. Eleven amino acid residues were identified that affect the sensitivity of Env to b12. Through site-directed mutagenesis, an amino acid substitution at position 182 in the V2 region of Env was confirmed to play a key role in regulating the b12 neutralization susceptibility. The introduction of V182L to a resistant strain enhanced its sensitivity to b12 more than twofold. Correspondingly, the introduction of L182V to a sensitive strain reduced its sensitivity to b12 more than tenfold. Amino acid substitution at positions 267 and 346 could both enhance the sensitivity to b12 more than twofold. However, no additive effect was observed when the three site mutageneses were introduced into the same strain, and the sensitivity was equivalent to the single V182L mutation. CRF07_BC is a major circulating recombinant form of HIV-1 prevalent in China. Our data may provide important information for understanding the molecular mechanism regulating the neutralization susceptibility of CRF07_BC viruses to b12 and may be helpful for a vaccine design targeting the CD4bs epitopes.

  13. Influence of five neutralizing products on intra-oral pH after rinsing with simulated gastric acid.

    PubMed

    Lindquist, Birgitta; Lingström, Peter; Fändriks, Lars; Birkhed, Dowen

    2011-08-01

    The aetiology of dental erosion may be of both extrinsic and intrinsic origin. The aim of the present study was to test the ability of various neutralizing products to raise the low intra-oral pH after an erosive exposure, in this case to gastric acid, which was simulated using hydrochloric acid (HCl). Eleven adults participated. They rinsed with 10 ml of 10 mM HCl (pH 2) or 10 ml of 100 mM HCl (pH 1) for 1 min, after which the pH was measured intra-orally for up to 30 min at four sites (two approximal, one buccal, and the dorsum of the tongue). After rinsing with the two acid solutions (pH 1 and pH 2), the following products were used: (i) antacid tablet; (ii) gum arabic lozenge; (iii) mineral water; (iv) milk; and (v) tap water (positive control). The negative control was no product use. The five test products were used for 2 min after the erosive challenge. All the products produced an initially higher pH compared with the negative control. The antacid tablet resulted in the greatest and most rapid increase in pH, followed by the lozenge. In dental practice, the use of any of the neutralizing products tested, especially the antacid tablet, could be recommended in order to increase the intra-oral pH after an erosive challenge. PMID:21726291

  14. Genetic diversity and distribution of bradyrhizobia nodulating peanut in acid-neutral soils in Guangdong Province.

    PubMed

    Chen, Jingyu; Hu, Meijuan; Ma, Huimin; Wang, Yongshan; Wang, En Tao; Zhou, Zhifeng; Gu, Jun

    2016-09-01

    To reveal the genetic diversity and geographic distribution of peanut (Arachis hypogaea L.) rhizobia in Guangdong Province, one of the main peanut producing regions in China, 216 bradyrhizobial isolates were trapped by peanut plants inoculated with soil samples (pH 4.7-7.4) collected from ten sites in Guangdong. Based on BOX-PCR fingerprinting analysis, 71 representative isolates were selected for sequence analyses of ribosomal IGS, recA, atpD and symbiotic gene nodA. As a result, 22 genospecies were detected in the peanut rhizobia, including eight minor groups or single strains corresponding to Bradyrhizobium diazoefficiens, B. japonicum, B. yuanmingense, B. arachidis, B. guangdongense, B. guangxiense, B. iriomotense and B. liaoningense, as well as 14 novel Bradyrhizobium genospecies covering the majority of isolates. Five symbiotic clusters were obtained based on the phylogenetic relationships of nodA genes, related to the soybean-nodulating or peanut-nodulating reference strains. Biogeographic patterns, which were mainly correlated with potassium content and pH, were detected in the peanut bradyrhizobial community in Guangdong Province. These findings enriched the diversity of peanut rhizobia, and added the K content as a special determinant for peanut rhizobial distribution in acid soils. PMID:27499533

  15. Antimicrobial activity of neutralized extracellular culture filtrates of lactic acid bacteria isolated from a cultured Indian milk product ('dahi').

    PubMed

    Varadaraj, M C; Devi, N; Keshava, N; Manjrekar, S P

    1993-12-01

    Neutralized extracellular culture filtrate obtained from isolates of Lactobacillus acidophilus, Lactobacillus delbruecki ssp. bulgaricus, Lactobacillus salivarius and Lactococcus lactis ssp. lactis from 'dahi' showed weak to moderate inhibition of Staphylococcus aureus, Bacillus cereus, Escherichia coli, Bacillus brevis, Bacillus circulans, Bacillus coagulans, Bacillus laterosporus, Bacillus subtilis and Pseudomonas aeruginosa when tested by the diffusion agar well assay method. The effective minimum quantity of lactic culture filtrates required to obtain complete inhibition of an inoculum of 10(3) cfu/ml of the bacteria tested was between 20 and 26% (vol/vol), as determined by the agar incorporation method. Neutralized extracellular culture filtrate of these lactic cultures added at a level of 10% in sterile, 10% reconstituted non-fat dry milk was able to either suppress or retard growth of selected bacterial cultures when incubated at 37 degrees C for 24 h. This study indicated the antimicrobial activity of dahi and the potential of using neutralized extracellular culture filtrate of lactic acid bacteria in the biopreservation of foods.

  16. Neutralization of soil aerosol and its impact on the distribution of acid rain over east Asia: Observations and model results

    NASA Astrophysics Data System (ADS)

    Wang, Zifa; Akimoto, Hajime; Uno, Itsushi

    2002-10-01

    A comprehensive Air Quality Prediction Modeling System is applied to simulate the pH values in precipitation and to investigate neutralization by soil aerosols and their influence on the distribution of acid rain over east Asia. A modified deflation module is designed to provide explicit information on the soil aerosol loading. Numerical simulation was performed for 1 year, from 15 December 1998 to 31 December 1999. Wet deposition monitoring data at 17 sites of the Acid Deposition Monitoring Network in east Asia in addition to State Environmental Protection Agency data were used to evaluate the model, and a reasonable agreement was obtained. Observed evidence clearly shows that in northern China acid deposition is heavily influenced and buffered by natural soil dust from desert and semiarid areas. The observed mean rainwater pH value in northern China is the highest, between 6.0 and 7.2, while in southern China, where many areas severely impacted by acid precipitation are located, the pH value is much lower, between 3.5 and 5. In Japan the mean pH value is 4.7, significantly higher than that in southern China, while in South Korea the pH value is intermediate between those in northern China and Japan. The model is capable of reproducing this geographical distribution of rainwater pH over east Asia. The simulation results for 1999 demonstrated strong neutralization of precipitation by soil aerosols over northeast Asia, and the distribution pattern of acid rain was also altered. The annual mean pH values in northern China and Korea show a remarkable increase of 0.8-2.5, while the increase in mean pH values over southern China and Japan are less than 0.1. The neutralization effects vary by season, with the greatest influence in spring, when pH values increased by 0.1-0.4 in Japan, 0.5-1.5 in Korea, and more than 2 in northern China.

  17. Effect of aspartame-derived phenylalanine on neutral amino acid uptake in human brain: a positron emission tomography study.

    PubMed

    Koeppe, R A; Shulkin, B L; Rosenspire, K C; Shaw, L A; Betz, A L; Mangner, T; Price, J C; Agranoff, B W

    1991-05-01

    The possible effects of elevation of the plasma phenylalanine level secondary to the ingestion of aspartame on brain amino acid uptake in human subjects have been investigated by means of positron emission tomography (PET). 1-[11C]Aminocyclohexanecarboxylate [( 11C]ACHC) is a poorly metabolized synthetic amino acid that crosses the blood-brain barrier by the same carrier that transports naturally occurring large neutral amino acids. Quantitative test-retest PET studies were performed on 15 individuals. Seven received two identical baseline scans, whereas eight received a baseline scan followed by a scan performed approximately 40-45 min following ingestion of an orange-flavored beverage containing 34 mg/kg of body weight of the low-calorie sweetener aspartame, a dose equivalent to the amount in 5 L of diet soft drink consumed all at once by the study subjects, weighing an average of 76 kg. The 40-45-min interval was selected to maximize the detection of possible decreases in ACHC uptake resulting from increased competition for the carrier, because the plasma phenylalanine level is known to peak at this time. We observed an 11.5% decrease in the amino acid transport rate constant K1 and a smaller decrease in the tissue distribution volume of ACHC (6%). Under conditions of normal dietary use, aspartame is thus unlikely to cause changes in brain amino acid uptake that are measurable by PET.

  18. Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles.

    PubMed

    Callejas, Juan F; McEnaney, Joshua M; Read, Carlos G; Crompton, J Chance; Biacchi, Adam J; Popczun, Eric J; Gordon, Thomas R; Lewis, Nathan S; Schaak, Raymond E

    2014-11-25

    Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of -10 mA cm(-2), FeP nanoparticles deposited at a mass loading of ∼1 mg cm(-2) on Ti substrates exhibited overpotentials of -50 mV in 0.50 M H2SO4 and -102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO2 produced H2 at rates and amounts that begin to approach those of Pt/TiO2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically.

  19. Permeation of membranes by the neutral form of amino acids and peptides: relevance to the origin of peptide translocation

    NASA Technical Reports Server (NTRS)

    Chakrabarti, A. C.; Deamer, D. W.; Miller, S. L. (Principal Investigator)

    1994-01-01

    The flux of amino acids and other nutrient solutes such as phosphate across lipid bilayers (liposomes) is 10(5) slower than facilitated inward transport across biological membranes. This suggest that primitive cells lacking highly evolved transport systems would have difficulty transporting sufficient nutrients for cell growth to occur. There are two possible ways by which early life may have overcome this difficulty: (1) The membranes of the earliest cellular life-forms may have been intrinsically more permeable to solutes; or (2) some transport mechanism may have been available to facilitate transbilayer movement of solutes essential for cell survival and growth prior to the evolution of membrane transport proteins. Translocation of neutral species represents one such mechanism. The neutral forms of amino acids modified by methylation (creating protonated weak bases) permeate membranes up to 10(10) times faster than charged forms. This increased permeability when coupled to a transmembrane pH gradient can result in significantly increased rates of net unidirectional transport. Such pH gradients can be generated in vesicles used to model protocells that preceded and were presumably ancestral to early forms of life. This transport mechanism may still play a role in some protein translocation processes (e.g. for certain signal sequences, toxins and thylakoid proteins) in vivo.

  20. Fast targeted analysis of 132 acidic and neutral drugs and poisons in whole blood using LC-MS/MS.

    PubMed

    Di Rago, Matthew; Saar, Eva; Rodda, Luke N; Turfus, Sophie; Kotsos, Alex; Gerostamoulos, Dimitri; Drummer, Olaf H

    2014-10-01

    The aim of this study was to develop an LC-MS/MS based screening technique that covers a broad range of acidic and neutral drugs and poisons by combining a small sample volume and efficient extraction technique with simple automated data processing. After protein precipitation of 100μL of whole blood, 132 common acidic and neutral drugs and poisons including non-steroidal anti-inflammatory drugs, barbiturates, anticonvulsants, antidiabetics, muscle relaxants, diuretics and superwarfarin rodenticides (47 quantitated, 85 reported as detected) were separated using a Shimadzu Prominence HPLC system with a C18 separation column (Kinetex XB-C18, 4.6mm×150mm, 5μm), using gradient elution with a mobile phase of 25mM ammonium acetate buffer (pH 7.5)/acetonitrile. The drugs were detected using an ABSciex(®) API 2000 LC-MS/MS system (ESI+ and -, MRM mode, two transitions per analyte). The method was fully validated in accordance with international guidelines. Quantification data obtained using one-point calibration compared favorably to that using multiple calibrants. The presented LC-MS/MS assay has proven to be applicable for determination of the analytes in blood. The fast and reliable extraction method combined with automated processing gives the opportunity for high throughput and fast turnaround times for forensic and clinical toxicology.

  1. Canine distemper virus neutralization activity is low in human serum and it is sensitive to an amino acid substitution in the hemagglutinin protein

    SciTech Connect

    Zhang, Xinsheng; Wallace, Olivia L.; Domi, Arban; Wright, Kevin J.; Driscoll, Jonathan; Anzala, Omu; Sanders, Eduard J.; Kamali, Anatoli; Allen, Susan; Fast, Pat; Gilmour, Jill; Price, Matt A.; Parks, Christopher L.

    2015-08-15

    Serum was analyzed from 146 healthy adult volunteers in eastern Africa to evaluate measles virus (MV) and canine distemper virus (CDV) neutralizing antibody (nAb) prevalence and potency. MV plaque reduction neutralization test (PRNT) results indicated that all sera were positive for MV nAbs. Furthermore, the 50% neutralizing dose (ND50) for the majority of sera corresponded to antibody titers induced by MV vaccination. CDV nAbs titers were low and generally were detected in sera with high MV nAb titers. A mutant CDV was generated that was less sensitive to neutralization by human serum. The mutant virus genome had 10 nucleotide substitutions, which coded for single amino acid substitutions in the fusion (F) and hemagglutinin (H) glycoproteins and two substitutions in the large polymerase (L) protein. The H substitution occurred in a conserved region involved in receptor interactions among morbilliviruses, implying that this region is a target for cross-reactive neutralizing antibodies. - Highlights: • Screened 146 serum samples for measles virus (MV) and canine distemper virus (CDV) neutralizing antibody (nAb). • MV nAb is prevalent in the sera. • CDV neutralizing activity is generally low or absent and when detected it is present in sera with high MV nAb titers. • A neutralization-resistant CDV mutant was isolated using human serum selection. • A mutation was identified in the receptor-binding region of CDV hemagglutinin protein that confers the neutralization resistance.

  2. Human monoclonal antibodies derived from a patient infected with 2009 pandemic influenza A virus broadly cross-neutralize group 1 influenza viruses

    SciTech Connect

    Pan, Yang; Sasaki, Tadahiro; Du, Anariwa; and others

    2014-07-18

    Highlights: • Influenza infection can elicit heterosubtypic antibodies to group 1 influenza virus. • Three human monoclonal antibodies were generated from an H1N1-infected patient. • The antibodies predominantly recognized α-helical stem of viral hemagglutinin (HA). • The antibodies inhibited HA structural activation during the fusion process. • The antibodies are potential candidates for future antibody therapy to influenza. - Abstract: Influenza viruses are a continuous threat to human public health because of their ability to evolve rapidly through genetic drift and reassortment. Three human monoclonal antibodies (HuMAbs) were generated in this study, 1H11, 2H5 and 5G2, and they cross-neutralize a diverse range of group 1 influenza A viruses, including seasonal H1N1, 2009 pandemic H1N1 (H1N1pdm) and avian H5N1 and H9N2. The three HuMAbs were prepared by fusing peripheral blood lymphocytes from an H1N1pdm-infected patient with a newly developed fusion partner cell line, SPYMEG. All the HuMAbs had little hemagglutination inhibition activity but had strong membrane-fusion inhibition activity against influenza viruses. A protease digestion assay showed the HuMAbs targeted commonly a short α-helix region in the stalk of the hemagglutinin. Furthermore, Ile45Phe and Glu47Gly double substitutions in the α-helix region made the HA unrecognizable by the HuMAbs. These two amino acid residues are highly conserved in the HAs of H1N1, H5N1 and H9N2 viruses. The HuMAbs reported here may be potential candidates for the development of therapeutic antibodies against group 1 influenza viruses.

  3. Modeling removal of Cd, Cu, Pb, and Zn in acidic groundwater during neutralization by ambient surface waters and groundwaters

    USGS Publications Warehouse

    Paulson, A.J.; Balistrieri, L.

    1999-01-01

    Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal

  4. Effects of USDA beef quality grade and cooking on fatty acid composition of neutral and polar lipid fractions.

    PubMed

    Legako, J F; Dinh, T T N; Miller, M F; Brooks, J C

    2015-02-01

    The effects of USDA beef quality grade (QG; Prime, Low Choice, and Standard; n=8) and cooking (RC) on fatty acid (FA) concentrations (mg/g dry matter) and percentages of neutral and polar lipid fractions (NL and PL, respectively)from strip steaks were explored. An increase in QG led to an accumulation of most FA, especially in the NL fraction (P < 0.001). Common effects on FA percentages were two-way interactions of either QG or RC with LF (P ≤ 0.019). Fatty acids were affected differently by QG and RC depending on their originating LF. Monounsaturated fatty acid (MUFA) and polyunsaturated fatty acid (PUFA) percentages of the PL were dependent on QG (P ≤ 0.014). Cooking and QG had minimal impact on FA percentages of the NL, however, greatly influenced PL MUFA and PUFA percentages (P b 0.001). There was evidence indicating that dry heat cookery affected not only PUFA, as generally thought, but also the MUFA of PL fraction.

  5. Acidic extracellular pH neutralizes the autophagy-inhibiting activity of chloroquine

    PubMed Central

    Pellegrini, Paola; Strambi, Angela; Zipoli, Chiara; Hägg-Olofsson, Maria; Buoncervello, Maria; Linder, Stig; De Milito, Angelo

    2014-01-01

    Acidic pH is an important feature of tumor microenvironment and a major determinant of tumor progression. We reported that cancer cells upregulate autophagy as a survival mechanism to acidic stress. Inhibition of autophagy by administration of chloroquine (CQ) in combination anticancer therapies is currently evaluated in clinical trials. We observed in 3 different human cancer cell lines cultured at acidic pH that autophagic flux is not blocked by CQ. This was consistent with a complete resistance to CQ toxicity in cells cultured in acidic conditions. Conversely, the autophagy-inhibiting activity of Lys-01, a novel CQ derivative, was still detectable at low pH. The lack of CQ activity was likely dependent on a dramatically reduced cellular uptake at acidic pH. Using cell lines stably adapted to chronic acidosis we could confirm that CQ lack of activity was merely caused by acidic pH. Moreover, unlike CQ, Lys-01 was able to kill low pH-adapted cell lines, although higher concentrations were required as compared with cells cultured at normal pH conditions. Notably, buffering medium pH in low pH-adapted cell lines reverted CQ resistance. In vivo analysis of tumors treated with CQ showed that accumulation of strong LC3 signals was observed only in normoxic areas but not in hypoxic/acidic regions. Our observations suggest that targeting autophagy in the tumor environment by CQ may be limited to well-perfused regions but not achieved in acidic regions, predicting possible limitations in efficacy of CQ in antitumor therapies. PMID:24492472

  6. Canine distemper virus neutralization activity is low in human serum and it is sensitive to an amino acid substitution in the hemagglutinin protein.

    PubMed

    Zhang, Xinsheng; Wallace, Olivia L; Domi, Arban; Wright, Kevin J; Driscoll, Jonathan; Anzala, Omu; Sanders, Eduard J; Kamali, Anatoli; Karita, Etienne; Allen, Susan; Fast, Pat; Gilmour, Jill; Price, Matt A; Parks, Christopher L

    2015-08-01

    Serum was analyzed from 146 healthy adult volunteers in eastern Africa to evaluate measles virus (MV) and canine distemper virus (CDV) neutralizing antibody (nAb) prevalence and potency. MV plaque reduction neutralization test (PRNT) results indicated that all sera were positive for MV nAbs. Furthermore, the 50% neutralizing dose (ND50) for the majority of sera corresponded to antibody titers induced by MV vaccination. CDV nAbs titers were low and generally were detected in sera with high MV nAb titers. A mutant CDV was generated that was less sensitive to neutralization by human serum. The mutant virus genome had 10 nucleotide substitutions, which coded for single amino acid substitutions in the fusion (F) and hemagglutinin (H) glycoproteins and two substitutions in the large polymerase (L) protein. The H substitution occurred in a conserved region involved in receptor interactions among morbilliviruses, implying that this region is a target for cross-reactive neutralizing antibodies. PMID:25880113

  7. Canine distemper virus neutralization activity is low in human serum and it is sensitive to an amino acid substitution in the hemagglutinin protein.

    PubMed

    Zhang, Xinsheng; Wallace, Olivia L; Domi, Arban; Wright, Kevin J; Driscoll, Jonathan; Anzala, Omu; Sanders, Eduard J; Kamali, Anatoli; Karita, Etienne; Allen, Susan; Fast, Pat; Gilmour, Jill; Price, Matt A; Parks, Christopher L

    2015-08-01

    Serum was analyzed from 146 healthy adult volunteers in eastern Africa to evaluate measles virus (MV) and canine distemper virus (CDV) neutralizing antibody (nAb) prevalence and potency. MV plaque reduction neutralization test (PRNT) results indicated that all sera were positive for MV nAbs. Furthermore, the 50% neutralizing dose (ND50) for the majority of sera corresponded to antibody titers induced by MV vaccination. CDV nAbs titers were low and generally were detected in sera with high MV nAb titers. A mutant CDV was generated that was less sensitive to neutralization by human serum. The mutant virus genome had 10 nucleotide substitutions, which coded for single amino acid substitutions in the fusion (F) and hemagglutinin (H) glycoproteins and two substitutions in the large polymerase (L) protein. The H substitution occurred in a conserved region involved in receptor interactions among morbilliviruses, implying that this region is a target for cross-reactive neutralizing antibodies.

  8. Transcriptional regulation of the sodium-coupled neutral amino acid transporter (SNAT2) by 17β-estradiol

    PubMed Central

    Velázquez-Villegas, Laura A.; Ortíz, Víctor; Ström, Anders; Torres, Nimbe; Engler, David A.; Matsunami, Risë; Ordaz-Rosado, David; García-Becerra, Rocío; López-Barradas, Adriana M.; Larrea, Fernando; Gustafsson, Jan-Åke; Tovar, Armando R.

    2014-01-01

    The sodium-coupled neutral amino acid transporter 2 (SNAT2) translocates small neutral amino acids into the mammary gland to promote cell proliferation during gestation. It is known that SNAT2 expression increases during pregnancy, and in vitro studies indicate that this transporter is induced by 17β-estradiol. In this study, we elucidated the mechanism by which 17β-estradiol regulates the transcription of SNAT2. In silico analysis revealed the presence of a potential estrogen response element (ERE) in the SNAT2 promoter. Reporter assays showed an increase in SNAT2 promoter activity when cotransfected with estrogen receptor alpha (ER-α) after 17β-estradiol stimulation. Deletion of the ERE reduced estradiol-induced promoter activity by 63%. Additionally, EMSAs and supershift assays showed that ER-α binds to the SNAT2 ERE and that this binding competes with the interaction of ER-α with its consensus ERE. An in vivo ChIP assay demonstrated that the binding of ER-α to the SNAT2 promoter gradually increased in the mammary gland during gestation and that maximal binding occurred at the highest 17β-estradiol serum concentration. Liquid chromatography-elevated energy mass spectrometry and Western blot analysis revealed that the SNAT2 ER-α–ERE complex contained poly(ADP-ribose) polymerase 1, Lupus Ku autoantigen protein p70, and glyceraldehyde 3-phosphate dehydrogenase (GAPDH) proteins and that the silencing of each of these proteins nearly abolished 17β-estradiol–stimulated SNAT2 promoter activity. Nuclear levels of GAPDH increased progressively during gestation in the mammary gland, and GAPDH binding was nucleotide-specific for the SNAT2 ERE. Thus, this study provides new insights into how the mammary epithelium adapts to control amino acid uptake through the transcriptional regulation of the SNAT2 transporter via 17β-estradiol. PMID:25056967

  9. Rat epididymal luminal fluid acid beta-D-galactosidase optimally hydrolyses glycoprotein substrate at neutral pH.

    PubMed Central

    Skudlarek, M D; Tulsiani, D R; Orgebin-Crist, M C

    1992-01-01

    Several glycosidases, purified and characterized from mammalian tissues, have been shown to be optimally active under acidic conditions when p-nitrophenyl (PNP) or 4-methylumbelliferyl glycosides are used as substrates. Although high levels of the glycosidases are present in the epididymal lumen, their physiological role remains uncertain. To be functional, the glycosidases are expected to be enzymatically active at or near the physiological pH of luminal fluid. In this report, we demonstrate that the rat epididymal luminal fluid beta-D-galactosidase, optimally active toward PNP beta-D-galactoside at pH 3.5, shows maximum activity towards a glycoprotein substrate ([Gal-3H]fetuin) at neutral pH. Several lines of evidence, including immunoprecipitation studies using antibody to the acid beta-D-galactosidase, and substrate competition studies, indicate that PNP galactosidase and [3H]Gal galactosidase activities are caused by a single enzyme, and that the two substrates are probably cleaved by the same catalytic site(s). Competition studies with various disaccharides indicate that this enzyme is capable of cleaving a variety of galactose linkages found in both O- and N-linked oligosaccharides. Molecular-sieve column chromatography of the beta-D-galactosidase of luminal fluid under several conditions of buffer and pH show that, whereas the enzyme eluted as a tetramer (apparent M(r) 320,000) under acidic conditions (pH 3.5-4.3), only dimers and monomers (apparent M(r) 180,000 and 92,000 respectively) were observed in neutral conditions (pH 6.8). This aggregation/dissociation phenomenon is reversible. These studies indicate that beta-D-galactosidase is present in the luminal fluid in dissociated forms, and is therefore optimally active towards glycoprotein substrates at physiological pH. The potential role of the enzyme in modification of sperm surface glycoproteins is discussed. PMID:1417750

  10. Neutral lipid biosynthesis in engineered Escherichia coli: jojoba oil-like wax esters and fatty acid butyl esters.

    PubMed

    Kalscheuer, Rainer; Stöveken, Tim; Luftmann, Heinrich; Malkus, Ursula; Reichelt, Rudolf; Steinbüchel, Alexander

    2006-02-01

    Wax esters are esters of long-chain fatty acids and long-chain fatty alcohols which are of considerable commercial importance and are produced on a scale of 3 million tons per year. The oil from the jojoba plant (Simmondsia chinensis) is the main biological source of wax esters. Although it has a multitude of potential applications, the use of jojoba oil is restricted, due to its high price. In this study, we describe the establishment of heterologous wax ester biosynthesis in a recombinant Escherichia coli strain by coexpression of a fatty alcohol-producing bifunctional acyl-coenzyme A reductase from the jojoba plant and a bacterial wax ester synthase from Acinetobacter baylyi strain ADP1, catalyzing the esterification of fatty alcohols and coenzyme A thioesters of fatty acids. In the presence of oleate, jojoba oil-like wax esters such as palmityl oleate, palmityl palmitoleate, and oleyl oleate were produced, amounting to up to ca. 1% of the cellular dry weight. In addition to wax esters, fatty acid butyl esters were unexpectedly observed in the presence of oleate. The latter could be attributed to solvent residues of 1-butanol present in the medium component, Bacto tryptone. Neutral lipids produced in recombinant E. coli were accumulated as intracytoplasmic inclusions, demonstrating that the formation and structural integrity of bacterial lipid bodies do not require specific structural proteins. This is the first report on substantial biosynthesis and accumulation of neutral lipids in E. coli, which might open new perspectives for the biotechnological production of cheap jojoba oil equivalents from inexpensive resources employing recombinant microorganisms.

  11. Neutral Lipid Biosynthesis in Engineered Escherichia coli: Jojoba Oil-Like Wax Esters and Fatty Acid Butyl Esters

    PubMed Central

    Kalscheuer, Rainer; Stöveken, Tim; Luftmann, Heinrich; Malkus, Ursula; Reichelt, Rudolf; Steinbüchel, Alexander

    2006-01-01

    Wax esters are esters of long-chain fatty acids and long-chain fatty alcohols which are of considerable commercial importance and are produced on a scale of 3 million tons per year. The oil from the jojoba plant (Simmondsia chinensis) is the main biological source of wax esters. Although it has a multitude of potential applications, the use of jojoba oil is restricted, due to its high price. In this study, we describe the establishment of heterologous wax ester biosynthesis in a recombinant Escherichia coli strain by coexpression of a fatty alcohol-producing bifunctional acyl-coenzyme A reductase from the jojoba plant and a bacterial wax ester synthase from Acinetobacter baylyi strain ADP1, catalyzing the esterification of fatty alcohols and coenzyme A thioesters of fatty acids. In the presence of oleate, jojoba oil-like wax esters such as palmityl oleate, palmityl palmitoleate, and oleyl oleate were produced, amounting to up to ca. 1% of the cellular dry weight. In addition to wax esters, fatty acid butyl esters were unexpectedly observed in the presence of oleate. The latter could be attributed to solvent residues of 1-butanol present in the medium component, Bacto tryptone. Neutral lipids produced in recombinant E. coli were accumulated as intracytoplasmic inclusions, demonstrating that the formation and structural integrity of bacterial lipid bodies do not require specific structural proteins. This is the first report on substantial biosynthesis and accumulation of neutral lipids in E. coli, which might open new perspectives for the biotechnological production of cheap jojoba oil equivalents from inexpensive resources employing recombinant microorganisms. PMID:16461689

  12. Highly conserved asparagine 82 controls the interaction of Na+ with the sodium-coupled neutral amino acid transporter SNAT2.

    PubMed

    Zhang, Zhou; Gameiro, Armanda; Grewer, Christof

    2008-05-01

    The neutral amino acid transporter 2 (SNAT2), which belongs to the SLC38 family of solute transporters, couples the transport of amino acid to the cotransport of one Na(+) ion into the cell. Several polar amino acids are highly conserved within the SLC38 family. Here, we mutated three of these conserved amino acids, Asn(82) in the predicted transmembrane domain 1 (TMD1), Tyr(337) in TMD7, and Arg(374) in TMD8; and we studied the functional consequences of these modifications. The mutation of N82A virtually eliminated the alanine-induced transport current, as well as amino acid uptake by SNAT2. In contrast, the mutations Y337A and R374Q did not abolish amino acid transport. The K(m) of SNAT2 for its interaction with Na(+), K(Na(+)), was dramatically reduced by the N82A mutation, whereas the more conservative mutation N82S resulted in a K(Na(+)) that was in between SNAT2(N82A) and SNAT2(WT). These results were interpreted as a reduction of Na(+) affinity caused by the Asn(82) mutations, suggesting that these mutations interfere with the interaction of SNAT2 with the sodium ion. As a consequence of this dramatic reduction in Na(+) affinity, the apparent K(m) of SNAT2(N82A) for alanine was increased 27-fold compared with that of SNAT2(WT). Our results demonstrate a direct or indirect involvement of Asn(82) in Na(+) coordination by SNAT2. Therefore, we predict that TMD1 is crucial for the function of SLC38 transporters and that of related families.

  13. Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling

    PubMed Central

    MacMillan, David W. C.; Overman, Larry E.

    2015-01-01

    Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved. PMID:26322524

  14. Hydrogeologic comparison of an acidic-lake basin with a neutral-lake basin in the West-Central Adirondack Mountains, New York

    USGS Publications Warehouse

    Peters, N.E.; Murdoch, Peter S.

    1985-01-01

    Two small headwater lake basins that receive similar amounts of acidic atmospheric deposition have significantly different lake outflow pH values; pH at Panther Lake (neutral) ranges from about 4.7 to 7; that at Woods Lake (acidic) ranges from about 4.3 to 5. A hydrologic analysis, which included monthly water budgets, hydrograph analysis, examination of flow duration and runoff recession curves, calculation of ground-water storage, and an analysis of lateral flow capacity of the soil, indicates that differences in lakewater pH can be attributed to differences in the ground-water contribution to the lakes. A larger percentage of the water discharged from the neutral lake is derived from ground water than that from the acidic lake. Ground water has a higher pH resulting from a sufficiently long residence time for neutralizing chemical reactions to occur with the till. The difference in ground-water contribution is attributed to a more extensive distribution of thick till (<3m) in the neutral-lake basin than in the acidic-lake basin; average thickness of till in the neutral-lake basin is 24m whereas that in the other is 2.3m. During the snowmelt period, as much as three months of accumulated precipitation may be released within two weeks causing the lateral flow capacity of the deeper mineral soil to be exceeded in the neutral-lake basin. This excess water moves over and through the shallow acidic soil horizons and causes the lakewater pH to decrease during snowmelt.Two small headwater lake basins that receive similar amounts of acidic atmospheric deposition have significantly different lake outflow pH values; pH at Panther Lake (neutral) ranges from about 4. 7 to 7; that at Woods Lake (acidic) ranges from about 4. 3 to 5. A hydrologic analysis, which included monthly water budgets, hydrograph analysis, examination of flow duration and runoff recession curves, calculation of ground-water storage, and an analysis of lateral flow capacity of the soil, indicates that

  15. Effects of aspartame and carbohydrate administration on human and rat plasma large neutral amino acid levels and rat brain amino acid and monoamine levels.

    PubMed

    Romano, M; Casacci, F; De Marchi, F; Pacei, T; Esteve, A; Lomuscio, G; Mennini, T; Salmona, M

    1989-01-01

    Thirty fasted human volunteers were given 0.83 and 8.3 mg aspartame/kg body weight alone, as part of a basal low carbohydrate meal (648 kcal, 10% carbohydrate) or as part of a high energy carbohydrate-rich meal (1290 kcal, 34% carbohydrate). Amino acid concentrations in plasma were determined before and 30, 60 and 180 min after the consumption of aspartame. Under these conditions, which mimic realistic aspartame consumption, aspartame had no significant effect on plasma concentration of any amino acid. In addition, the effect of aspartame alone or with carbohydrates on plasma and brain amino acid levels was studied in rats after acute or subacute (14 d) oral treatment. In subacute dosing experiments aspartame was included in the diet. Brain monoamine concentrations were also measured in the same animals. Plasma concentrations of large neutral amino acids were modified under acute conditions. In contrast, after subacute treatment no significant differences in plasma or brain amino acid concentrations or in brain monoamine concentrations were observed.

  16. Kinetics of Antibody Aggregation at Neutral pH and Ambient Temperatures Triggered by Temporal Exposure to Acid.

    PubMed

    Imamura, Hiroshi; Honda, Shinya

    2016-09-15

    The purification process of an antibody in manufacturing involves temporal exposure of the molecules to low pH followed by neutralization-pH-shift stress-which causes aggregation. It remains unclear how aggregation triggered by pH-shift stress grows at neutral pH and how it depends on the temperature in an ambient range. We used static and dynamic light scattering to monitor the time-dependent evolution of the aggregate size of the pH-shift stressed antibody between 4.0 and 40.0 °C. A power-law relationship between the effective molecular weight and the effective hydrodynamic radius was found, indicating that the aggregates were fractal with a dimension of 1.98. We found that the aggregation kinetics in the lower-temperature range, 4.0-25.0 °C, were well described by the Smoluchowski aggregation equation. The temperature dependence of the effective aggregation rate constant gave 13 ± 1 kcal/mol of endothermic activation energy. Temporal acid exposure creates an enriched population of unfolded protein molecules that are competent of aggregating. Therefore, the energetically unfavorable unfolding step is not required and the aggregation proceeds faster. These findings provide a basis for predicting the growth of aggregates during storage under practical, ambient conditions. PMID:27537343

  17. Quantifying the role of forest soil and bedrock in the acid neutralization of surface water in steep hillslopes.

    PubMed

    Asano, Yuko; Uchida, Taro

    2005-02-01

    The role of soil and bedrock in acid neutralizing processes has been difficult to quantify because of hydrological and biogeochemical uncertainties. To quantify those roles, hydrochemical observations were conducted at two hydrologically well-defined, steep granitic hillslopes in the Tanakami Mountains of Japan. These paired hillslopes are similar except for their soils; Fudoji is leached of base cations (base saturation <6%), while Rachidani is covered with fresh soil (base saturation >30%), because the erosion rate is 100-1000 times greater. The results showed that (1) soil solution pH at the soil-bedrock interface at Fudoji (4.3) was significantly lower than that of Rachidani (5.5), (2) the hillslope discharge pH in both hillslopes was similar (6.7-6.8), and (3) at Fudoji, 60% of the base cations leaching from the hillslope were derived from bedrock, whereas only 20% were derived from bedrock in Rachidani. Further, previously published results showed that the stream pH could not be predicted from the acid deposition rate and soil base saturation status. These results demonstrate that bedrock plays an especially important role when the overlying soil has been leached of base cations. These results indicate that while the status of soil acidification is a first-order control on vulnerability to surface water acidification, in some cases such as at Fudoji, subsurface interaction with the bedrock determines the sensitivity of surface water to acidic deposition.

  18. Plasma and brain kinetics of large neutral amino acids and of striatum monoamines in rats given aspartame.

    PubMed

    Romano, M; Diomede, L; Guiso, G; Caccia, S; Perego, C; Salmona, M

    1990-05-01

    Two doses (250 and 1000 mg/kg body weight) of aspartame were administered orally to male rats, and plasma and brain phenylalanine and tyrosine kinetic profiles were studied. In both plasma and brain the maximum increase in phenylalanine and tyrosine levels was reached 60 min after treatment. The changes in brain levels of phenylalanine or tyrosine 0, 60, 120 or 180 min after treatment with 1000 mg AMP/kg were directly correlated with the ratio of the plasma concentration of phenylalanine or tyrosine to the overall plasma concentration of the other large neutral amino acids. The time course of monoamine and metabolite concentrations, in the corpora striatum of the brain, was studied after an oral dose of 500 mg phenylalanine/kg. No significant modifications of monoamine levels were found at any of the times studied, up to 5 hr after dosing.

  19. Detection of conspecific alarm cues by juvenile salmonids under neutral and weakly acidic conditions: laboratory and field tests.

    PubMed

    Leduc, Antoine O H C; Kelly, Jocelyn M; E Brown, Grant

    2004-04-01

    A variety of fishes possess damage-released chemical alarm cues, which play a critical role in the detection and avoidance of potential predation threats. Recently, we have demonstrated that the ability of fathead minnows ( Pimephales promelas) and finescale dace ( Phoxinus neogaeus) to detect and respond to conspecific alarm cues is significantly reduced under weakly acidic conditions (pH 6.0). Rainbow trout ( Oncorhynchus mykiss) and brook charr ( Salvelinus fontinalis) possess an analogous alarm cue system. However, it is unknown if the trout alarm cue system is likewise affected by relatively small changes in pH. In addition, previous studies have not verified this phenomenon under natural conditions. We conducted laboratory and field trials to examine the potential effects of acute exposure to weakly acidic (pH 6.0) conditions on the detection and response of conspecific alarm cues by juvenile trout. Our laboratory results demonstrate that while juvenile rainbow trout exhibit significant increases in antipredator behaviour under normal pH conditions (pH 7.0-7.2), they do not respond to the presence of conspecific chemical alarm cues (i.e. response is not different from controls) under weakly acidic conditions. Similarly, a wild strain of brook charr in their natural streams near Sudbury, Ontario, failed to detect conspecific alarm cues in a weakly acidic stream (mean pH 6.11) while they responded to these cues in a neutral stream (mean pH of 6.88). This is the first demonstration that relatively small changes in ambient pH can influence alarm responses under natural conditions. These data suggest significant, sub-lethal effects of acid precipitation on natural waterways.

  20. Detection of conspecific alarm cues by juvenile salmonids under neutral and weakly acidic conditions: laboratory and field tests.

    PubMed

    Leduc, Antoine O H C; Kelly, Jocelyn M; E Brown, Grant

    2004-04-01

    A variety of fishes possess damage-released chemical alarm cues, which play a critical role in the detection and avoidance of potential predation threats. Recently, we have demonstrated that the ability of fathead minnows ( Pimephales promelas) and finescale dace ( Phoxinus neogaeus) to detect and respond to conspecific alarm cues is significantly reduced under weakly acidic conditions (pH 6.0). Rainbow trout ( Oncorhynchus mykiss) and brook charr ( Salvelinus fontinalis) possess an analogous alarm cue system. However, it is unknown if the trout alarm cue system is likewise affected by relatively small changes in pH. In addition, previous studies have not verified this phenomenon under natural conditions. We conducted laboratory and field trials to examine the potential effects of acute exposure to weakly acidic (pH 6.0) conditions on the detection and response of conspecific alarm cues by juvenile trout. Our laboratory results demonstrate that while juvenile rainbow trout exhibit significant increases in antipredator behaviour under normal pH conditions (pH 7.0-7.2), they do not respond to the presence of conspecific chemical alarm cues (i.e. response is not different from controls) under weakly acidic conditions. Similarly, a wild strain of brook charr in their natural streams near Sudbury, Ontario, failed to detect conspecific alarm cues in a weakly acidic stream (mean pH 6.11) while they responded to these cues in a neutral stream (mean pH of 6.88). This is the first demonstration that relatively small changes in ambient pH can influence alarm responses under natural conditions. These data suggest significant, sub-lethal effects of acid precipitation on natural waterways. PMID:14758533

  1. Preparation of an adsorbent based on polymeric ionic liquid for the simultaneous extraction of acidic, basic and neutral pollutants.

    PubMed

    Chen, Lei; Huang, Xiaojia

    2016-09-30

    In this study, coextraction of acidic, basic and neutral pollutants was realized with a new adsorbent based on polymeric ionic liquid (PIL). In the presence of a porogen solvent containing 1-propanol and 1,4-butanediol, an ionic liquid, 1-vinyl-3-octylimidazolium tetrafluoraborate was used as monomer to copolymerize with dual cross-linkers (divinylbenzene and N,N-methylene-bisacrylamide) to form the adsorbent for stir cake sorptive extraction (SCSE). Phenols, aromatic amines and parabens were selected as acidic, basic and neutral model analytes, respectively. The effects of preparation conditions and extraction parameters on the extraction performance of SCSE/PIL were investigated thoroughly. Under the optimized conditions, the prepared adsorbent showed satisfactory coextraction performance to the selected analytes with multiply interactions. At the same time, simple and sensitive analytical method for simultaneous determination of phenols, aromatic amines and parabens in environmental water samples was developed by the combination of SCSE/PIL with high-performance liquid chromatography with diode array detection. Low limits of detection (S/N=3) and quantification limits (S/N=10) of the proposed method for the targeted analytes were achieved within the range of 0.064-0.30μg/L and 0.21-0.99μg/L, respectively. The precision of the proposed method was evaluated in terms of intra- and inter-assay variability calculated as relative standard deviation (RSD), and it was found that the RSD values were all below 10%. Ultimately, the applicability of developed method was successfully confirmed by analyzing lake, reservoir and river water samples. Recoveries obtained for the determination of targeted analytes in spiking samples ranged from 70.0% to 112%, with RSDs within the range of 1.6-9.8%. PMID:27613147

  2. The role of anaerobic bacteria in the neutralization of acid mine drainage. [Desulfovibrio

    SciTech Connect

    Bell, P.E.

    1988-01-01

    In contrast to the acidic water column, the sediments underlying Lake Anna, which receives acid mine drainage, are circumneutral and contain 1-4 meq alkalinity/L. Indirect fluorescent antibody counts of a methanogen (strain CA) and a sulfate reducer (Desulfovibrio strain SM) demonstrated that these organisms were present in the sediments at numbers of approximately 10{sup 6} bacteria/mL sediment. Anaerobic heterotrophs in the sediments underlying the acidified arm of the lake outnumbered anaerobic heterotrophs in a non-acidified arm of the lake. A major storm event resulted in the deposition of 11 cm of oxidized, acidic new sediment material over the older circumneutral sediments. The Eh in the new sediments decreased by 200 mV within one week after the storm event. The pH and alkalinity increased even in the 1-cm layer by two weeks after the storm and products of sulfate reduction (acid volatile sulfide) increased at three weeks after the storm. This suggests that biological processes other than sulfate reduction were responsible for the initial buffering of these sediments. Laboratory experiments using the sulfate reducer and two anaerobes (also isolated from the sediments) suggested that alkalinity production during sulfate reduction decreases with decreasing carbon concentration. Generation of alkalinity was found not to be a simple function of sulfate reduction or of iron reduction. The generation of alkalinity was found to be a function of the carbon source, and concentration, organisms present, and mineral phase formed. Iron reduction rates in the sediments of Contrary Creek ranged from 4.9-27.8 mM/m{sup 2}-sediment-day. Alkalinity was produced in the floc layer in the absence of sulfate reduction. Iron reduction could be responsible for the mineralization of 15-90% of the carbon input to this system.

  3. Group Exchange between Ketones and Carboxylic Acids through Directing Group Assisted Rh-Catalyzed Reorganization of Carbon Skeletons.

    PubMed

    Lei, Zhi-Quan; Pan, Fei; Li, Hu; Li, Yang; Zhang, Xi-Sha; Chen, Kang; Wang, Xin; Li, Yu-Xue; Sun, Jian; Shi, Zhang-Jie

    2015-04-22

    The Rh(I)-catalyzed direct reorganization of organic frameworks and group exchanges between carboxylic acids and aryl ketones was developed with the assistance of directing group. Biaryls, alkenylarenes, and alkylarenes were produced in high efficiency from aryl ketones and the corresponding carboxylic acids by releasing the other molecule of carboxylic acids and carbon monoxide. A wide range of functional groups were well compatible. The exchanges between two partners were proposed to take place on the Rh-(III) center of key intermediates, supported by experimental mechanistic studies and computational calculations. The transformation unveiled the new catalytic pathway of the group transfer of two organic molecules.

  4. Group Exchange between Ketones and Carboxylic Acids through Directing Group Assisted Rh-Catalyzed Reorganization of Carbon Skeletons.

    PubMed

    Lei, Zhi-Quan; Pan, Fei; Li, Hu; Li, Yang; Zhang, Xi-Sha; Chen, Kang; Wang, Xin; Li, Yu-Xue; Sun, Jian; Shi, Zhang-Jie

    2015-04-22

    The Rh(I)-catalyzed direct reorganization of organic frameworks and group exchanges between carboxylic acids and aryl ketones was developed with the assistance of directing group. Biaryls, alkenylarenes, and alkylarenes were produced in high efficiency from aryl ketones and the corresponding carboxylic acids by releasing the other molecule of carboxylic acids and carbon monoxide. A wide range of functional groups were well compatible. The exchanges between two partners were proposed to take place on the Rh-(III) center of key intermediates, supported by experimental mechanistic studies and computational calculations. The transformation unveiled the new catalytic pathway of the group transfer of two organic molecules. PMID:25843169

  5. Cholesterol balance and fecal neutral steroid and bile acid excretion in normal men fed dietary fats of different fatty acid composition

    PubMed Central

    Connor, William E.; Witiak, Donald T.; Stone, Daniel B.; Armstrong, Mark L.

    1969-01-01

    Six normal men were fed formula diets containing either highly saturated fat (cocoa butter, iodine value 32) or polyunsaturated fat (corn oil, iodine value 125). The sterol balance technique was used to compare the changes in serum cholesterol concentration with the excretion of fecal steroids. The method used for the analysis of fecal steroids was chemical, with a final identification and quantification by gas-liquid chromatography. It was confirmed that the chemical method for fecal steroid analysis was accurate and reproducible. The three dietary periods were each 3 wk in length. In sequence, cocoa butter (period I), corn oil, and cocoa butter (period III) were fed at 40% of the total calories. All diets were cholesterol free, contained similar amounts of plant sterols, and were identical in other nutrients. Corn oil had a hypocholesterolemic effect. Mean serum cholesterol concentrations were 222 mg/100 ml (cocoa butter, period I), 177 during corn oil, and 225 after the return to cocoa butter. Individual fecal steroids were determined from stools pooled for 7 days. Both neutral steroids and bile acids were altered significantly by dietary polyunsaturated fat. The change in bile acid excretion was considerably greater than the change in neutral steroids. Corn oil caused a greater fecal excretion of both deoxycholic and lithocholic acids. The total mean excretion (milligrams per day) of fecal steroids was 709 for cocoa butter (period I), 915 for corn oil, and 629 for the second cocoa butter period. The enhanced total fecal steroid excretion by the polyunsaturated fat of corn oil created a negative cholesterol balance vis-à-vis the saturated fat of cocoa butter. The hypocholesterolemic effect of polyunsaturated fat was associated with total fecal sterol excretion twice greater than the amount of cholesterol calculated to leave the plasma. This finding suggested possible loss of cholesterol from the tissues as well. Images PMID:5796351

  6. Net Acid Production, Acid Neutralizing Capacity, and Associated Mineralogical and Geochemical Characteristics of Animas River Watershed Igneous Rocks Near Silverton, Colorado

    USGS Publications Warehouse

    Yager, Douglas B.; Choate, LaDonna; Stanton, Mark R.

    2008-01-01

    This report presents results from laboratory and field studies involving the net acid production (NAP), acid neutralizing capacity (ANC), and magnetic mineralogy of 27 samples collected in altered volcanic terrain in the upper Animas River watershed near Silverton, Colo., during the summer of 2005. Sampling focused mainly on the volumetrically important, Tertiary-age volcanic and plutonic rocks that host base- and precious-metal mineralization in the study area. These rocks were analyzed to determine their potential for neutralization of acid-rock drainage. Rocks in the study area have been subjected to a regional propylitic alteration event, which introduced calcite, chlorite (clinochlore), and epidote that have varying amounts and rates of acid neutralizing capacity (ANC). Locally, hydrothermal alteration has consumed any ANC and introduced minerals, mainly pyrite, that have a high net acid production (NAP). Laboratory studies included hydrogen pyroxide (H2O2) acid digestion and subsequent sodium hydroxide (NaOH) titration to determine NAP, and sulfuric acid (H2SO4) acid titration experiments to determine ANC. In addition to these environmental rock-property determinations, mineralogical, chemical, and petrographic characteristics of each sample were determined through semiquantitative X-ray diffractometry (Rietveld method), optical mineralogy, wavelength dispersive X-ray fluorescence, total carbon-carbonate, and inductively coupled plasma?mass spectrometric analysis. An ANC ranking was assigned to rock samples based on calculated ANC quantity in kilograms/ton (kg/t) calcium carbonate equivalent and ratios of ANC to NAP. Results show that talus near the southeast Silverton caldera margin, composed of andesite clasts of the Burns Member of the Silverton Volcanics, has the highest ANC (>100 kg/t calcium carbonate equivalent) with little to no NAP. The other units found to have moderate to high ANC include (a) andesite lavas and volcaniclastic rocks of the San Juan

  7. CuI/1,10-phen/PEG promoted decarboxylation of 2,3-diarylacrylic acids: synthesis of stilbenes under neutral and microwave conditions with an in situ generated recyclable catalyst.

    PubMed

    Zou, Yong; Huang, Qi; Huang, Tong-Kun; Ni, Qing-Chun; Zhang, En-Sheng; Xu, Tian-Long; Yuan, Mu; Li, Jun

    2013-09-25

    A series of trans- or cis-stilbenes have been synthesized in good to excellent yields via a functional group-dependent decarboxylation process from the corresponding 2,3-diaryl acrylic acids in a neutral CuI/1,10-phen/PEG-400 system under microwave conditions. The in situ generation of the recyclable catalytic complex, the use of environmentally benign solvent PEG-400, the operational simplicity, the short reaction times, as well as the functional group-dependent chemo- and stereo-selectivity have made the decarboxylation process a highly efficient and applicable protocol. PMID:24057265

  8. Regulation of amino acid transporters in pluripotent cell populations in the embryo and in culture; novel roles for sodium-coupled neutral amino acid transporters.

    PubMed

    Tan, Boon Siang Nicholas; Rathjen, Peter D; Harvey, Alexandra J; Gardner, David K; Rathjen, Joy

    2016-08-01

    The developmental outcomes of preimplantation mammalian embryos are regulated directly by the surrounding microenvironment, and inappropriate concentrations of amino acids, or the loss of amino acid-sensing mechanisms, can be detrimental and impact further development. A specific role for l-proline in the differentiation of embryonic stem (ES) cells, a cell population derived from the blastocyst, has been shown in culture. l-proline acts as a signalling molecule, exerting its effects through cell uptake and subsequent metabolism. Uptake in ES cells occurs predominantly through the sodium-coupled neutral amino acid transporter 2, Slc38a2 (SNAT2). Dynamic expression of amino acid transporters has been shown in the early mammalian embryo, reflecting functional roles for amino acids in embryogenesis. The expression of SNAT2 and family member Slc38a1 (SNAT1) was determined in mouse embryos from the 2-cell stage through to the early post-implantation pre-gastrulation embryo. Key changes in expression were validated in cell culture models of development. Both transporters showed temporal dynamic expression patterns and changes in intracellular localisation as differentiation progressed. Changes in transporter expression likely reflect different amino acid requirements during development. Findings include the differential expression of SNAT1 in the inner and outer cells of the compacted morula and nuclear localisation of SNAT2 in the trophectoderm and placental lineages. Furthermore, SNAT2 expression was up-regulated in the epiblast prior to primitive ectoderm formation, an expression pattern consistent with a role for the transporter in later developmental decisions within the pluripotent lineage. We propose that the differential expression of SNAT2 in the epiblast provides evidence for an l-proline-mediated mechanism contributing to the regulation of embryonic development. PMID:27373508

  9. The effect of enteral supplementation of specific neutral and acidic oligosaccharides on the faecal microbiota and intestinal microenvironment in preterm infants.

    PubMed

    Westerbeek, E A M; Slump, R A; Lafeber, H N; Knol, J; Georgi, G; Fetter, W P F; van Elburg, R M

    2013-02-01

    We aimed to determine the effects of enteral supplementation of a prebiotic mixture of neutral and acidic oligosaccharides (scGOS/lcFOS/pAOS) on the faecal microbiota and microenvironment in preterm infants. Furthermore, we determined the influence of perinatal factors on the development of the faecal microbiota. In a randomised controlled trial, preterm infants with gestational age <32 weeks and/or birth weight <1,500 g received enteral supplementation of scGOS/lcFOS/pAOS or placebo (maltodextrin) between days 3 and 30 of life. Faecal microbiota, as measured with fluorescent in situ hybridisation (FISH), and microenvironment [short-chain fatty acids (SCFAs), pH, sIgA] were measured at four time points: before the start of the study and at days 7, 14 and 30 of life. In total, 113 preterm infants were included. Enteral supplementation of the prebiotic mixture increased the total bacteria count at day 14 (Exp 3.92; 95 % confidence interval [CI] 1.18-13.04, p = 0.03), but not at day 30 (Exp 1.73; 95 % CI 0.60-5.03, p = 0.31). There was a trend toward increased bifidobacteria counts. There was a delayed intestinal colonisation of all bacteria. Enteral supplementation of the prebiotic mixture decreased the faecal pH (Exp 0.71; 95 % CI 0.54-0.93, p = 0.01) and there was a trend toward increased acetic acid compared to the placebo group (Exp 1.09; 95 % CI 0.99-1.20, p = 0.10). There was no effect on sIgA (Exp 1.94; 95 % CI 0.28-13.27, p = 0.50). Antibiotics decreased the total bacteria count (Exp 0.13; 95 % CI 0.08-0.22, p < 0.001). Enteral supplementation of a prebiotic mixture of neutral and acidic oligosaccharides increases the postnatal intestinal colonisation. However, the extensive use of broad-spectrum antibiotics in preterm infants decreased the growth of all intestinal microbiota, thereby, delaying the normal microbiota development.

  10. Quantifying amine permeation sources with acid neutralization: calibrations and amines measured in coastal and continental atmospheres

    NASA Astrophysics Data System (ADS)

    Freshour, N. A.; Carlson, K. K.; Melka, Y. A.; Hinz, S.; Panta, B.; Hanson, D. R.

    2014-04-01

    An acid titration method for quantifying amine permeation rates was used to calibrate an Ambient pressure Proton transfer Mass Spectrometer (AmPMS) that monitors ambient amine compounds. The method involves capturing amines entrained in a N2 flow by bubbling it through an acidified solution (~ 10-5 M HCl), and the amines are quantified via changes in solution pH with time. Home-made permeation tubes had permeation rates (typically tens of pmol s-1) that depended on the type of amine and tubing and on temperature. Calibrations of AmPMS yielded sensitivities for ammonia, methyl amine, dimethyl amine, and trimethyl amine that are close to the sensitivity assuming a gas-kinetic, ion-molecule rate coefficient. The permeation tubes were also designed to deliver a reproducible amount of amine to a flow reactor where nucleation with sulfuric acid was studied. The high proton affinity compound dimethyl sulfoxide (DMSO), linked to oceanic environments, was also studied and AmPMS is highly sensitive to it. AmPMS was deployed recently in two field campaigns and mixing ratios are reported for ammonia, alkyl amines, and DMSO and correlations between these species and with particle formation events are discussed.

  11. Amine permeation sources characterized with acid neutralization and sensitivities of an amine mass spectrometer

    NASA Astrophysics Data System (ADS)

    Freshour, N. A.; Carlson, K. K.; Melka, Y. A.; Hinz, S.; Panta, B.; Hanson, D. R.

    2014-10-01

    An acid titration method for quantifying amine permeation rates was used to calibrate an Ambient pressure Proton transfer Mass Spectrometer (AmPMS) that monitors ambient amine compounds. The method involves capturing amines entrained in a N2 flow by bubbling it through an acidified solution (~10-5 M HCl), and the amines are quantified via changes in solution pH with time. Home-made permeation tubes had permeation rates (typically tens of pmol s-1) that depended on the type of amine and tubing and on temperature. Calibrations of AmPMS yielded sensitivities for ammonia, methylamine, dimethylamine, and trimethylamine that are close to the sensitivity assuming a gas-kinetic, ion-molecule rate coefficient. The permeation tubes were also designed to deliver a reproducible amount of amine to a flow reactor where nucleation with sulfuric acid was studied. The high proton affinity compound dimethyl sulfoxide (DMSO), linked to oceanic environments, was also studied and AmPMS is highly sensitive to it. AmPMS was deployed recently in two field campaigns and, using these sensitivities, mixing ratios for ammonia and the alkyl amines are derived from the signals. Correlations between these species and with particle formation events are discussed.

  12. The unique stability of Vibrio proteolyticus neutral protease under alkaline conditions affords a selective step for purification and use in amino acid-coupling reactions.

    PubMed

    Durham, D R

    1990-08-01

    A procedure is described for the purification of a neutral protease from fermentation broths of Vibrio proteolyticus. The key feature of the purification scheme is the selective, irreversible inactivation of a contaminating exoenzyme, aminopeptidase, by alkali treatment, rather than removal of this enzyme by conventional chromatographic methods. Fermentation broths or concentrates were brought to pH 11.5 to 11.7 by Na2CO3-NaOH addition and incubated at 25 degrees C until aminopeptidase activity was diminished. The alkali treatment resulted in greater than 99% reduction of aminopeptidase activity with minimal loss of neutral protease activity. The neutral protease could be further purified to apparent homogeneity by QA-52 cellulose chromatography. The alkali treatment of fermentation concentrates was also useful for preparation of V. proteolyticus neutral protease to effect the coupling of N-protected aspartic acid and phenylalanine methyl ester for the production of N-aspartylphenylalanine methyl ester, a precursor for the sweetener aspartame.

  13. Inactivation of Escherichia coli by photochemical reaction of ferrioxalate at slightly acidic and near-neutral pHs.

    PubMed

    Cho, Min; Lee, Yunho; Chung, Hyenmi; Yoon, Jeyong

    2004-02-01

    Fenton chemistry, which is known to play an effective role in degrading toxic chemicals, is difficult to apply to disinfection in water treatment, since its reaction is effective only at the acidic pH of 3. The presence of oxalate ions and UV-visible light, which is known as a photoferrioxalate system, allows the Fe(III) to be dissolved at slightly acidic and near-neutral pHs and maintains the catalytic reaction of iron. This study indicates that the main oxidizing species in the photoferrioxalate system responsible for microorganism inactivation is OH radical. Escherichia coli was used as an indicator microorganism. The CT value (OH radical concentration x contact time; used to indicate the effect of the combination of the concentration of the disinfectant and the contact time on inactivation) for a 2-log inactivation of E. coli was approximately 1.5 x 10(-5) mg/liter/min, which is approximately 2,700 times lower than that of ozone as estimated by the delayed Chick-Watson model. Since the light emitted by the black light blue lamp is similar to sunlight in the specific wavelength range of 300 to 420 nm, the photoferrioxalate system, which can have a dual function, treating water for both organic pollutants and microorganisms simultaneously, shows promise for the treatment of water or wastewater in remote or rural sites. However, the photoferrioxalate disinfection system is slower in inactivating microorganisms than conventional disinfectants are. PMID:14766597

  14. Inactivation of Escherichia coli by Photochemical Reaction of Ferrioxalate at Slightly Acidic and Near-Neutral pHs

    PubMed Central

    Cho, Min; Lee, Yunho; Chung, Hyenmi; Yoon, Jeyong

    2004-01-01

    Fenton chemistry, which is known to play an effective role in degrading toxic chemicals, is difficult to apply to disinfection in water treatment, since its reaction is effective only at the acidic pH of 3. The presence of oxalate ions and UV-visible light, which is known as a photoferrioxalate system, allows the Fe(III) to be dissolved at slightly acidic and near-neutral pHs and maintains the catalytic reaction of iron. This study indicates that the main oxidizing species in the photoferrioxalate system responsible for microorganism inactivation is OH radical. Escherichia coli was used as an indicator microorganism. The CT value (OH radical concentration × contact time; used to indicate the effect of the combination of the concentration of the disinfectant and the contact time on inactivation) for a 2-log inactivation of E. coli was approximately 1.5 × 10−5 mg/liter/min, which is approximately 2,700 times lower than that of ozone as estimated by the delayed Chick-Watson model. Since the light emitted by the black light blue lamp is similar to sunlight in the specific wavelength range of 300 to 420 nm, the photoferrioxalate system, which can have a dual function, treating water for both organic pollutants and microorganisms simultaneously, shows promise for the treatment of water or wastewater in remote or rural sites. However, the photoferrioxalate disinfection system is slower in inactivating microorganisms than conventional disinfectants are. PMID:14766597

  15. Inactivation of Escherichia coli by photochemical reaction of ferrioxalate at slightly acidic and near-neutral pHs.

    PubMed

    Cho, Min; Lee, Yunho; Chung, Hyenmi; Yoon, Jeyong

    2004-02-01

    Fenton chemistry, which is known to play an effective role in degrading toxic chemicals, is difficult to apply to disinfection in water treatment, since its reaction is effective only at the acidic pH of 3. The presence of oxalate ions and UV-visible light, which is known as a photoferrioxalate system, allows the Fe(III) to be dissolved at slightly acidic and near-neutral pHs and maintains the catalytic reaction of iron. This study indicates that the main oxidizing species in the photoferrioxalate system responsible for microorganism inactivation is OH radical. Escherichia coli was used as an indicator microorganism. The CT value (OH radical concentration x contact time; used to indicate the effect of the combination of the concentration of the disinfectant and the contact time on inactivation) for a 2-log inactivation of E. coli was approximately 1.5 x 10(-5) mg/liter/min, which is approximately 2,700 times lower than that of ozone as estimated by the delayed Chick-Watson model. Since the light emitted by the black light blue lamp is similar to sunlight in the specific wavelength range of 300 to 420 nm, the photoferrioxalate system, which can have a dual function, treating water for both organic pollutants and microorganisms simultaneously, shows promise for the treatment of water or wastewater in remote or rural sites. However, the photoferrioxalate disinfection system is slower in inactivating microorganisms than conventional disinfectants are.

  16. Long-term effect of wholemeal bread on stool weight, transit time, fecal bile acids, fats, and neutral sterols.

    PubMed

    Eastwood, M A; Elton, R A; Smith, J H

    1986-03-01

    Stool weight, fecal constituents, bile acids, fat, neutral sterols, and intestinal transit time were recorded in 28 subjects over 18 mo. During the first 12 mo the subjects ate white bread. They were studied for an initial period of 7 days, and after 6 mo (study period 1). For the first 6 mo they ate their usual intake of bread, they then increased their white bread intake by 62 g/day for 6 mo (study period 2). The subjects ate a self-selected diet throughout the 18 mo study. During the last 6 mo (study period 3) the subjects replaced white bread by the same amount of wholemeal bread as in study period 2. No increase in stool weight occurred until study period 3 when there was an increase of 20%. There developed a linear relationship between stool weight and intestinal transit time which was not found during the initial first and second study periods. A seasonal influence on serum cholesterol was not observed during the wholemeal bread period. Fecal bile acid excretion was unchanged throughout the experiment.

  17. Production of L-lactic acid by a thermophilic Bacillus mutant using sodium hydroxide as neutralizing agent.

    PubMed

    Qin, Jiayang; Wang, Xiuwen; Zheng, Zhaojuan; Ma, Cuiqing; Tang, Hongzhi; Xu, Ping

    2010-10-01

    A sodium lactate tolerant mutant strain named Bacillus sp. Na-2 was obtained and applied to sodium hydroxide-based L-lactic acid (LA) production process. The influences of aeration and pH were investigated to further improve the resistance of strain Na-2 against sodium lactate stress and to obtain the most efficient L-LA production process. Although mild aeration was favorable for cell growth and L-LA production, vigorous aeration resulted in a metabolic shift from homolactic to mixed-acid/acetoin fermentation. Therefore, a two-stage aeration control strategy was employed. Optimum pH was found to be 6.0. A total of 106.0 g/l L-LA was produced in 30 h by Bacillus sp. Na-2 using sodium hydroxide as neutralizing agent. Productivity, conversion rate and optical purity were 3.53 g/l/h, 94% and 99.5%, respectively. The remarkable fermentation traits of Bacillus sp. Na-2 and the environment-friendly characteristics of NaOH-based process represent new insight for industrial scale production of L-LA.

  18. Recombinant D. radiodurans cells for bioremediation of heavy metals from acidic/neutral aqueous wastes.

    PubMed

    Misra, Chitra Seetharam; Appukuttan, Deepti; Kantamreddi, Venkata Siva Satyanarayana; Rao, Amara S; Apte, Shree Kumar

    2012-01-01

    The stability and superior metal bioremediation ability of genetically engineered Deinococcus radiodurans cells, expressing a non-specific acid phosphatase, PhoN in high radiation environment has already been established. The lyophilized recombinant DrPhoN cells retained PhoN activity and uranium precipitation ability. Such cells also displayed an extended shelf life of 6 months during storage at room temperature and showed surface associated precipitation of uranium as well as other metals like cadmium. Lyophilized cells, immobilized in polyacrylamide gels could be used for uranium bioprecipitation in a flow through system resulting in 70% removal from 1mM input uranium solution and a loading of 1 g uranium/g dry weight cells. Compared with a batch process which achieved a loading of 5.7 g uranium/g biomass, the efficiency of the column process was low due to clogging of the column by the precipitate.

  19. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

    DOE PAGES

    Liberman-Martin, Allegra L.; Bergman, Robert G.; Tilley, T. Don

    2015-04-16

    Bis(perfluorocatecholato)silane Si(cat(F)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat(F)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BAr(F)4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

  20. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound

    SciTech Connect

    Liberman-Martin, Allegra L.; Bergman, Robert G.; Tilley, T. Don

    2015-04-16

    Bis(perfluorocatecholato)silane Si(cat(F)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat(F)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BAr(F)4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

  1. Lewis Acidity of Bis(perfluorocatecholato)silane: Aldehyde Hydrosilylation Catalyzed by a Neutral Silicon Compound.

    PubMed

    Liberman-Martin, Allegra L; Bergman, Robert G; Tilley, T Don

    2015-04-29

    Bis(perfluorocatecholato)silane Si(cat(F))2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N'-diisopropylbenzamide. The potent Lewis acidity of Si(cat(F))2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BAr(F)4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

  2. Recombinant D. radiodurans cells for bioremediation of heavy metals from acidic/neutral aqueous wastes.

    PubMed

    Misra, Chitra Seetharam; Appukuttan, Deepti; Kantamreddi, Venkata Siva Satyanarayana; Rao, Amara S; Apte, Shree Kumar

    2012-01-01

    The stability and superior metal bioremediation ability of genetically engineered Deinococcus radiodurans cells, expressing a non-specific acid phosphatase, PhoN in high radiation environment has already been established. The lyophilized recombinant DrPhoN cells retained PhoN activity and uranium precipitation ability. Such cells also displayed an extended shelf life of 6 months during storage at room temperature and showed surface associated precipitation of uranium as well as other metals like cadmium. Lyophilized cells, immobilized in polyacrylamide gels could be used for uranium bioprecipitation in a flow through system resulting in 70% removal from 1mM input uranium solution and a loading of 1 g uranium/g dry weight cells. Compared with a batch process which achieved a loading of 5.7 g uranium/g biomass, the efficiency of the column process was low due to clogging of the column by the precipitate. PMID:22179144

  3. Review of Alpha-Ketoglutaric Acid (AKGA) Hydrazine and Monomethylhydrazine (MMH) Neutralizing Compound

    NASA Technical Reports Server (NTRS)

    Dibbern, Andreas W.; Beeson, Harold D.; Greene, Benjamin; Giordano, Thomas J.

    2009-01-01

    The Johnson Space Center (JSC) White Sands Test Facility (WSTF) and NASA Engineering and Safety Center (NESC) were requested by NASA Associate Administrator for Space Operations to perform an evaluation of a proposed hydrazine/monomethylhydrazine (MMH) fuel treatment method using alpha-ketoglutaric acid (AKGA). This evaluation request was prompted by preliminary tests at the Kennedy Space Center (KSC), suggesting cost and operational benefits to NASA for the Space Shuttle Program (SSP) and other hardware decontamination and decommissioning, in addition to hydrazine and MMH waste treatment activities. This paper provides the team's position on the current KSC and New Mexico Highlands University (NMHU) efforts toward implementing the AKGA treatment technology with flight hardware, ground support equipment (GSE), hydrazine and MMH spills, and vapor control. This evaluation is current to the last data examined (approximately September 2008).

  4. Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

    1995-01-01

    Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the ??-ether or ??-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic ??-ether and ??-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

  5. Trophic niches of sympatric tropical tuna in the Western Indian Ocean inferred by stable isotopes and neutral fatty acids

    NASA Astrophysics Data System (ADS)

    Sardenne, Fany; Bodin, Nathalie; Chassot, Emmanuel; Amiel, Aurélien; Fouché, Edwin; Degroote, Maxime; Hollanda, Stéphanie; Pethybridge, Heidi; Lebreton, Benoit; Guillou, Gaël; Ménard, Frédéric

    2016-08-01

    This study examined the trophic ecology of three sympatric tropical tuna species (bigeye BET, skipjack SKJ, and yellowfin YFT) sampled in the Western Indian Ocean throughout 2013. Specifically we explored inter-specific resource partitioning and ontogenetic variability using neutral fatty acids and stable isotope analysis of liver and muscle from small (⩽100 cm fork length, FL) and large (>100 cm FL) tuna collected in mixed schools at the surface by purse-seine. Both biochemical tracers were used to calculate trophic niche indices that collectively revealed high potential for resource overlap, especially among small tuna. Resource overlap appeared strongest between BET and YFT, with SKJ tissues having high carbon isotope (δ13C) values (-17 ± 0.3‰), lower nitrogen isotope (δ15N) values (11.4 ± 0.6‰), and higher relative proportion of poly-unsaturated fatty acids (PUFA) than the two other species, indicating a different diet. Size was found to be a strong predictor for most biochemical tracers in the three species with δ13C, δ15N and total lipid content in the liver. In the larger species (YFT and BET), proportions of mono-unsaturated fatty acids typically increased with size, while quantities of PUFA decreased. In addition to ontogenetic variability, trophic markers were shown to vary between sampling area and season: higher lipid reserves and δ15N values, and lower δ13C values occurred during monsoon periods around Seychelles than in the Mozambique Channel (parted from about 1500 km). Our multi-tracer approach reveals the magnitude of potential competitive interactions in mixed tropical tuna schools at both small and large sizes and demonstrates that ontogenetic niche differentiation acts as a major factor of coexistence in tropical tuna.

  6. Effect of temperature, hydraulic residence time and elevated PCO2 on acid neutralization within a pulsed limestone bed reactor

    USGS Publications Warehouse

    Watten, B.J.; Lee, P.C.; Sibrell, P.L.; Timmons, M.B.

    2007-01-01

    Limestone has potential for reducing reagent costs and sludge volume associated with treatment of acid mine drainage, but its use is restricted by slow dissolution rates and the deposition of Fe, Al and Mn-based hydrolysis products on reactive surfaces. We evaluated a pulsed limestone bed (PLB) reactor (15 L/min capacity) that uses a CO2 pretreatment step to accelerate dissolution and hydraulic shearing forces provided by intermittent fluidization to abrade and carry away surface scales. We established the effects of hydraulic residence time (HRT, 5.1-15.9 min), temperature (T, 12-22 ??C) and CO2 tension (PCO2, 34.5-206.8 kPa) on effluent quality when inlet acidity (Acy) was fixed at 440 mg/L (pH=2.48) with H2SO4. The PLB reactor neutralized all H+ acidity (N=80) while concurrently providing unusually high levels of effluent alkalinity (247-1028 mg/L as CaCO3) that allow for side-stream treatment with blending. Alkalinity (Alk) yields rose with increases in PCO2, HRT and settled bed height (BH, cm) and decreased with T following the relationship (R2=0.926; p<0.001): (Alk)non-filtered=-548.726+33.571??(PCO2)0.5+33.671??(HRT)+7.734??(BH)-5.197??(T). Numerical modeling showed CO2 feed requirements for a target Alk yield decrease with increases in HRT, T and the efficiency of off-gas (CO2) recycling. ?? 2007 Elsevier Ltd. All rights reserved.

  7. Effects of aspartame and glucose administration on brain and plasma levels of large neutral amino acids and brain 5-hydroxyindoles.

    PubMed

    Yokogoshi, H; Roberts, C H; Caballero, B; Wurtman, R J

    1984-07-01

    Administration of the artificial sweetener aspartame (L-aspartylphenylalanylmethyl ester; 200 mg/kg) by gavage to rats caused large increments in brain and plasma levels of phenylalanine and its product tyrosine. Glucose administration (3 g/kg, by gavage, a dose sufficient to cause insulin-mediated reductions in plasma levels of the large neutral amino acids leucine, isoleucine, and valine) also elevated brain phenylalanine and tyrosine, and enhanced the increments caused by the aspartame, nearly doubling the rise in brain phenylalanine. Each animal's brain phenylalanine or tyrosine levels were highly correlated (r = 0.97 and 0.99, respectively) with its plasma phenylalanine or tyrosine ratios, affirming that aspartame's effects on the brain amino acids result from the changes it produces in plasma composition. As described previously, glucose consumption increased brain tryptophan levels, and consequently, brain levels of the 5-hydroxyindoles serotonin and 5-hydroxyindoleacetic acid. Aspartame alone had no effect on these compounds but completely blocked the changes in 5-hydroxyindoles caused by glucose. Each animal's brain level of tryptophan (r = 0.89) and 5-hydroxyindoles (r = 0.74) was also significantly correlated with its plasma tryptophan ratio, affirming that the effects of glucose or aspartame on these brain constituents also result from the changes they produce in plasma composition. The aspartame-glucose combination also reduced brain levels of leucine, isoleucine, and valine to a significantly greater extent than aspartame or glucose alone. These observations indicate that high aspartame doses can generate major neurochemical changes in rats, especially when consumed along with carbohydrate-containing foods. However, they should not in any way be interpreted as demonstrating that aspartame significantly affects the human brain.

  8. Effects of saliva on starch-thickened drinks with acidic and neutral pH.

    PubMed

    Hanson, Ben; Cox, Ben; Kaliviotis, Efstathios; Smith, Christina H

    2012-09-01

    Powdered maize starch thickeners are used to modify drink consistency in the clinical management of dysphagia. Amylase is a digestive enzyme found in saliva which breaks down starch. This action is dependent on pH, which varies in practice depending on the particular drink. This study measured the effects of human saliva on the viscosity of drinks thickened with a widely used starch-based thickener. Experiments simulated a possible clinical scenario whereby saliva enters a cup and contaminates a drink. Citric acid (E330) was added to water to produce a controlled range of pH from 3.0 to 7.0, and several commercially available drinks with naturally low pH were investigated. When saliva was added to thickened water, viscosity was reduced to less than 1% of its original value after 10-15 min. However, lowering pH systematically slowed the reduction in viscosity attributable to saliva. At pH 3.5 and below, saliva was found to have no significant effect on viscosity. The pH of drinks in this study ranged from 2.6 for Coca Cola to 6.2 for black coffee. Again, low pH slowed the effect of saliva. For many popular drinks, having pH of 3.6 or less, viscosity was not significantly affected by the addition of saliva. PMID:22210234

  9. Influence of phosphate and silica on U(VI) precipitation from acidic and neutralized wastewaters

    SciTech Connect

    Kanematsu, Masakazu; Perdrial, Nicolas; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

    2014-06-03

    Uranium speciation and physical-chemical characteristics were studied in solids precipitated from synthetic acidic to circumneutral wastewaters in the presence and absence of dissolved silica and phosphate to examine thermodynamic and kinetic controls on phase formation. Composition of synthetic wastewater was based on disposal sites 216-U-8 and 216-U-12 Cribs at the Hanford site (WA, USA). In the absence of dissolved silica or phosphate, crystalline or amorphous uranyl oxide hydrates, either compreignacite or meta-schoepite, precipitated at pH 5 or 7 after 30 d of reaction, in agreement with thermodynamic calculations. In the presence of 1 mM dissolved silica representative of groundwater concentrations, amorphous phases dominated by compreignacite precipitated rapidly at pH 5 or 7 as a metastable phase and formation of poorly-crystalline boltwoodite, the thermodynamically stable uranyl silicate phase, was slow. In the presence of phosphate (3 mM), meta-ankoleite initially precipitated as the primary phase at pH 3, 5, or 7 regardless of the presence of 1 mM dissolved silica. Analysis of precipitates by U LIII-edge EXAFS indicated that “autunite-type” sheets of meta-ankoleite transformed to “phosphuranylite-type” sheets after 30 d of reaction, probably due to Ca substitution in the structure. Low solubility of uranyl phosphate phases limits dissolved U(VI) concentrations but differences in particle size, crystallinity, and precipitate composition vary with pH and base cation concentration, which will influence the thermodynamic and kinetic stability of these phases.

  10. Comparison of acidic and neutral PH root conditioners prior to a coronally positioned flap to treat gingival recession

    PubMed Central

    Ahmadi, Roya Shariatmadar; Awwadi, Mohammd Reza; Moatazed, Shilan; Rezaei, Fatemeh; Hajisadeghi, Samira

    2014-01-01

    Background: Localized gingival recession can be treated successfully via coronally positioned flap (CPF) and additional use of root surface demineralization agents. The purpose of this study was to evaluate the effects of additional use of ethylene diamine tetraacetic acid (EDTA) and citric acid as a root conditioner in association with CPF to cover localized buccal gingival recessions. Materials and Methods: Twenty-seven patients with 66 Miller class I buccal gingival recession ≥ 2 mm on single-rooted teeth were studied. Patients were randomly assigned: CPF with EDTA gel (test 1) and CPF with saturated citric acid (test 2) or CPF alone (control). Clinical parameters were measured at baseline and 1, 2, 3 and 6 months after surgery; assessment included recession depth (RD), clinical attachment level (CAL), probing depth (PD) and height of keratinized gingiva (HKG). SPSS version-20 was used to perform all statistical analyses. Data was reported as Mean ± SD. Age, RD, CAL, PD, and HKG before treatment and after 6 months among study groups were compared by one-way ANOVA followed by the Tukey test. The level of significance was considered to be less than 0.05. Results: At 6 months, all treatment modalities showed significant root coverage and gain in CAL. RD was reduced from 2.86 ± 0.76 mm to 0.55±0.53 mm in the EDTA group and from 2.37±0.57 mm to 1.03±0.43 mm in the acid group and from 2.37±0.54 mm to 0.85±0.49 mm in the control group. The average percentage of root coverage for the EDTA, acid, and control groups were 80.73%, 52.16%, and 64.50%, respectively. At 6 months, there was a significant difference (P < 0.05) in all parameters for the EDTA group (except HKG that did not vary among the groups). Conclusion: Root preparation with EDTA was an effective procedure to cover localized gingival recessions and significantly improved the amount of root coverage obtained. PMID:25097639

  11. Trans-10, cis-12 conjugated linoleic acid reduces neutral lipid content and may affect cryotolerance of in vitro-produced crossbred bovine embryos

    PubMed Central

    2014-01-01

    Background Due to high neutral lipids accumulation in the cytoplasm, in vitro-produced embryos from Bos primigenius indicus and their crosses are more sensitive to chilling and cryopreservation than those from Bos primigenius taurus. The objective of the present study was to evaluate the effects of trans-10, cis-12 conjugated linoleic acid (CLA) on the development and cryotolerance of crossbred Bos primigenius taurus x Bos primigenius indicus embryos produced in vitro, and cultured in the presence of fetal calf serum. Bovine zygotes (n = 1,692) were randomly assigned to one of the following treatment groups: 1) Control, zygotes cultured in Charles Rosenkrans 2 amino acid (CR2aa) medium (n = 815) or 2) CLA, zygotes cultured in CR2aa medium supplemented with 100 μmol/L of trans-10, cis-12 CLA (n = 877). Embryo development (cleavage and blastocyst rates evaluated at days 3 and 8 of culture, respectively), lipid content at morula stage (day 5) and blastocyst cryotolerance (re-expansion and hatching rates, evaluated 24 and 72 h post-thawing, respectively) were compared between groups. Additionally, selected mRNA transcripts were measured by Real–Time PCR in blastocyst stage. Results The CLA treatment had no effect on cleavage and blastocyst rates, or on mRNA levels for genes related to cellular stress and apoptosis. On the other hand, abundance of mRNA for the 1-acylglycerol-3-phosphate 0-acyltransferase-encoding gene (AGPAT), which is involved in triglycerides synthesis, and consequently neutral lipid content, were reduced by CLA treatment. A significant increase was observed in the re-expansion rate of embryos cultured with trans-10, cis-12 CLA when compared to control (56.3 vs. 34.4%, respectively, P = 0.002). However, this difference was not observed in the hatching rate (16.5 vs. 14.0%, respectively, P = 0.62). Conclusions The supplementation with trans-10, cis-12 CLA isomer in culture medium reduced the lipid content of in vitro produced

  12. Knockdown of a nutrient amino acid transporter gene LdNAT1 reduces free neutral amino acid contents and impairs Leptinotarsa decemlineata pupation

    PubMed Central

    Fu, Kai-Yun; Guo, Wen-Chao; Ahmat, Tursun; Li, Guo-Qing

    2015-01-01

    A Leptinotarsa decemlineata SLC6 NAT gene (LdNAT1) was cloned. LdNAT1 was highly expressed in the larval alimentary canal especially midgut. LdNAT1 mRNA levels were high right after the molt and low just before the molt. JH and a JH analog pyriproxyfen activated LdNAT1 expression. RNAi of an allatostatin gene LdAS-C increased JH and upregulated LdNAT1 transcription. Conversely, silencing of a JH biosynthesis gene LdJHAMT decreased JH and reduced LdNAT1 expression. Moreover, 20E and an ecdysteroid agonist halofenozide repressed LdNAT1 expression, whereas a decrease in 20E by RNAi of an ecdysteroidogenesis gene LdSHD and disruption of 20E signaling by knockdown of LdE75 and LdFTZ-F1 activated LdNAT1 expression. Thus, LdNAT1 responded to both 20E and JH. Moreover, knockdown of LdNAT1 reduced the contents of cysteine, histidine, isoleucine, leucine, methionine, phenylalanine and serine in the larval bodies and increased the contents of these amino acids in the larval feces. Furthermore, RNAi of LdNAT1 inhibited insulin/target of rapamycin pathway, lowered 20E and JH titers, reduced 20E and JH signaling, retarded larval growth and impaired pupation. These data showed that LdNAT1 was involved in the absorption of several neutral amino acids critical for larval growth and metamorphosis. PMID:26657797

  13. X-ray absorption and resonance raman spectroscopy of human myeloperoxidase at neutral and acid pH.

    PubMed

    Yue, K T; Taylor, K L; Kinkade, J M; Sinclair, R B; Powers, L S

    1997-04-01

    Myeloperoxidase (MPO), an important enzyme in the oxygen-dependent host defense system of human polymorphonuclear leukocytes, utilizes hydrogen peroxide to catalyze the production of hypochlorous acid, an oxidizing bactericidal agent. While MPO shows significant sequence homology with other peroxidases and this homology is particularly striking among the active-site residues, MPO exhibits unusual spectral features and the unique ability to catalyze the oxidation of chloride ions. We have investigated the MPO active-site with X-ray absorption (XAS) and resonance Raman (RRS) spectroscopies at neutral pH and also at the physiological acidic pH (pH approximately 3) and have compared these results with those of horseradish peroxidase (HRP). At pH 7.5, XAS results show that the iron heme active site is 6-coordinate where the distal ligand is likely nitrogen or oxygen, but not sulfur. The heme is distorted compared to HRP, other peroxidases, and heme compounds, but at pH approximately 3, the distal ligand is lost and the heme is less distorted. RRS results under identical pH conditions show that the skeletal core-size sensitive modes and v3 are shifted to higher frequency at pH approximately 3 indicating a 6- to 5-coordination change of high spin ferric heme. In addition, a new band at 270 cm(-1) is observed at pH approximately 3 which is consistent with the loss of the sixth ligand. The higher symmetry of the heme at pH approximately 3 is reflected by a single v4 mode in the (RRS) spectrum. HRP also loses its loosely associated distal water at this pH, but little change in heme distortion is observed. This change suggests that loss of the distal ligand in MPO releases stress on the heme which may facilitate binding of chloride ion.

  14. Sources and relative reactivities of amino acids, neutral sugars, and lignin in an intermittently anoxic marice environment

    SciTech Connect

    Cowie, G.L.; Hedges, J.I. ); Calvert, S.E. )

    1992-05-01

    A sediment-trap sample, representing an annual average particle flux at 50 m in Saanich Inlet, British Columbia, was analyzed for its elemental, amino acid, neutral sugar, and lignin composition. The results uniformly indicate primarily marine organic matter sources for all samples, although relatively higher terrigenous contributions are evident in the sediments. The [delta][sup 13]C values of trap materials also point to primarily autochthonous particle fluxes. Comparison of annual average water-column fluxes to sediment accumulation rates indicates undersampling of sinking particles due to lateral sediment inputs at depth. The anoxic benthic interface appears to be an important site of diagenesis, and selective removal is observed both at compound-class and molecular levels. Preferential loss of marine organic material is indicated by the calculated [delta][sup 13]C value and biochemical composition of the substrate. Concentrations of all measured organic constituents decreased with depth in the uniformly varved 0-14 cm sediment interval, and suggest in situ degradation. Relative reactivities of the biochemical classes indicate a change in diagenetic substrate from that utilized above and at the benthic interface. With the exception of the amino acids, however, diagenesis is generally less selective in the sediments. Protein, polysaccharide, and lignin contributions to total organic carbon decrease from 37% in the sediment-trap sample to 22% at the bottom of the 0.14 cm sediment interval. These biochemicals represent over 40 and 50-60% of the degraded carbon and nitrogen, respectively, and thus are important nutrients for the benthic and water-column communities.

  15. Large neutral amino acids levels in primate cerebrospinal fluid do not confirm competitive transport under baseline conditions.

    PubMed

    Bongiovanni, Rodolfo; Mchaourab, Ali S; McClellan, Frances; Elsworth, John; Double, Manda; Jaskiw, George E

    2016-10-01

    In rodents, transport of large neutral amino acids (LNAAs) across the blood brain barrier (BBB) and blood-cerebrospinal fluid (CSF) barrier is mediated by high affinity carriers. Net brain LNAA levels are thought to be determined mainly by this competitive transport from plasma. Since the affinity for LNAA transport at the BBB in primates is considerably higher than in rodents, brain influx and by extension LNAA brain levels, should be even more dependent on competitive transport. Given that LNAA levels in CSF and brain interstitial fluid are usually similar, we analyzed serum and CSF of fasted subjects (n=24) undergoing spinal anesthesia and calculated brain influx and transporter occupancy using a conventional model of transport. Despite predicted near-full transporter saturation (99.7%), correlations between CSF levels and brain influx were modest, limited to tyrosine (r=0.60, p<0.002) and tryptophan (r=0.50, p<0.01) and comparable to correlations between CSF and serum levels. We also analyzed serum and CSF in (n=5) fasted vervet monkeys. Tyrosine and phenylalanine levels in CSF were positively correlated with those in serum, but correlations with calculated brain influx, which takes competition into account, were weaker or absent. We conclude that in primates i) baseline CSF LNAA levels do not confirm competitive transport, ii) brain LNAA levels should not be estimated on the basis of serum indices alone. This has implications for amino acid challenge studies and for neuropsychiatric disorders associated with dysregulated LNAA transport in which quantitative information about brain LNAA levels is needed. PMID:27521685

  16. Technique development for characterization of metalloorganics in acid-base-neutral fractions of heavy petroleum residues: Topical report

    SciTech Connect

    Pearson, C.D.; Green, J.B.

    1988-01-01

    A novel approach for the characterization of metallorganic compounds in heavy petroleum residues has been developed. Wilmington 1000/sup 0/ F+ and Mayan 925/sup 0/ F+ residues and hydrotreated products were separated into acid-base-neutral (ABN) fractions by a unique nonaqueous ion-exchange technique developed at NIPER. The metal complexes in the feeds, hydrotreated products and ABN fractions were then characterized by determining the total vanadium and nickel and by measuring the vanadium and nickel porphyrin content of each fraction. Molecular weight distribution profiles of the vanadium and nickel compounds in the feed, 400/sup 0/C hydrotreated product and corresponding ABN fractions were obtained by size exclusion chromatography/inductively coupled plasma. The majority of the metal appeared to be in non-porphyrinic form. The vanadium and nickel complexes were distributed into all of the ABN fractions. In the feed and the whole hydrotreated products the porphyrin levels decreased as hydrotreating temperatures increased. In contrast to previously reported work, porphyrins do not always decrease when hydrotreated. The amount of porphyrins in certain ABN fractions increased after hydrotreating at moderate temperatures. The Mayan V and Ni complexes were more resistant to hydrotreating than the Wilmington metal complexes; in particular, the high molecular weight Mayan metal complexes were more resistant to hydrotreating than the high molecular weight Wilmington metal complexes. 15 refs., 11 figs., 10 tabs.

  17. Enhanced dissolution and oral bioavailability of aripiprazole nanosuspensions prepared by nanoprecipitation/homogenization based on acid-base neutralization.

    PubMed

    Xu, Ying; Liu, Xiaoyi; Lian, Ruyue; Zheng, Siji; Yin, Zongning; Lu, Yi; Wu, Wei

    2012-11-15

    In this study, aripiprazole (APZ), a weak alkaline drug with pH-dependent solubility, was selected as model drug to examine the feasibility of preparing nanosuspensions using nanoprecipitation/homogenization technique based on acid-base neutralization. The related substances in nanosuspensions prepared under optimal conditions were slightly increased as compared with APZ raw material. The resultant APZ nanosuspensions showed a mean particle size of 350 nm with polydispersion index (PI) value of 0.20. Good physical stability was kept for over 40 days. SEM observation showed the morphology of oval crystals with rough surface. Nanosuspensions significantly increased the solubility as well as the dissolution of APZ due to the decreased particle size. Differential scanning calorimetry and powder X-ray diffractometry confirmed the crystallinity of APZ in nanosuspensions. APZ nanosuspensions got maximum absorption rate and extent comparing with APZ commercial tablet and suspensions with relative bioavailability of 123.43 ± 12.98% and 171.41 ± 14.62%, respectively. This technique has the potential to prepare nanosuspensions of insoluble drugs with pH-dependent solubility. PMID:22989976

  18. Aspartame and sucrose produce a similar increase in the plasma phenylalanine to large neutral amino acid ratio in healthy subjects.

    PubMed

    Burns, T S; Stargel, W W; Tschanz, C; Kotsonis, F N; Hurwitz, A

    1991-01-01

    Aspartame (L-aspartyl-L-phenylalanine methyl ester) consumption has been postulated to increase brain phenylalanine levels by increasing the molar ratio of the plasma phenylalanine concentration to the sum of the plasma concentrations of the other large neutral amino acids (Phe/LNAA). Dietary manipulations with carbohydrate or protein can also produce changes in the Phe/LNAA value. To compare the effects of aspartame and carbohydrate on Phe/LNAA, beverages sweetened with aspartame, sucrose, and aspartame plus sucrose, and unsweetened beverage were ingested by 8 healthy, fasted subjects in a randomized, four-way crossover design. The beverages were sweetened with an amount of aspartame (500 mg) and/or sucrose (100 g) approximately equivalent to that used to sweeten 1 liter of soft drink. The baseline-corrected plasma Phe/LNAA values did not differ significantly following ingestion of aspartame or sucrose. Following aspartame alone, the high mean ratio increased 26% over baseline 1 h after ingestion. Following sucrose alone, the high mean ratio increased 19% at 2.5 h. Sucrose increased the Phe/LNAA value due to an insulin-mediated decrease in the plasma LNAA, while aspartame increased the ratio by increasing the plasma Phe concentration. These findings indicate that similar increases in plasma Phe/LNAA occur when healthy, fasting subjects ingest amounts of equivalent sweetness of sucrose or aspartame.

  19. Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

    SciTech Connect

    Assary, R. S.; Redfern, P. C.; Greeley, J.; Curtiss, L. A.

    2011-03-28

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  20. Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

    PubMed

    Assary, Rajeev S; Redfern, Paul C; Greeley, Jeffrey; Curtiss, Larry A

    2011-04-21

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved. PMID:21443225

  1. Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

    SciTech Connect

    Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey P.; Curtiss, Larry A.

    2011-04-21

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  2. Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

    SciTech Connect

    Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey; Curtiss, Larry A.

    2011-03-28

    Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large, about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.

  3. Enhanced sensitivity to neutralizing antibodies in a variant of equine infectious anemia virus is linked to amino acid substitutions in the surface unit envelope glycoprotein.

    PubMed Central

    Cook, R F; Berger, S L; Rushlow, K E; McManus, J M; Cook, S J; Harrold, S; Raabe, M L; Montelaro, R C; Issel, C J

    1995-01-01

    Serial passage of the prototype (PR) cell-adapted Wyoming strain of equine infectious anemia virus (EIAV) in fetal donkey dermal (FDD) rather than fetal horse (designated fetal equine kidney [FEK]) cell cultures resulted in the generation of a variant virus strain which produced accelerated cytopathic effects in FDD cells and was 100- to 1,000-fold more sensitive to neutralizing antibodies than its parent. This neutralization-sensitive variant was designated the FDD strain. Although there were differences in glycosylation between the PR and FDD strains, passage of the FDD virus in FEK cells did not reduce its sensitivity to neutralizing antibody. Nucleotide sequencing of the region encoding the surface unit (SU) protein from the FDD strain revealed nine amino acid substitutions compared with the PR strain. Two of these substitutions resulted in changes in the polarity of charge, four caused the introduction of a charged residue, and three had no net change in charge. Nucleotide sequence analysis was extended to the region of the FDD virus genome encoding the extracellular domain of the transmembrane envelope glycoprotein (TM). Unlike the situation with the FDD virus coding region, there were minor variations in nucleotide sequence between individual molecular clones containing this region of the TM gene. Although each clone contained three nucleotide substitutions compared with the PR strain, only one of these was common to all, and this did not affect the amino acid content. Of the remaining two nucleotide substitutions, only one resulted in an amino acid change, and in each case, this change appeared to be conservative. To determine if amino acid substitutions in the SU protein of FDD cell-grown viruses were responsible for the enhanced sensitivity to neutralizing antibodies, chimeric viruses were constructed by using an infectious molecular clone of EIAV. These chimeric viruses contained all of the amino acid substitutions found in the FDD virus strain and were

  4. Characterization and diagenesis of strong-acid carboxyl groups in humic substances

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Brown, G.K.; Reddy, M.M.

    2003-01-01

    A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

  5. Three-dimensional structure of Schistosoma japonicum glutathione S-transferase fused with a six-amino acid conserved neutralizing epitope of gp41 from HIV

    NASA Technical Reports Server (NTRS)

    Lim, Kap; Ho, Joseph X.; Keeling, Kim; Gilliland, Gary L.; Ji, Xinhua; Rueker, Florian; Carter, Daniel C.

    1994-01-01

    The 3-dimensional crystal structure of glutathione S-transferase (GST) of Schistosoma japonicum (Sj) fused with a conserved neutralizing epitope on gp41 (glycoprotein, 41 kDa) of human immunodeficiency virus type 1 (HIV-1) was determined at 2.5 A resolution. The structure of the 3-3 isozyme rat GST of the mu gene class was used as a molecular replacement model. The structure consists of a 4-stranded beta-sheet and 3 alpha-helices in domain 1 and 5 alpha-helices in domain 2. The space group of the Sj GST crystal is P4(sub 3)2(sub 1)2 with unit cell dimensions of a = b = 94.7 A, and c = 58.1 A. The crystal has 1 GST monomer per asymmetric unit, and 2 monomers that form an active dimer are related by crystallographic 2-fold symmetry. In the binding site, the ordered structure of reduced glutathione is observed. The gp41 peptide (Glu-Leu-Asp-Lys-Trp-Ala) fused to the C-terminus of Sj GST forms a loop stabilized by symmetry-related GSTs. The Sj GST structure is compared with previously determined GST structures of mammalian gene classes mu, alpha, and pi. Conserved amino acid residues among the 4 GSTs that are important for hydrophobic and hydrophilic interactions for dimer association and glutathione binding are discussed.

  6. Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

    SciTech Connect

    Li, J.

    1999-04-01

    A novel anion-exchange resin containing three amine groups was prepared by reaction of a chloromethylated polystyrene-divinylbenzene (PS-DVB) resin with diethylenetriamine. After being protonated by contact with an aqueous acid, this resin can be used for ion chromatographic separation of anions. The charge on the resins can be varied from +1 to +3 by changing the mobile phase pH. The selectivity of the new ion exchangers for various inorganic anions was quite different from that of conventional anion exchangers. The performance of this new anion exchanger was studied by changing the pH and the concentration of the eluent, and several different eluents were used with some common anions as testing analytes. Conductivity detection and UV-visible detection were applied to detect the anions after separation. The new resin can also be used for HPLC separation of neutral organic compounds. Alkylphenols and alkylbenzenes were separated with this new polymeric resin, and excellent separations were obtained under simple conditions. This report contains Chapter 1: General introduction and Chapter 6: General conclusions.

  7. Use of neutral capillaries for the enantioseparation of N-benzoylated amino acids by capillary electrophoresis with bromobalhimycin as chiral selector.

    PubMed

    Peng, Yongbo; Zhang, Tingting; Wang, Tingting; Liu, Zhenghua; Crommen, Jacques; Jiang, Zhengjin

    2013-05-01

    In this study, the partial filling technique on both polycationic polymer hexadimethrine bromide (HDB) modified capillary and eCAP neutral capillary were systematically compared in order to enhance the enantioseparation ability of bromobalhimycin as CE additive. The separation conditions, such as pH, the plug length, and the concentration of bromobalhimycin, etc., were optimized in order to obtain satisfactory separations. As expected, for all tested 28 N-benzoylated amino acids, up to five times higher enantioresolutions were obtained on the eCAP neutral capillary compared to that on the polycationic polymer hexadimethrine bromide modified capillary. Moreover, 26 of 28 tested racemic compounds were almost baseline- resolved without observing any interference from the front of the plug of bromobalhimycin. Although the limitation of longer running time on the neutral capillary, it allows the use of higher content of bromobalhimycin in the running buffer without any interference on the detection of analytes when enantioseparations are more difficult to obtain.

  8. Effect of Extraction Conditions on the Saccharide (Neutral and Acidic) Composition of the Crude Pectic Extract from Various Agro-Industrial Residues.

    PubMed

    Babbar, Neha; Roy, Sandra Van; Wijnants, Marc; Dejonghe, Winnie; Caligiani, Augusta; Sforza, Stefano; Elst, Kathy

    2016-01-13

    The influence of different extraction methodologies was assessed on the composition of both neutral (arabinose, rhamnose, galactose) and acidic (galacturonic acid) pectic polysaccharides obtained from four agro-industrial residues, namely, berry pomace (BP), onion hulls (OH), pressed pumpkin (PP), and sugar beet pulp (SBP). For acidic pectic polysaccharides, the extraction efficiency was obtained as BP (nitric acid-assisted extraction, 2 h, 62.9%), PP (enzymatic-assisted extraction, 12 h, 75.0%), SBP (enzymatic-assisted extraction, 48 h, 89.8%; and nitric acid-assisted extraction, 4 h, 76.5%), and OH (sodium hexametaphosphate-assisted extraction, 0.5 h, 100%; and ammonium oxalate-assisted extraction, 0.5 h, 100%). For neutral pectic polysaccharides, the following results were achieved: BP (enzymatic-assisted extraction, 24 h, 85.9%), PP (nitric acid-assisted extraction, 6 h, 82.2%), and SBP (enzymatic assisted extraction, 48 h, 97.5%; and nitric acid-assisted extraction, 4 h, 83.2%). On the basis of the high recovery of pectic sugars, SBP and OH are interesting candidates for the further purification of pectin and production of pectin-derived products.

  9. Nucleic acids encoding modified human immunodeficiency virus type 1 (HIV-1) group M consensus envelope glycoproteins

    DOEpatents

    Haynes, Barton F.; Gao, Feng; Korber, Bette T.; Hahn, Beatrice H.; Shaw, George M.; Kothe, Denise; Li, Ying Ying; Decker, Julie; Liao, Hua-Xin

    2011-12-06

    The present invention relates, in general, to an immunogen and, in particular, to an immunogen for inducing antibodies that neutralizes a wide spectrum of HIV primary isolates and/or to an immunogen that induces a T cell immune response. The invention also relates to a method of inducing anti-HIV antibodies, and/or to a method of inducing a T cell immune response, using such an immunogen. The invention further relates to nucleic acid sequences encoding the present immunogens.

  10. Reactive geothermal transport simulations to study the formation mechanism of an impermeable barrier between acidic and neutral fluid zones in the Onikobe Geothermal Field, Japan

    NASA Astrophysics Data System (ADS)

    Todaka, Norifumi; Akasaka, Chitoshi; Xu, Tianfu; Pruess, Karsten

    2004-05-01

    Two types of fluids are encountered in the Onikobe geothermal reservoir (Japan): one is neutral and the other is acidic. It is hypothesized that acidic fluid might be upwelling along a fault zone from magma and that an impermeable barrier might be present between the acidic and neutral fluid zones. To test such a conceptual model and to study the geochemical behavior due to mixing of the two fluids, reactive geothermal transport simulations under both natural and production conditions were carried out using the code TOUGHREACT. Results indicate Mn-rich smectite precipitates near the mixing front. Precipitation of sphalerite and galena occurs in a similar region as the Mn-rich smectite. Precipitation of these minerals depends on pH and temperature. In addition, quartz, pyrite, and calcite precipitate in the shallow zone resulting in further development of caprock. The changes in porosity and permeability due to precipitation of Mn-rich smectite are small compared with that of quartz, calcite, and pyrite. However, the smectite precipitation is likely to fill open fractures and to form an impermeable barrier between acidic and neutral fluid regions. The simulated mineral assemblage is generally consistent with observations in the Onikobe field. The numerical simulations described here provide useful insight into geochemical behavior and formation of impermeable barriers from fluid mixing. The method presented in this paper may be useful in fundamental analysis of hydrothermal systems and in the exploration of geothermal reservoirs, including chemical evolution, mineral alteration, mineral scaling, and changes in porosity and permeability.

  11. Using self-consistent Gibbs free energy surfaces to calculate size distributions of neutral and charged clusters for the sulfuric acid-water binary system

    NASA Astrophysics Data System (ADS)

    Smith, J. A.; Froyd, K. D.; Toon, O. B.

    2012-12-01

    We construct tables of reaction enthalpies and entropies for the association reactions involving sulfuric acid vapor, water vapor, and the bisulfate ion. These tables are created from experimental measurements and quantum chemical calculations for molecular clusters and a classical thermodynamic model for larger clusters. These initial tables are not thermodynamically consistent. For example, the Gibbs free energy of associating a cluster consisting of one acid molecule and two water molecules depends on the order in which the cluster was assembled: add two waters and then the acid or add an acid and a water and then the second water. We adjust the values within the tables using the method of Lagrange multipliers to minimize the adjustments and produce self-consistent Gibbs free energy surfaces for the neutral clusters and the charged clusters. With the self-consistent Gibbs free energy surfaces, we calculate size distributions of neutral and charged clusters for a variety of atmospheric conditions. Depending on the conditions, nucleation can be dominated by growth along the neutral channel or growth along the ion channel followed by ion-ion recombination.

  12. Neutralization of non-vaccine human papillomavirus pseudoviruses from the A7 and A9 species groups by bivalent HPV vaccine sera

    PubMed Central

    Draper, Eve; Bissett, Sara L.; Howell-Jones, Rebecca; Edwards, Debbie; Munslow, Graham; Soldan, Kate; Beddows, Simon

    2011-01-01

    The majority of cervical cancers are associated with infection by one or more Human Papillomavirus (HPV) types from just two distinct Alpha-Papillomavirus species groups, A7 and A9. The extent to which the current HPV16/18 vaccines will protect against other genetically related HPV types is of interest to inform vaccine implementation, cervical disease surveillance and the development of second generation HPV vaccines. The aim of this study was to determine the frequency and titer of neutralizing antibodies against a range of A7 (18, 39, 45, 59, 68) and A9 (16, 31, 33, 35, 52, 58) HPV types using sera from individuals immunized with the bivalent HPV vaccine within the school-based, UK national HPV immunization programme. Serum samples were collected from 69 girls aged 13–14 years, a median 5.9 months (inter-quartile range, IQR, 5.7–6.0) after their third vaccine dose. Cross-neutralizing antibodies against HPV31, HPV33, HPV35 and HPV45 were common and strongly associated with the titer for the related vaccine-type, but were considerably lower (<1%) than their related vaccine type-specific response. The low prevalence of these HPV types in the population and the ages within the study cohort suggest these responses are due to vaccination. It is unclear whether such low levels of neutralizing antibodies would be sufficient to protect at the site of infection in the absence of other immune effectors but the coincidence with HPV types reported from efficacy studies is intriguing. The utility of neutralizing antibodies as surrogate markers of protection remains to be determined. PMID:21939712

  13. Enhanced phagocytosis of group A streptococci M type 6 by oleic acid

    SciTech Connect

    Speert, D.P.; Quie, P.G.; Wannamaker, L.W.

    1981-04-01

    M protein, located on the surface fimbriae of group A streptococci, is antiphagocytic by unknown means. It is known that oleic acid kills group A streptococci and distorts the fimbriae. The effect of oleic acid on phagocytosis of group A streptococci was examined. Phagocytosis of a strain possessing M protein (M+) and its M- variant was assessed by uptake of radiolabeled bacteria and by chemiluminescence. The M- but not the M+ streptococci were well phagocytized and induced chemiluminescence. Oleic acid-killed and heat-killed streptococci (both M+ and M-) were readily phagocytized and induced sustained chemiluminescence. M+ streptococci killed by ultraviolet irradiation were inefficiently phagocytized and did not induce chemiluminescence. Oleic acid-killed M+ streptococci absorbed type-specific antibody. An extract of M protein reduced the bactericidal capacity of oleic acid. It is proposed that oleic acid may bind to and alter the M protein of group A streptococci and thereby enhance phagocytosis.

  14. Neutralizer optimization

    NASA Technical Reports Server (NTRS)

    Patterson, Michael J.; Mohajeri, Kayhan

    1991-01-01

    The preliminary results of a test program to optimize a neutralizer design for 30 cm xenon ion thrusters are discussed. The impact of neutralizer geometry, neutralizer axial location, and local magnetic fields on neutralizer performance is discussed. The effect of neutralizer performance on overall thruster performance is quantified, for thruster operation in the 0.5-3.2 kW power range. Additionally, these data are compared to data published for other north-south stationkeeping (NSSK) and primary propulsion xenon ion thruster neutralizers.

  15. Mathematical modeling of cadmium(II) solvent extraction from neutral and acidic chloride media using Cyanex 923 extractant as a metal carrier.

    PubMed

    Leopold, A A; Coll, M T; Fortuny, A; Rathore, N S; Sastre, A M

    2010-10-15

    This paper describes experimental work and the mathematical modeling of solvent extraction of cadmium(II) from neutral and acidic aqueous chloride media with a Cyanex 923 extractant in Exxol D-100. Solvent extraction experiments were carried out to analyze the influence of variations in the composition of the aqueous and organic phases on the efficiency of cadmium(II) extraction. In neutral and acidic chloride conditions, the extraction of cadmium(II) by the organophosphorous extractant Cyanex 923 (L) is based on the solvation mechanism of neutral H(n)CdCl((2+n)) species and the formation of H(n)CdCl((2+n))L(q) complexes in the organic phase, where n=0, 1, 2 and q=1, 2. The mathematical model of cadmium(II) extraction was derived from the mass balances and chemical equilibria involved in the separation system. The model was computed with the Matlab software. The equilibrium parameters for metal extraction, i.e. the stability constants of the aqueous Cd-Cl complexes, the formation constants of the acidic Cd-Cl species and the metal equilibrium extraction constants, were proposed. The optimized constants were appropriate, as there was good agreement when the model was fitted to the experimental data for each of the experiments.

  16. Evaluation of selected static methods used to estimate element mobility, acid-generating and acid-neutralizing potentials associated with geologically diverse mining wastes

    USGS Publications Warehouse

    Hageman, Philip L.; Seal, Robert R.; Diehl, Sharon F.; Piatak, Nadine M.; Lowers, Heather

    2015-01-01

    A comparison study of selected static leaching and acid–base accounting (ABA) methods using a mineralogically diverse set of 12 modern-style, metal mine waste samples was undertaken to understand the relative performance of the various tests. To complement this study, in-depth mineralogical studies were conducted in order to elucidate the relationships between sample mineralogy, weathering features, and leachate and ABA characteristics. In part one of the study, splits of the samples were leached using six commonly used leaching tests including paste pH, the U.S. Geological Survey (USGS) Field Leach Test (FLT) (both 5-min and 18-h agitation), the U.S. Environmental Protection Agency (USEPA) Method 1312 SPLP (both leachate pH 4.2 and leachate pH 5.0), and the USEPA Method 1311 TCLP (leachate pH 4.9). Leachate geochemical trends were compared in order to assess differences, if any, produced by the various leaching procedures. Results showed that the FLT (5-min agitation) was just as effective as the 18-h leaching tests in revealing the leachate geochemical characteristics of the samples. Leaching results also showed that the TCLP leaching test produces inconsistent results when compared to results produced from the other leaching tests. In part two of the study, the ABA was determined on splits of the samples using both well-established traditional static testing methods and a relatively quick, simplified net acid–base accounting (NABA) procedure. Results showed that the traditional methods, while time consuming, provide the most in-depth data on both the acid generating, and acid neutralizing tendencies of the samples. However, the simplified NABA method provided a relatively fast, effective estimation of the net acid–base account of the samples. Overall, this study showed that while most of the well-established methods are useful and effective, the use of a simplified leaching test and the NABA acid–base accounting method provide investigators fast

  17. Preservation of glutamic acid-iron chelate into montmorillonite to efficiently degrade Reactive Blue 19 in a Fenton system under sunlight irradiation at neutral pH

    NASA Astrophysics Data System (ADS)

    Huang, Zhujian; Wu, Pingxiao; Gong, Beini; Yang, Shanshan; Li, Hailing; Zhu, Ziao; Cui, Lihua

    2016-05-01

    To further enhance the visible light responsive property and the chemical stability of Fe/clay mineral catalysts, glutamic acid-iron chelate intercalated montmorillonite (G-Fe-Mt) was developed. The physiochemical properties of G-Fe-Mt were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), etc. The results showed that glutamic acid-iron chelates were successfully intercalated into the gallery of montmorillonite and the intercalated glutamic acid-iron chelate molecules were well preserved. The product G-Fe-Mt displayed excellent catalytic performance in heterogeneous photo-Fenton reaction under sunlight irradiation at acidic and neutral pH values. The chelation and the visible light responsiveness of glutamic acid produce a synergistic effect leading to greatly enhanced sunlight-Fenton reaction catalyzed by the heterogeneous G-Fe-Mt under neutral pH. G-Fe-Mt is a promising catalyst for advanced oxidation processes.

  18. Enthalpies and constants of dissociation of several neutral and cationic acids in aqueous and methanol/water solutions at various temperatures.

    PubMed

    Shoghi, Elham; Romero, Lilian; Reta, Mario; Ràfols, Clara; Bosch, Elisabeth

    2009-05-01

    The acidic dissociation enthalpies and constants of anilinium, protonated tris(hydroxymethyl)aminomethane (HTris(+)), benzoic and acetic acids, have been determined at several temperatures in pure water and in methanol/water mixtures by potentiometry and by isothermal titration microcalorimetry (ITC). The pK(a) values determined by both techniques are in accordance when the dissociation process involves large amounts of heat. However, for the neutral acids the ITC technique gave slightly lower pK(a) values than those from potentiometry at the highest temperatures studied due to the small amounts of heat involved in the acidic dissociation. The dissociation enthalpies have been determined directly by calorimetry and the obtained values slightly decrease with the increase of temperature. Therefore, only a rough estimation of the dissociation enthalpies can be obtained from potentiometric pK(a) by means of the Van't Hoff approach.

  19. Enthalpies and constants of dissociation of several neutral and cationic acids in aqueous and methanol/water solutions at various temperatures.

    PubMed

    Shoghi, Elham; Romero, Lilian; Reta, Mario; Ràfols, Clara; Bosch, Elisabeth

    2009-05-01

    The acidic dissociation enthalpies and constants of anilinium, protonated tris(hydroxymethyl)aminomethane (HTris(+)), benzoic and acetic acids, have been determined at several temperatures in pure water and in methanol/water mixtures by potentiometry and by isothermal titration microcalorimetry (ITC). The pK(a) values determined by both techniques are in accordance when the dissociation process involves large amounts of heat. However, for the neutral acids the ITC technique gave slightly lower pK(a) values than those from potentiometry at the highest temperatures studied due to the small amounts of heat involved in the acidic dissociation. The dissociation enthalpies have been determined directly by calorimetry and the obtained values slightly decrease with the increase of temperature. Therefore, only a rough estimation of the dissociation enthalpies can be obtained from potentiometric pK(a) by means of the Van't Hoff approach. PMID:19261425

  20. Laser neutralization

    SciTech Connect

    Peterson, O.G.

    1986-06-17

    Laser photodetachment of the excess electron to neutralize relativistic ions offers many advantages over the more conventional collisional methods using gases or thin foils as the neutralization agents. Probably the two most important advantages of laser photodetachment are the generation of a compact and low divergence beam, and the production of intense neutral beams at very high efficiency (approximately 90%). The high intensities or high current densities of the neutral beam result from the fixed maximum divergence that can be added to the beam by photodetachment of the charge using laser intensity of fixed wavelength and incident angle. The high neutralization efficiency is possible because there is no theoretical maximum to the neutralization efficiency, although higher efficiencies require higher laser powers and, therefore, costs. Additional advantages include focusability of the laser light onto the ion beam to maximize its efficacy. There certainly is no residual gas left in the particle beam path as is typical with gas neutralizers. The photodetachment process leaves the neutral atoms in the ground state so there is no excited state fluorescence to interfere with the subsequent beam sensing. Finally, since the beams to be neutralized are very high powered, for a large range of neutralization efficiencies the neutral beam can be increased more by increasing the power to the laser neutralizer than by adding an equal amount of power to the primary accelerator. 26 figs.

  1. Three-dimensional structure of Schistosoma japonicum glutathione S-transferase fused with a six-amino acid conserved neutralizing epitope of gp41 from HIV

    NASA Technical Reports Server (NTRS)

    Lim, K.; Ho, J. X.; Keeling, K.; Gilliland, G. L.; Ji, X.; Ruker, F.; Carter, D. C.

    1994-01-01

    The 3-dimensional crystal structure of glutathione S-transferase (GST) of Schistosoma japonicum (Sj) fused with a conserved neutralizing epitope on gp41 (glycoprotein, 41 kDa) of human immunodeficiency virus type 1 (HIV-1) (Muster T et al., 1993, J Virol 67:6642-6647) was determined at 2.5 A resolution. The structure of the 3-3 isozyme rat GST of the mu gene class (Ji X, Zhang P, Armstrong RN, Gilliland GL, 1992, Biochemistry 31:10169-10184) was used as a molecular replacement model. The structure consists of a 4-stranded beta-sheet and 3 alpha-helices in domain 1 and 5 alpha-helices in domain 2. The space group of the Sj GST crystal is P4(3)2(1)2, with unit cell dimensions of a = b = 94.7 A, and c = 58.1 A. The crystal has 1 GST monomer per asymmetric unit, and 2 monomers that form an active dimer are related by crystallographic 2-fold symmetry. In the binding site, the ordered structure of reduced glutathione is observed. The gp41 peptide (Glu-Leu-Asp-Lys-Trp-Ala) fused to the C-terminus of Sj GST forms a loop stabilized by symmetry-related GSTs. The Sj GST structure is compared with previously determined GST structures of mammalian gene classes mu, alpha, and pi. Conserved amino acid residues among the 4 GSTs that are important for hydrophobic and hydrophilic interactions for dimer association and glutathione binding are discussed.

  2. Evaluation of the potential of indigenous calcareous shale for neutralization and removal of arsenic and heavy metals from acid mine drainage in the Taxco mining area, Mexico.

    PubMed

    Romero, F M; Núñez, L; Gutiérrez, M E; Armienta, M A; Ceniceros-Gómez, A E

    2011-02-01

    In the Taxco mining area, sulfide mineral oxidation from inactive tailings impoundments and abandoned underground mines has produced acid mine drainage (AMD; pH 2.2-2.9) enriched in dissolved concentrations (mg l⁻¹) sulfate, heavy metals, and arsenic (As): SO₄²⁻ (pH 1470-5454), zinc (Zn; 3.0-859), iron (Fe; pH 5.5-504), copper (Cu; pH 0.7-16.3), cadmium (Cd; pH 0.3-6.7), lead (Pb; pH < 0.05-1.8), and As (pH < 0.002-0.6). Passive-treatment systems using limestone have been widely used to remediate AMD in many parts of the world. In limestone-treatment systems, calcite simultaneously plays the role of neutralizing and precipitating agent. However, the acid-neutralizing potential of limestone decreases when surfaces of the calcite particles become less reactive as they are progressively coated by metal precipitates. This study constitutes first-stage development of passive-treatment systems for treating AMD in the Taxco mine area using indigenous calcareous shale. This geologic material consists of a mixture of calcite, quartz, muscovite, albite, and montmorillonite. Results of batch leaching test indicate that calcareous shale significantly increased the pH (to values of 6.6-7.4) and decreased heavy metal and As concentrations in treated mine leachates. Calcareous shale had maximum removal efficiency (100%) for As, Pb, Cu, and Fe. The most mobile metals ions were Cd and Zn, and their average percentage removal was 87% and 89%, respectively. In this natural system (calcareous shale), calcite provides a source of alkalinity, whereas the surfaces of quartz and aluminosilicate minerals possibly serve as a preferred locus of deposition for metals, resulting in the neutralizing agent (calcite) beings less rapidly coated with the precipitating metals and therefore able to continue its neutralizing function for a longer time.

  3. Use of zirconium oxychloride to neutralize HF in the microwave-assisted acid dissolution of ceramic glazes for their chemical analysis by ICP-OES.

    PubMed

    Dondi, M; Fabbri, B; Mingazzini, C

    1998-04-01

    The use of a zirconium compound (ZrOCl(2)) to neutralize HF in the microwave-assisted acid dissolution of ceramic glazes for their chemical analysis was tested. Zr is a strong complexing agent for the fluorine ion and permits the determination of those elements which would form insoluble fluorides. The use of Zr implies strong spectral interferences and a high salt content; however, we found that at least 27 elements can be measured with low detection limits, and satisfactory precision and accuracy. In addition, the use of ZrOCl(2) would permit the complete analysis of a ceramic glaze with a single attack when acid-resistant mineral phases are not present. For potassium determinations in acid matrix, the addition of an ionization buffer was studied in order to increase sensitivity, avoiding ionization interferences and non-linear calibration curves. PMID:18967112

  4. The role of calcium ions in the photocatalytic oxidation of humic acid at neutral pH.

    PubMed

    Mariquit, Eden G; Salim, Chris; Hinode, Hirofumi

    2008-10-01

    Humic acids (HAs) are natural organic matter derived from the decomposition of plant, algal, and microbial materials. They belong to the group of the most predominant type of natural organic matter present in ground and surface waters. HAs affect the mobility and bioavailability of aquatic contaminants. However, if they are left unremoved from the water before water treatment processes, they can form carcinogenic disinfection by-products, such as trihalomethanes, haloacetic acids, and other halogenated disinfection by-products, that can pose a threat to human beings. An advanced oxidation process using UV light and a commercially available titanium dioxide was used to oxidize HA at a pH that is similar to that of natural water. The effect of adding calcium ions to the adsorption and the photocatalytic oxidation of HAs was studied. The effect of varying the TiO(2) load was also investigated. The experiment was done using a photochemical batch reactor equipped with a mercury lamp emitting light with wavelengths of 310-580 nm. The absorbances by the samples were determined at wavelengths of 254 nm and 436 nm, which represent the aromatic-compound content of and the color of the solution, respectively. Results indicated calcium ions have an effect on both the adsorption and the photocatalytic oxidation of HA at a pH within 8.0 +/- 0.5. Calcium ions facilitated adsorption of HA onto the surface of TiO(2) and resulted to faster photocatalytic oxidation. The data were plotted with respect to the normalized absorbances and irradiation time. PMID:18991939

  5. Boronic acid as an efficient anchor group for surface modification of solid polyvinyl alcohol.

    PubMed

    Nishiyabu, Ryuhei; Shimizu, Ai

    2016-07-28

    We report the use of boronic acid as an anchor group for surface modification of solid polyvinyl alcohol (PVA); the surfaces of PVA microparticles, films, and nanofibers were chemically modified with boronic acid-appended fluorescent dyes through boronate esterification using a simple soaking technique in a short time under ambient conditions. PMID:27311634

  6. Coordinated Regulation of the Neutral Amino Acid Transporter SNAT2 and the Protein Phosphatase Subunit GADD34 Promotes Adaptation to Increased Extracellular Osmolarity*

    PubMed Central

    Krokowski, Dawid; Jobava, Raul; Guan, Bo-Jhih; Farabaugh, Kenneth; Wu, Jing; Majumder, Mithu; Bianchi, Massimiliano G.; Snider, Martin D.; Bussolati, Ovidio; Hatzoglou, Maria

    2015-01-01

    Cells respond to shrinkage induced by increased extracellular osmolarity via programmed changes in gene transcription and mRNA translation. The immediate response to this stress includes the induction of expression of the neutral amino acid transporter SNAT2. Increased SNAT2-mediated uptake of neutral amino acids is an essential adaptive mechanism for restoring cell volume. In contrast, stress-induced phosphorylation of the α subunit of the translation initiation factor eIF2 (eIF2α) can promote apoptosis. Here we show that the response to mild hyperosmotic stress involves regulation of the phosphorylation of eIF2α by increased levels of GADD34, a regulatory subunit of protein phosphatase 1 (PP1). The induction of GADD34 was dependent on transcriptional control by the c-Jun-binding cAMP response element in the GADD34 gene promoter and posttranscriptional stabilization of its mRNA. This mechanism differs from the regulation of GADD34 expression by other stresses that involve activating transcription factor 4 (ATF4). ATF4 was not translated during hyperosmotic stress despite an increase in eIF2α phosphorylation. The SNAT2-mediated increase in amino acid uptake was enhanced by increased GADD34 levels in a manner involving decreased eIF2α phosphorylation. It is proposed that the induction of the SNAT2/GADD34 axis enhances cell survival by promoting the immediate adaptive response to stress. PMID:26041779

  7. Determination of structural and vibrational spectroscopic features of neutral and anion forms of dinicotinic acid by using NMR, infrared and Raman experimental methods combined with DFT and HF.

    PubMed

    Kose, E; Bardak, F; Atac, A; Karabacak, M; Cipiloglu, M A

    2013-10-01

    In this study; the experimental (NMR, infrared and Raman) and theoretical (HF and DFT) analysis of dinicotinic acid were presented. (1)H and (13)C NMR spectra were recorded in DMSO solution and chemical shifts were calculated by using the gauge-invariant atomic orbital (GIAO) method. The vibrational spectra of dinicotinic acid were recorded by FT-Raman and FT-IR spectra in the range of 4000-10 cm(-1) and 4000-400 cm(-1), respectively. To determine the most stable neutral conformer of molecule, the selected torsion angle was changed every 10° and molecular energy profile was calculated from 0° to 360°. The geometrical parameters and energies were obtained for all conformers form from density functional theory (DFT/B3LYP) and HF with 6-311++G(d,p) basis set calculations. However, the results of the most stable neutral and two anion forms (anion(-1) and anion(-2) forms) of dinicotinic acid are reported here. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational wavenumbers, calculated with scaled quantum mechanics (SQM) method and PQS program. PMID:23747433

  8. Determination of structural and vibrational spectroscopic features of neutral and anion forms of dinicotinic acid by using NMR, infrared and Raman experimental methods combined with DFT and HF

    NASA Astrophysics Data System (ADS)

    Kose, E.; Bardak, F.; Atac, A.; Karabacak, M.; Cipiloglu, M. A.

    2013-10-01

    In this study; the experimental (NMR, infrared and Raman) and theoretical (HF and DFT) analysis of dinicotinic acid were presented. 1H and 13C NMR spectra were recorded in DMSO solution and chemical shifts were calculated by using the gauge-invariant atomic orbital (GIAO) method. The vibrational spectra of dinicotinic acid were recorded by FT-Raman and FT-IR spectra in the range of 4000-10 cm-1 and 4000-400 cm-1, respectively. To determine the most stable neutral conformer of molecule, the selected torsion angle was changed every 10° and molecular energy profile was calculated from 0° to 360°. The geometrical parameters and energies were obtained for all conformers form from density functional theory (DFT/B3LYP) and HF with 6-311++G(d,p) basis set calculations. However, the results of the most stable neutral and two anion forms (anion-1 and anion-2 forms) of dinicotinic acid are reported here. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational wavenumbers, calculated with scaled quantum mechanics (SQM) method and PQS program.

  9. A surprising substituent effect provides a superior boronic acid catalyst for mild and metal-free direct Friedel-Crafts alkylations and prenylations of neutral arenes.

    PubMed

    Ricardo, Carolynne L; Mo, Xiaobin; McCubbin, J Adam; Hall, Dennis G

    2015-03-01

    The development of more general and efficient catalytic processes for Friedel-Crafts alkylations is an important objective of interest toward the production of pharmaceuticals and commodity chemicals. Herein, 2,3,4,5-tetrafluorophenylboronic acid was identified as a potent air- and moisture-tolerant metal-free catalyst that significantly improves the scope of direct Friedel-Crafts alkylations of a variety of slightly activated and neutral arenes, including polyarenes, with allylic and benzylic alcohols. This method also provides a simple alternative for the direct installation of prenyl units commonly found in naturally occurring arenes. Alkylations with benzylic alcohols occur under exceptionally mild conditions. PMID:25678266

  10. Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

    SciTech Connect

    Shao, Yanqiu; Liu, Heng; Yu, Xiaofang; Guan, Jingqi; Kan, Qiubin

    2012-03-15

    Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

  11. Tautomerism in neutral histidine.

    PubMed

    Bermúdez, Celina; Mata, Santiago; Cabezas, Carlos; Alonso, José L

    2014-10-01

    Histidine is an important natural amino acid, involved in many relevant biological processes, which, because of its physical properties, proved difficult to characterize experimentally in its neutral form. In this work, neutral histidine has been generated in the gas phase by laser ablation of solid samples and its N(ε)H tautomeric form unraveled through its rotational spectrum. The quadrupole hyperfine structure, arising from the existing three (14)N nuclei, constituted a site-specifically probe for revealing the tautomeric form as well as the side chain configuration of this proteogenic amino acid.

  12. Solving nucleic acid structures by molecular replacement: examples from group II intron studies

    SciTech Connect

    Marcia, Marco Humphris-Narayanan, Elisabeth; Keating, Kevin S.; Somarowthu, Srinivas; Rajashankar, Kanagalaghatta; Pyle, Anna Marie

    2013-11-01

    Strategies for phasing nucleic acid structures by molecular replacement, using both experimental and de novo designed models, are discussed. Structured RNA molecules are key players in ensuring cellular viability. It is now emerging that, like proteins, the functions of many nucleic acids are dictated by their tertiary folds. At the same time, the number of known crystal structures of nucleic acids is also increasing rapidly. In this context, molecular replacement will become an increasingly useful technique for phasing nucleic acid crystallographic data in the near future. Here, strategies to select, create and refine molecular-replacement search models for nucleic acids are discussed. Using examples taken primarily from research on group II introns, it is shown that nucleic acids are amenable to different and potentially more flexible and sophisticated molecular-replacement searches than proteins. These observations specifically aim to encourage future crystallographic studies on the newly discovered repertoire of noncoding transcripts.

  13. Hydrogen-bond acidic functionalized carbon nanotubes (CNTs) with covalently-bound hexafluoroisopropanol groups

    SciTech Connect

    Fifield, Leonard S.; Grate, Jay W.

    2010-06-01

    Fluorinated hydrogen-bond acidic groups are directly attached to the backbone of single walled carbon nanotubes (SWCNTs) without the introduction of intermediate electron donating surface groups. Hexafluoroalcohol functional groups are exceptionally strong hydrogen bond acids, and are added to the nanotube surface using the aryl diazonium approach to create hydrogen-bond acidic carbon nanotube (CNT) surfaces. These groups can promote strong hydrogen-bonding interactions with matrix materials in composites or with molecular species to be concentrated and sensed. In the latter case, this newly developed material is expected to find useful application in chemical sensors and in CNT-based preconcentrator devices for the detection of pesticides, chemical warfare agents and explosives.

  14. G2(+)M study on N-alkylamino cation affinities of neutral main-group element hydrides: trends across the periodic table.

    PubMed

    Geng, Song; Wu, Ding-Lu; Yang, Jing; Wei, Xi-Guang; Zhu, Jun; Zhang, Hai-Bo; Ren, Yi; Lau, Kai-Chung

    2014-05-01

    We have made an extensive theoretical exploration of gas-phase N-alkylamino cation affinities (NAAMCA), including amino cation affinities (AMCA) and N-dimethylamino cation affinities (NDMAMCA), of neutral main-group element hydrides of groups 15-17 and periods 2-4 in the periodic table by using the G2(+)M method. Some similarities and differences are found between NAAMCA and the corresponding alkyl cation affinities (ACA) of H(n)X. Our calculations show that the AMCA and NDMAMCA are systematically lower than the corresponding proton affinities (PA) for H(n)X. In general, there is no linear correlation between NAAMCA and PA of H(n)X. Instead, the correlations exist only within the central elements X in period 2, or periods 3-4, which is significantly different from the reasonable correlations between ACA and PA for all H(n)X. NAAMCA (H(n)X) are weaker than NAAMCA (H(n-1)X(-)) by more than 700 kJ/mol and generally stronger than ACA (H(n)X), with three exceptions: H2ONR2(+)(R = H, Me) and HFNH2(+). These new findings can be rationalized by the negative hyperconjugation and Pauli repulsion.

  15. G2(+)M study on N-alkylamino cation affinities of neutral main-group element hydrides: trends across the periodic table.

    PubMed

    Geng, Song; Wu, Ding-Lu; Yang, Jing; Wei, Xi-Guang; Zhu, Jun; Zhang, Hai-Bo; Ren, Yi; Lau, Kai-Chung

    2014-05-01

    We have made an extensive theoretical exploration of gas-phase N-alkylamino cation affinities (NAAMCA), including amino cation affinities (AMCA) and N-dimethylamino cation affinities (NDMAMCA), of neutral main-group element hydrides of groups 15-17 and periods 2-4 in the periodic table by using the G2(+)M method. Some similarities and differences are found between NAAMCA and the corresponding alkyl cation affinities (ACA) of H(n)X. Our calculations show that the AMCA and NDMAMCA are systematically lower than the corresponding proton affinities (PA) for H(n)X. In general, there is no linear correlation between NAAMCA and PA of H(n)X. Instead, the correlations exist only within the central elements X in period 2, or periods 3-4, which is significantly different from the reasonable correlations between ACA and PA for all H(n)X. NAAMCA (H(n)X) are weaker than NAAMCA (H(n-1)X(-)) by more than 700 kJ/mol and generally stronger than ACA (H(n)X), with three exceptions: H2ONR2(+)(R = H, Me) and HFNH2(+). These new findings can be rationalized by the negative hyperconjugation and Pauli repulsion. PMID:24738576

  16. Cooperative effect of water molecules in the self-catalyzed neutral hydrolysis of isocyanic acid: a comprehensive theoretical study.

    PubMed

    Wei, Xi-Guang; Sun, Xiao-Ming; Wu, Xiao-Peng; Geng, Song; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

    2011-08-01

    The detailed reaction mechanism for the water-assisted hydrolysis of isocyanic acid, HNCO + (n + 1) H(2)O → CO(2) + NH(3) + nH(2)O (n = 0-6), taking place in the gas phase, has been investigated. All structures were optimized and characterized at the MP2/6-31 + G level of theory, and then re-optimized at MP2/6-311++G. The seven explicit water molecules participating in the hydrolysis can be divided into two groups, one directly involved in the proton relay, and the other located in the vicinity of the substrate playing the cooperative role by engaging in hydrogen-bonding to HN = C = O. Two possible reaction pathways, the addition of water molecule across the C = N bond or across the C = O bond, are discussed, and the former is proved to be more favorable energetically. Our calculations suggest that, in the most kinetically favorable pathway for the titled hydrolysis, three water molecules are directly participating in the hydrogen transfer via an eight-membered cyclic transition state, while the other four water molecules catalyze the hydrolysis of HN = C = O by forming three eight-membered cooperative loops near the substrate. This strain-free hydrogen-bond network leads to the best estimated rate-determining activation energy of 24.9 kJ mol(-1) at 600 K, in excellent agreement with the gas-phase kinetic experimental result, 25.8 kJ mol(-1). PMID:21161555

  17. Amine Chemistry at Aqueous Interfaces: The Study of Organic Amines in Neutralizing Acidic Gases at an Air/Water Surface Using Vibrational Sum Frequency Spectroscopy

    NASA Astrophysics Data System (ADS)

    McWilliams, L.; Wren, S. N.; Valley, N. A.; Richmond, G.

    2014-12-01

    Small organic bases have been measured in atmospheric samples, with their sources ranging from industrial processing to animal husbandry. These small organic amines are often highly soluble, being found in atmospheric condensed phases such as fogwater and rainwater. Additionally, they display acid-neutralization ability often greater than ammonia, yet little is known regarding their kinetic and thermodynamic properties. This presentation will describe the molecular level details of a model amine system at the vapor/liquid interface in the presence of acidic gas. We find that this amine system shows very unique properties in terms of its bonding, structure, and orientation at aqueous surfaces. The results of our studies using a combination of computation, vibrational sum frequency spectroscopy, and surface tension will report the properties inherent to these atmospherically relevant species at aqueous surfaces.

  18. Structural acid-base chemistry in the metallic state: how μ3-neutralization drives interfaces and helices in Ti21Mn25.

    PubMed

    Stacey, Timothy E; Fredrickson, Daniel C

    2013-08-01

    Intermetallic phases remain a large class of compounds whose vast structural diversity is unaccounted for by chemical theory. A recent resurgence of interest in intermetallics, due to their potential in such applications as catalysis and thermoelectricity, has intensified the need for models connecting their compositions to their structures and stability. In this Article, we illustrate how the μ3-acidity model, an extension of the acid/base concept based on the Method of Moments, offers intuitive explanations for puzzling structural progressions occurring in intermetallics formed between transition metals. Simple CsCl-type structures are frequently observed for phases with near 1:1 ratios of transition metals. However, in two compounds, TiCu and Ti21Mn25, structures are adopted which deviate from this norm. μ3-Acidity analysis shows that the formation of CsCl-type phases in these exceptional systems would yield an imbalance in the acid/base strength pairing, resulting in overneutralization of the weaker partner and thus instability. Intriguing geometrical features emerge in response, which serve to improve the neutralization of the constituent elements. In both TiCu and Ti21Mn25, part of the structure shields weaker acids or bases from their stronger partners by enhancing homoatomic bonding in the sublattice of the weaker acid or base. In TiCu, this protection is accomplished by developing doubled layers of Ti atoms to reduce their heteroatomic contacts. In Ti21Mn25 the structural response is more extreme: Ti-poor TiMn2 domains are formed to guard Mn from the Ti atoms, while the remaining Ti segregates to regions between the TiMn2 domains. The geometrical details of this arrangement fine-tune the acid/base interactions for an even greater level of stability. The most striking of these occurs in the Ti-rich region, where a paucity of Mn neighbors leads to difficulty in achieving strong neutralization. The Ti atoms arrange themselves in helical tubes, maximizing

  19. The influence of total organic carbon (TOC) on the relationship between acid neutralizing capacity (ANC) and fish status in Norwegian lakes.

    PubMed

    Lydersen, Espen; Larssen, Thorjørn; Fjeld, Eirik

    2004-06-29

    Acid neutralizing capacity (ANC) is the parameter most commonly used as chemical indicator for fish response to acidification. Empirical relationships between fish status of surface waters and ANC have been documented earlier. ANC is commonly calculated as the difference between base cations ([BC]=[Ca2+]+[Mg2+]+[N+]+[K+]) and strong acid anions ([SAA]=[SO4(2)-]+[NO3-]+[Cl-]). This is a very robust calculation of ANC, because none of the parameters incorporated are affected by the partial pressure of CO2, in contrast to the remaining major ions in waters, pH ([H+]), aluminum ([Aln+]), alkalinity ([HCO3-/CO3(2)-]) and organic anions ([An-]). Here we propose a modified ANC calculation where the permanent anionic charge of the organic acids is assumed as a part of the strong acid anions. In many humic lakes, the weak organic acids are the predominant pH-buffering system. Because a significant amount of the weak organic acids have pK-values<3.0-3.5, these relatively strong acids will permanently be deprotonated in almost all natural waters (i.e. pH>4.5). This means that they will be permanently present as anions, equal to the strong acid inorganic anions, SO4(2)-, NO3- and Cl-. In the literature, natural organic acids are often described as triprotic acids with a low pK1 value. Assuming a triprotic model, we suggest to add 1/3 of the organic acid charge density to the strong acid anions in the ANC calculation. The suggested organic acid adjusted ANC (ANC(OAA)), is then calculated as follows: ANC(OAA)=[BC]-([SAA]+1/3CD*TOC) where TOC is total organic carbon (mg C L(-1)), and CD=10.2 is charge density of the organic matter (microeq/mg C), based on literature data from Swedish lakes. ANC(OAA) gives significant lower values of ANC in order to achieve equal fish status compared with the traditional ANC calculation. Using ANC(OAA) the humic conditions in lakes are better taken into account. This may also help explain observations of higher ANC needed to have reproducing fish

  20. Trans-9-octadecenoic acid is biologically neutral and does not regulate the low density lipoprotein receptor as the cis isomer does in the hamster.

    PubMed

    Woollett, L A; Daumerie, C M; Dietschy, J M

    1994-09-01

    The concentration of cholesterol carried in low density lipoproteins (LDL-C) is primarily determined by the rate at which LDL-C is produced (Jt) and the rate at which the liver takes up this particle through receptor-dependent transport (Jm). The accumulation of specific dietary fatty acids in the liver profoundly alters these kinetic parameters and will either increase hepatic receptor activity or further suppress Jm, depending upon the particular fatty acid that enriches the various lipid pools. This study tests the thesis that the cellular effects of each fatty acid are determined by the ability of that lipid to act as an effective substrate for cholesteryl ester formation by examining the metabolic effects of either cis-9-octadecenoic acid (18:1(9c)), the preferred substrate for esterification, or trans-9-octadecenoic acid (18:1(9t)), a poor substrate for this reaction. When fed to hamsters for 30 days, the steady-state concentration of cholesteryl esters was markedly increased by the 18:1(9c), as compared to the 18:1(9t), compound. In animals receiving the 18:1(9c) fatty acid, hepatic receptor activity was significantly increased, LDL-C production was suppressed, and the steady-state LDL-C concentration was reduced. In contrast, the 18:1(9t) fatty acid did not significantly alter Jm, Jt, or the plasma LDL-C level from those values found in the control animals fed an isocaloric amount of a biologically neutral fatty acid, octanoic acid. Despite these different effects on the parameters of LDL metabolism, neither the cis nor trans fatty acid altered net cholesterol delivery to the liver from de novo sterol synthesis in any tissue in the body or from uptake of dietary cholesterol across the intestine. Therefore, these studies provide strong support for the thesis that fatty acids exert regulatory effects on hepatic LDL receptor activity by altering the distribution of cholesterol in the hepatocyte between a putative regulatory pool and the inert pool of

  1. A high load of non-neutral amino-acid polymorphisms explains high protein diversity despite moderate effective population size in a marine bivalve with sweepstakes reproduction.

    PubMed

    Harrang, Estelle; Lapègue, Sylvie; Morga, Benjamin; Bierne, Nicolas

    2013-02-01

    Marine bivalves show among the greatest allozyme diversity ever reported in Eukaryotes, putting them historically at the heart of the neutralist-selectionist controversy on the maintenance of genetic variation. Although it is now acknowledged that this high diversity is most probably a simple consequence of a large population size, convincing support for this explanation would require a rigorous assessment of the silent nucleotide diversity in natural populations of marine bivalves, which has not yet been done. This study investigated DNA sequence polymorphism in a set of 37 nuclear loci in wild samples of the flat oyster Ostrea edulis. Silent diversity was found to be only moderate (0.7%), and there was no departure from demographic equilibrium under the Wright-Fisher model, suggesting that the effective population size might not be as large as might have been expected. In accordance with allozyme heterozygosity, nonsynonymous diversity was comparatively very high (0.3%), so that the nonsynonymous to silent diversity ratio reached a value rarely observed in any other organism. We estimated that one-quarter of amino acid-changing mutations behave as neutral in O. edulis, and as many as one-third are sufficiently weakly selected to segregate at low frequency in the polymorphism. Finally, we inferred that one oyster is expected to carry more than 4800 non-neutral alleles (or 4.2 cM(-1)). We conclude that a high load of segregating non-neutral amino-acid polymorphisms contributes to high protein diversity in O. edulis. The high fecundity of marine bivalves together with an unpredictable and highly variable success of reproduction and recruitment (sweepstakes reproduction) might produce a greater decoupling between Ne and N than in other organisms with lower fecundities, and we suggest this could explain why a higher segregating load could be maintained for a given silent mutation effective size.

  2. A High Load of Non-neutral Amino-Acid Polymorphisms Explains High Protein Diversity Despite Moderate Effective Population Size in a Marine Bivalve With Sweepstakes Reproduction

    PubMed Central

    Harrang, Estelle; Lapègue, Sylvie; Morga, Benjamin; Bierne, Nicolas

    2013-01-01

    Marine bivalves show among the greatest allozyme diversity ever reported in Eukaryotes, putting them historically at the heart of the neutralist−selectionist controversy on the maintenance of genetic variation. Although it is now acknowledged that this high diversity is most probably a simple consequence of a large population size, convincing support for this explanation would require a rigorous assessment of the silent nucleotide diversity in natural populations of marine bivalves, which has not yet been done. This study investigated DNA sequence polymorphism in a set of 37 nuclear loci in wild samples of the flat oyster Ostrea edulis. Silent diversity was found to be only moderate (0.7%), and there was no departure from demographic equilibrium under the Wright-Fisher model, suggesting that the effective population size might not be as large as might have been expected. In accordance with allozyme heterozygosity, nonsynonymous diversity was comparatively very high (0.3%), so that the nonsynonymous to silent diversity ratio reached a value rarely observed in any other organism. We estimated that one-quarter of amino acid-changing mutations behave as neutral in O. edulis, and as many as one-third are sufficiently weakly selected to segregate at low frequency in the polymorphism. Finally, we inferred that one oyster is expected to carry more than 4800 non-neutral alleles (or 4.2 cM−1). We conclude that a high load of segregating non-neutral amino-acid polymorphisms contributes to high protein diversity in O. edulis. The high fecundity of marine bivalves together with an unpredictable and highly variable success of reproduction and recruitment (sweepstakes reproduction) might produce a greater decoupling between Ne and N than in other organisms with lower fecundities, and we suggest this could explain why a higher segregating load could be maintained for a given silent mutation effective size. PMID:23390609

  3. Interpretation of concentration-discharge patterns in acid-neutralizing capacity during storm flow in three small, forested catchments in Shenandoah National Park, Virginia

    USGS Publications Warehouse

    Rice, K.C.; Chanat, J.G.; Hornberger, G.M.; Webb, J.R.

    2004-01-01

    Episodic concentration-discharge (c-Q) plots are a popular tool for interpreting the hydrochemical response of small, forested catchments. Application of the method involves assuming an underlying conceptual model of runoff processes and comparing observed c-Q looping patterns with those predicted by the model. We analyzed and interpreted c-Q plots of acid-neutralizing capacity (ANC) for 133 storms collected over a 7-year period from three catchments in Shenandoah National Park, Virginia. Because of their underlying lithologies the catchments represent a gradient in both hydrologic and geochemical behavior, ranging from a flashy, acidic, poorly buffered catchment to a moderate, neutral, well-buffered catchment. The relative frequency of observed anticlockwise c-Q loops in each catchment decreased along this gradient. Discriminant function analysis indicated that prestorm base flow ANC was an important predictor of loop rotation direction; however, the strength of the predictive relationship decreased along the same gradient. The trends were consistent with several equally plausible three-component mixing models. Uncertainty regarding end-member timing and relative volume and possible time variation in end-member concentrations were key factors precluding identification of a unique model. The inconclusive results obtained on this large data set suggest that identification of underlying runoff mechanisms on the basis of a small number of c-Q plots without additional supporting evidence is likely to be misleading.

  4. Acid neutralizing capacity and leachate results for igneous rocks, with associated carbon contents of derived soils, Animas River AML site, Silverton, Colorado

    USGS Publications Warehouse

    Yager, Douglas B.; Stanton, Mark R.; Choate, LaDonna M.; Burchell,

    2009-01-01

    Mine planning efforts have historically overlooked the possible acid neutralizing capacity (ANC) that local igneous rocks can provide to help neutralize acidmine drainage. As a result, limestone has been traditionally hauled to mine sites for use in neutralizing acid drainage. Local igneous rocks, when used as part of mine life-cycle planning and acid mitigation strategy, may reduce the need to transport limestone to mine sites because these rocks can contain acid neutralizing minerals. Igneous hydrothermal events often introduce moderately altered mineral assemblages peripheral to more intensely altered rocks that host metal-bearing veins and ore bodies. These less altered rocks can contain ANC minerals (calcite-chlorite-epidote) and are referred to as a propylitic assemblage. In addition, the carbon contents of soils in areas of new mining or those areas undergoing restoration have been historically unknown. Soil organic carbon is an important constituent to characterize as a soil recovery benchmark that can be referred to during mine cycle planning and restoration.
    This study addresses the mineralogy, ANC, and leachate chemistry of propylitic volcanic rocks that host polymetallic mineralization in the Animas River watershed near the historical Silverton, Colorado, mining area. Acid titration tests on volcanic rocks containing calcite (2 – 20 wt %) and chlorite (6 – 25 wt %), have ANC ranging from 4 – 146 kg/ton CaCO3 equivalence. Results from a 6-month duration, kinetic reaction vessel test containing layered pyritic mine waste and underlying ANC volcanic rock (saturated with deionized water) indicate that acid generating mine waste (pH 2.4) has not overwhelmed the ANC of propylitic volcanic rocks (pH 5.8). Sequential leachate laboratory experiments evaluated the concentration of metals liberated during leaching. Leachate concentrations of Cu-Zn-As-Pb for ANC volcanic rock are one-to-three orders of magnitude lower when compared to leached

  5. On the neutral to acidic character of the dark terrains mineral assemblage of Europa's surface, and its implication for the ocean composition: Geochemistry, Spectroscopy and Terrestrial analogs

    NASA Astrophysics Data System (ADS)

    Prieto-Ballesteros, O.; Fernandez-Remolar, D. C.; Fernandez-Sampedro, M.; Martin-Redondo, M. P.; Gomez, F.; Kargel, J. S.

    Since the Galileo NIMS sensor obtained the spectral data of the surface of Europa, several laboratory studies have been performed to ascertain the composition of the dark terrains. Some hydrated salts and acids have been proposed to explain the spectral signatures of these areas, but no single mineral fit is completely suitable. Until now, a flash frozen aqueous mixture of magnesium and sodium sulfate with sulphuric acid is the better match. The structural relationship of these materials to the geological features (such as fractures) and geochemical models of chondrite alteration indicate that they are originally endogenic. However, as some authors have already proposed, the high radiation environment has to modify these substances. The cryogenesis of the observed mineralogy may provide some clues about the compositional characteristics of the potential global water ocean of Europa, if this ocean constitutes the source. The crystallization path of the original cryomagmas will determine the final paragenesis observed on the surface. Fractional crystallization of the briny magmas may produce mineral differentiation, resulting in an enrichment of the acidic components as the temperature decreases due to the lower melting point of these materials. But if the solidification occurs as flash freezing, neutral to acidic mineral assemblages are possible. In this case, the original composition would be of Mg-Na sulphates-rich, and the acidic character would occur mainly by radiolysis. A sulphuric acid component should be a secondary product from the alteration of the sulfate paragenesis produced by radiolysis at low temperature, although endogenic acid brines should not be totally rejected. Terrestrial analogs to these chemistries are useful to constrain the habitability of the ocean environment and supply natural brines for new experiments. Several crystallization experiments have been done with brines from Tirez lake (central Spain), and the results show different final

  6. Elucidation of high micro-heterogeneity of an acidic-neutral trichotoxin mixture from Trichoderma harzianum by electrospray ionization quadrupole time-of-flight mass spectrometry.

    PubMed

    Suwan, S; Isobe, M; Kanokmedhakul, S; Lourit, N; Kanokmedhakul, K; Soytong, K; Koga, K

    2000-12-01

    The high micro-heterogeneity of an acidic-neutral trichotoxin mixture from T. harzianum, PC01, was elucidated using a modern tandem mass spectrometer equipped with an electrospray ionization source, a hybrid quadrupole-orthogonal accelerator and a reflectron time-of-flight analyzer. The trichotoxins appeared predominantly in six possible doubly charged pseudo molecular ions with three different adducts (H, Na and K) as [M + 2H](2+), [M + H + Na](2+), [M + H + K](2+), [M + 2Na](2+), [M + Na + K](2+) and [M + 2K](2+). The singly charged pseudomolecular ions, [M + H](+), [M + Na](+) and [M + K](+), occurred only in low abundance when the cone voltages were higher than 30 V. Additional singly charged fragments, b(12) and y"6 (complementary N- and C-terminal fragments), were obtained in high abundance using high cone voltages. The peak patterns of both singly and doubly charged molecular adducts revealed that this trichotoxin mixture contained several components having 6-7 molecular masses with a consecutive 14 u difference among members in the same molecular adduct series. Furthermore, well resolved isotopic peaks of every doubly or singly charged ions and their reproducible peak intensity allowed the identification of the mixing of acidic trichotoxins 1 u molecular mass heavier than the neutral counterparts in the sample. Tandem mass spectrometric (MS/MS) analyses of various singly charged b(12) and y"6 ions supported the sequence deduction of the major and minor components and also the position of Glu in the sequences of these acidic molecules. The setting of either low or high resolution of the quadrupole mass filter unit together with a suitable variation of the collision voltage for any MS/MS precursor were the tools for extracting a number of mixed components and obtaining the major and minor sequences of these precursor peaks. The nature of the MS/MS fragmentation and the data assignment of three major doubly charged ions, [M + 2H](2+), [M + K + H](2+) and [M

  7. Solving nucleic acid structures by molecular replacement: examples from group II intron studies

    PubMed Central

    Marcia, Marco; Humphris-Narayanan, Elisabeth; Keating, Kevin S.; Somarowthu, Srinivas; Rajashankar, Kanagalaghatta; Pyle, Anna Marie

    2013-01-01

    Structured RNA molecules are key players in ensuring cellular viability. It is now emerging that, like proteins, the functions of many nucleic acids are dictated by their tertiary folds. At the same time, the number of known crystal structures of nucleic acids is also increasing rapidly. In this context, molecular replacement will become an increasingly useful technique for phasing nucleic acid crystallographic data in the near future. Here, strategies to select, create and refine molecular-replacement search models for nucleic acids are discussed. Using examples taken primarily from research on group II introns, it is shown that nucleic acids are amenable to different and potentially more flexible and sophisticated molecular-replacement searches than proteins. These observations specifically aim to encourage future crystallographic studies on the newly discovered repertoire of noncoding transcripts. PMID:24189228

  8. The impacts of neutralized acid mine drainage contaminated water on the expression of selected endocrine-linked genes in juvenile Mozambique tilapia Oreochromis mossambicus exposed in vivo.

    PubMed

    Truter, Johannes Christoff; va Wyk, Johannes Hendrik; Oberholster, Paul Johan; Botha, Anna-Maria

    2014-02-01

    Acid mine drainage (AMD) is a global environmental concern due to detrimental impacts on river ecosystems. Little is however known regarding the biological impacts of neutralized AMD on aquatic vertebrates despite excessive discharge into watercourses. The aim of this investigation was to evaluate the endocrine modulatory potential of neutralized AMD, using molecular biomarkers in the teleost fish Oreochromis mossambicus in exposure studies. Surface water was collected from six locations downstream of a high density sludge (HDS) AMD treatment plant and a reference site unimpacted by AMD. The concentrations of 28 elements, including 22 metals, were quantified in the exposure water in order to identify potential links to altered gene expression. Relatively high concentrations of manganese (~ 10mg/l), nickel (~ 0.1mg/l) and cobalt (~ 0.03 mg/l) were detected downstream of the HDS plant. The expression of thyroid receptor-α (trα), trβ, androgen receptor-1 (ar1), ar2, glucocorticoid receptor-1 (gr1), gr2, mineralocorticoid receptor (mr) and aromatase (cyp19a1b) was quantified in juvenile fish after 48 h exposure. Slight but significant changes were observed in the expression of gr1 and mr in fish exposed to water collected directly downstream of the HDS plant, consisting of approximately 95 percent neutralized AMD. The most pronounced alterations in gene expression (i.e. trα, trβ, gr1, gr2, ar1 and mr) was associated with water collected further downstream at a location with no other apparent contamination vectors apart from the neutralized AMD. The altered gene expression associated with the "downstream" locality coincided with higher concentrations of certain metals relative to the locality adjacent to the HDS plant which may indicate a causative link. The current study provides evidence of endocrine disruptive activity associated with neutralized AMD contamination in regard to alterations in the expression of key genes linked to the thyroid, interrenal and

  9. Fatty acid neutral losses observed in tandem mass spectrometry with collision-induced dissociation allows regiochemical assignment of sulfoquinovosyl-diacylglycerols.

    PubMed

    Zianni, Rosalia; Bianco, Giuliana; Lelario, Filomena; Losito, Ilario; Palmisano, Francesco; Cataldi, Tommaso R I

    2013-02-01

    A full characterization of sulfoquinovosyldiacylglycerols (SQDGs) in the lipid extract of spinach leaves has been achieved using liquid chromatography/electrospray ionization-linear quadrupole ion trap mass spectrometry (MS). Low-energy collision-induced dissociation tandem MS (MS/MS) of the deprotonated species [M - H](-) was exploited for a detailed study of sulfolipid fragmentation. Losses of neutral fatty acids from the acyl side chains (i.e. [M - H - RCOOH](-)) were found to prevail over ketene losses ([M - H - R'CHCO](-)) or carboxylates of long-chain fatty acids ([RCOO](-)), as expected for gas-phase acidity of SQDG ions. A new concerted mechanism for RCOOH elimination, based on a charge-remote fragmentation, is proposed. The preferential loss of a fatty acids molecule from the sn-1 position (i.e. [M - H - R(1)COOH](-)) of the glycerol backbone, most likely due to kinetic control of the gas-phase fragmentation process, was exploited for the regiochemical assignment of the investigated sulfolipids. As a result, 24 SQDGs were detected and identified in the lipid extract of spinach leaves, their number and variety being unprecedented in the field of plant sulfolipids. Moreover, the prevailing presence of a palmitic acyl chain (16:0) on the glycerol sn-2 position of spinach SQDGs suggests a prokaryotic or chloroplastic path as the main route for their biosynthesis.

  10. Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.-1: Buffering capacity of dissolved organic carbon in soil solutions

    USGS Publications Warehouse

    Iggy, Litaor M.; Thurman, E.M.

    1988-01-01

    Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai-, derived from DOC at sample pH and the concentration of organic anion, Ax- at the equivalence point were calculated using carboxyl contents from isolated and purified humic material from soil solutions. Subtracting Ax- from Ai- yields the contribution of humic substances to the buffering capacity (Aequiv.-). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado. ?? 1988.

  11. Propagated fixed-bed mixed-acid fermentation: effect of volatile solid loading rate and agitation at near-neutral pH.

    PubMed

    Golub, Kristina W; Golub, Stacey R; Meysing, Daniel M; Holtzapple, Mark T

    2012-11-01

    To increase conversion and product concentration, mixed-acid fermentation can use a countercurrent strategy where solids and liquids pass in opposite directions through a series of fermentors. To limit the requirement for moving solids, this study employed a propagated fixed-bed fermentation, where solids were stationary and only liquid was transferred. To evaluate the role of agitation, continuous mixing was compared with periodic mixing. The periodically mixed fermentation had similar conversion, but lower yield and selectivity. Increasing volatile solid loading rate from 1.5 to 5.1g non-acid volatile solids/(L(liq)·d) and increasing liquid retention time decreased yield, conversion, selectivity, but increased product concentrations. Compared to a previous study at high pH (~9), this study achieved higher performance at near neutral pH (~6.5) and optimal C-N ratios. Compared to countercurrent fermentation, propagated fixed-bed fermentations have similar selectivities and produce similar proportions of acetic acid, but have lower yields, conversion, productivities, and acid concentrations. PMID:22995159

  12. Propagated fixed-bed mixed-acid fermentation: effect of volatile solid loading rate and agitation at near-neutral pH.

    PubMed

    Golub, Kristina W; Golub, Stacey R; Meysing, Daniel M; Holtzapple, Mark T

    2012-11-01

    To increase conversion and product concentration, mixed-acid fermentation can use a countercurrent strategy where solids and liquids pass in opposite directions through a series of fermentors. To limit the requirement for moving solids, this study employed a propagated fixed-bed fermentation, where solids were stationary and only liquid was transferred. To evaluate the role of agitation, continuous mixing was compared with periodic mixing. The periodically mixed fermentation had similar conversion, but lower yield and selectivity. Increasing volatile solid loading rate from 1.5 to 5.1g non-acid volatile solids/(L(liq)·d) and increasing liquid retention time decreased yield, conversion, selectivity, but increased product concentrations. Compared to a previous study at high pH (~9), this study achieved higher performance at near neutral pH (~6.5) and optimal C-N ratios. Compared to countercurrent fermentation, propagated fixed-bed fermentations have similar selectivities and produce similar proportions of acetic acid, but have lower yields, conversion, productivities, and acid concentrations.

  13. Inorganic ions in ambient fine particles over a National Park in central India: Seasonality, dependencies between SO42-, NO3-, and NH4+, and neutralization of aerosol acidity

    NASA Astrophysics Data System (ADS)

    Kumar, Samresh; Sunder Raman, Ramya

    2016-10-01

    suggested that in NH4+ rich samples, NO3- and non-sea salt SO42- were almost entirely neutralized by NH4+. In NH4+ poor samples, in addition to NH4+ non-sea salt K+ played a role in acidity neutralization. These observations are unlike those reported for PM10 and total suspended particles (TSP) over other locations in India, where mineral aerosol species (specifically Ca2+) played an important role in neutralizing acidic species. Additionally, both during 2012 and 2013, the aerosol acidity showed a pronounced seasonality - the aerosol was alkaline or near-neutral during the winter and post-monsoon seasons, while during the pre-monsoon and monsoon seasons it was acidic.

  14. Acidic extracellular pH neutralizes the autophagy-inhibiting activity of chloroquine: implications for cancer therapies.

    PubMed

    Pellegrini, Paola; Strambi, Angela; Zipoli, Chiara; Hägg-Olofsson, Maria; Buoncervello, Maria; Linder, Stig; De Milito, Angelo

    2014-04-01

    Acidic pH is an important feature of tumor microenvironment and a major determinant of tumor progression. We reported that cancer cells upregulate autophagy as a survival mechanism to acidic stress. Inhibition of autophagy by administration of chloroquine (CQ) in combination anticancer therapies is currently evaluated in clinical trials. We observed in 3 different human cancer cell lines cultured at acidic pH that autophagic flux is not blocked by CQ. This was consistent with a complete resistance to CQ toxicity in cells cultured in acidic conditions. Conversely, the autophagy-inhibiting activity of Lys-01, a novel CQ derivative, was still detectable at low pH. The lack of CQ activity was likely dependent on a dramatically reduced cellular uptake at acidic pH. Using cell lines stably adapted to chronic acidosis we could confirm that CQ lack of activity was merely caused by acidic pH. Moreover, unlike CQ, Lys-01 was able to kill low pH-adapted cell lines, although higher concentrations were required as compared with cells cultured at normal pH conditions. Notably, buffering medium pH in low pH-adapted cell lines reverted CQ resistance. In vivo analysis of tumors treated with CQ showed that accumulation of strong LC3 signals was observed only in normoxic areas but not in hypoxic/acidic regions. Our observations suggest that targeting autophagy in the tumor environment by CQ may be limited to well-perfused regions but not achieved in acidic regions, predicting possible limitations in efficacy of CQ in antitumor therapies. PMID:24492472

  15. Synthesis and Monolayer Behaviors of Novel Hybrid Corynomycolic Acids Containing Semifluoroalkyl Groups.

    PubMed

    Kawase, Tokuzo; Tamaki, Kazuki; Oida, Tatsuo

    2016-01-01

    In this work, novel hybrid-type corynomycolic acids [hybrid-OH and hybrid-COOH, with semifluoroalkyl groups (Rf-(CH2)n-: Rf = C4F9, n = 6 and Rf = C6F13, n = 3) located on the carbon atoms attached to the hydroxyl and carboxylic acid groups (C-OH and C-COOH), respectively] were successfully synthesized. The behaviors and formation of hybrid corynomycolic acid monolayers at the air-water interface were investigated by surface tension and surface pressure-area (π-A) measurements to clarify the effects of the Rf chain length, position of the semifluoroalkyl group, and surfactant molecule stereochemistry. Compared to dialkyl corynomycolic acid, both the critical micelle concentration (CMC) and the surface tension at the CMC (γCMC) of hybrid corynomycolic acids were reduced by the presence of the Rf group. With respect to the surface tension versus log concentration (γ vs. log C) isotherms, all syn-isomers of the hybrid-OH and hybrid-COOH acids showed two break points, while the anti-isomers showed only one break point. These different isotherms can be explained in terms of the steric repulsion between the two hydrophilic groups (OH and COO(-)), which depend on the stereochemistry of the surfactant. No effect of the location of the semifluoroalkyl group was observed. With respect to the formation of a monolayer film, four parameters-the lift-off area (AL), zero-pressure molecular area (A0), maximum of the Gibbs elastic modulus [EG (max)], and monolayer collapse pressure (πc)-were measured. Both AL and A0 of all hybrid corynomycolic acids were larger than the corresponding dialkyl acids due to the bulky and rigid Rf groups. Interestingly, syn- and anti-hybrids had almost identical isotherms on compression, although the values of πc of anti-hybrids were higher than those of syn-isomers. In addition, the values of EG (max) of hybrid-COOHs were slightly larger than those of the corresponding hybrid-OHs. Using the nascent soap method (agent-in-oil method), we found that

  16. Modeling the hydrolysis of perfluorinated compounds containing carboxylic and phosphoric acid ester functions and sulfonamide groups.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2010-01-01

    Temperature-dependent rate constants were estimated for the acid- and base-catalyzed and neutral hydrolysis reactions of perfluorinated telomer acrylates (FTAcrs) and phosphate esters (FTPEs), and the S(N)1 and S(N)2 hydrolysis reactions of fluorotelomer iodides (FTIs). Under some environmental conditions, hydrolysis of monomeric FTAcrs could be rapid (half-lives of several years in marine systems and as low as several days in some landfills) and represent a dominant portion of their overall degradation. Abiotic hydrolysis of monomeric FTAcrs may be a significant contributor to current environmental loadings of fluorotelomer alcohols (FTOHs) and perfluoroalkyl carboxylic acids (PFCAs). Polymeric FTAcrs are expected to be hydrolyzed more slowly, with estimated half-lives in soil and natural waters ranging between several centuries to several millenia absent additional surface area limitations on reactivity. Poor agreement was found between the limited experimental data on FTPE hydrolysis and computational estimates, requiring more detailed experimental data before any further modeling can occur on these compounds or their perfluoroalkyl sulfonamidoethanol phosphate ester (PFSamPE) analogs. FTIs are expected to have hydrolytic half-lives of about 130 days in most natural waters, suggesting they may be contributing to substantial FTOH and PFCA inputs in aquatic systems. Perfluoroalkyl sulfonamides (PFSams) appear unlikely to undergo abiotic hydrolysis at the S-N, C-S, or N-C linkages under environmentally relevant conditions, although potentially facile S-N hydrolysis via intramolecular catalysis by ethanol and acetic acid amide substituents warrants further investigation. PMID:20390888

  17. Bile acid inhibition of taurocholate uptake by rat hepatocytes: role of OH groups

    SciTech Connect

    Bellentani, S.; Hardison, W.G.M.; Marchegiano, P.; Zanasi, G.; Manenti, F.

    1987-03-01

    To define further the structural specificity of the taurocholate uptake site, the authors studied the ability of a variety of taurine-conjugated bile acids with differing hydroxyl substituents on the sterol moiety to inhibit (/sup 14/C) taurocholate uptake. Rat hepatocytes isolated by collagenase perfusion were incubated in a tris (hydroxymethyl) aminomethane-phosphate buffer containing (/sup 14/C)taurocholate in the presence or absence of inhibitor bile acid. Stronger inhibitors were studied at a fixed concentration of 5 ..mu..M, weaker ones at 25 ..mu..M. Initial uptake velocity was measured. Uptake velocity could then be related to taurocholate concentration and a V/sub max/ and K/sub m/ could be determined by applying a nonlinear least squares fit to the data obtained with or without inhibitor. The kinetic parameters allowed the determination of the type of inhibition and of inhibition constants (K/sub i/) of the various test bile acids. The data indicate that bile acids containing a 6- or 7-OH group exhibit competitive inhibition, whereas bile acids with no 6- or 7-OH group exhibit noncompetitive inhibition. Of the compounds exhibiting competitive inhibition, K/sub i/ varied with the number of hydroxyl groups on the sterol moiety. They conclude that the presence of absence of a 6- or 7-OH group dictates the mechanism of inhibition; the number of hydroxyl substituents determines the potency of competitive inhibition.

  18. Structural characterization of neutral and acidic oligosaccharides in the milks of strepsirrhine primates: greater galago, aye-aye, Coquerel's sifaka and mongoose lemur.

    PubMed

    Taufik, Epi; Fukuda, Kenji; Senda, Akitsugu; Saito, Tadao; Williams, Cathy; Tilden, Chris; Eisert, Regina; Oftedal, Olav; Urashima, Tadasu

    2012-04-01

    The structures of milk oligosaccharides were characterized for four strepsirrhine primates to examine the extent to which they resemble milk oligosaccharides in other primates. Neutral and acidic oligosaccharides were isolated from milk of the greater galago (Galagidae: Otolemur crassicaudatus), aye-aye (Daubentoniidae: Daubentonia madagascariensis), Coquerel's sifaka (Indriidae: Propithecus coquereli) and mongoose lemur (Lemuridae: Eulemur mongoz), and their chemical structures were characterized by (1)H-NMR spectroscopy. The oligosaccharide patterns observed among strepsirrhines did not appear to correlate to phylogeny, sociality or pattern of infant care. Both type I and type II neutral oligosaccharides were found in the milk of the aye-aye, but type II predominate over type I. Only type II oligosaccharides were identified in other strepsirrhine milks. α3'-GL (isoglobotriose, Gal(α1-3)Gal(β1-4)Glc) was found in the milks of Coquerel's sifaka and mongoose lemur, which is the first report of this oligosaccharide in the milk of any primate species. 2'-FL (Fuc(α1-2)Gal(β1-4)Glc) was found in the milk of an aye-aye with an ill infant. Oligosaccharides containing the Lewis x epitope were found in aye-aye and mongoose lemur milk. Among acidic oligosaccharides, 3'-N-acetylneuraminyllactose (3'-SL-NAc, Neu5Ac(α2-3)Gal(β1-4)Glc) was found in all studied species, whereas 6'-N-acetylneuraminyllactose (6'-SL-NAc, Neu5Ac(α2-6)Gal(β1-4)Glc) was found in all species except greater galago. Greater galago milk also contained 3'-N-glycolylneuraminyllactose (3'-SL-NGc, Neu5Gc(α2-3)Gal(β1-4)Glc). The finding of a variety of neutral and acidic oligosaccharides in the milks of strepsirrhines, as previously reported for haplorhines, suggests that such constituents are ancient rather than derived features, and are as characteristic of primate lactation is the classic disaccharide, lactose.

  19. Structural characterization of neutral and acidic oligosaccharides in the milks of strepsirrhine primates: greater galago, aye-aye, Coquerel's sifaka and mongoose lemur.

    PubMed

    Taufik, Epi; Fukuda, Kenji; Senda, Akitsugu; Saito, Tadao; Williams, Cathy; Tilden, Chris; Eisert, Regina; Oftedal, Olav; Urashima, Tadasu

    2012-04-01

    The structures of milk oligosaccharides were characterized for four strepsirrhine primates to examine the extent to which they resemble milk oligosaccharides in other primates. Neutral and acidic oligosaccharides were isolated from milk of the greater galago (Galagidae: Otolemur crassicaudatus), aye-aye (Daubentoniidae: Daubentonia madagascariensis), Coquerel's sifaka (Indriidae: Propithecus coquereli) and mongoose lemur (Lemuridae: Eulemur mongoz), and their chemical structures were characterized by (1)H-NMR spectroscopy. The oligosaccharide patterns observed among strepsirrhines did not appear to correlate to phylogeny, sociality or pattern of infant care. Both type I and type II neutral oligosaccharides were found in the milk of the aye-aye, but type II predominate over type I. Only type II oligosaccharides were identified in other strepsirrhine milks. α3'-GL (isoglobotriose, Gal(α1-3)Gal(β1-4)Glc) was found in the milks of Coquerel's sifaka and mongoose lemur, which is the first report of this oligosaccharide in the milk of any primate species. 2'-FL (Fuc(α1-2)Gal(β1-4)Glc) was found in the milk of an aye-aye with an ill infant. Oligosaccharides containing the Lewis x epitope were found in aye-aye and mongoose lemur milk. Among acidic oligosaccharides, 3'-N-acetylneuraminyllactose (3'-SL-NAc, Neu5Ac(α2-3)Gal(β1-4)Glc) was found in all studied species, whereas 6'-N-acetylneuraminyllactose (6'-SL-NAc, Neu5Ac(α2-6)Gal(β1-4)Glc) was found in all species except greater galago. Greater galago milk also contained 3'-N-glycolylneuraminyllactose (3'-SL-NGc, Neu5Gc(α2-3)Gal(β1-4)Glc). The finding of a variety of neutral and acidic oligosaccharides in the milks of strepsirrhines, as previously reported for haplorhines, suggests that such constituents are ancient rather than derived features, and are as characteristic of primate lactation is the classic disaccharide, lactose. PMID:22311613

  20. Improved volatile fatty acids anaerobic production from waste activated sludge by pH regulation: Alkaline or neutral pH?

    PubMed

    Ma, Huijun; Chen, Xingchun; Liu, He; Liu, Hongbo; Fu, Bo

    2016-02-01

    In this study, the anaerobic fermentation was carried out for volatile fatty acids (VFAs) production at different pH (between 7.0 and 10.0) conditions with untreated sludge and heat-alkaline pretreated waste activated sludge. In the fermentation with untreated sludge, the extent of hydrolysis of organic matters and extent of acidification at alkaline pH are 54.37% and 30.37%, respectively, resulting in the highest VFAs yield at 235.46mg COD/gVS of three pH conditions. In the fermentation with heat-alkaline pretreated sludge, the acidification rate and VFAs yield at neutral pH are 30.98% and 240.14mg COD/gVS, respectively, which are higher than that at other pH conditions. With the glucose or bovine serum albumin as substrate for VFAs production, the neutral pH showed a higher VFAs concentration than the alkaline pH condition. The results of terminal restriction fragment length polymorphism (T-RFLP) analysis indicated that the alkaline pH caused low microbial richness. Based on the results in this study, we demonstrated that the alkaline pH is favor of hydrolysis of organic matter in sludge while neutral pH improved the acidogenesis for the VFAs production from sludge. Our finding is obvious different to the previous research and helpful for the understanding of how heat-alkaline pretreatment and alkaline fermentation influence the VFAs production, and beneficial to the development of VFAs production process.

  1. Effect of pentoxifylline on arachidonic acid metabolism, neutral lipid synthesis and accumulation during induction of the lipocyte phenotype by retinol in murine hepatic stellate cell.

    PubMed

    Cardoso, Carla C A; Paviani, Ernani R; Cruz, Lavínia A; Guma, Fátima C R; Borojevic, Radovan; Guaragna, Regina M

    2003-12-01

    In liver fibrosis, the quiescent hepatic stellate cells (HSC) are activated to proliferate and express the activated myofibroblast phenotype, losing fat droplets and the stored vitamin A, and depositing more extracellular matrix. Therapeutic strategies for liver fibrosis are focused on HSC. Pentoxifylline (PTF), an analog of the methylxanthine, prevents the biochemical and histological changes associated with animal liver fibrosis. The aim of the present study was to investigate the phenotypic change of myofibroblasts into quiescent lipocytes by PTF and/or retinol, using a permanent cell line GRX that represents murine HSC. We studied the action of both drugs on the synthesis of neutral lipids, activity of phospholipase A2 (PLA2), release of arachidonic acid (AA) and prostaglandins synthesis. Accumulation and synthesis of neutral lipids was dependent upon association of retinol with PTF. PTF (0.5 mg/mL) alone did not induce lipid accumulation and synthesis, but in cells induced by physiologic concentration of retinol (1-2.5 microM), it increased the quantity of stored lipids. Retinol and PTF (5 microM and 0.1 mg/mL, respectively) had a synergistic effect on neutral lipid synthesis and accumulation. In higher PTF concentrations (0.5 and 0.7 mg/ml), the synthesis was stimulated but accumulation decreased. Membrane-associated PLA2 activity decreased after PTF treatment, which increased the AA release 8 fold, and significantly increased the production of PGE2, but not of PGF2. However, when in presence of retinol, we observed a slightly higher increase in PGE2 and PGF2a production. In conclusion, PTF treatment generated an excess of free AA. We propose that retinol counteracts the action of PTF on the AA release and PGs production, even though both drugs stimulated the lipocyte induction in the HSC. PMID:14674680

  2. Matrix-assisted laser desorption/ionization mass spectrometry of neutral and acidic oligosaccharides with collision-induced dissociation.

    PubMed

    Mechref, Y; Baker, A G; Novotny, M V

    1998-12-15

    Using ribonuclease B and human alpha 1-acid glycoprotein (AGP) as model glycoproteins, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry with collision-induced dissociation (CID) is validated here as an effective tool for oligosaccharide sequencing. The spectra acquired for high-mannose and complex oligosaccharide structures show characteristic fragments resulting from cleavages of the glycosidic bonds and a few cross-ring cleavages. Esterification of the sialic acid residues is essential in stabilizing the acidic N-linked oligosaccharides. An important analytical feature observed in all acquired spectra is the occurrence of cleavages on the same antenna up to the branching point, as deduced from the absence of fragmentation due to the simultaneous cleavages on two or more antennas.

  3. Synthesis, characterization, and biocompatibility of biodegradable hyperbranched polyglycerols from acid-cleavable ketal group functionalized initiators.

    PubMed

    Shenoi, Rajesh A; Lai, Benjamin F L; Kizhakkedathu, Jayachandran N

    2012-10-01

    Herein we report the synthesis of biodegradable hyperbranched polyglycerols (BHPGs) having acid-cleavable core structure by anionic ring-opening multibranching polymerization (ROMBP) of glycidol using initiators bearing dimethyl and cyclohexyl ketal groups. Five different multifunctional initiators carrying one to four ketal groups and two to four hydroxyl groups per molecule were synthesized. The hydroxyl carrying initiators containing one ketal group per molecule were synthesized from ethylene glycol. An alkyne-azide click reaction was used for synthesizing initiators containing multiple cyclohexyl ketal linkages and hydroxyl groups. The synthesized BHPGs exhibited monomodal molecular weight distributions and polydispersity in the range of 1.2 to 1.6, indicating the controlled nature of the polymerizations. The polymers were relatively stable at physiological pH but degraded at acidic pH values. The polymer degradation was dependent on the type of ketal structure present in the BHPG; polymers with cyclohexyl ketal groups degraded at much slower rates than those with dimethyl ketal groups at a given pH. Good control of polymer degradation was achieved under mild acidic conditions by changing the structure of ketal linkages. A precise control of the molecular weight of the degraded HPG was achieved by controlling the number of ketal groups within the core, as revealed from the gel permeation chromatography (GPC) analyses. The decrease in the polymer molecular weights upon degradation was correlated well with the number of ketal groups in their core structure. Our data support the suggestion that glycidol was polymerized uniformly from all hydroxyl groups of the initiators. BHPGs and their degradation products were highly biocompatible, as measured by blood coagulation, complement activation, platelet activation, and cell viability assays. The controlled degradation profiles of these polymers together with their excellent biocompatibility make them suitable for drug

  4. Lipoteichoic acid-binding and biological properties of T protein of group A streptococcus.

    PubMed

    Johnson, R H; Simpson, W A; Dale, J B; Ofek, I; Beachey, E H

    1980-08-01

    T protein was extracted with trypsin from an avirulent, M protein-deficient, type 1 group A Streptococcus and purified by ammonium sulfate precipitation and anion-exchange chromatography. The latter procedure removed contaminating lipoteichoic acid (LTA) from the T protein, which consisted of a heterogeneous mixture of polypeptides resistant to digestion by trypsin and ranged in molecular size from 160,000 to 200,000 daltons. Threonine, aspartic acid, glutamic acid, lysine, and valine were the most predominant amino acids. The binding of LTA to an affinity column of T protein was reversible with increasing concentrations of ethanol but not with increasing ionic strength. T protein bound less palmitic acid and LTA than did fatty acid-free bovine albumin and did not stimulate human peripheral lymphocytes. Because the surface and cell wall distribution of the T proteins and LTA appear similar, the possibility exists that T proteins and LTA may interact in situ by weakly hydrophobic bonds. Such ligand-ligand interaction may be indirectly involved in the adherence of group A streptococci to host cell membranes that is known to be mediated by LTA.

  5. Modelling removal mechanisms of Pb, Cu, Zn and Cd in acidic groundwater during the neutralization by ambient surface and ground waters

    USGS Publications Warehouse

    Paulson, Anthony J.; Balistrieri, Laurie S.

    1999-01-01

    Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.

  6. Rh-catalyzed sulfonic acid group directed ortho C-H olefination of arenes.

    PubMed

    Dong, Yi; Liu, Gang

    2013-09-21

    A Rh-catalyzed ortho C-H olefination of arenes directed by a sulfonic acid group was developed with good yields and a broad reaction scope. Efficient performance of the catalyst caused this electron-poor aromatic C-H to be activated effectively and unactivated alkenes are also suitable for this reaction.

  7. Fatty acid composition of breast milk from three racial groups from Penang, Malaysia.

    PubMed

    Kneebone, G M; Kneebone, R; Gibson, R A

    1985-04-01

    The fatty acid composition of samples of breast milk obtained from 51 mothers (26 Malay, 15 Chinese, 10 Indian) residing in Penang, Malaysia was determined by gas chromatography. Despite living in close physical proximity the mothers from the three racial groups showed distinct cultural differences in dietary intake. These differences were reflected in differences in the fatty acid composition of breast milk samples. The milk of Chinese mothers was generally less saturated (41%) than that of Malay and Indian mothers (52 and 50% respectively). The milk of Chinese mothers was also richer in linoleic acid (17%) than that of Malay and Indian mothers (9% and 11% respectively). Overall the level of individual fatty acids fell within the range of values reported for Western mothers on well nourished diets and pointed to breast milk of high standard despite large variations in the diet of Malaysian mothers. PMID:3984928

  8. Fatty acid composition of breast milk from three racial groups from Penang, Malaysia.

    PubMed

    Kneebone, G M; Kneebone, R; Gibson, R A

    1985-04-01

    The fatty acid composition of samples of breast milk obtained from 51 mothers (26 Malay, 15 Chinese, 10 Indian) residing in Penang, Malaysia was determined by gas chromatography. Despite living in close physical proximity the mothers from the three racial groups showed distinct cultural differences in dietary intake. These differences were reflected in differences in the fatty acid composition of breast milk samples. The milk of Chinese mothers was generally less saturated (41%) than that of Malay and Indian mothers (52 and 50% respectively). The milk of Chinese mothers was also richer in linoleic acid (17%) than that of Malay and Indian mothers (9% and 11% respectively). Overall the level of individual fatty acids fell within the range of values reported for Western mothers on well nourished diets and pointed to breast milk of high standard despite large variations in the diet of Malaysian mothers.

  9. Partitioning the variation within the acid neutralizing capacity of surface waters in Scotland in relation to land cover, soil and atmospheric depositional factors.

    PubMed

    Kernan, M R; Helliwell, R C

    2001-01-29

    A method of decomposing the variation in the acid neutralizing capacity (ANC) of surface waters in Scotland is described. Using national datasets, a series of variables relating to 703 catchments across Scotland is divided into three components representing (i) land cover, (ii) soil and (iii) atmospheric deposition/altitude. Redundancy analysis (RDA) and (partial) redundancy analysis are used to quantify the amount of variation in ANC uniquely attributable to each of these components, independent of the effects of the others. The variation accounted for by covarying combinations of these components is also determined. Approximately 55% of the total variation in ANC across the 703 sites is explained by the variables representing catchment characteristics and atmospheric deposition. Of this, 8.5%, 2.4% and 6.9% are uniquely attributable to the land cover, soil and deposition/altitude components, respectively. A further 38% of ANC variation is associated with the covariation between components, with 18% accounted for by the combination of all three. Approximately 45% of the variation in ANC remains unexplained. The results reflect the integrated nature of catchment processes and demonstrate, for these data, that it is a combination of land cover, soil and deposition and altitude factors which most explain variation in freshwater ANC level. The approach offers a tool with which to assess the sensitivity of surface waters to acid deposition at a regional scale and provides a way of identifying regional differences in catchment response to acid loading.

  10. Hydrophobic End-Modulated Amino-Acid-Based Neutral Hydrogelators: Structure-Specific Inclusion of Carbon Nanomaterials.

    PubMed

    Choudhury, Pritam; Mandal, Deep; Brahmachari, Sayanti; Das, Prasanta Kumar

    2016-04-01

    Hydrophobic end-modulated l-phenylalanine-containing triethylene glycol monomethyl ether tagged neutral hydrogelators (1-4) are developed. Investigations determine the gelators' structure-dependent inclusion of carbon nanomaterials (CNMs) in the self-assembled fibrillar network (SAFIN). The gelators (1, 3, and 4) can immobilize water and aqueous buffer (pH 3-7) with a minimum gelator concentration of 10-15 mg mL(-1). The hydrophobic parts of the gelators are varied from a long chain (C-16) to an extended aromatic pyrenyl moiety, and their abilities to integrate 1 D and 2 D allotropes of carbon (i.e., single-walled carbon nanotubes (SWNTs) and graphene oxide (GO), respectively) within the gel are investigated. Gelator 1, containing a long alkyl chain (C-16), can include SWNTs, whereas the pyrene-containing 4 can include both SWNTs and GO. Gelator 3 fails to incorporate SWNTs or GO owing to its slow rate of gelation and possibly a mismatch between the aggregated structure and CNMs. The involvement of various forces in self-aggregated gelation and physicochemical changes occurring through CNM inclusion are examined by spectroscopic and microscopic techniques. The distinctive pattern of self-assembly of gelators 1 and 4 through J- and H-type aggregation might facilitate the structure-specific CNM inclusion. Inclusion of SWNTs/GO within the hydrogel matrix results in a reinforcement in mechanical stiffness of the composites compared with that of the native hydrogels.

  11. Influence of the morphology and impurities of Ni(OH){sub 2} on the synthesis of neutral Ni(II)-amino acid complexes

    SciTech Connect

    Rodriguez-Gonzalez, Vicente; Marceau, Eric Che, Michel; Pepe, Claude

    2007-12-15

    Synthesis of neutral complexes of Ni{sup 2+} with amino acids has often been reported on a qualitative basis, with a lack of information on the parameters involved in the dissolution of the nickel-containing solid precursor. This paper reports on a systematic study of the reactivity of Ni(OH){sub 2} toward glycine in aqueous solution. The crystallinity and size of hydroxide particles are found to be key parameters in the rapid glycine-promoted dissolution of the hydroxide and synthesis of [Ni(glycinate){sub 2}(H{sub 2}O){sub 2}]. These parameters derive from the nature of the salt used to prepare the hydroxide. Ni(II) chloride leads to the most reactive solid precursor, because of the presence of defects in the Ni(OH){sub 2} sheets arrangements, assigned to the substitution of Cl{sup -} ions to OH{sup -} ions at the edges of the particles. The reaction between this hydroxide and glycine at 80 deg. C is quantitative after 7 min and similar rates of dissolution are obtained with other amino acids, alanine or histidine, the reaction with serine being slower. When the hydroxide contains nitrate or carbonate ions, a glycinato complex with composition similar to [Ni(glycinate){sub 2}(H{sub 2}O){sub 2}], but with a different crystal structure, is also formed. Spectroscopic results may suggest a structure involving bridging ligands. - Graphical abstract: Ni(OH){sub 2} solid precursors can be readily selected on the basis of their defects, themselves stemming from the nickel salt chosen for precipitation, to rapidly synthesize neutral Ni(II)-aminoacid complexes by ligand-promoted dissolution.

  12. Development of Acid Functional Groups and Lactones During the Thermal Degradation of Wood and Wood Components

    USGS Publications Warehouse

    Rutherford, David W.; Wershaw, Robert L.; Reeves, James B.

    2008-01-01

    Black carbon (pyrogenic materials including chars) in soils has been recognized as a substantial portion of soil organic matter, and has been shown to play a vital role in nutrient cycling; however, little is known concerning the properties of this material. Previous studies have largely been concerned with the creation of high-surface-area materials for use as sorbents. These materials have been manufactured at high temperature and have often been activated. Chars occurring in the environment can be formed over a wide range of temperature. Because it is extremely difficult to isolate black carbon once it has been incorporated in soils, chars produced in the laboratory under controlled conditions can be used to investigate the range of properties possible for natural chars. This report shows that charring conditions (temperature and time) have substantial impact on the acid functional group and lactone content of chars. Low temperatures (250?C) and long charring times (greater than 72 hours) produce chars with the highest acid functional group and lactone content. The charring of cellulose appears to be responsible for the creation of the acid functional group and lactones. The significance of this study is that low-temperature chars can have acid functional group contents comparable to humic materials (as high as 8.8 milliequivalents per gram). Acid functional group and lactone content decreases as charring temperature increases. The variation in formation conditions expected under natural fire conditions will result in a wide range of sorption properties for natural chars which are an important component of soil organic matter. By controlling the temperature and duration of charring, it is possible to tailor the sorption properties of chars, which may be used as soil amendments.

  13. THE M81 GROUP DWARF IRREGULAR GALAXY DDO 165. I. HIGH-VELOCITY NEUTRAL GAS IN A POST-STARBURST SYSTEM

    SciTech Connect

    Cannon, John M.; Most, Hans P.; Skillman, Evan D.; Weisz, Daniel R.; Warren, Steven R.; Cook, David; Dolphin, Andrew E.; Kennicutt, Robert C.; Lee, Janice; Seth, Anil; Walter, Fabian E-mail: skillman@astro.umn.edu E-mail: warren@astro.umn.edu E-mail: adolphin@raytheon.com E-mail: jlee@obs.carnegiescience.edu E-mail: walter@mpia.de

    2011-07-01

    We present new multi-configuration Very Large Array H I spectral line observations of the M81 group dwarf irregular post-starburst galaxy DDO 165. The H I morphology is complex, with multiple column density peaks surrounding a large region of very low H I surface density that is offset from the center of the stellar distribution. The bulk of the neutral gas is associated with the southern section of the galaxy; a secondary peak in the north contains {approx}15% of the total H I mass. These components appear to be kinematically distinct, suggesting that either tidal processes or large-scale blowout have recently shaped the interstellar medium (ISM) of DDO 165. Using spatially resolved position-velocity maps, we find multiple localized high-velocity gas features. Cross-correlating with radius-velocity analyses, we identify eight shell/hole structures in the ISM with a range of sizes ({approx}400-900 pc) and expansion velocities ({approx}7-11 km s{sup -1}). These structures are compared with narrow- and broadband imaging from the Kitt Peak National Observatory and the Hubble Space Telescope (HST). Using the latter data, recent works have shown that DDO 165's previous 'burst' phase was extended temporally ({approx}>1 Gyr). We thus interpret the high-velocity gas features, H I holes, and kinematically distinct components of the galaxy in the context of the immediate effects of 'feedback' from recent star formation (SF). In addition to creating H I holes and shells, extended SF events are capable of creating localized high-velocity motion of the surrounding interstellar material. A companion paper connects the energetics from the H I and HST data.

  14. A Neutralizing Monoclonal IgG1 Antibody of Platelet-Activating Factor Acetylhydrolase SsE Protects Mice against Lethal Subcutaneous Group A Streptococcus Infection

    PubMed Central

    Liu, Mengyao; Feng, Wenchao; Zhu, Hui

    2015-01-01

    Group A Streptococcus (GAS) can cause life-threatening invasive infections, including necrotizing fasciitis. There are no effective treatments for severe invasive GAS infections. The platelet-activating factor (PAF) acetylhydrolase SsE produced by GAS is required for invasive GAS to evade innate immune responses and to invade soft tissues. This study determined whether the enzymatic activity of SsE is critical for its function in GAS skin invasion and inhibition of neutrophil recruitment and whether SsE is a viable target for immunotherapy for severe invasive GAS infections. An isogenic derivative of M1T1 strain MGAS5005 producing SsE with an S178A substitution (SsES178A), an enzymatically inactive SsE mutant protein, was generated. This strain induced higher levels of neutrophil infiltration and caused smaller lesions than MGAS5005 in subcutaneous infections of mice. This phenotype is similar to that of MGAS5005 sse deletion mutants, indicating that the enzymatic activity of SsE is critical for its function. An anti-SsE IgG1 monoclonal antibody (MAb), 2B11, neutralized the PAF acetylhydrolase activity of SsE. Passive immunization with 2B11 increased neutrophil infiltration, reduced skin invasion, and protected mice against MGAS5005 infection. However, 2B11 did not protect mice when it was administered after MGAS5005 inoculation. MGAS5005 induced vascular effusion at infection sites at early hours after GAS inoculation, suggesting that 2B11 did not always have access to infection sites. Thus, the enzymatic activity of SsE mediates its function, and SsE has the potential to be included in a vaccine but is not a therapeutic target. An effective MAb-based immunotherapy for severe invasive GAS infections may need to target virulence factors that are critical for systemic survival of GAS. PMID:25916987

  15. Neutralization of an acidic surface mine lake using organic additives. Final research report, 1 July 1991-1 October 1993

    SciTech Connect

    Brugam, R.B.

    1993-10-01

    We added 9.1 metric tons of manure to a pH 2.9 acid coal mine lake in Southern Illinois to test whether the added organic matter would support sulfate and iron reduction by anaerobic bacteria resulting in the production of alkalinity and a rise in pH. The added organic matter did cause a rise in pH in the deep water of the lake, but the effect did not increase the pH of the whole lake. Experiments in laboratory microcosms at 23 C show that lake sediment treated with manure can permanently raise the pH of acid mine drainage. In the open lake diffusion of oxygen into the anaerobic zones of the water column and low water temperatures in the winter limited the effects of sulfate and iron reduction to the deep water of the lake during summer thermal stratification.

  16. A comparison of the effects of amide and acid groups at the C-terminus on the collision-induced dissociation of deprotonated peptides.

    PubMed

    Bokatzian-Johnson, Samantha S; Stover, Michele L; Dixon, David A; Cassady, Carolyn J

    2012-09-01

    The dissociative behavior of peptide amides and free acids was explored using low-energy collision-induced dissociation and high level computational theory. Both positive and negative ion modes were utilized, but the most profound differences were observed for the deprotonated species. Deprotonated peptide amides produce a characteristic c(m-2)(-) product ion (where m is the number of residues in the peptide) that is either absent or in low abundance in the analogous peptide acid spectrum. Peptide acids show an enhanced formation of c(m-3)(-); however, this is not generally as pronounced as c(m-2)(-) production from amides. The most notable occurrence of an amide-specific product ion is for laminin amide (YIGSR-NH(2)) and this case was investigated using several modified peptides. Mechanisms involving 6- and 9-membered ring formation were proposed, and their energetic properties were investigated using G3(MP2) molecular orbital theory calculations. For example, with C-terminal deprotonation of pentaglycine amide, formation of c(m-2)(-) and a 6-membered ring diketopiperazine neutral requires >31.6 kcal/mol, which is 26.1 kcal/mol less than the analogous process involving the peptide acid. The end group specific fragmentation of peptide amides in the negative ion mode may be useful for identifying such groups in proteomic applications.

  17. A Comparison of the Effects of Amide and Acid Groups at the C-Terminus on the Collision-Induced Dissociation of Deprotonated Peptides

    NASA Astrophysics Data System (ADS)

    Bokatzian-Johnson, Samantha S.; Stover, Michele L.; Dixon, David A.; Cassady, Carolyn J.

    2012-09-01

    The dissociative behavior of peptide amides and free acids was explored using low-energy collision-induced dissociation and high level computational theory. Both positive and negative ion modes were utilized, but the most profound differences were observed for the deprotonated species. Deprotonated peptide amides produce a characteristic cm-2 - product ion (where m is the number of residues in the peptide) that is either absent or in low abundance in the analogous peptide acid spectrum. Peptide acids show an enhanced formation of cm-3 -; however, this is not generally as pronounced as cm-2 - production from amides. The most notable occurrence of an amide-specific product ion is for laminin amide (YIGSR-NH2) and this case was investigated using several modified peptides. Mechanisms involving 6- and 9-membered ring formation were proposed, and their energetic properties were investigated using G3(MP2) molecular orbital theory calculations. For example, with C-terminal deprotonation of pentaglycine amide, formation of cm-2 - and a 6-membered ring diketopiperazine neutral requires >31.6 kcal/mol, which is 26.1 kcal/mol less than the analogous process involving the peptide acid. The end group specific fragmentation of peptide amides in the negative ion mode may be useful for identifying such groups in proteomic applications.

  18. Amino acid residues required for fast Na(+)-channel inactivation: charge neutralizations and deletions in the III-IV linker.

    PubMed Central

    Patton, D E; West, J W; Catterall, W A; Goldin, A L

    1992-01-01

    The cytoplasmic linker connecting domains III and IV of the voltage-gated Na+ channel is thought to be involved in fast inactivation. This linker is highly conserved among the various Na+ channels that have been cloned. In the rat brain IIA Na+ channel, it consists of 53 amino acids of which 15 are charged. To investigate the role of this linker in inactivation, we mutated all 15 of the charged residues in various combinations. All but one of these mutants expressed functional channels, and all of these inactivated with kinetics similar to the wild-type channel. We then constructed a series of deletion mutations that span the III-IV linker to determine if any region of the linker is essential for fast inactivation. Deletion of the first 10 amino acids completely eliminated fast inactivation in the channel, whereas deletion of the last 10 amino acids had no substantial effect on inactivation. These results demonstrate that some residues in the amino end of the III-IV linker are critical for fast Na(+)-channel inactivation, but that the highly conserved positively charged and paired negatively charged residues are not essential. PMID:1332059

  19. Rh(III)-catalyzed synthesis of sultones through C-H activation directed by a sulfonic acid group.

    PubMed

    Qi, Zisong; Wang, Mei; Li, Xingwei

    2014-09-01

    A new rhodium-catalyzed synthesis of sultones via the oxidative coupling of sulfonic acids with internal alkynes is described. The reaction proceeds via aryl C-H activation assisted by a sulfonic acid group.

  20. Targeted toxicological screening for acidic, neutral and basic substances in postmortem and antemortem whole blood using simple protein precipitation and UPLC-HR-TOF-MS.

    PubMed

    Telving, Rasmus; Hasselstrøm, Jørgen Bo; Andreasen, Mette Findal

    2016-09-01

    A broad targeted screening method based on broadband collision-induced dissociation (bbCID) ultra-performance liquid chromatography high-resolution time-of-flight mass spectrometry (UPLC-HR-TOF-MS) was developed and evaluated for toxicological screening of whole blood samples. The acidic, neutral and basic substances covered by the method were identified in postmortem and antemortem whole blood samples from forensic autopsy cases, clinical forensic cases and driving under the influence of drugs (DUID) cases by a reverse target database search. The screening method covered 467 substances. Validation was performed on spiked whole blood samples and authentic postmortem and antemortem whole blood samples. For most of the basic drugs, the established cut-off limits were very low, ranging from 0.25ng/g to 50ng/g. The established cut-off limits for most neutral and acidic drugs, were in the range from 50ng/g to 500ng/g. Sample preparation was performed using simple protein precipitation of 300μL of whole blood with acetonitrile and methanol. Ten microliters of the reconstituted extract were injected and separated within a 13.5min UPLC gradient reverse-phase run. Positive electrospray ionization (ESI) was used to generate the ions in the m/z range of 50-1000. Fragment ions were generated by bbCID. Identification was based on retention time, accurate mass, fragment ion(s) and isotopic pattern. A very sensitive broad toxicological screening method using positive electrospray ionization UPLC-HR-TOF-MS was achieved in one injection. This method covered basic substances, substances traditionally analyzed in negative ESI (e.g., salicylic acid), small highly polar substances such as beta- and gamma-hydroxybutyric acid (BHB and GHB, respectively) and highly non-polar substances such as amiodarone. The new method was shown to combine high sensitivity with a very broad scope that has not previously been reported in toxicological whole blood screening when using only one injection

  1. Antihypertensive neutral lipid

    DOEpatents

    Snyder, F.L.; Blank, M.L.

    1984-10-26

    The invention relates to the discovery of a class of neutral acetylated either-linked glycerolipids having the capacity to lower blood presure in warm-blooded animals. This physiological effect is structure sensitive requiring a long chain alkyl group at the sn-1 position and a short carbon chain acyl group (acetyl or propionyl) at the sn-2 position, and a hydroxyl group at the sn-3 position.

  2. Antihypertensive neutral lipid

    DOEpatents

    Snyder, Fred L.; Blank, Merle L.

    1986-01-01

    The invention relates to the discovery of a class of neutral acetylated ether-linked glycerolipids having the capacity to lower blood pressure in warm-blooded animals. This physiological effect is structure sensitive requiring a long chain alkyl group at the sn-1 position and a short carbon chain acyl group (acetyl or propionyl) at the sn-2 position, and a hydroxyl group at the sn-3 position.

  3. Gas-Phase Reactivity of Carboxylic Acid Functional Groups with Carbodiimides

    PubMed Central

    Prentice, Boone M.; Gilbert, Joshua D.; Stutzman, John R.; Forrest, William P.; McLuckey, Scott A.

    2012-01-01

    Gas-phase modification of carboxylic acid functionalities is performed via ion/ion reactions with carbodiimide reagents [N-cyclohexyl-N′-(2-morpholinoethyl)carbodiimide (CMC) and [3-(3-Ethylcarbodiimide-1-yl)propyl]trimethylaminium (ECPT). Gas-phase ion/ion covalent chemistry requires the formation of a long-lived complex. In this instance, the complex is stabilized by an electrostatic interaction between the fixed charge quaternary ammonium group of the carbodiimide reagent cation and the analyte dianion. Subsequent activation results in characteristic loss of an isocyanate derivative from one side of the carbodiimide functionality, a signature for this covalent chemistry. The resulting amide bond is formed on the analyte at the site of the original carboxylic acid. Reactions involving analytes that do not contain available carboxylic acid groups (e.g., they have been converted to sodium salts) or reagents that do not have the carbodiimide functionality do not undergo a covalent reaction. This chemistry is demonstrated using PAMAM generation 0.5 dendrimer, ethylenediaminetetraacetic acid (EDTA), and the model peptide DGAILDGAILD. This work demonstrates the selective gas-phase covalent modification of carboxylic acid functionalities. PMID:23208744

  4. A Convenient, General Synthesis of 1,1-Dimethylallyl Esters as Protecting Groups for Carboxylic Acids

    PubMed Central

    Sedighi, Minoo; Lipton, Mark A.

    2006-01-01

    Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided. PMID:15816730

  5. A convenient, general synthesis of 1,1-dimethylallyl esters as protecting groups for carboxylic acids.

    PubMed

    Sedighi, Minoo; Lipton, Mark A

    2005-04-14

    [reaction: see text] Carboxylic acids were converted in high yield to their 1,1-dimethylallyl (DMA) esters in two steps. Palladium-catalyzed deprotection of DMA esters was shown to be compatible with tert-butyl, benzyl, and Fmoc protecting groups, and Fmoc deprotection could be carried out selectively in the presence of DMA esters. DMA esters were also shown to be resistant to nucleophilic attack, suggesting that they will serve as alternatives to tert-butyl esters when acidic deprotection conditions need to be avoided.

  6. Effect of HEPES buffer on the uptake and transport of P-glycoprotein substrates and large neutral amino acids

    PubMed Central

    Luo, Shuanghui; Pal, Dhananjay; Shah, Sujay J.; Kwatra, Deep; Paturi, Kalyani D.; Mitra, Ashim. K.

    2010-01-01

    HEPES has been widely employed as an organic buffer agent in cell culture medium as well as uptake and transport experiments in vitro. However, concentrations of HEPES used in such studies vary from one laboratory to another. In this study, we investigated the effect of HEPES on the uptake and bidirectional transport of P-gp substrates employing both Caco-2 and MDCK-MDR1 cells. ATP-dependent uptake of glutamic acid was also examined. ATP production was further quantified applying ATP Determination Kit. An addition of HEPES to the cellular washing and incubation media significantly altered the uptake and transport of P-gp substrates in both Caco-2 and MDCK-MDR1 cells. Uptake of P-gp substrates substantially diminished as the HEPES concentration was raised to 25 mM. Bidirectional (A-B and B-A) transport studies revealed that permeability ratio of PappB-A to PappA-B in the presence of 25 mM HEPES was significantly higher than control. The uptake of phenylalanine is an ATP-independent process, whereas the accumulation of glutamic acid is ATP-dependent. While phenylalanine uptake remained unchanged glutamic acid uptake was elevated with the addition of HEPES. Verapamil is an inhibitor of P-gp mediated uptake, elevation of cyclosporine uptake in the presence of 5 μM verapamil was compromised by the presence of 25 mM HEPES. The results of ATP assay indicated that HEPES stimulated the production of ATP. This study suggests that the addition of HEPES in the medium modulated the energy dependent efflux and uptake processes. The effect of HEPES on P-gp mediated drug efflux and transport may provide some mechanistic insight into possible reasons for inconsistencies in the results reported from various laboratories. PMID:20163160

  7. Size-controlled dissolution of silver nanoparticles at neutral and acidic pH conditions: kinetics and size changes.

    PubMed

    Peretyazhko, Tanya S; Zhang, Qingbo; Colvin, Vicki L

    2014-10-21

    Silver nanoparticles (Ag(NP)) are widely utilized in increasing number of medical and consumer products due to their antibacterial properties. Once released to aquatic system, Ag(NP) undergoes oxidative dissolution leading to production of toxic Ag(+). Dissolved Ag(+) can have a severe impact on various organisms, including indigenous microbial communities, fungi, alga, plants, vertebrates, invertebrates, and human cells. Therefore, it is important to investigate fate of Ag(NP) and determine physico-chemicals parameters that control Ag(NP) behavior in the natural environment. Nanoparticle size might have a dominant effect on Ag(NP) dissolution in natural waters. In this work, we investigated size-dependent dissolution of AgNP exposed to ultrapure deionized water (pH ≈ 7) and acetic acid (pH 3) and determined changes in nanoparticle size after dissolution. Silver nanoparticles stabilized by thiol functionalized methoxyl polyethylene glycol (PEGSH) of 6 nm (Ag(NP_)6), 9 nm (Ag(NP_)9), 13 nm (Ag(NP_)13), and 70 nm (Ag(NP_)70) were prepared. The results of dissolution experiments showed that the extent of AgNP dissolution in acetic acid was larger than in water. Solubility of Ag(NP) increased with the size decrease and followed the order Ag(NP_)6 > Ag(NP_)9 > Ag(NP_)13 > Ag(NP_)70 in both water and acetic acid. Transmission electron microscopy (TEM) was applied to characterize changes in size and morphology of the AgNP after dissolution in water. Analysis of Ag(NP) by TEM revealed that the particle morphology did not change during dissolution. The particles remained approximately spherical in shape, and no visible aggregation was observed in the samples. TEM analysis also demonstrated that Ag(NP_)6, Ag(NP_)9, and Ag(NP_)13 increased in size after dissolution likely due to Ostwald ripening. PMID:25265014

  8. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    PubMed

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

  9. Influence of the morphology and impurities of Ni(OH) 2 on the synthesis of neutral Ni(II)-amino acid complexes

    NASA Astrophysics Data System (ADS)

    Rodríguez-González, Vicente; Marceau, Eric; Che, Michel; Pepe, Claude

    2007-12-01

    Synthesis of neutral complexes of Ni 2+ with amino acids has often been reported on a qualitative basis, with a lack of information on the parameters involved in the dissolution of the nickel-containing solid precursor. This paper reports on a systematic study of the reactivity of Ni(OH) 2 toward glycine in aqueous solution. The crystallinity and size of hydroxide particles are found to be key parameters in the rapid glycine-promoted dissolution of the hydroxide and synthesis of [Ni(glycinate) 2(H 2O) 2]. These parameters derive from the nature of the salt used to prepare the hydroxide. Ni(II) chloride leads to the most reactive solid precursor, because of the presence of defects in the Ni(OH) 2 sheets arrangements, assigned to the substitution of Cl - ions to OH - ions at the edges of the particles. The reaction between this hydroxide and glycine at 80 °C is quantitative after 7 min and similar rates of dissolution are obtained with other amino acids, alanine or histidine, the reaction with serine being slower. When the hydroxide contains nitrate or carbonate ions, a glycinato complex with composition similar to [Ni(glycinate) 2(H 2O) 2], but with a different crystal structure, is also formed. Spectroscopic results may suggest a structure involving bridging ligands.

  10. Efficacy of Neutral Electrolyzed Water, Quaternary Ammonium and Lactic Acid-Based Solutions in Controlling Microbial Contamination of Food Cutting Boards Using a Manual Spraying Technique.

    PubMed

    Al-Qadiri, Hamzah M; Ovissipour, Mahmoudreza; Al-Alami, Nivin; Govindan, Byju N; Shiroodi, Setareh Ghorban; Rasco, Barbara

    2016-05-01

    Bactericidal activity of neutral electrolyzed water (NEW), quaternary ammonium (QUAT), and lactic acid-based solutions was investigated using a manual spraying technique against Salmonella Typhimurium, Escherichia coli O157:H7, Campylobacter jejuni, Listeria monocytogenes and Staphylococcus aureus that were inoculated onto the surface of scarred polypropylene and wooden food cutting boards. Antimicrobial activity was also examined when using cutting boards in preparation of raw chopped beef, chicken tenders or salmon fillets. Viable counts of survivors were determined as log10 CFU/100 cm(2) within 0 (untreated control), 1, 3, and 5 min of treatment at ambient temperature. Within the first minute of treatment, NEW and QUAT solutions caused more than 3 log10 bacterial reductions on polypropylene surfaces whereas less than 3 log10 reductions were achieved on wooden surfaces. After 5 min of treatment, more than 5 log10 reductions were achieved for all bacterial strains inoculated onto polypropylene surfaces. Using NEW and QUAT solutions within 5 min reduced Gram-negative bacteria by 4.58 to 4.85 log10 compared to more than 5 log10 reductions in Gram-positive bacteria inoculated onto wooden surfaces. Lactic acid treatment was significantly less effective (P < 0.05) compared to NEW and QUAT treatments. A decline in antimicrobial effectiveness was observed (0.5 to <2 log10 reductions were achieved within the first minute) when both cutting board types were used to prepare raw chopped beef, chicken tenders or salmon fillets. PMID:27027449

  11. Geochemical characterisation of seepage and drainage water quality from two sulphide mine tailings impoundments: Acid mine drainage versus neutral mine drainage

    USGS Publications Warehouse

    Heikkinen, P.M.; Raisanen, M.L.; Johnson, R.H.

    2009-01-01

    Seepage water and drainage water geochemistry (pH, EC, O2, redox, alkalinity, dissolved cations and trace metals, major anions, total element concentrations) were studied at two active sulphide mine tailings impoundments in Finland (the Hitura Ni mine and Luikonlahti Cu mine/talc processing plant). The data were used to assess the factors influencing tailings seepage quality and to identify constraints for water treatment. Changes in seepage water quality after equilibration with atmospheric conditions were evaluated based on geochemical modelling. At Luikonlahti, annual and seasonal changes were also studied. Seepage quality was largely influenced by the tailings mineralogy, and the serpentine-rich, low sulphide Hitura tailings produced neutral mine drainage with high Ni. In contrast, drainage from the high sulphide, multi-metal tailings of Luikonlahti represented typical acid mine drainage with elevated contents of Zn, Ni, Cu, and Co. Other factors affecting the seepage quality included weathering of the tailings along the seepage flow path, process water input, local hydrological settings, and structural changes in the tailings impoundment. Geochemical modelling showed that pH increased and some heavy metals were adsorbed to Fe precipitates after net alkaline waters equilibrated with the atmosphere. In the net acidic waters, pH decreased and no adsorption occurred. A combination of aerobic and anaerobic treatments is proposed for Hitura seepages to decrease the sulphate and metal loading. For Luikonlahti, prolonged monitoring of the seepage quality is suggested instead of treatment, since the water quality is still adjusting to recent modifications to the tailings impoundment.

  12. Boronic Acid Group: A Cumbersome False Negative Case in the Process of Drug Design.

    PubMed

    Katsamakas, Sotirios; Papadopoulos, Anastasios G; Hadjipavlou-Litina, Dimitra

    2016-01-01

    Herein we present, an exhaustive docking analysis considering the case of autotaxin (ATX). HA155, a small molecule inhibitor of ATX, is co-crystallized. In order to further extract conclusions on the nature of the bond formed between the ligands and the amino acid residues of the active site, density functional theory (DFT) calculations were undertaken. However, docking does not provide reproducible results when screening boronic acid derivatives and their binding orientations to protein drug targets. Based on natural bond orbital (NBO) calculations, the formed bond between Ser/Thr residues is characterized more accurately as a polar covalent bond instead of a simple nonpolar covalent one. The presented results are acceptable and could be used in screening as an active negative filter for boron compounds. The hydroxyl groups of amino acids are bonded with the inhibitor's boron atom, converting its hybridization to sp³. PMID:27617984

  13. Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte

    PubMed Central

    Gorlin, Yelena; Jaramillo, Thomas F.

    2014-01-01

    The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, and sodium hydroxide). We determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community. PMID:25357131

  14. Substrate selection for fundamental studies of electrocatalysts and photoelectrodes: inert potential windows in acidic, neutral, and basic electrolyte.

    PubMed

    Benck, Jesse D; Pinaud, Blaise A; Gorlin, Yelena; Jaramillo, Thomas F

    2014-01-01

    The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, and sodium hydroxide). We determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community.

  15. H-binding groups in lignite vs. soil humic acids: NICA-Donnan and spectroscopic parameters

    SciTech Connect

    Drosos, M.; Jerzykiewicz, M.; Deligiannakis, Y.

    2009-04-15

    A comparative study has been carried out for two sets of humic acids isolated from lignites and soils. H-binding data were analyzed using the NICA-Donnan model, for three Greek lignite humic acids (HA) plus IHSS Leonardite reference HA, and five Greek soil HAs plus a commercial peat HA. {sup 13}C-CP-MAS NMR and H-binding data provide quantitative estimates for functional groups, showing that lignite HAs of diverse origin have strikingly homogeneous properties, while the H-binding structural units of soil HAs are characterized by a large degree of variability. Consistent differences between soil HA vs. lignite HA are revealed at the level of functional groups' concentrations. In the pH range 4 to 10, soil HA showed a charge variation < 3 (equiv kg{sup -1}) while lignite HAs showed a higher charge variation > 3.5 (equiv kg{sup -1}).

  16. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    PubMed

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. PMID:22940339

  17. Effects of acidic functional groups on dielectric properties of sodium alginates and carrageenans in water.

    PubMed

    Tsubaki, Shuntaro; Hiraoka, Masanori; Hadano, Shingo; Okamura, Kei; Ueda, Tadaharu; Nishimura, Hiroshi; Kashimura, Keiichiro; Mitani, Tomohiko

    2015-01-22

    This study investigated the dielectric properties of sodium alginates and carrageenans in water at frequencies between 100 MHz and 20 GHz in regard to water-hydrocolloid interactions via acidic functional groups. Both sodium alginates and carrageenans showed conduction loss at lower frequencies and dielectric loss at higher frequencies. Reduction and desulfation of sodium alginates and carrageenans, which decreased the numbers of acidic functional groups, decreased their conduction loss. In addition, H(+)-form carrageenans showed the highest ionic conduction. Correlational analysis of dielectric properties and related physical parameters showed that the loss tangent (tanδ) of the hydrocolloid solution was determined by the conductivity of the aqueous solution. Especially at pH below 2, strong H(+) conduction was associated with high tanδ probably due to the Grotthuss mechanism. The molecular dynamics of free water and H(+), viscosity conditions were also suggested to be associated with dielectric property of water-hydrocolloid system. PMID:25439871

  18. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    PubMed

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction.

  19. Selective functionalization of hollow nanospheres with Acid and base groups for cascade reactions.

    PubMed

    Gao, Jinsuo; Zhang, Xueying; Lu, Yong; Liu, Shaomin; Liu, Jian

    2015-05-11

    The inner-surface functionalization of hollow silica spheres has rarely been reported and is still a challenging topic. Herein, we report a deacetalization-Henry cascade reaction catalyzed by dual-functionalized mesoporous silica hollow nanospheres with basic amine groups (NH2 ) on the internal shell and carboxylic acid groups (COOH) on the external shell. The selective functionalization has been realized by a combination of "step-by-step post-grafting" and "cationic surfactant-assisted selective etching" strategy. Compared to unisolated catalyst, the selectively isolated acidic and basic dual catalyst provides excellent catalytic performance for the deacetalization-Henry cascade reaction in terms of both activity (>99 %) and selectivity (95 %).

  20. Neutral Atmospheres

    NASA Astrophysics Data System (ADS)

    Mueller-Wodarg, I. C. F.; Strobel, D. F.; Moses, J. I.; Waite, J. H.; Crovisier, J.; Yelle, R. V.; Bougher, S. W.; Roble, R. G.

    This paper summarizes the understanding of aeronomy of neutral atmospheres in the solar system, discussing most planets as well as Saturn's moon Titan and comets. The thermal structure and energy balance is compared, highlighting the principal reasons for discrepancies amongst the atmospheres, a combination of atmospheric composition, heliocentric distance and other external energy sources not common to all. The composition of atmospheres is discussed in terms of vertical structure, chemistry and evolution. The final section compares dynamics in the upper atmospheres of most planets and highlights the importance of vertical dynamical coupling as well as magnetospheric forcing in auroral regions, where present. It is shown that a first order understanding of neutral atmospheres has emerged over the past decades, thanks to the combined effects of spacecraft and Earth-based observations as well as advances in theoretical modeling capabilities. Key gaps in our understanding are highlighted which ultimately call for a more comprehensive programme of observation and laboratory measurements.

  1. Neutral Atmospheres

    NASA Astrophysics Data System (ADS)

    Mueller-Wodarg, I. C. F.; Strobel, D. F.; Moses, J. I.; Waite, J. H.; Crovisier, J.; Yelle, R. V.; Bougher, S. W.; Roble, R. G.

    2008-08-01

    This paper summarizes the understanding of aeronomy of neutral atmospheres in the solar system, discussing most planets as well as Saturn’s moon Titan and comets. The thermal structure and energy balance is compared, highlighting the principal reasons for discrepancies amongst the atmospheres, a combination of atmospheric composition, heliocentric distance and other external energy sources not common to all. The composition of atmospheres is discussed in terms of vertical structure, chemistry and evolution. The final section compares dynamics in the upper atmospheres of most planets and highlights the importance of vertical dynamical coupling as well as magnetospheric forcing in auroral regions, where present. It is shown that a first order understanding of neutral atmospheres has emerged over the past decades, thanks to the combined effects of spacecraft and Earth-based observations as well as advances in theoretical modeling capabilities. Key gaps in our understanding are highlighted which ultimately call for a more comprehensive programme of observation and laboratory measurements.

  2. Rh(III)-catalyzed decarboxylative ortho-heteroarylation of aromatic carboxylic acids by using the carboxylic acid as a traceless directing group.

    PubMed

    Qin, Xurong; Sun, Denan; You, Qiulin; Cheng, Yangyang; Lan, Jingbo; You, Jingsong

    2015-04-01

    Highly selective decarboxylative ortho-heteroarylation of aromatic carboxylic acids with various heteroarenes has been developed through Rh(III)-catalyzed two-fold C-H activation, which exhibits a wide substrate scope of both aromatic carboxylic acids and heteroarenes. The use of naturally occurring carboxylic acid as the directing group avoids troublesome extra steps for installation and removal of an external directing group.

  3. Enumeration of Thiobacilli within pH-Neutral and Acidic Mine Tailings and Their Role in the Development of Secondary Mineral Soil

    PubMed Central

    Southam, G.; Beveridge, T. J.

    1992-01-01

    The Lemoine tailings of Chibougamau, Quebec, Canada, were deposited as a pH-neutral mineral conglomerate consisting of aluminum-silicates, iron-aluminum-silicates, pyrite, chalcopyrite, and sphalerite. These tailings are colonized by an active population of Thiobacillus ferrooxidans which is localized to an acid zone occupying 40% of the tailings' surface. This population peaked at 7 × 108 most probable number per gram of tailings during July and August 1990 and extended to a depth of 40 cm from the surface. Examination of samples over this depth profile by transmission electron microscopy and electron dispersive spectroscopy revealed a microbially mediated mineral transition from sulfides (below 40 cm) to chlorides and phosphates (at the surface). Silicate minerals were unaltered by microbial action. Transmission electron microscopy showed a tight association between Thiobacillus species and the sulfide minerals, which helps account for their prominence in tailings environments. Accurate enumeration of T. ferrooxidans from tailings required the disruption of their bonding to the mineral interface. Vortexing of a 10% aqueous suspension of the tailings material prior to most-probable-number analysis best facilitated this release. Even though heavy metals were highly mobile under acidic conditions at the Lemoine tailings, it was evident by transmission electron microscopy and electron dispersive spectroscopy that they were being immobilized as bona fide fine-grain minerals containing iron, copper, chlorine, phosphorus, and oxygen on bacterial surfaces and exopolymers. This biomineralization increased with increasing bacterial numbers and was most evident in the upper 3 cm of the acidic zone. Images PMID:16348721

  4. Evaluation of Tetrahydrobiopterin Therapy with Large Neutral Amino Acid Supplementation in Phenylketonuria: Effects on Potential Peripheral Biomarkers, Melatonin and Dopamine, for Brain Monoamine Neurotransmitters

    PubMed Central

    Yano, Shoji; Moseley, Kathryn; Fu, Xiaowei; Azen, Colleen

    2016-01-01

    Background Phenylketonuria (PKU) is due to a defective hepatic enzyme, phenylalanine (Phe) hydroxylase. Transport of the precursor amino acids from blood into the brain for serotonin and dopamine synthesis is reported to be inhibited by high blood Phe concentrations. Deficiencies of serotonin and dopamine are involved in neurocognitive dysfunction in PKU. Objective (1) To evaluate the effects of sapropterin (BH4) and concurrent use of large neutral amino acids (LNAA) on the peripheral biomarkers, melatonin and dopamine with the hypothesis they reflect brain serotonin and dopamine metabolism. (2) To evaluate synergistic effects with BH4 and LNAA. (3) To determine the effects of blood Phe concentrations on the peripheral biomarkers concentrations. Methods Nine adults with PKU completed our study consisting of four 4-week phases: (1) LNAA supplementation, (2) Washout, (3) BH4 therapy, and (4) LNAA with BH4 therapy. An overnight protocol measured plasma amino acids, serum melatonin, and 6-sulfatoxymelatonin and dopamine in first void urine after each phase. Results (1) Three out of nine subjects responded to BH4. A significant increase of serum melatonin levels was observed in BH4 responders with decreased blood Phe concentration. No significant change in melatonin, dopamine or Phe levels was observed with BH4 in the subjects as a whole. (2) Synergistic effects with BH4 and LNAA were observed in serum melatonin in BH4 responders. (3) The relationship between serum melatonin and Phe showed a significant negative slope (p = 0.0005) with a trend toward differing slopes among individual subjects (p = 0.066). There was also a negative association overall between blood Phe and urine 6-sulfatoxymelatonin and dopamine (P = 0.040 and 0.047). Conclusion Blood Phe concentrations affected peripheral monoamine neurotransmitter biomarker concentrations differently in each individual with PKU. Melatonin levels increased with BH4 therapy only when blood Phe decreased. Monitoring

  5. Sensitivity analyses of MAGIC modelled predictions of future impacts of whole-tree harvest on soil calcium supply and stream acid neutralizing capacity.

    PubMed

    Zetterberg, Therese; Köhler, Stephan J; Löfgren, Stefan

    2014-10-01

    Forest biofuel is a main provider of energy in Sweden and the market is expected to grow even further in the future. Removal of logging residues via harvest can lead to short-term acidification but the long-term effects are largely unknown. The objectives of this study were to 1) model the long-term effect of whole-tree harvest (WTH) on soil and stream water acidity and 2) perform sensitivity analyses by varying the amounts of logging residues, calcium (Ca(2+)) concentrations in tree biomass and site productivity in nine alternate scenarios. Data from three Swedish forested catchments and the Model of Acidification of Groundwater in Catchments (MAGIC) were used to simulate changes in forest soil exchangeable Ca(2+) pools and stream water acid neutralizing capacity (ANC) at Gammtratten, Kindla and Aneboda. Large depletions in soil Ca(2+) supply and a reversal of the positive trend in stream ANC were predicted for all three sites after WTH. However, the magnitude of impact on stream ANC varied depending on site and the concentration of mobile strong acid anions. Contrary to common beliefs, the largest decrease in modelled ANC was observed at the well-buffered site Gammtratten. The effects at Kindla and Aneboda were much more limited and not large enough to offset the general recovery from acidification. Varying the tree biomass Ca(2+) concentrations exerted the largest impact on modelled outcome. Site productivity was the second most important variable whereas changing biomass amounts left on site only marginally affected the results. The outcome from the sensitivity analyses pointed in the same direction of change as in the base scenario, except for Kindla where soil Ca(2+) pools were predicted to be replenished under a given set of input data. The reliability of modelled outcome would increase by using site-specific Ca(2+) concentrations in tree biomass and field determined identification of site productivity. PMID:25046610

  6. Human neutral amino acid transporter ASCT1: Structure of the gene (SLC1A4) and localization to chromosome 2p13-p15

    SciTech Connect

    Hofmann, K.; Dueker, M.; Stoffel, W.

    1994-11-01

    Screening for cDNAs encoding proteins similar to the sodium-coupled glutamate transporter GLAST1 led to the isolation of a cDNA clone coding for a protein that turned out to be identical to the recently described neutral amino acid transporter ASCT1. The new member of the GLAST-related transporter family does not transport glutamate or aspartate but alanine, serine, cysteine, and threonine instead. The expressed sequence tag EST02446, a short cDNA sequence found in the course of a large-scale sequencing project of human brain-derived cDNA, showed significant similarity to the eukaryotic glutamate transporter GLAST1 and was therefore used as probe in the search for further glutamate transporter cDNAs. Fragments of the cDNA were used for the isolation and characterization of human ASCT1 genomic clones. The ORF of 1572 bp encoding 524 amino acid residues is distributed over 8 exons, which span at least 40 kb of human chromosomal DNA. The ASCT1 gene locus was assigned to chromosome 2p13-p15 by chromosomal in situ suppression (CISS) studies. The gene structure is not related to any other previously characterized transporter gene. In contrast to the genes of the sodium-coupled nonglutamate neurotransmitter transporters, it shows no obvious correspondence between intron/exon structure and transmembrane organization. The transcription start site in human liver tissue was determined by primer extension analysis to be located 291 bp upstream of the initiating ATG codon. The DNA region immediately upstream of the transcription start lacks any TATA or CAAT boxes but contains several bindings sites for the transcription factors Sp1 and Egr-1. The ASCT1 gene (SLC1A4) structure reported here will facilitate the characterization of the genes of the other members of the GLAST-related transporter family and might be useful in the elucidation of amino acid transport-related defects. 36 refs., 5 figs., 1 tab.

  7. A METHOD FOR AUTOMATED ANALYSIS OF 10 ML WATER SAMPLES CONTAINING ACIDIC, BASIC, AND NEUTRAL SEMIVOLATILE COMPOUNDS LISTED IN USEPA METHOD 8270 BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    EPA Science Inventory

    Data is presented showing the progress made towards the development of a new automated system combining solid phase extraction (SPE) with gas chromatography/mass spectrometry for the single run analysis of water samples containing a broad range of acid, base and neutral compounds...

  8. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    SciTech Connect

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  9. Origin of saline, neutral-pH, reduced epithermal waters by reaction of acidic magmatic gas condensates with wall rock

    SciTech Connect

    Reed, M.H. . Dept. of Geological Sciences)

    1993-04-01

    Fluid inclusions in quartz and sphalerite of epithermal veins containing galena, sphalerite and chalcopyrite with silver sulfides and electrum commonly have salinities of 2 to 10 weight percent NaCl equivalent. Examples include Bohemia, OR, Comstock, NV, and Creede, CO. Salinities in such base metal-rich systems are apparently greater than those in gold-adularia, base metal-poor systems such as Sleeper, NV, Republic, WA, and Hishikare, Kyushu. Saline epithermal fluids are commonly assumed to have been derived from saline magmatic brines, from local host formations, as has been suggested for Creede, or from evaporative concentration (boiling) of more dilute meteoric ground water. Another possibility, which may be the most common origin, is reaction of wall rocks with magmatic gas condensates rich in HCl and sulfuric acid. A mixture of one part Augustine Volcanic gas condensate in 10 parts cold ground water has a pH of 0.7 and the dominant cation is H[sup +] by a factor of 10[sup 4]. Calculated reaction of this condensate mixture with andesite at 300 C to a water/rock ratio (w/r) of 4.6 yields an NaCl-dominated fluid with a total salinity of 2.1 wt %. and pH 3.7. Further reaction, to w/r 0.14 yields a fluid salinity of 2.6 wt % and pH of 5.7; this fluid is in equilibrium with a propylitic alteration assemblage. Aqueous sulfide accumulates during the rock reaction as sulfate is reduced to sulfide when ferrous iron is oxidized to ferric iron. Sulfide concentration in the latter fluid is 32 ppm, far exceeding sulfate concentration. In the overall reaction, hydrogen ion is exchanged for base cations (including base metals) and sulfate is reduced to sulfide.

  10. Partial amino acid sequences around sulfhydryl groups of soybean beta-amylase.

    PubMed

    Nomura, K; Mikami, B; Morita, Y

    1987-08-01

    Sulfhydryl (SH) groups of soybean beta-amylase were modified with 5-(iodoaceto-amidoethyl)aminonaphthalene-1-sulfonate (IAEDANS) and the SH-containing peptides exhibiting fluorescence were purified after chymotryptic digestion of the modified enzyme. The sequence analysis of the peptides derived from the modification of all SH groups in the denatured enzyme revealed the existence of six SH groups, in contrast to five reported previously. One of them was found to have extremely low reactivity toward SH-reagents without reduction. In the native state, IAEDANS reacted with 2 mol of SH groups per mol of the enzyme (SH1 and SH2) accompanied with inactivation of the enzyme owing to the modification of SH2 located near the active site of this enzyme. The selective modification of SH2 with IAEDANS was attained after the blocking of SH1 with 5,5'-dithiobis-(2-nitrobenzoic acid). The amino acid sequences of the peptides containing SH1 and SH2 were determined to be Cys-Ala-Asn-Pro-Gln and His-Gln-Cys-Gly-Gly-Asn-Val-Gly-Asp-Ile-Val-Asn-Ile-Pro-Ile-Pro-Gln-Trp, respectively.

  11. Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

    NASA Astrophysics Data System (ADS)

    Gammons, Christopher H.; Wood, Scott A.; Nimick, David A.

    2005-08-01

    Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in

  12. Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

    USGS Publications Warehouse

    Gammons, C.H.; Wood, S.A.; Nimick, D.A.

    2005-01-01

    Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in

  13. Molecular characterization of an acidic region deletion mutant of Cockayne syndrome group B protein.

    PubMed

    Sunesen, M; Selzer, R R; Brosh, R M; Balajee, A S; Stevnsner, T; Bohr, V A

    2000-08-15

    Cockayne syndrome (CS) is a human genetic disorder characterized by post-natal growth failure, neurological abnormalities and premature aging. CS cells exhibit high sensitivity to UV light, delayed RNA synthesis recovery after UV irradiation and defective transcription-coupled repair (TCR). Two genetic complementation groups of CS have been identified, designated CS-A and CS-B. The CSB gene encodes a helicase domain and a highly acidic region N-terminal to the helicase domain. This study describes the genetic characterization of a CSB mutant allele encoding a full deletion of the acidic region. We have tested its ability to complement the sensitivity of UV61, the hamster homolog of human CS-B cells, to UV and the genotoxic agent N-acetoxy-2-acetylaminofluorene (NA-AAF). Deleting 39 consecutive amino acids, of which approximately 60% are negatively charged, did not impact on the ability of the protein to complement the sensitive phenotype of UV61 cells to either UV or NA-AAF. Our data indicate that the highly acidic region of CSB is not essential for the TCR and general genome repair pathways of UV- and NA-AAF-induced DNA lesions. PMID:10931931

  14. Synthesis and Monolayer Behaviors of Succinic Acid-Type Gemini Surfactants Containing Semifluoroalkyl Groups.

    PubMed

    Kawase, Tokuzo; Nagase, Youhei; Oida, Tatsuo

    2016-01-01

    In this work, novel succinic acid-type gemini surfactants containing semifluoroalkyl groups, dl- and meso-2,3-bis[Rf-(CH2)n]-succinic acids (Rf = C4F9, C6F13, C8F17; n = 2, 9), were successfully synthesized, and the effects of Rf, methylene chain length (n), and stereochemistry on their monolayer behaviors were studied. Critical micelle concentrations (CMC) of dl- and meso-2,3-bis[C4F9(CH2)9]-succinic acids were one order of magnitude smaller than that of the corresponding 1+1 type surfactant, C4F9(CH2)9COOH. From surface pressure-area (π-A) measurements, the lift-off areas of the geminis were found to decrease in the order C4F9 ≥ C6F13 > C8F17, regardless of methylene chain length and stereochemistry. The zero-pressure molecular areas of the geminis were twice those of the corresponding 1+1 type surfactants. Based on Gibbs compression modulus analysis, it was clarified that 2,3-bis[C8F17(CH2)n]-succinic gemini with short methylene chains (n = 2) would form more rigid monolayers than those having long methylene chains (n = 9). Unlike for 2,3-bis(alkyl)-succinic acids, the effects of stereochemistry on the monolayer behavior of semifluoroalkylated geminis were small.

  15. Synthesis and Monolayer Behaviors of Succinic Acid-Type Gemini Surfactants Containing Semifluoroalkyl Groups.

    PubMed

    Kawase, Tokuzo; Nagase, Youhei; Oida, Tatsuo

    2016-01-01

    In this work, novel succinic acid-type gemini surfactants containing semifluoroalkyl groups, dl- and meso-2,3-bis[Rf-(CH2)n]-succinic acids (Rf = C4F9, C6F13, C8F17; n = 2, 9), were successfully synthesized, and the effects of Rf, methylene chain length (n), and stereochemistry on their monolayer behaviors were studied. Critical micelle concentrations (CMC) of dl- and meso-2,3-bis[C4F9(CH2)9]-succinic acids were one order of magnitude smaller than that of the corresponding 1+1 type surfactant, C4F9(CH2)9COOH. From surface pressure-area (π-A) measurements, the lift-off areas of the geminis were found to decrease in the order C4F9 ≥ C6F13 > C8F17, regardless of methylene chain length and stereochemistry. The zero-pressure molecular areas of the geminis were twice those of the corresponding 1+1 type surfactants. Based on Gibbs compression modulus analysis, it was clarified that 2,3-bis[C8F17(CH2)n]-succinic gemini with short methylene chains (n = 2) would form more rigid monolayers than those having long methylene chains (n = 9). Unlike for 2,3-bis(alkyl)-succinic acids, the effects of stereochemistry on the monolayer behavior of semifluoroalkylated geminis were small. PMID:26743669

  16. Biochemical distributions (amino acids, neutral sugars, and lignin phenols) among size-classes of modern marine sediments from the Washington coast

    NASA Astrophysics Data System (ADS)

    Keil, Richard G.; Tsamakis, Elizabeth; Giddings, J. Calvin; Hedges, John I.

    1998-04-01

    lignin phenol yields and low acid/aldehyde ratios. Clay-size fractions are enriched in nitrogenous components, as reflected by elevated yields of total and basic amino acids (especially lysine). Silt- and sand-size fractions rich in quartz and albite show slightly higher yields of neutral amino acids. Consistent trends across all size classes and among the different depositional settings illustrates that only a small portion of the organic matter is present as distinct organic debris (e.g. pollen, vascular plant tissues, etc.), but that this debris can be isolated in specific size classes. The data for surface-associated organic matter are consistent with, but not conclusive of, selective partitioning of some organic matter to specific mineral surfaces. The dominant size class-specific trends in organic matter composition are due to changes in both source and diagenetic alteration.

  17. A united physicochemical description of the protonation and metal ion complexation equilibria of natural organic acids (humic and fulvic acids). 2. Influence of polyelectrolyte properties and functional group heterogeneity on the protonation equilibria of fulvic acid

    USGS Publications Warehouse

    Ephraim, J.; Alegret, S.; Mathuthu, A.; Bicking, M.; Malcolm, R.L.; Marinsky, J.A.

    1986-01-01

    Potentiometric studies of the neutralization of several fulvic acid sources with standard base in aqueous and nonaqueous media have been conducted. Analysis of the results with a recently developed unified physicochemical model has shown that the protonation behavior of these fulvic acid sources is a reflection of (1) their polyelectrolyte nature and (2) their heterogeneity. It has been possible to ascribe the polyelectrolyte properties observed to a rather inflexible fulvic acid molecule whose variably charged surface is impermeable to simple electrolyte. ?? 1986 American Chemical Society.

  18. Macromitophagy, neutral lipids synthesis, and peroxisomal fatty acid oxidation protect yeast from "liponecrosis", a previously unknown form of programmed cell death.

    PubMed

    Sheibani, Sara; Richard, Vincent R; Beach, Adam; Leonov, Anna; Feldman, Rachel; Mattie, Sevan; Khelghatybana, Leila; Piano, Amanda; Greenwood, Michael; Vali, Hojatollah; Titorenko, Vladimir I

    2014-01-01

    We identified a form of cell death called "liponecrosis." It can be elicited by an exposure of the yeast Saccharomyces cerevisiae to exogenous palmitoleic acid (POA). Our data imply that liponecrosis is: (1) a programmed, regulated form of cell death rather than an accidental, unregulated cellular process and (2) an age-related form of cell death. Cells committed to liponecrotic death: (1) do not exhibit features characteristic of apoptotic cell death; (2) do not display plasma membrane rupture, a hallmark of programmed necrotic cell death; (3) akin to cells committed to necrotic cell death, exhibit an increased permeability of the plasma membrane for propidium iodide; (4) do not display excessive cytoplasmic vacuolization, a hallmark of autophagic cell death; (5) akin to cells committed to autophagic death, exhibit a non-selective en masse degradation of cellular organelles and require the cytosolic serine/threonine protein kinase Atg1p for executing the death program; and (6) display a hallmark feature that has not been reported for any of the currently known cell death modalities-namely, an excessive accumulation of lipid droplets where non-esterified fatty acids (including POA) are deposited in the form of neutral lipids. We therefore concluded that liponecrotic cell death subroutine differs from the currently known subroutines of programmed cell death. Our data suggest a hypothesis that liponecrosis is a cell death module dynamically integrated into a so-called programmed cell death network, which also includes the apoptotic, necrotic, and autophagic modules of programmed cell death. Based on our findings, we propose a mechanism underlying liponecrosis. PMID:24196447

  19. Macromitophagy, neutral lipids synthesis, and peroxisomal fatty acid oxidation protect yeast from “liponecrosis”, a previously unknown form of programmed cell death

    PubMed Central

    Sheibani, Sara; Richard, Vincent R; Beach, Adam; Leonov, Anna; Feldman, Rachel; Mattie, Sevan; Khelghatybana, Leila; Piano, Amanda; Greenwood, Michael; Vali, Hojatollah; Titorenko, Vladimir I

    2014-01-01

    We identified a form of cell death called “liponecrosis.” It can be elicited by an exposure of the yeast Saccharomyces cerevisiae to exogenous palmitoleic acid (POA). Our data imply that liponecrosis is: (1) a programmed, regulated form of cell death rather than an accidental, unregulated cellular process and (2) an age-related form of cell death. Cells committed to liponecrotic death: (1) do not exhibit features characteristic of apoptotic cell death; (2) do not display plasma membrane rupture, a hallmark of programmed necrotic cell death; (3) akin to cells committed to necrotic cell death, exhibit an increased permeability of the plasma membrane for propidium iodide; (4) do not display excessive cytoplasmic vacuolization, a hallmark of autophagic cell death; (5) akin to cells committed to autophagic death, exhibit a non-selective en masse degradation of cellular organelles and require the cytosolic serine/threonine protein kinase Atg1p for executing the death program; and (6) display a hallmark feature that has not been reported for any of the currently known cell death modalities—namely, an excessive accumulation of lipid droplets where non-esterified fatty acids (including POA) are deposited in the form of neutral lipids. We therefore concluded that liponecrotic cell death subroutine differs from the currently known subroutines of programmed cell death. Our data suggest a hypothesis that liponecrosis is a cell death module dynamically integrated into a so-called programmed cell death network, which also includes the apoptotic, necrotic, and autophagic modules of programmed cell death. Based on our findings, we propose a mechanism underlying liponecrosis. PMID:24196447

  20. Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet

    2015-01-01

    In this study, the structural and vibrational analysis of 3,4-pyridinedicarboxylic acid (3,4-PDCA) are presented using experimental techniques as FT-IR, FT-Raman, NMR, UV and quantum chemical calculations. FT-IR and FT-Raman spectra of 3,4-pyridinedicarboxylic acid in the solid phase are recorded in the region 4000-400 cm-1 and 4000-50 cm-1, respectively. The geometrical parameters and energies of all different and possible monomer, dimer, anion-1 and anion-2 conformers of 3,4-PDCA are obtained from Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) basis set. There are sixteen conformers (C1sbnd C16) for this molecule (neutral form). The most stable conformer of 3,4-PDCA is the C1 conformer. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. 1H and 13C NMR spectra are recorded and the chemical shifts are calculated by using DFT/B3LYP methods with 6-311++G(d,p) basis set. The UV absorption spectrum of the studied compound is recorded in the range of 200-400 nm by dissolved in ethanol. The optimized geometric parameters were compared with experimental data via the X-ray results derived from complexes of this molecule. In addition these, molecular electrostatic potential (MEP), thermodynamic and electronic properties, HOMO-LUMO energies and Mulliken atomic charges, are performed.

  1. Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: a combined experimental and theoretical study.

    PubMed

    Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet

    2015-01-25

    In this study, the structural and vibrational analysis of 3,4-pyridinedicarboxylic acid (3,4-PDCA) are presented using experimental techniques as FT-IR, FT-Raman, NMR, UV and quantum chemical calculations. FT-IR and FT-Raman spectra of 3,4-pyridinedicarboxylic acid in the solid phase are recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The geometrical parameters and energies of all different and possible monomer, dimer, anion(-1) and anion(-2) conformers of 3,4-PDCA are obtained from Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) basis set. There are sixteen conformers (C1C16) for this molecule (neutral form). The most stable conformer of 3,4-PDCA is the C1 conformer. The complete assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. (1)H and (13)C NMR spectra are recorded and the chemical shifts are calculated by using DFT/B3LYP methods with 6-311++G(d,p) basis set. The UV absorption spectrum of the studied compound is recorded in the range of 200-400 nm by dissolved in ethanol. The optimized geometric parameters were compared with experimental data via the X-ray results derived from complexes of this molecule. In addition these, molecular electrostatic potential (MEP), thermodynamic and electronic properties, HOMO-LUMO energies and Mulliken atomic charges, are performed. PMID:25072741

  2. Comparison of simulants to actual neutralized current acid waste: Process and product testing of three NCAW core samples from Tanks 101-AZ and 102-AZ

    SciTech Connect

    Morrey, E.V.; Tingey, J.M.

    1996-04-01

    A vitrification plant is planned to process the high-level waste (HLW) solids from Hanford Site tanks into canistered glass logs for disposal in a national repository. Programs have been established within the Pacific Northwest Laboratory Vitrification Technology Development (PVTD) Project to test and model simulated waste to support design, feed processability, operations, permitting, safety, and waste-form qualification. Parallel testing with actual radioactive waste is being performed on a laboratory-scale to confirm the validity of using simulants and glass property models developed from simulants. Laboratory-scale testing has been completed on three radioactive core samples from tanks 101-AZ and 102-AZ containing neutralized current acid waste (NCAW), which is one of the first waste types to be processed in the high-level waste vitrification plant under a privatization scenario. Properties of the radioactive waste measured during process and product testing were compared to simulant properties and model predictions to confirm the validity of simulant and glass property models work. This report includes results from the three NCAW core samples, comparable results from slurry and glass simulants, and comparisons to glass property model predictions.

  3. Comparison of simulants to actual neutralized current acid waste: process and product testing of three NCAW core samples from Tanks 101-AZ and 102-AZ

    SciTech Connect

    Morrey, E.V.; Tingey, J.M.; Elliott, M.L.

    1996-10-01

    A vitrification plant is planned to process the high-level waste (HLW) solids from Hanford Site tanks into canistered glass logs for disposal in a national repository. Programs were established within the Pacific Northwest Laboratory Vitrification Technology Development (PVTD) Project to test and model simulated waste to support design, feed processability, operations, permitting, safety, and waste-form qualification. Parallel testing with actual radioactive waste was performed on a laboratory-scale to confirm the validity of using simulants and glass property models developed from simulants. Laboratory-scale testing has been completed on three radioactive core samples from tanks 101-AZ and 102-AZ containing neutralized current acid waste (NCAW), which is one of the first waste types to be processed in the high-level waste vitrification plant under a privatization scenario. Properties of the radioactive waste measured during process and product testing were compared to simulant properties and model predictions to confirm the validity of simulant and glass property ,models work. This report includes results from the three NCAW core samples, comparable results from slurry and glass simulants, and comparisons to glass property model predictions.

  4. A new effective process for production of curdlan oligosaccharides based on alkali-neutralization treatment and acid hydrolysis of curdlan particles in water suspension.

    PubMed

    Li, Jing; Zhu, Li; Zheng, Zhi-Yong; Zhan, Xiao-Bei; Lin, Chi-Chung; Zong, Yu; Li, Wei-Jiang

    2013-10-01

    Biologically active β-1,3-oligosaccharides with rapidly growing biomedical applications are produced from hydrolysis of curdlan polysaccharide. The water-insoluble curdlan impedes its hydrolysis efficiency which is enhanced by our newly developed alkali-neutralization treatment process to increase the stability of curdlan suspension to more than 20 days, while the untreated control settled within 5 min. A putative double-layer structure model comprising of a compact core and a hydrated outer layer was proposed to describe the treated curdlan particles based on sedimentation and scanning electron microscopy observation. This model was verified by single- and two-step acid hydrolysis, indicative of the reduced susceptibility to hydrolysis when close to the compact core. Electrospray ionization-mass spectrometry, thin-layer chromatography analyses, and effective HPLC procedure led to the development of improved process to produce purified individual β-1,3-oligosaccharides with degrees of polymerization from 2 to 10 and potential for biomedical applications from curdlan hydrolyzate. Our new curdlan oligosaccharide production process offers an even better alternative to the previously published processes.

  5. Effect of aspartame and protein, administered in phenylalanine-equivalent doses, on plasma neutral amino acids, aspartate, insulin and glucose in man.

    PubMed

    Møller, S E

    1991-05-01

    Six human males each received 0.56 g phenylalanine (Phe) in the form of 1.0 g aspartame or 12.2 g bovine albumin in 200 ml water or water alone. Venous blood samples collected before consumption and during the following 4 hr were assayed for plasma levels of large, neutral amino acids (LNAA), aspartate, insulin and glucose. The area under the curve for plasma Phe was 40% greater, although not significant, after aspartame compared with albumin intake. The indicated increased clearance rate of plasma Phe after albumin may be caused by the significant increase of insulin, on which aspartame had no effect. There was a significant main effect of aspartame for plasma tyrosine but not for tryptophan, valine, isoleucine or leucine. Plasma aspartate was significantly increased at 0.25 hr after the aspartame intake. The percentage Phe/LNAA decreased slightly in response to albumin but increased 55% after aspartame and remained significantly increased for 2 hr. Tyrosine/LNAA increased and tryptophan/LNAA decreased modestly after aspartame intake. The study showed that the intake of aspartame in a not unrealistically high dose produced a marked and persistent increase of the availability of Phe to the brain, which was not observed after protein intake. The study indicated, furthermore, that Phe was cleared faster from the plasma after consumption of protein compared with aspartame.

  6. Effect of manganese and iron at a neutral and acidic pH on the hematology of the banded Tilapia (Tilapia sparrmanii)

    SciTech Connect

    Wepener, V.; Van Vuren, J.H.J.; Du Preez, H.H.

    1992-10-01

    The pollution of natural water bodies is a common phenomenon in developing countries. Increases in population densities lead to increased mining and industrial activities in the area. With the establishment of gold and coal mines in South Africa, several industrial zones were created to support the mining industry. Many of these industries consist of heavy metal processing factories. Over the years pollution from the mines has led to acidification of the streams and lakes in the Transvaal. It was also found that high concentrations of heavy metals occurred in the water, sediments, plants and fish tissue in the affected water systems. Of all the heavy metals, iron and manganese were found in the highest concentrations. In order to determine the subtle, non-lethal effects induced by sublethal concentrations of heavy metals on the physiology of fish, it is necessary to monitor certain clinical parameters. The use of hematological methods as indicators of sublethal stress can supply valuable information concerning the physiological reactions of fish in a changing environment. The reason for this is the close association between the circulatory system of the fish and the external environment. The objective of the present paper was to evaluate the effects of manganese and iron at a neutral and acidic pH on the hematology of Tilapia sparrmanii. 19 refs., 2 figs.

  7. [Preparation, characterization and adsorption performance of mesoporous activated carbon with acidic groups].

    PubMed

    Li, Kun-Quan; Li, Ye; Zheng, Zheng; Zhang, Yu-Xuan

    2013-06-01

    Mesoporous activated carbons containing acidic groups were prepared with cotton stalk based fiber as raw materials and H3PO4 as activating agent by one step carbonization method. Effects of impregnation ratio, carbonization temperature and heat preservation time on the yield, elemental composition, oxygen-containing acid functional groups and adsorptive capacity of activated carbon were studied. The adsorption capacity of the prepared activated carbon AC-01 for p-nitroaniline and Pb(II) was studied, and the adsorption mechanism was also suggested according to the equilibrium experimental results. The maximum yield of activated carbons prepared from cotton stalk fiber reached 35.5% when the maximum mesoporous volume and BET surface area were 1.39 cm3 x g(-1) and 1 731 m2 x g(-1), respectively. The activated carbon AC-01 prepared under a H3 PO4/precursor ratio of 3:2 and activated at 900 degrees C for 90 min had a total pore volume of 1.02 cm3 x g(-1), a micoporous ratio of 31%, and a mesoporous ratio of 65%. The pore diameter of the mesoporous activated carbon was mainly distributed in the range of 2-5 nm. The Langmuir maximum adsorption capacities of Pb(II) and p-nitroaniline on cotton stalk fiber activated carbon were 123 mg x g(-1) and 427 mg x g(-1), respectively, which were both higher than those for commercial activated carbon fiber ACF-CK. The equilibrium adsorption experimental data showed that mesopore and oxygen-containing acid functional groups played an important role in the adsorption. PMID:23947073

  8. Zn(OTf)2-promoted chemoselective esterification of hydroxyl group bearing carboxylic acids.

    PubMed

    Mamidi, Narsimha; Manna, Debasis

    2013-03-15

    Selective esterification of aliphatic and aromatic carboxylic acids with various alcohols is studied using triphenylphosphine, I2, and a catalytic amount of Zn(OTf)2. Use of this catalyst allows the formation of esters at a faster rate with good to excellent yield by activating the in situ generated acyloxyphosphonium ion intermediate. During the esterification process, both their aromatic and aliphatic hydroxyl groups are fully preserved from transesterification. The results show that the bulkiness and the reactivity of this doubly activated intermediate III control the selectivity and the rate of the reaction, respectively. The method is also useful for direct amidation reactions.

  9. Synthesis and physicochemical properties of polysiloxane functionalized with aminoacetic acid groups

    NASA Astrophysics Data System (ADS)

    Lakiza, N. V.; Neudachina, L. K.

    2016-07-01

    Polysiloxane functionalized with aminoacetic acid groups was synthesized using sol-gel technology. Elemental analysis and FTIR spectroscopy were used to determine the composition of the polysiloxane show that it is a mesoporous material with a developed surface (109.4 m2/g). It was found that the selective properties of carboxymethylated polysiloxane towards transition metal ions simultaneously present in an ammonium acetate solution change in the order Zn < Cu > Ni > Co > Pb > Cd. It was shown that the sorption of copper(II) ions by carboxymethylated aminopropylpolysiloxane with particle sizes of 50-71 μm reaches its maximum level within 2 h; the rate-limiting step of the process is the chemical reaction between the ions and the polysiloxane functional groups; and the pseudo-second-order model is the best way of describing sorption.

  10. Protodeboronation of ortho- and para-phenol boronic acids and application to ortho and meta functionalization of phenols using boronic acids as blocking and directing groups.

    PubMed

    Lee, Chun-Young; Ahn, Su-Jin; Cheon, Cheol-Hong

    2013-12-01

    The first metal-free thermal protodeboronation of ortho- and para-phenol boronic acids in DMSO was developed. The protodeboronation was successfully applied to the synthesis of ortho- and meta-functionalized phenols using the boronic acid moiety as a blocking group and a directing group, respectively. Mechanistic studies suggested that this protodeboronation proceeds through the coordination of water to the boron atom followed by σ-bond metathesis.

  11. Fully automated online solid phase extraction coupled directly to liquid chromatography-tandem mass spectrometry. Quantification of sulfonamide antibiotics, neutral and acidic pesticides at low concentrations in surface waters.

    PubMed

    Stoob, Krispin; Singer, Heinz P; Goetz, Christian W; Ruff, Matthias; Mueller, Stephan R

    2005-12-01

    A fully automated online solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) instrumental setup has been developed for the quantification of sulfonamide antibiotics and pesticides in natural water. The direct coupling of an online solid phase extraction cartridge (Oasis HLB) to LC-MS/MS was accomplished using column switching techniques. High sensitivity in the low ng/L range was achieved by large volume injections of 18 mL with a combination of a tri-directional auto-sampler and a dispenser system. This setup allowed high sample throughput with a minimum of investment costs. Special emphasis was placed on low cross contamination. The chosen approach is suitable for research as well as for monitoring applications. The flexible instrumental setup was successfully optimised for different important groups of bioactive chemicals resulting in three trace analytical methods for quantification of (i) sulfonamide antibiotics and their acetyl metabolites; (ii) neutral pesticides (triazines, phenylureas, amides, chloracetanilides) and (iii) acidic pesticides (phenoxyacetic acids and triketones). Absolute extraction recoveries from 85 to 112% were obtained for the different analytes. More than 500 samples could be analyzed with one extraction cartridge. The inter-day precision of the method was excellent indicated by relative standard deviations between 1 and 6%. High accuracy was achieved by the developed methods resulting in maximum deviation relative to the spiked amount of 8-15% for the different analytes. Detection limits for various environmental samples were between 0.5 and 5 ng/L. Matrix induced ion suppression was in general smaller than 25%. The performance of the online methods was demonstrated with measurements of concentration dynamics of sulfonamide antibiotics and pesticides concentrations in a little creek during rain fall events.

  12. Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

    NASA Astrophysics Data System (ADS)

    Gammons, Christopher H.; Nimick, David A.; Parker, Stephen R.; Cleasby, Thomas E.; McCleskey, R. Blaine

    2005-05-01

    Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe 2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.

  13. Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

    USGS Publications Warehouse

    Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R.B.

    2005-01-01

    Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.

  14. Correlation of biological value of feed phosphates with their solubility in water, dilute hydrogen chloride, dilute citric acid, and neutral ammonium citrate.

    PubMed

    Sullivan, T W; Douglas, J H; Gonzalez, N J; Bond, P L

    1992-12-01

    Relative biological values (BV) of 36 feed phosphates were determined with female turkeys in bioassays of 21-day duration using three response criteria: weight gain, tibia ash percentage, and gain:feed ratio. Calcium phosphate, dibasic dihydrate (United States Pharmacopeia) was the reference standard. Nine mono-dicalcium phosphates (M-DCP, 21.0% phosphorus), 13 di-monocalcium phosphates (D-MCP, 18.5% phosphorus), and 14 defluorinated phosphates (DFP, 18.0% phosphorus) were evaluated. The average relative BV for M-DCP, D-MCP, and DFP samples were 97.6, 94.6, and 90.8%, respectively. Solubility of phosphates was determined by four recognized methods. The solvents were water, .4% HCl, 2.0% citric acid (CA), and neutral ammonium citrate (NAC). Water solubility of M-DCP samples was greater (67.5%) than that of D-MCP (38.8%) and DFP (8.9%) samples. Correlation of water solubility of phosphates to their relative BV was quite low, and water solubility was a poor indicator of BV. When .4% HCl was the solvent, correlation coefficients (r) were .55, .33, and .72 for M-DCP, D-MCP, and DFP, respectively. Based on these results and prediction equations, .4% HCl solubility would be inappropriate for estimating BV of M-DCP and D-MCP samples. Solubility of feed phosphates (mainly D-MCP and DFP) in 2.0% CA or NAC was positively correlated with BV; the r values were .87 to .95. Both of these solubility tests provided a good index of BV. However, it would seem inappropriate and risky to replace bioassays totally with these tests. Feed phosphate users could perform either the 2.0% CA or NAC solubility test easily as a screen for BV along with other quality control procedures (i.e., phosphorus, calcium, sodium, and fluoride determinations).

  15. Activation of neutral-sphingomyelinase, MAPKs, and p75 NTR-mediating caffeic acid phenethyl ester–induced apoptosis in C6 glioma cells

    PubMed Central

    2014-01-01

    Background Caffeic acid phenethyl ester (CAPE), a component of propolis, is reported to possess anti-inflammatory, anti-bacterial, anti-viral, and anti-tumor activities. Previously, our laboratory demonstrated the in vitro and in vivo bioactivity of CAPE and addressed the role of p53 and the p38 mitogen-activated protein kinase (MAPK) pathway in regulating CAPE-induced apoptosis in C6 glioma cells. Results C6 cancer cell lines were exposed to doses of CAPE; DNA fragmentation and MAPKs and NGF/P75NTR levels were then determined. SMase activity and ceramide content measurement as well as western blotting analyses were performed to clarify molecular changes. The present study showed that CAPE activated neutral sphingomyelinase (N-SMase), which led to the ceramide-mediated activation of MAPKs, including extracellular signal-regulated kinase (ERK), Jun N-terminus kinase (JNK), and p38 MAPK. In addition, CAPE increased the expression of nerve growth factor (NGF) and p75 neurotrophin receptor (p75NTR). The addition of an N-SMase inhibitor, GW4869, established that NGF/p75NTR was the downstream target of N-SMase/ceramide. Pretreatment with MAPK inhibitors demonstrated that MEK/ERK and JNK acted upstream and downstream, respectively, of NGF/p75NTR. Additionally, CAPE-induced caspase 3 activation and poly [ADP-ribose] polymerase cleavage were reduced by pretreatment with MAPK inhibitors, a p75NTR peptide antagonist, or GW4869. Conclusions Taken together, N-SMase activation played a pivotal role in CAPE-induced apoptosis by activation of the p38 MAPK pathway and NGF/p75NTR may explain a new role of CAPE induced apoptosis in C6 glioma. PMID:24997497

  16. Are carboxyl groups the most acidic sites in amino acids? Gas-phase acidities, photoelectron spectra, and computations on tyrosine, p-hydroxybenzoic acid, and their conjugate bases.

    PubMed

    Tian, Zhixin; Wang, Xue-Bin; Wang, Lai-Sheng; Kass, Steven R

    2009-01-28

    Deprotonation of tyrosine in the gas phase was found to occur preferentially at the phenolic site, and the conjugate base consists of a 70:30 mixture of phenoxide and carboxylate anions at equilibrium. This result was established by developing a chemical probe for differentiating these two isomers, and the presence of both ions was confirmed by photoelectron spectroscopy. Equilibrium acidity measurements on tyrosine indicated that deltaG(acid)(o) = 332.5 +/- 1.5 kcal mol(-1) and deltaH(acid)(o) = 340.7 +/- 1.5 kcal mol(-1). Photoelectron spectra yielded adiabatic electron detachment energies of 2.70 +/- 0.05 and 3.55 +/- 0.10 eV for the phenoxide and carboxylate anions, respectively. The H/D exchange behavior of deprotonated tyrosine was examined using three different alcohols (CF3CH2OD, C6H5CH2OD, and CH3CH2OD), and incorporation of up to three deuterium atoms was observed. Two pathways are proposed to account for these results, and all of the experimental findings are supplemented with B3LYP/aug-cc-pVDZ and G3B3 calculations. In addition, it was found that electrospray ionization of tyrosine from a 3:1 (v/v) CH3OH/H2O solution using a commercial source produces a deprotonated [M-H]- anion with the gas-phase equilibrium composition rather than the structure of the ion that exists in aqueous media. Electrospray ionization from acetonitrile, however, leads largely to the liquid-phase (carboxylate) structure. A control molecule, p-hydroxybenzoic acid, was found to behave in a similar manner. Thus, the electrospray conditions that are employed for the analysis of a compound can alter the isomeric composition of the resulting anion.

  17. Intrinsic acidity of aluminum, chromium (III) and iron (III) μ 3-hydroxo functional groups from ab initio electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Dixon, David A.; Felmy, Andrew R.

    2000-05-01

    Density functional calculations are performed on M 3(OH) 7(H 2O) 62+ and M 3O(OH) 6(H 2O) 6+ clusters for MAl, Cr(III), and Fe(III), allowing determination of the relative acidities of the μ 3-hydroxo and aquo functional groups. Contrary to previous predictions and rationalizations, Fe 3OH and Al 3OH groups have nearly the same intrinsic acidity, while Cr 3OH groups are significantly more acidic. The gas-phase acidity of the Fe 3OH site is in good agreement with the value predicted by the molecular mechanics model previously used to estimate the relative acidities of surface sites on iron oxides. [ J. R. Rustad et al. (1996)Geochim. Cosmochim. Acta 60, 1563]. Acidities of aquo functional groups were also computed for Al and Cr. The AlOH 2 site is more acidic than the Al 3OH site, whereas the Cr 3OH site is more acidic than the CrOH 2 site. These findings predict that the surface charging behavior of chromium oxides/oxyhydroxides should be distinguishable from their Fe, Al counterparts. The calculations also provide insight into why the lepidocrocite/boehmite polymorph is not observed for CrOOH.

  18. Functional groups of sialic acids involved in binding to siglecs (sialoadhesins) deduced from interactions with synthetic analogues.

    PubMed

    Kelm, S; Brossmer, R; Isecke, R; Gross, H J; Strenge, K; Schauer, R

    1998-08-01

    The siglecs, formerly called sialoadhesins, are a family of I-type lectins binding to sialic acids on the cell surface. Five members of this family have been identified: sialoadhesin, myelin-associated glycoprotein (MAG), Schwann cell myelin protein (SMP), CD22 and CD33. We have investigated the relevance of substituents at position C-9 and in the N-acetyl group of N-acetylneuraminic acid, using a series of synthetic sialic-acid analogues either on resialylated human erythrocytes or as free alpha-glycosides in hapten inhibition. All five siglecs require the hydroxy group at C-9 for binding, suggesting hydrogen bonding of this substituent with the binding site. Remarkable differences were found among the proteins in their specificity for modifications of the N-acetyl group. Whereas sialoadhesin, MAG and SMP do not tolerate a hydroxy group as in N-glycolylneuraminic acid, they bind to halogenated acetyl residues. In the case of MAG, N-fluoroacetylneuraminic acid is bound about 17-fold better than N-acetylneuraminic acid. In contrast, human and murine CD22 both show good affinity for N-glycolylneuraminic acid, but only human CD22 bound the halogenated compounds. In conclusion, our data indicate that interactions of the hydroxy group at position 9 and the N-acyl substituent contribute significantly to the binding strength. PMID:9738906

  19. Evaluation of the cyclopentane-1,2-dione as a potential bio-isostere of the carboxylic acid functional group

    PubMed Central

    Gay, Bryant; Huang, Longchuan; Robinson, Katie Herbst; James, Michael; Trojanowski, John Q.; Lee, Virginia M.Y.; Brunden, Kurt R.

    2014-01-01

    Cycloalkylpolyones hold promise in drug design as carboxylic acid bio-isosteres. To investigate cyclopentane-1,2-diones as potential surrogates of the carboxylic acid functional group, the acidity, tautomerism, and geometry of hydrogen bonding of representative compounds were evaluated. Prototypic derivatives of the known thromboxane A2 prostanoid (TP) receptor antagonist, 3-(3-(2-((4-chlorophenyl)sulfonamido)-ethyl)phenyl)propanoic acid, in which the carboxylic acid moiety is replaced by the cyclopentane-1,2-dione unit, were synthesized and evaluated as TP receptor antagonists. Cyclopentane-1,2-dione derivative 9 was found to be a potent TP receptor antagonist with an IC50 value comparable to that of the parent carboxylic acid. These results indicate that the cyclopentane-1,2-dione may be a potentially useful carboxylic acid bio-isostere. PMID:25127105

  20. A Label as a Hidden Persuader: Chemists' Neutralization Concept.

    ERIC Educational Resources Information Center

    Schmidt, Hans-Jurgen

    1991-01-01

    Identifies and describes the problems students have with the concept of neutralization. Analysis of over 7,500 students' answers to test questions over neutralization showed that many students understand the concept in its original meaning. Students assumed that in any neutralization reaction a neutral solution is formed, even if a weak acid or…

  1. A simple colorimetric chemosensor bearing a carboxylic acid group with high selectivity for CN-

    NASA Astrophysics Data System (ADS)

    Park, Gyeong Jin; Choi, Ye Won; Lee, Dongkuk; Kim, Cheal

    2014-11-01

    A new simple ‘naked eye' chemosensor 1 (sodium (E)-2-((2-(3-hydroxy-2-naphthoyl)hydrazono)methyl)benzoate) has been synthesized for detection of CN- in a mixture of DMF/H2O (9:1). The sensor 1 comprises of a naphthoic hydrazide as efficient hydrogen bonding donor group and a benzoic acid as the moiety with the water solubility. The receptor 1 showed high selectivity toward cyanide ions in a 1:1 stoichiometric manner, which induces a fast color change from colorless to yellow for CN- over other anions. Therefore, receptor 1 could be useful for cyanide detection in aqueous environment, displaying a high distinguishable selectivity from hydrogen bonded anions and being clearly visible to the naked eye.

  2. Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes

    PubMed Central

    Ling, Xiao; Bonn, Mischa

    2016-01-01

    Abstract The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel‐cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion‐cast membranes. As a result, a disproportionally large amount of non‐bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel‐cell membranes. PMID:26895211

  3. Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes.

    PubMed

    Ling, Xiao; Bonn, Mischa; Parekh, Sapun H; Domke, Katrin F

    2016-03-14

    The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel-cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion-cast membranes. As a result, a disproportionally large amount of non-bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel-cell membranes.

  4. Copoly(arlene ether)s containing pendant sulfonic acid groups as proton exchange membrane

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik; Robertson, Gilles; Guiver, Michael

    2008-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The P AE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sP AE and sP AEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC{sub v}(wet) (volume-based, wet state)) of 1.77 and 2.55 meq./cm{sup 3}, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5-51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the area of outstanding properties in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based). Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  5. Role of hydroxyl group in the inhibitive action of benzoic acid toward corrosion of aluminum in nitric acid

    SciTech Connect

    Yadav, P.N.S.; Singh, A.K.; Wadhwani, R.

    1999-10-01

    Corrosion inhibition action of benzoic acid, p-hydroxy benzoic acid, 2-4-dihydroxy benzoic acid, and 3-4-5-trihydroxy benzoic acid toward aluminum alloy 3003 (UNS A93003) in 20% (wt%) nitric acid (HNO{sub 3}) using different concentrations of these compounds at 30 C, 40 C, and 50 C has been studied thoroughly. 3-4-5-trihydroxy benzoic acid (inhibition efficiency (IE): 30% and 72%) was the most effective inhibitor followed by 2-4-dihydroxy benzoic acid (IE: 22% to 62%) p-hydroxy benzoic acid (IE: 11% to 52%), and benzoic acid (IE: 2.5% to 15%). IE increased with concentration and its maximum value was observed at 0.5% concentration of all inhibitors used. The percentage of IE of the inhibitors decreased with an increase in temperature from 30 C to 50 C. Values of heat adsorption and activation energy were calculated from weight loss data, which came out in the range for the reaction occurring at the surface. The behavior of inhibitors studied deviated from the Langmuir isotherm. The IE of higher hydroxy species was improved when more hydroxy centers were added. Anodic and cathodic polarization curves were shifted toward lower current density regions in the presence of inhibitors. This revealed that they were mixed inhibitors.

  6. Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids.

    PubMed

    Martín-Sómer, Ana; Mó, Otilia; Yáñez, Manuel; Guillemin, Jean-Claude

    2015-01-21

    The intrinsic acidity of CH2[double bond, length as m-dash]CHXH2, HC[triple bond, length as m-dash]CXH2 (X = N, P, As, Sb) derivatives and of their complexes with BeH2 and BH3 has been investigated by means of high-level density functional theory and molecular orbital ab initio calculations, using as a reference the ethyl saturated analogues. The acidity of the free systems steadily increases down the group for the three series of derivatives, ethyl, vinyl and ethynyl. The association with both beryllium dihydride and borane leads to a very significant acidity enhancement, being larger for BeH2 than for BH3 complexes. This acidity enhancement, for the unsaturated compounds, is accompanied by a change in the acidity trends down the group, which do not steadily decrease but present a minimum value for both the vinyl- and the ethynyl-phosphine. When the molecule acting as the Lewis acid is beryllium dihydride, the π-type complexes in which the BeH2 molecules interact with the double or triple bond are found, in some cases, to be more stable, in terms of free energies, than the conventional complexes in which the attachment takes place at the heteroatom, X. The most important finding, however, is that P, As, and Sb ethynyl complexes with BeH2 do not behave as P, As, or Sb Brønsted acids, but unexpectedly as Be acids.

  7. Blood groups and red cell acid phosphatase types in a Mixteca population resident in Mexico City.

    PubMed

    Buentello, L.; García, P.; Lisker, R.; Salamanca, F.; Peñaloza, R.

    1999-01-01

    Several blood groups, ABO, Rh, Ss, Fy, Jk, and red cell acid phosphatase (ACP) types were studied in a native Mixteca population that has resided in Mexico City since 1950. Gene frequencies were obtained and used to establish admixture estimates with blacks and whites. The subjects came from three different geographical areas: High Mixteca, Low Mixteca, and Coast Mixteca. All frequencies were in Hardy-Weinberg equilibrium. The difference in the ABO frequencies was statistically significant when subjects from the three areas were compared simultaneously. Rh frequencies differed only between the High and the Low Mixteca populations. The ACP frequencies were similar between the Low Mixteca population and a previously reported Mestizo population. However, there were significant differences between the High Mixteca group and a Mestizo population, all the subjects being from Oaxaca. This is the first report of Ss, Fy, Jk, and ACP frequencies in a Mixteca population. Am. J. Hum. Biol. 11:525-529, 1999. Copyright 1999 Wiley-Liss, Inc.

  8. Effect of molecular chirality on racemate stability: alpha-amino acids with nonpolar R groups.

    PubMed

    Huang, Jun; Yu, Lian

    2006-02-15

    A racemate of two opposite and resolvable enantiomers is generally assumed to be more stable than the corresponding conglomerate. Demonstrating this structure-stability relation, however, has proved difficult owing to a sampling bias (data available only for systems whose racemates are stable enough to exist) and a possible kinetic bias (racemates may be easier to crystallize than conglomerates from racemic media). As a new approach to studying the relation, we determined how the relative stability of the conglomerate and the racemate changes with the molecule's degree of chirality in a series of alpha-amino acids with nonpolar R groups. We found that the excess energy of the conglomerate over the racemate, (E(C) - E(R)), increases with the size of the R group, a measure of the molecule's chirality. If valid in general, this relation demonstrates a tendency for chiral molecules to form racemates rather than conglomerates. Because of the entropy effect on crystal stability, however, the excess free energy of the conglomerate over the racemate, (G(C) - G(R)), shows no simple relation with the degree of chirality at the temperatures of study (-3 to 180 degrees C).

  9. Guidelines on the clinical use for the detection of neutralizing antibodies (NAbs) to IFN beta in multiple sclerosis therapy: report from the Italian Multiple Sclerosis Study group.

    PubMed

    Bertolotto, Antonio; Capobianco, Marco; Amato, Maria Pia; Capello, Elisabetta; Capra, Ruggero; Centonze, Diego; Di Ioia, Maria; Gallo, Antonio; Grimaldi, Luigi; Imberti, Luisa; Lugaresi, Alessandra; Mancinelli, Chiara; Marrosu, Maria Giovanna; Moiola, Lucia; Montanari, Enrico; Romano, Silvia; Musu, Luigina; Paolicelli, Damiano; Patti, Francesco; Pozzilli, Carlo; Rossi, Silvia; Salvetti, Marco; Tedeschi, Gioachino; Tola, Maria Rosaria; Trojano, Maria; Troiano, Maria; Zaffaroni, Mauro; Malucchi, Simona

    2014-02-01

    Interferon beta (IFNβ) was the first specific disease-modifying treatment licensed for relapsing-remitting multiple sclerosis, and is still one of the most commonly prescribed treatments. A strong body of evidence supports the effectiveness of IFNβ preparations in reducing the annual relapse rate, magnetic resonance (MRI) disease activity and disease progression. However, the development of binding/neutralizing antibodies (BAbs/NAbs) during treatment negatively affects clinical and MRI outcomes. Therefore, guidelines for the clinical use for the detection of NAbs in MS may result in better treatment of these patients. In October 2012, a panel of Italian neurologists from 17 MS clinics convened in Milan to review and discuss data on NAbs and their clinical relevance in the treatment of MS. In this paper, we report the panel's recommendations for the use of IFNβ Nabs detection in the early identification of IFNβ non-responsiveness and the management of patients on IFNβ treatment in Italy, according to a model of therapeutically appropriate care.

  10. Fatty acid profiles of blood lipids in a population group in Tibet: correlations with diet and environmental conditions.

    PubMed

    Risé, Patrizia; Marangoni, Franca; Martiello, Antonella; Colombo, Claudio; Manzoni, Cristina; Marconi, Claudio; Cattabeni, Flaminio; Galli, Claudio

    2008-01-01

    The aim of this study was to compare blood fatty acid profiles of two population groups: Italian and Tibetan, differing with regard to ethnic, life style and environmental aspects. Additionally the collection of two staple foods provided the opportunity to analyze typical Tibetan dishes. A new, simple, rapid, and substantially non invasive method for fatty acid (FA) analysis of blood lipids was applied to healthy Italian (n=14) and Tibetan (n=13) subjects. Blood drops obtained from the ear lobe of Tibetans or the fingertip of Italians were adsorbed by a special strip of paper and processed for fatty acid analysis. The fatty acid profiles of the two groups are different, and environmental factors, such as dietary fats and altitudes of Milan, Italy (a low altitude site), and Lhasa, Tibet (a high altitude site) appear to contribute to these differences. More specifically, in Ti-betans higher levels of monounsaturated fatty acids, including the 22 and 24 carbon molecules, were found. This appears to be derived mainly from locally consumed fats (mustard seed oil), and are associated with lower levels of total polyunsaturated fatty acids and higher levels of selected omega 3 fatty acids, when compared to the Italians. These relatively higher levels of monounsaturated fatty acids may also indicate means of adaptation to local prooxidant conditions. The observed differences in blood fatty acid profiles in Tibetans vs. Italians appear to result both from dietary factors and adaptation to local environmental conditions such as the high altitude of the Tibetan location.

  11. Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: a progress report.

    PubMed

    Steininger, H; Schuster, M; Kreuer, K D; Kaltbeitzel, A; Bingöl, B; Meyer, W H; Schauff, S; Brunklaus, G; Maier, J; Spiess, H W

    2007-04-21

    The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC

  12. Characterization of Group V Dubnium Homologs on DGA Extraction Chromatography Resin from Nitric and Hydrofluoric Acid Matrices

    SciTech Connect

    Despotopulos, J D; Sudowe, R

    2012-02-21

    somewhere between Nb and Pa. Much more recent studies have examined the properties of Db from HNO{sub 3}/HF matrices, and suggest Db forms complexes similar to those of Pa. Very little experimental work into the behavior of element 114 has been performed. Thermochromatography experiments of three atoms of element 114 indicate that the element 114 is at least as volatile as Hg, At, and element 112. Lead was shown to deposit on gold at temperatures about 1000 C higher than the atoms of element 114. Results indicate a substantially increased stability of element 114. No liquid phase studies of element 114 or its homologs (Pb, Sn, Ge) or pseudo-homologs (Hg, Cd) have been performed. Theoretical predictions indicate that element 114 is should have a much more stable +2 oxidation state and neutral state than Pb, which would result in element 114 being less reactive and less metallic than Pb. The relativistic effects on the 7p{sub 1/2} electrons are predicted to cause a diagonal relationship to be introduced into the periodic table. Therefore, 114{sup 2+} is expected to behave as if it were somewhere between Hg{sup 2+}, Cd{sup 2+}, and Pb{sup 2+}. In this work two commercially available extraction chromatography resins are evaluated, one for the separation of Db homologs and pseudo?homologs from each other as well as from potential interfering elements such as Group IV Rf homologs and actinides, and the other for separation of element 114 homologs. One resin, Eichrom's DGA resin, contains a N,N,N',N'-tetra-n-octyldiglycolamide extractant, which separates analytes based on both size and charge characteristics of the solvated metal species, coated on an inert support. The DGA resin was examined for Db chemical systems, and shows a high degree of selectivity for tri-, tetra-, and hexavalent metal ions in multiple acid matrices with fast kinetics. The other resin, Eichrom's Pb resin, contains a di-t-butylcyclohexano 18-crown-6 extractant with isodecanol solvent, which separates

  13. An aldehyde group-based P-acid probe for selective fluorescence turn-on sensing of cysteine and homocysteine.

    PubMed

    Yang, Chunlei; Wang, Xiu; Shen, Lei; Deng, Wenping; Liu, Haiyun; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2016-06-15

    A highly sensitive and selective turn on fluorescent probe P-acid-aldehyde (P-CHO) is developed for the determination of cysteine (Cys) and homocysteine (Hcy). The probe is designed and synthesized by incorporating the specific functional group aldehyde group for thiols into a stable π-conjugated material 4,4'-(2,5-dimethoxy-1,4-phenylene) bis(ethyne-2,1-diyl) dibenzoic acid (P-acid). The probe fluorescence is quenched through donor photoinduced electron transfer (d-PET) between the fluorophore (P-acid) and the recognition group (aldehyde group). In the presence of thiols, Cys and Hcy can selectively react with aldehyde group of the probe because the inhibition of d-PET between fluorophore and recognition group. Therefore, a turn-on fluorescent sensor was established for the fluorescence recovery. Under the optimized conditions, the fluorescence response of probe is directly proportional to the concentration of Cys in the range of 4-95 NM L(-1), with a detection limit 3.0 nM. In addition, the sensing system exhibits good selectively toward Cys and Hcy in the presence of other amino acids. It has been successfully applied for bioimaging of Cys and Hcy in living cells with low cell toxicity.

  14. Antihypertensive neutral lipid

    SciTech Connect

    Snyder, F.L.; Blank, M.L.

    1986-06-17

    A method is described for treating a warm-blooded animal comprising administering to the animal a neutral glycerolipid with a 12 to 20 carbon alkyl group at the sn-1 position, a short carbon chain acyl group at the sn-2 position and a hydroxyl group at the sn-3 position in an amount sufficient to lower the arterial blood pressure of the animal. A method is also described for treating a warm-blooded animal comprising administering a composition consisting essentially of a 1-alkyl-2-acetyl (or propionyl)-sn glycerol in combination with a 1-alkyl-2-acetyl-sn-glycero-3-phosphocholine, wherein the 1-alkyl groups contain 12 to 20 carbon atoms, dissolved in an inert pharmaceutically acceptable solvent in amounts sufficient to lower the arterial blood pressure of the animal.

  15. A combination of omega-3 fatty acids, folic acid and B-group vitamins is superior at lowering homocysteine than omega-3 alone: A meta-analysis.

    PubMed

    Dawson, Samantha Loren; Bowe, Steven John; Crowe, Timothy Charles

    2016-06-01

    The aim of the study was to assess whether omega-3 polyunsaturated fatty acid supplementation alone or in combination with folic acid and B-group vitamins is effective in lowering homocysteine. The Medline Ovid, Embase and Cochrane databases were searched for randomized-controlled trial studies that intervened with omega-3 supplementation (with or without folic acid) and measured changes in homocysteine concentration. Studies were pooled using a random effects model for meta-analysis. Three different models were analyzed: all trials combined, omega-3 polyunsaturated fatty acid trials, and omega-3 polyunsaturated fatty acids with folic acid and B-group vitamin trials. Nineteen studies were included, consisting of 3267 participants completing 21 trials. Studies were heterogeneous; varying by dose, duration and participant health conditions. Across all trials, omega-3 supplementation was effective in lowering homocysteine by an average of 1.18μmol/L (95%CI: (-1.89, -0.48), P=.001). The average homocysteine-lowering effect was greater when omega-3 supplementation was combined with folic acid and B-group vitamins (-1.37μmol/L, 95%CI: (-2.38, -0.36), P<.01) compared to omega-3 supplementation alone (-1.09μmol/L 95%CI: (-2.04, -0.13), P=.03). Omega-3 polyunsaturated fatty acid supplementation was associated with a modest reduction in homocysteine. For the purposes of reducing homocysteine, a combination of omega-3s (0.2-6g/day), folic acid (150 - 2500μg/day) and vitamins B6 and B12 may be more effective than omega-3 supplementation alone.

  16. A combination of omega-3 fatty acids, folic acid and B-group vitamins is superior at lowering homocysteine than omega-3 alone: A meta-analysis.

    PubMed

    Dawson, Samantha Loren; Bowe, Steven John; Crowe, Timothy Charles

    2016-06-01

    The aim of the study was to assess whether omega-3 polyunsaturated fatty acid supplementation alone or in combination with folic acid and B-group vitamins is effective in lowering homocysteine. The Medline Ovid, Embase and Cochrane databases were searched for randomized-controlled trial studies that intervened with omega-3 supplementation (with or without folic acid) and measured changes in homocysteine concentration. Studies were pooled using a random effects model for meta-analysis. Three different models were analyzed: all trials combined, omega-3 polyunsaturated fatty acid trials, and omega-3 polyunsaturated fatty acids with folic acid and B-group vitamin trials. Nineteen studies were included, consisting of 3267 participants completing 21 trials. Studies were heterogeneous; varying by dose, duration and participant health conditions. Across all trials, omega-3 supplementation was effective in lowering homocysteine by an average of 1.18μmol/L (95%CI: (-1.89, -0.48), P=.001). The average homocysteine-lowering effect was greater when omega-3 supplementation was combined with folic acid and B-group vitamins (-1.37μmol/L, 95%CI: (-2.38, -0.36), P<.01) compared to omega-3 supplementation alone (-1.09μmol/L 95%CI: (-2.04, -0.13), P=.03). Omega-3 polyunsaturated fatty acid supplementation was associated with a modest reduction in homocysteine. For the purposes of reducing homocysteine, a combination of omega-3s (0.2-6g/day), folic acid (150 - 2500μg/day) and vitamins B6 and B12 may be more effective than omega-3 supplementation alone. PMID:27188895

  17. Aspirin's Active Metabolite Salicylic Acid Targets High Mobility Group Box 1 to Modulate Inflammatory Responses.

    PubMed

    Choi, Hyong Woo; Tian, Miaoying; Song, Fei; Venereau, Emilie; Preti, Alessandro; Park, Sang-Wook; Hamilton, Keith; Swapna, G V T; Manohar, Murli; Moreau, Magali; Agresti, Alessandra; Gorzanelli, Andrea; De Marchis, Francesco; Wang, Huang; Antonyak, Marc; Micikas, Robert J; Gentile, Daniel R; Cerione, Richard A; Schroeder, Frank C; Montelione, Gaetano T; Bianchi, Marco E; Klessig, Daniel F

    2015-01-01

    Salicylic acid (SA) and its derivatives have been used for millennia to reduce pain, fever and inflammation. In addition, prophylactic use of acetylsalicylic acid, commonly known as aspirin, reduces the risk of heart attack, stroke and certain cancers. Because aspirin is rapidly de-acetylated by esterases in human plasma, much of aspirin's bioactivity can be attributed to its primary metabolite, SA. Here we demonstrate that human high mobility group box 1 (HMGB1) is a novel SA-binding protein. SA-binding sites on HMGB1 were identified in the HMG-box domains by nuclear magnetic resonance (NMR) spectroscopic studies and confirmed by mutational analysis. Extracellular HMGB1 is a damage-associated molecular pattern molecule (DAMP), with multiple redox states. SA suppresses both the chemoattractant activity of fully reduced HMGB1 and the increased expression of proinflammatory cytokine genes and cyclooxygenase 2 (COX-2) induced by disulfide HMGB1. Natural and synthetic SA derivatives with greater potency for inhibition of HMGB1 were identified, providing proof-of-concept that new molecules with high efficacy against sterile inflammation are attainable. An HMGB1 protein mutated in one of the SA-binding sites identified by NMR chemical shift perturbation studies retained chemoattractant activity, but lost binding of and inhibition by SA and its derivatives, thereby firmly establishing that SA binding to HMGB1 directly suppresses its proinflammatory activities. Identification of HMGB1 as a pharmacological target of SA/aspirin provides new insights into the mechanisms of action of one of the world's longest and most used natural and synthetic drugs. It may also provide an explanation for the protective effects of low-dose aspirin usage. PMID:26101955

  18. Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes

    SciTech Connect

    Dae Sik, Kim; Yu Seung, Kim; Gilles, Robertson; Guiver, Michael D

    2009-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and P AEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (OS) of 1.0 had high ion exchange capacities (IEC{sub v})(wet) (volume-based, wet state) of 1.77 and 2.55 meq./cm3, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5 -51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  19. Aspirin's Active Metabolite Salicylic Acid Targets High Mobility Group Box 1 to Modulate Inflammatory Responses.

    PubMed

    Choi, Hyong Woo; Tian, Miaoying; Song, Fei; Venereau, Emilie; Preti, Alessandro; Park, Sang-Wook; Hamilton, Keith; Swapna, G V T; Manohar, Murli; Moreau, Magali; Agresti, Alessandra; Gorzanelli, Andrea; De Marchis, Francesco; Wang, Huang; Antonyak, Marc; Micikas, Robert J; Gentile, Daniel R; Cerione, Richard A; Schroeder, Frank C; Montelione, Gaetano T; Bianchi, Marco E; Klessig, Daniel F

    2015-06-18

    Salicylic acid (SA) and its derivatives have been used for millennia to reduce pain, fever and inflammation. In addition, prophylactic use of acetylsalicylic acid, commonly known as aspirin, reduces the risk of heart attack, stroke and certain cancers. Because aspirin is rapidly de-acetylated by esterases in human plasma, much of aspirin's bioactivity can be attributed to its primary metabolite, SA. Here we demonstrate that human high mobility group box 1 (HMGB1) is a novel SA-binding protein. SA-binding sites on HMGB1 were identified in the HMG-box domains by nuclear magnetic resonance (NMR) spectroscopic studies and confirmed by mutational analysis. Extracellular HMGB1 is a damage-associated molecular pattern molecule (DAMP), with multiple redox states. SA suppresses both the chemoattractant activity of fully reduced HMGB1 and the increased expression of proinflammatory cytokine genes and cyclooxygenase 2 (COX-2) induced by disulfide HMGB1. Natural and synthetic SA derivatives with greater potency for inhibition of HMGB1 were identified, providing proof-of-concept that new molecules with high efficacy against sterile inflammation are attainable. An HMGB1 protein mutated in one of the SA-binding sites identified by NMR chemical shift perturbation studies retained chemoattractant activity, but lost binding of and inhibition by SA and its derivatives, thereby firmly establishing that SA binding to HMGB1 directly suppresses its proinflammatory activities. Identification of HMGB1 as a pharmacological target of SA/aspirin provides new insights into the mechanisms of action of one of the world's longest and most used natural and synthetic drugs. It may also provide an explanation for the protective effects of low-dose aspirin usage.

  20. Molecular Structures, Acid-Base Properties, and Formation of Group 6 Transition Metal Hydroxides

    SciTech Connect

    Li, Shenggang; Guenther, Courtney L.; Kelley, Matthew S.; Dixon, David A.

    2011-04-28

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the group 6 metal (M = Cr, Mo, W) hydroxides: MO3-m(OH)2m (m = 1-3), M2O6-m(OH)2m (m = 1-5), M3O9-m(OH)2m (m = 1, 2), and M4O11(OH)2. The calculations were done up to the complete basis set (CBS) limit for the CCSD(T) method. Molecular structures of many low-energy conformers/isomers were located. Brønsted acidities in the gas phase and pKa values in aqueous solution were predicted for MO3-m(OH)2m (m = 1-3) and MnO3n-1(OH)2 (n = 2-4). In addition, Brønsted basicities and Lewis acidities (fluoride affinities) were predicted for MO3-m(OH)2m (m = 1-3) as well as the metal oxide clusters MnO3n (n = 1-3). The metal hydroxides were predicted to be strong Brønsted acids and weak to modest Brønsted bases and Lewis acids. The pKa values can have values as negative as -31. Potential energy surfaces for the hydrolysis of the MnO3n (n = 1-4) clusters were calculated. Heats of formation of the metal hydroxides were predicted from the calculated reaction energies, and the agreement with the limited available experimental data is good. The first hydrolysis step leading to the formation of MnO3n-1(OH)2 was predicted to be exothermic, with the exothermicity becoming less negative as n increases and essentially converged at n = 3. Reaction rate constants for the hydrogen transfer steps were calculated using transition state theory and RRKM theory. Further hydrolysis of MnO3n-1(OH)2 tends to be endothermic especially for M = Cr. Fifty-five DFT exchange-correlation functionals were benchmarked for the calculations of the reaction energies, complexation energies, and reaction barriers by comparing to our CCSD(T) results. Overall, the DFT results for the potential energy surfaces are semiquantitatively correct, but no single functional works for all processes and all three metals. Among the functionals benchmarked, the wB97, wB97X, B1B95, B97-1, mPW1LYP, and X3LYP functionals have the best

  1. Photoinductive activity of humic acid fractions with the presence of Fe(III): the role of aromaticity and oxygen groups involved in fractions.

    PubMed

    Ou, Xiaoxia; Chen, Shuo; Quan, Xie; Zhao, Huimin

    2008-06-01

    Relationship between the photoinductive activity and the properties of humic acids (HA) fractions were investigated with and without Fe(III). Three fractions were separated based on the molecular weight (M(w)) and were obtained following the order of M(w): F(A)>F(B)>F(C). Compared to F(A) and F(B), photodegradation of atrazine under simulated sunlight was much faster in solution containing F(C), whose structure was dominated by greater aromaticity, more oxygen groups and fluorophores. The interaction of HA fractions and Fe(III) was studied using fluorescence spectrometry and F(C) had the largest quenching constant. The capacity of electron transfer, estimated from the amount of photoformed Fe(II), was also highest for F(C). Thus, the Fe(III)-F(C) complex was efficient in phototransformation of atrazine in nearly neutral aqueous solutions. These results suggest that the aromaticity and oxygen groups content of HA exert great influence on the binding ability of metals and on the fate of pollutants in natural waters.

  2. Evaluation of the number of ionogenic groups of inulinase by acid-base titration.

    PubMed

    Kovaleva, T A; Holyavka, M G; Rezvan, S G; Kozhedub, S V

    2008-06-01

    Acid base titration showed that Aspergillus awamori inulinase includes 178 asparaginic and glutamic acid residues, 20 histidine, 10 serine, and 34 lysine and tyrosine residues. Denaturation temperature for this enzyme was calculated using analysis of the proportion of stabilizing and destabilizing amino acids in the molecule.

  3. Removal of textile dyes and metallic ions using polyelectrolytes and macroelectrolytes containing sulfonic acid groups.

    PubMed

    Caldera Villalobos, M; Peláez Cid, A A; Herrera González, Ana M

    2016-07-15

    This work reports the removal of textile dyes and metallic ions by means of adsorption and coagulation-flocculation using two polyelectrolytes and two macroelectrolytes containing sulfonic acid groups. The adsorption of textile dyes was studied in aqueous solutions containing cationic dyes and in wastewater containing a vat dye. Also, removal of vat and naphthol dyes was studied using the process of coagulation-flocculation. The results show these materials possess elevated adsorption capacity, and they accomplished removal rates above 97% in aqueous solutions. The removal of the vat dye improved the quality of the wastewater notably, and an uncolored effluent was obtained at the end of the treatment. The treatment using adsorption decreased the values for coloration, conductivity, suspended solids, and pH. The removal of vat and naphthol dyes by means of coagulation-flocculation was studied as well, and removal rates of 90% were obtained. The polyelectrolytes and macroelectrolytes also proved effective in the adsorption of metallic ions in wastewater. The treatment using adsorption accomplished high removal rates of metallic ions, and it showed greater selectivity towards Cu(2+), Fe(3+) and Pb(2+). A decrease in the content of solids as well as the values for COD and conductivity was observed in the wastewater as well. The analyses of FT-IR indicated that cationic dyes and metallic ions were chemisorbed by means of ionic exchange.

  4. Light and heavy dansyl reporter groups in food chemistry: amino acid assay in beverages.

    PubMed

    Mazzotti, Fabio; Benabdelkamel, Hicham; Di Donna, Leonardo; Athanassopoulos, Constantinos M; Napoli, Anna; Sindona, Giovanni

    2012-07-01

    5-Dimethylamino-1-sulfonyl naphthalene (DNS, commonly referred as dansyl) is a functionality, bearing well-established properties in directing the fragmentation, by mass spectrometry (MS), of the corresponding ionized sulfonylated derivatives. This property is shared also by its labeled analogs. The use of d(0)/d(6) DNS derivatives is now exploited in the application of the well-established isotope dilution mass spectrometric approach in the assay of complex mixtures. A new method for the quantitation of amino acids (AAs) in beverages is therefore presented, which relies on liquid chromatographic separation of their N-dansylated derivatives followed by comparative electrospray tandem MS/MS of the d(0)/d(6) isobaric mixtures. Labeled and unlabeled DNS derivatives of the selected AAs are readily available by microwave-assisted synthetic protocols. The novelty of the method is represented by the use of heavy and light DNS-isotopologue providing suitable reporter groups. Multiple-reaction monitoring has been applied in the assay of AAs in wine, pineapple juice and bergamot juice with good-to-excellent results as proved by both relative standard deviation, lower than 15%, and by the accuracy values in the range 90-110%.

  5. Removal of textile dyes and metallic ions using polyelectrolytes and macroelectrolytes containing sulfonic acid groups.

    PubMed

    Caldera Villalobos, M; Peláez Cid, A A; Herrera González, Ana M

    2016-07-15

    This work reports the removal of textile dyes and metallic ions by means of adsorption and coagulation-flocculation using two polyelectrolytes and two macroelectrolytes containing sulfonic acid groups. The adsorption of textile dyes was studied in aqueous solutions containing cationic dyes and in wastewater containing a vat dye. Also, removal of vat and naphthol dyes was studied using the process of coagulation-flocculation. The results show these materials possess elevated adsorption capacity, and they accomplished removal rates above 97% in aqueous solutions. The removal of the vat dye improved the quality of the wastewater notably, and an uncolored effluent was obtained at the end of the treatment. The treatment using adsorption decreased the values for coloration, conductivity, suspended solids, and pH. The removal of vat and naphthol dyes by means of coagulation-flocculation was studied as well, and removal rates of 90% were obtained. The polyelectrolytes and macroelectrolytes also proved effective in the adsorption of metallic ions in wastewater. The treatment using adsorption accomplished high removal rates of metallic ions, and it showed greater selectivity towards Cu(2+), Fe(3+) and Pb(2+). A decrease in the content of solids as well as the values for COD and conductivity was observed in the wastewater as well. The analyses of FT-IR indicated that cationic dyes and metallic ions were chemisorbed by means of ionic exchange. PMID:27082258

  6. Community Genomic and Proteomic Analyses of Chemoautotrophic Iron-Oxidizing "Leptospirillum rubarum" (Group II) and "Leptospirillum ferrodiazotrophum" (Group III) Bacteria in Acid Mine Drainage Biofilms

    SciTech Connect

    Goltsman, Daniela; Denef, Vincent; Singer, Steven; Verberkmoes, Nathan C; Lefsrud, Mark G; Mueller, Ryan; Dick, Gregory J.; Sun, Christine; Wheeler, Korin; Zelma, Adam; Baker, Brett J.; Hauser, Loren John; Land, Miriam L; Shah, Manesh B; Thelen, Michael P.; Hettich, Robert {Bob} L; Banfield, Jillian F.

    2009-01-01

    We analyzed near-complete population (composite) genomic sequences for coexisting acidophilic iron-oxidizing Leptospirillum group II and III bacteria (phylum Nitrospirae) and an extrachromosomal plasmid from a Richmond Mine, Iron Mountain, CA, acid mine drainage biofilm. Community proteomic analysis of the genomically characterized sample and two other biofilms identified 64.6% and 44.9% of the predicted proteins of Leptospirillum groups II and III, respectively, and 20% of the predicted plasmid proteins. The bacteria share 92% 16S rRNA gene sequence identity and >60% of their genes, including integrated plasmid-like regions. The extrachromosomal plasmid carries conjugation genes with detectable sequence similarity to genes in the integrated conjugative plasmid, but only those on the extrachromosomal element were identified by proteomics. Both bacterial groups have genes for community-essential functions, including carbon fixation and biosynthesis of vitamins, fatty acids, and biopolymers (including cellulose); proteomic analyses reveal these activities. Both Leptospirillum types have multiple pathways for osmotic protection. Although both are motile, signal transduction and methyl-accepting chemotaxis proteins are more abundant in Leptospirillum group III, consistent with its distribution in gradients within biofilms. Interestingly, Leptospirillum group II uses a methyl-dependent and Leptospirillum group III a methyl-independent response pathway. Although only Leptospirillum group III can fix nitrogen, these proteins were not identified by proteomics. The abundances of core proteins are similar in all communities, but the abundance levels of unique and shared proteins of unknown function vary. Some proteins unique to one organism were highly expressed and may be key to the functional and ecological differentiation of Leptospirillum groups II and III.

  7. Carboxylic Acids as A Traceless Activation Group for Conjugate Additions: A Three-Step Synthesis of (±)-Pregabalin

    PubMed Central

    2015-01-01

    The direct application of carboxylic acids as a traceless activation group for radical Michael additions has been accomplished via visible light-mediated photoredox catalysis. Photon-induced oxidation of a broad series of carboxylic acids, including hydrocarbon-substituted, α-oxy, and α-amino acids, provides a versatile CO2-extrusion platform to generate Michael donors without the requirement for organometallic activation or propagation. A diverse array of Michael acceptors is amenable to this new conjugate addition strategy. An application of this technology to a three-step synthesis of the medicinal agent pregabalin (commercialized by Pfizer under the trade name Lyrica) is also presented. PMID:25032785

  8. Community genomic and proteomic analysis of chemoautotrophic, iron-oxidizing "Leptospirillum rubarum" (Group II) and Leptospirillum ferrodiazotrophum (Group III) in acid mine drainage biofilms

    SciTech Connect

    Goltsman, Daniela; Denef, Vincent; Singer, Steven; Verberkmoes, Nathan C; Lefsrud, Mark G; Mueller, Ryan; Dick, Gregory J.; Sun, Christine; Wheeler, Korin; Zelma, Adam; Baker, Brett J.; Hauser, Loren John; Land, Miriam L; Shah, Manesh B; Thelen, Michael P.; Hettich, Robert {Bob} L; Banfield, Jillian F.

    2009-01-01

    We analyzed near-complete population (composite) genomic sequences for coexisting acidophilic iron-oxidizing Leptospirillum Groups II and III bacteria (phylum Nitrospirae) and an extrachromosomal plasmid from a Richmond Mine, CA acid mine drainage (AMD) biofilm. Community proteomic analysis of the genomically characterized sample and two other biofilms identified 64.6% and 44.9% of the predicted proteins of Leptospirillum Groups II and III, respectively and 20% of the predicted plasmid proteins. The bacteria share 92% 16S rRNA gene sequence identity and > 60% of their genes, including integrated plasmid-like regions. The extrachromosomal plasmid encodes conjugation genes with detectable sequence similarity to genes in the integrated conjugative plasmid, but only those on the extrachromosomal element were identified by proteomics. Both bacteria have genes for community-essential functions, including carbon fixation, biosynthesis of vitamins, fatty acids and biopolymers (including cellulose); proteomic analyses reveal these activities. Both Leptospirillum types have multiple pathways for osmotic protection. Although both are motile, signal transduction and methyl-accepting chemotaxis proteins are more abundant in Leptospirillum Group III, consistent with its distribution in gradients within biofilms. Interestingly, Leptospirillum Group II uses a methyl-dependent and Leptospirillum Group III a methyl-independent response pathway. Although only Leptospirillum Group III can fix nitrogen, these proteins were not identified by proteomics. Abundances of core proteins are similar in all communities, but abundance levels of unique and shared proteins of unknown function vary. Some proteins unique to one organism were highly expressed and may be key to the functional and ecological differentiation of Leptospirillum Groups II and III.

  9. Formation of a Metal-to-Nitrogen Bond of Normal Length by a Neutral Sufonamide Group within a Tridentate Ligand. A New Approach to Radiopharmaceutical Bioconjugation

    PubMed Central

    Perera, Theshini; Abhayawardhana, Pramuditha; Marzilli, Patricia A.; Fronczek, Frank R.

    2014-01-01

    We demonstrate that a tertiary sulfonamide group, N(SO2R)R′2, can re-hybridize to form a M–N bond of normal length even when the group is in a linear tridentate ligand, such as in the new tridentate N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). N(SO2R)dpa ligands were used to prepare fac-[Re(CO)3(N(SO2R)dpa)](PF6 or BF4) complexes. Structural characterization of the new complexes established that the tertiary sulfonamide nitrogen atom binds to Re with concomitant sp2-to-sp3 re-hybridization, facilitating facial coordination. The new fac-[Re(CO)3(N(SO2R)dpa)]X structures provide the only examples for any metal with the sulfonamide as part of a noncyclic linear tridentate ligand and with a normal metal-to-nitrogen(tertiary sulfonamide) bond length. Rare previous examples of such normal M–N bonds have been found only in more constrained situations, such as with tripodal tetradentate ligands. Our long-term objectives for the new tridentate N(SO2R)dpa ligands are to develop the fundamental chemistry relevant to the eventual use of the fac-[MI(CO)3]+ core (M = 99mTc, 186/188Re) in imaging and therapy. The sulfonamide group uniquely contributes to two of our goals: expanding ways to conjugate the fac-[MI(CO)3]+ core to biological molecules and also developing new symmetrical tridentate ligands that can coordinate facially to this core. Tests of our conjugation method, conducted by linking the fac-[ReI(CO)3]+ core to a new tetraarylporphyrin (T(N(SO2C6H4)dpa)P) as well as to a dansyl (5-(dimethylamino)naphthalene-1-sulfonyl) group, demonstrate that large molecular fragments can be tethered via a coordinated tertiary sulfonamide linkage to this core. PMID:23421481

  10. Characterization of acid functional groups of carbon dots by nonlinear regression data fitting of potentiometric titration curves

    NASA Astrophysics Data System (ADS)

    Alves, Larissa A.; de Castro, Arthur H.; de Mendonça, Fernanda G.; de Mesquita, João P.

    2016-05-01

    The oxygenated functional groups present on the surface of carbon dots with an average size of 2.7 ± 0.5 nm were characterized by a variety of techniques. In particular, we discussed the fit data of potentiometric titration curves using a nonlinear regression method based on the Levenberg-Marquardt algorithm. The results obtained by statistical treatment of the titration curve data showed that the best fit was obtained considering the presence of five Brønsted-Lowry acids on the surface of the carbon dots with constant ionization characteristics of carboxylic acids, cyclic ester, phenolic and pyrone-like groups. The total number of oxygenated acid groups obtained was 5 mmol g-1, with approximately 65% (∼2.9 mmol g-1) originating from groups with pKa < 6. The methodology showed good reproducibility and stability with standard deviations below 5%. The nature of the groups was independent of small variations in experimental conditions, i.e. the mass of carbon dots titrated and initial concentration of HCl solution. Finally, we believe that the methodology used here, together with other characterization techniques, is a simple, fast and powerful tool to characterize the complex acid-base properties of these so interesting and intriguing nanoparticles.

  11. Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups.

    PubMed

    Tsai, Hui-Hsu Gavin; Chiu, Po-Jui; Jheng, Guang-Liang; Ting, Chun-Chiang; Pan, Yu-Chi; Kao, Hsien-Ming

    2011-07-01

    Well-ordered cubic mesoporous silicas SBA-1 functionalized with sulfonic acid groups have been synthesized through in situ oxidation of mercaptopropyl groups with H(2)O(2) via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strong acidic conditions. Various synthesis parameters such as the amounts of H(2)O(2) and MPTMS on the structural ordering of the resultant materials were systematically investigated. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), multinuclear solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, (29)Si{(1)H} 2D HETCOR (heteronuclear correlation) NMR spectroscopy, thermogravimetric analysis (TGA), and nitrogen sorption measurements. By using (13)C CPMAS NMR technique, the status of the incorporated thiol groups and their transformation to sulfonic acid groups can be monitored and, as an extension, to define the optimum conditions to be used for the oxidation reaction to be quantitative. In particular, (29)Si{(1)H} 2D HETCOR NMR revealed that the protons in sulfonic acid groups are in close proximity to the silanol Q(3) species, but not close enough to form a hydrogen bond.

  12. Iron binding efficiency of polyphenols: Comparison of effect of ascorbic acid and ethylenediaminetetraacetic acid on catechol and galloyl groups.

    PubMed

    Tamilmani, Poonkodi; Pandey, Mohan Chandra

    2016-04-15

    Dietary polyphenols are markedly studied for their antioxidant activity. They also have a negative impact on nutrition whereby they interfere with iron absorption. Common dietary polyphenols include: catechins, flavonols, flavanols, flavones, anthocyanins, proanthocyanidins and phenolic acids. Ascorbic acid (AA) and Ethylenediaminetetraacetic acid (EDTA) are commonly used to counter act this reaction and increase iron bioavailability. This study was aimed at determining the effect of AA and EDTA on the catechol or galloyl iron binding ability of pure phenolics, coffee and tea. Phenolic concentrations of 40, 80, 610, 240, 320, 400, 520 and 900 μg/ml were tested against six levels of AA and EDTA. These effects were studied in detail using Multivariate Analysis of Variance (MANOVA) with the hypothesis that there would be one or more mean differences between the ratio of enhancer and the different concentrations of samples tested. AA was found to be more efficient than EDTA in a way that lesser quantity is required for completely overcoming negative iron binding effects of polyphenols and similar samples.

  13. Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation

    NASA Astrophysics Data System (ADS)

    Brown, Robert; Stuart, Scott S.; Houel, Stephane; Ahn, Natalie G.; Old, William M.

    2015-07-01

    Collision-induced dissociation (CID) remains the predominant mass spectrometry-based method for identifying phosphorylation sites in complex mixtures. Unfortunately, the gas-phase reactivity of phosphoester bonds results in MS/MS spectra dominated by phosphoric acid (H3PO4) neutral loss events, suppressing informative peptide backbone cleavages. To understand the major drivers of H3PO4 neutral loss, we performed robust nonparametric statistical analysis of local and distal sequence effects on the magnitude and variability of neutral loss, using a collection of over 35,000 unique phosphopeptide MS/MS spectra. In contrast to peptide amide dissociation pathways, which are strongly influenced by adjacent amino acid side chains, we find that neutral loss of H3PO4 is affected by both proximal and distal sites, most notably basic residues and the peptide N-terminal primary amine. Previous studies have suggested that protonated basic residues catalyze neutral loss through direct interactions with the phosphate. In contrast, we find that nearby basic groups decrease neutral loss regardless of mobility class, an effect only seen by stratifying spectra by charge-mobility. The most inhibitory bases are those immediately N-terminal to the phosphate, presumably because of steric hindrances in catalyzing neutral loss. Further evidence of steric effects is shown by the presence of proline, which can dramatically reduce the presence of neutral loss when between the phosphate and a possible charge donor. In mobile proton spectra, the N-terminus is the strongest predictor of high neutral loss, with proximity to the N-terminus essential for peptides to exhibit the highest levels of neutral loss.

  14. Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation.

    PubMed

    Brown, Robert; Stuart, Scott A; Stuart, Scott S; Houel, Stephane; Ahn, Natalie G; Old, William M

    2015-07-01

    Collision-induced dissociation (CID) remains the predominant mass spectrometry-based method for identifying phosphorylation sites in complex mixtures. Unfortunately, the gas-phase reactivity of phosphoester bonds results in MS/MS spectra dominated by phosphoric acid (H3PO4) neutral loss events, suppressing informative peptide backbone cleavages. To understand the major drivers of H3PO4 neutral loss, we performed robust nonparametric statistical analysis of local and distal sequence effects on the magnitude and variability of neutral loss, using a collection of over 35,000 unique phosphopeptide MS/MS spectra. In contrast to peptide amide dissociation pathways, which are strongly influenced by adjacent amino acid side chains, we find that neutral loss of H3PO4 is affected by both proximal and distal sites, most notably basic residues and the peptide N-terminal primary amine. Previous studies have suggested that protonated basic residues catalyze neutral loss through direct interactions with the phosphate. In contrast, we find that nearby basic groups decrease neutral loss regardless of mobility class, an effect only seen by stratifying spectra by charge-mobility. The most inhibitory bases are those immediately N-terminal to the phosphate, presumably because of steric hindrances in catalyzing neutral loss. Further evidence of steric effects is shown by the presence of proline, which can dramatically reduce the presence of neutral loss when between the phosphate and a possible charge donor. In mobile proton spectra, the N-terminus is the strongest predictor of high neutral loss, with proximity to the N-terminus essential for peptides to exhibit the highest levels of neutral loss.

  15. Large-Scale Examination of Factors Influencing Phosphopeptide Neutral Loss during Collision Induced Dissociation

    PubMed Central

    Brown, Robert; Stuart, Scott A.; Houel, Stephane; Ahn, Natalie G.; Old, William M.

    2015-01-01

    Collision-induced dissociation (CID) remains the predominant mass spectrometry based method for identifying phosphorylation sites in complex mixtures. Unfortunately, the gas-phase reactivity of phosphoester bonds results in MS/MS spectra dominated by phosphoric acid (H3PO4) neutral loss events, suppressing informative peptide backbone cleavages. To understand the major drivers of H3PO4 neutral loss, we performed robust non-parametric statistical analysis of local and distal sequence effects on the magnitude and variability of neutral loss, using a collection of over 35,000 unique phosphopeptide MS/MS spectra. In contrast to peptide amide dissociation pathways, which are strongly influenced by adjacent amino acid side chains, we find that neutral loss of H3PO4 is affected by both proximal and distal sites, most notably basic residues and the peptide N-terminal primary amine. Previous studies have suggested that protonated basic residues catalyze neutral loss through direct interactions with the phosphate. In contrast, we find that nearby basic groups decrease neutral loss regardless of mobility class, an effect only seen by stratifying spectra by charge-mobility. The most inhibitory bases are those immediately N-terminal to the phosphate, presumably due to steric hindrances in catalyzing neutral loss. Further evidence of steric effects is shown by the presence of proline which can dramatically reduce the presence of neutral loss when between the phosphate and a possible charge donor. In mobile proton spectra the N-terminus is the strongest predictor of high neutral loss, with proximity to the N-terminus essential for peptides to exhibit the highest levels of neutral loss. PMID:25851653

  16. Remediation of grey forest soils heavily polluted with heavy metals by means of their leaching at acidic pH followed by the soil reclamation by means of neutralization and bacterial manure addition

    NASA Astrophysics Data System (ADS)

    Georgiev, Plamen; Groudev, Stoyan; Spasova, Irena; Nicolova, Marina

    2014-05-01

    Some grey forest soils in Western Bulgaria are heavily polluted with heavy metals (copper, lead, and zinc), arsenic, and uranium due to the infiltration of acid mine drainage generated at the abandoned uranium mine Curilo. This paper presents some results from a study about soil remediation based on the contaminants leaching from the topsoil by means of irrigation with solutions containing sulphuric acid or its in situ generation by means of sulphur-oxidizing chemolithotrophic bacteria in or without the presence of finely cut straw. These methods were tested in large scale zero suction lysimeters. The approaches based on S° and finely cut straw addition was the most efficient amongst the tested methods and for seven months of soil remediation the concentration of all soil contaminants were decreased below the relevant Maximum Admissible Concentration (MAC). Neutralization of the soil acidity was applied as a next stage of soil reclamation by adding CaCO3 and cow manure. As a result, soil pH increased from strongly acidic (2.36) to slightly acidic (6.15) which allowed subsequent addition of humic acids and bacterial manure to the topsoil. The soil habitat changed in this way facilitated the growth of microorganisms which restored the biogeochemical cycles of nitrogen and carbon to the levels typical for non-polluted grey forest soil.

  17. Evidence for size and charge permselectivity of rat ascending colon. Effects of ricinoleate and bile salts on oxalic acid and neutral sugar transport.

    PubMed Central

    Kathpalia, S C; Favus, M J; Coe, F L

    1984-01-01

    We have measured unidirectional transmural fluxes of oxalate and neutral sugars across rat ascending colon in vitro, under short-circuit conditions, to characterize permeability barriers selective for size and charge. Ionic oxalate appears to be transported preferentially to sodium oxalate. Mucosal addition of taurocholate (1 mM), deoxycholate (1 mM), or ricinoleate (1 mM) increased bidirectional oxalate fluxes, and the ricinoleate effects were independent of medium calcium. Bidirectional fluxes of uncharged sugar molecules fell sharply at molecular weights above 76 (molecular radius above 3 A), and oxalate transport was retarded relative to that of uncharged molecules of similar size, suggesting that there is both size and charge permselectivity. Ricinoleate increased fluxes of all neutral molecules tested but changed neither the exclusion limits nor the cation selectivity of the epithelium. Bile salts and ricinoleate increase oxalate transport, probably by making more channels available, but do not alter size and charge selectivity. PMID:6432849

  18. Augmentation of the Lipopolysaccharide-Neutralizing Activities of Human Cathelicidin CAP18/LL-37-Derived Antimicrobial Peptides by Replacement with Hydrophobic and Cationic Amino Acid Residues

    PubMed Central

    Nagaoka, Isao; Hirota, Satoko; Niyonsaba, François; Hirata, Michimasa; Adachi, Yoshiyuki; Tamura, Hiroshi; Tanaka, Shigenori; Heumann, Didier

    2002-01-01

    Mammalian myeloid and epithelial cells express various peptide antibiotics (such as defensins and cathelicidins) that contribute to the innate host defense against invading microorganisms. Among these peptides, human cathelicidin CAP18/LL-37 (L1 to S37) possesses not only potent antibacterial activity against gram-positive and gram-negative bacteria but also the ability to bind to gram-negative lipopolysaccharide (LPS) and neutralize its biological activities. In this study, to develop peptide derivatives with improved LPS-neutralizing activities, we utilized an 18-mer peptide (K15 to V32) of LL-37 as a template and evaluated the activities of modified peptides by using the CD14+ murine macrophage cell line RAW 264.7 and the murine endotoxin shock model. By replacement of E16 and K25 with two L residues, the hydrophobicity of the peptide (18-mer LL) was increased, and by further replacement of Q22, D26, and N30 with three K residues, the cationicity of the peptide (18-mer LLKKK) was enhanced. Among peptide derivatives, 18-mer LLKKK displayed the most powerful LPS-neutralizing activity: it was most potent at binding to LPS, inhibiting the interaction between LPS and LPS-binding protein, and attaching to the CD14 molecule, thereby suppressing the binding of LPS to CD14+ cells and attenuating production of tumor necrosis factor alpha (TNF-α) by these cells. Furthermore, in the murine endotoxin shock model, 18-mer LLKKK most effectively suppressed LPS-induced TNF-α production and protected mice from lethal endotoxin shock. Together, these observations indicate that the LPS-neutralizing activities of the amphipathic human CAP18/LL-37-derived 18-mer peptide can be augmented by modifying its hydrophobicity and cationicity, and that 18-mer LLKKK is the most potent of the peptide derivatives, with therapeutic potential for gram-negative bacterial endotoxin shock. PMID:12204946

  19. Extruded linseed and rapeseed both influenced fatty acid composition of total lipids and their polar and neutral fractions in longissimus thoracis and semitendinosus muscles of finishing Normand cows.

    PubMed

    Habeanu, Mihaela; Thomas, Agnès; Bispo, Esperanza; Gobert, Mylène; Gruffat, Dominique; Durand, Denys; Bauchart, Dominique

    2014-01-01

    The effects of extruded linseed and rapeseed on lipids and FA composition of total, polar and neutral lipids of longissimus thoracis (LT) and semitendinosus (ST) muscles were investigated in 21 Normand cull cows. Animals were assigned in a 100 d finishing period to straw (30%) and concentrate (70%) based (C) or the same diet supplemented with linseed (L) or with rapeseed (66%) plus linseed (33%) (RL). Beef polar and neutral lipids were purified by liquid chromatography and their FA analysed by GLC. Trans and cis 18:1, purified by HPLC from total FA methyl esters, were analysed by GLC-MS. L and LR diets did not increase beef lipid deposition, but had modified FA composition of both LT and ST muscles in favouring deposition of 18:3n-3 and 9cis,11tr 18:2 (CLA), mainly to the detriment of 18:1∆9 cis (neutral lipids) and 18:2n-6 (polar lipids). However, they did not favour deposition of LC n-3 PUFA in the two muscles, but had increased deposition of trans 18:1 significantly, especially of ∆13tr to ∆16tr isoforms to the detriment of ∆10tr 18:1 (L diet) and of ∆11tr 18:1 (RL diet).

  20. Inhibition of Human Group IIA-Secreted Phospholipase A2 and THP-1 Monocyte Recruitment by Maslinic Acid.

    PubMed

    Yap, Wei Hsum; Ahmed, Nafees; Lim, Yang Mooi

    2016-10-01

    Maslinic acid is a natural pentacyclic triterpenoid which has anti-inflammatory properties. A recent study showed that secretory phospholipase A2 (sPLA2) may be a potential binding target of maslinic acid. The human group IIA (hGIIA)-sPLA2 is found in human sera and their levels are correlated with severity of inflammation. This study aims to determine whether maslinic acid interacts with hGIIA-sPLA2 and inhibits inflammatory response induced by this enzyme. It is shown that maslinic acid enhanced intrinsic fluorescence of hGIIA-sPLA2 and inhibited its enzyme activity in a concentration-dependent manner. Molecular docking revealed that maslinic acid binds to calcium binding and interfacial phospholipid binding site, suggesting that it inhibit access of catalytic calcium ion for enzymatic reaction and block binding of the enzyme to membrane phospholipid. The hGIIA-sPLA2 enzyme is also responsible in mediating monocyte recruitment and differentiation. Results showed that maslinic acid inhibit hGIIA-sPLA2-induced THP-1 cell differentiation and migration, and the effect observed is specific to hGIIA-sPLA2 as cells treated with maslinic acid alone did not significantly affect the number of adherent and migrated cells. Considering that hGIIA-sPLA2 enzyme is known to hydrolyze glyceroacylphospholipids present in lipoproteins and cell membranes, maslinic acid may bind and inhibit hGIIA-sPLA2 enzymatic activity, thereby reduces the release of fatty acids and lysophospholipids which stimulates monocyte migration and differentiation. This study is the first to report on the molecular interaction between maslinic acid and inflammatory target hGIIA-sPLA2 as well as its effect towards hGIIA-sPLA2-induced THP-1 monocyte adhesive and migratory capabilities, an important immune-inflammation process in atherosclerosis.

  1. Thiomers: Influence of molecular mass and thiol group content of poly(acrylic acid) on efflux pump inhibition.

    PubMed

    Grabovac, Vjera; Laffleur, Flavia; Bernkop-Schnürch, Andreas

    2015-09-30

    The aim of the present study was to investigate the influence of molecular mass and thiol group content of poly(acrylic acid)-cysteine conjugates on the permeation of sulforhodamine 101 and penicillin G. acting as substrates for multidrug resistance-associated protein 2 efflux pump. Poly(acrylic acids) of 2 kDa, 100 kDa, 250 kDa, 450 kDa and 3000 kDa were conjugated with cysteine. The thiol group content of all these polymers was in the range from 343.3 ± 48.4 μmol/g to 450.3 ± 76.1 μmol/g. Transport studies were performed on rat small intestine mounted in Ussing-type chambers. Since 250 kDa poly(acrylic acid) showed the highest permeation enhancing effect, additionally thiolated 250 kDa polyacrylates displaying 157.2 μmol/g, 223.0 ± 18.1 and 355.9 μmol/g thiol groups were synthesized in order to investigate the influence of thiol group content on the permeation enhancement. The permeation of sulforhodamine was 3.93- and 3.85-fold improved using 250 kDa poly(acrylic acid)-cysteine conjugate exhibiting 355.9 ± 39.5 μmol/g and 223.0 ± 18.1 μmol/g thiol groups. Using the same conjugates the permeation of penicillin G was 1.70- and 1.59-fold improved, respectively. The study demonstrates that thiolated poly(acrylic acid) inhibits Mrp2 mediated transport and that the extent of inhibition depends on the molecular mass and degree of thiolation of the polymer. PMID:26238816

  2. Thiomers: Influence of molecular mass and thiol group content of poly(acrylic acid) on efflux pump inhibition.

    PubMed

    Grabovac, Vjera; Laffleur, Flavia; Bernkop-Schnürch, Andreas

    2015-09-30

    The aim of the present study was to investigate the influence of molecular mass and thiol group content of poly(acrylic acid)-cysteine conjugates on the permeation of sulforhodamine 101 and penicillin G. acting as substrates for multidrug resistance-associated protein 2 efflux pump. Poly(acrylic acids) of 2 kDa, 100 kDa, 250 kDa, 450 kDa and 3000 kDa were conjugated with cysteine. The thiol group content of all these polymers was in the range from 343.3 ± 48.4 μmol/g to 450.3 ± 76.1 μmol/g. Transport studies were performed on rat small intestine mounted in Ussing-type chambers. Since 250 kDa poly(acrylic acid) showed the highest permeation enhancing effect, additionally thiolated 250 kDa polyacrylates displaying 157.2 μmol/g, 223.0 ± 18.1 and 355.9 μmol/g thiol groups were synthesized in order to investigate the influence of thiol group content on the permeation enhancement. The permeation of sulforhodamine was 3.93- and 3.85-fold improved using 250 kDa poly(acrylic acid)-cysteine conjugate exhibiting 355.9 ± 39.5 μmol/g and 223.0 ± 18.1 μmol/g thiol groups. Using the same conjugates the permeation of penicillin G was 1.70- and 1.59-fold improved, respectively. The study demonstrates that thiolated poly(acrylic acid) inhibits Mrp2 mediated transport and that the extent of inhibition depends on the molecular mass and degree of thiolation of the polymer.

  3. Pristine environments harbor a new group of oligotrophic 2,4-dichlorophenoxyacetic acid-degrading bacteria.

    PubMed Central

    Kamagata, Y; Fulthorpe, R R; Tamura, K; Takami, H; Forney, L J; Tiedje, J M

    1997-01-01

    2,4-Dichlorophenoxyacetic acid (2,4-D)-degrading bacteria were isolated from pristine environments which had no history of 2,4-D exposure. By using 2,4-D dye indicator medium or 14C-labeled 2,4-D medium, six strains were isolated from eight enrichment cultures capable of degrading 2,4-D. Phylogenetic analyses based on 16S ribosomal DNA (rDNA) sequencing and physiological properties revealed that one isolate from Hawaiian volcanic soil could be classified in the genus Variovorax (a member of the beta subdivision of the class Proteobacteria) and that the other five isolates from Hawaiian volcanic soils, Saskatchewan forest soil, and Chilean forest soil have 16S rDNAs with high degrees of similarity to those of the Bradyrhizobium group (a member of the alpha subdivision of the class Proteobacteria). All the isolates grow slowly on either nutrient media (0.1 x Bacto Peptone-tryptone-yeast extract-glucose [PTYG] or 0.1 x Luria broth [LB] medium) or 2,4-D medium, with mean generation times of 16 to 30 h, which are significantly slower than previously known 2,4-D degraders. Nutrient-rich media such as full-strength PTYG and LB medium did not allow their growth. PCR amplification using internal consensus sequences of tfdA (a gene encoding an enzyme for the first step of 2,4-D mineralization, found in pJP4 of Alcaligenes eutrophus JMP134 and some other 2,4-D-degrading bacteria) as primers and Southern hybridization with pJP4-tfdA as a probe revealed that the isolate belonging to the genus Variovorax carried the tfdA gene. This gene was transmissible to A. eutrophus JMP228 carrying a plasmid with a mutant tfdA gene. The other five isolates did not appear to carry tfdA, and 2,4-D-specific alpha-ketoglutarate-dependent dioxygenase activity could not be detected in cell lysates. These results indicate that 2,4-D-degrading bacteria in pristine environments are slow-growing bacteria and that most of their phylogenies and catabolic genes differ from those of 2,4-D degraders

  4. 5'to 3' nucleic acid synthesis using 3'-photoremovable protecting group

    DOEpatents

    Pirrung, Michael C.; Shuey, Steven W.; Bradley, Jean-Claude

    1999-01-01

    The present invention relates, in general, to a method of synthesizing a nucleic acid, and, in particular, to a method of effecting 5' to 3' nucleic acid synthesis. The method can be used to prepare arrays of oligomers bound to a support via their 5' end. The invention also relates to a method of effecting mutation analysis using such arrays. The invention further relates to compounds and compositions suitable for use in such methods.

  5. 5[prime] to 3[prime] nucleic acid synthesis using 3[prime]-photoremovable protecting group

    DOEpatents

    Pirrung, M.C.; Shuey, S.W.; Bradley, J.C.

    1999-06-01

    The present invention relates, in general, to a method of synthesizing a nucleic acid, and, in particular, to a method of effecting 5[prime] to 3[prime] nucleic acid synthesis. The method can be used to prepare arrays of oligomers bound to a support via their 5[prime] end. The invention also relates to a method of effecting mutation analysis using such arrays. The invention further relates to compounds and compositions suitable for use in such methods.

  6. NMR contour maps as a new parameter of carboxyl's OH groups in amino acids recognition: A reason of tRNA-amino acid conjugation

    NASA Astrophysics Data System (ADS)

    Monajjemi, Majid; Wayne, Robert; Boggs, James E.

    2014-03-01

    In this work, we have applied a statistical method by computing statistical nucleus-independent chemical shifts (SNICS) in point of probes motions within a spatial shielding and de-shielding spaces around the OH groups of some amino acids. NMR contour maps as a new parameter have been created for amino-acyl-tRNA conjugation, by using a computational method to identify this model theoretically, it is critical to understand the reasons for tRNA-amino acid conjugation. DFT, NMR, 3D Gaussian distribution and Monte Carlo methods have been applied for Methionine, Serine, Histidine, Glycine and Glutamine to investigate the structural stability in the active parts of the amino acid-tRNA linkage by chemical shielding effects.

  7. Acetic acid bacteria: A group of bacteria with versatile biotechnological applications.

    PubMed

    Saichana, Natsaran; Matsushita, Kazunobu; Adachi, Osao; Frébort, Ivo; Frebortova, Jitka

    2015-11-01

    Acetic acid bacteria are gram-negative obligate aerobic bacteria assigned to the family Acetobacteraceae of Alphaproteobacteria. They are members of the genera Acetobacter, Gluconobacter, Gluconacetobacter, Acidomonas, Asaia, Kozakia, Swaminathania, Saccharibacter, Neoasaia, Granulibacter, Tanticharoenia, Ameyamaea, Neokomagataea, and Komagataeibacter. Many strains of Acetobacter and Komagataeibacter have been known to possess high acetic acid fermentation ability as well as the acetic acid and ethanol resistance, which are considered to be useful features for industrial production of acetic acid and vinegar, the commercial product. On the other hand, Gluconobacter strains have the ability to perform oxidative fermentation of various sugars, sugar alcohols, and sugar acids leading to the formation of several valuable products. Thermotolerant strains of acetic acid bacteria were isolated in order to serve as the new strains of choice for industrial fermentations, in which the cooling costs for maintaining optimum growth and production temperature in the fermentation vessels could be significantly reduced. Genetic modifications by adaptation and genetic engineering were also applied to improve their properties, such as productivity and heat resistance.

  8. Acetic acid bacteria: A group of bacteria with versatile biotechnological applications.

    PubMed

    Saichana, Natsaran; Matsushita, Kazunobu; Adachi, Osao; Frébort, Ivo; Frebortova, Jitka

    2015-11-01

    Acetic acid bacteria are gram-negative obligate aerobic bacteria assigned to the family Acetobacteraceae of Alphaproteobacteria. They are members of the genera Acetobacter, Gluconobacter, Gluconacetobacter, Acidomonas, Asaia, Kozakia, Swaminathania, Saccharibacter, Neoasaia, Granulibacter, Tanticharoenia, Ameyamaea, Neokomagataea, and Komagataeibacter. Many strains of Acetobacter and Komagataeibacter have been known to possess high acetic acid fermentation ability as well as the acetic acid and ethanol resistance, which are considered to be useful features for industrial production of acetic acid and vinegar, the commercial product. On the other hand, Gluconobacter strains have the ability to perform oxidative fermentation of various sugars, sugar alcohols, and sugar acids leading to the formation of several valuable products. Thermotolerant strains of acetic acid bacteria were isolated in order to serve as the new strains of choice for industrial fermentations, in which the cooling costs for maintaining optimum growth and production temperature in the fermentation vessels could be significantly reduced. Genetic modifications by adaptation and genetic engineering were also applied to improve their properties, such as productivity and heat resistance. PMID:25485864

  9. Protein structure and neutral theory of evolution.

    PubMed

    Ptitsyn, O B; Volkenstein, M V

    1986-08-01

    The neutral theory of evolution is extended to the origin of protein molecules. Arguments are presented which suggest that the amino acid sequences of many globular proteins mainly represent "memorized" random sequences while biological evolution reduces to the "editing" these random sequences. Physical requirements for a functional globular protein are formulated and it is shown that many of these requirement do not involve strategical selection of amino acid sequences during biological evolution but are inherent also for typical random sequences. In particular, it is shown that random sequences of polar and amino acid residues can form alpha-helices and beta-strand with lengths and arrangement along the chain similar to those in real globular proteins. These alpha- and beta-regions in random sequences can form three-dimensional folding patterns also similar to those in proteins. The arguments are presented suggesting that even the tight packing of side groups inside protein core do not require very strong biological selection of amino acid sequences either. Thus many structural features of real proteins can exist also in random sequences and the biological selection is needed mainly for the creation of active site of protein and for their stability under physiological conditions.

  10. The Effect of Methyl, Hydroxyl, and Ketone Functional Groups on the Heterogeneous Oxidation of Succinic Acid Aerosol by OH Radicals

    NASA Astrophysics Data System (ADS)

    Chan, M.; Zhang, H.; Wilson, K. R.

    2013-12-01

    The heterogeneous oxidation of atmospheric organic aerosols can influence their effects on climate, human health, and visibility. During oxidation, functionalization occurs when an oxygenated functional group is added to a molecule, leaving the carbon skeleton intact. Fragmentation involves carbon-carbon bond cleavage and produces two products with smaller carbon numbers than the parent compound. To gain better insights into how the molecular structure of more oxygenated organic compounds affects heterogeneous reactivity, succinic acid aerosols are photo-oxidized in an aerosol flow tube reactor, and the reaction products are analyzed using Direct Analysis in Real Time Mass Spectrometry for online chemical analysis. The effect of various functional groups (CH3, OH, C=O) along the carbon backbone on the heterogeneous reaction mechanisms are also investigated using model compounds. For this series of compounds, the formation of more oxygenated products through functionalization can be explained by well-known condensation-phase reactions such as Russell and Bennett and Summers. The number of fragmentation products is found to increase with the presence of OH and CH3 groups. This can be attributed to the increased number of tertiary carbons, enhancing the fragmentation after multiple oxidation steps. Smaller dicaids (oxalic acid and malonic acid) can be formed through the fragmentation processes in the heterogeneous oxidation of succinic acid. The effect of molecular structure on reaction kinetics, volatilization, and the relative importance of functionalization and fragmentation pathways will be discussed.

  11. Neutral penta- and hexacoordinate silicon(IV) complexes containing two bidentate ligands derived from the alpha-amino acids (S)-alanine, (S)-phenylalanine, and (S)-tert-leucine.

    PubMed

    Cota, Smaranda; Beyer, Matthias; Bertermann, Rüdiger; Burschka, Christian; Götz, Kathrin; Kaupp, Martin; Tacke, Reinhold

    2010-06-11

    The neutral hexacoordinate silicon(IV) complex 6 (SiO(2)N(4) skeleton) and the neutral pentacoordinate silicon(IV) complexes 7-11 (SiO(2)N(2)C skeletons) were synthesized from Si(NCO)(4) and RSi(NCO)(3) (R = Me, Ph), respectively. The compounds were structurally characterized by solid-state NMR spectroscopy (6-11), solution NMR spectroscopy (6 and 10), and single-crystal X-ray diffraction (8 and 11 were studied as the solvates 8 x CH(3)CN and 11 x C(5)H(12) x 0.5 CH(3)CN, respectively). The silicon(IV) complexes 6 (octahedral Si-coordination polyhedron) and 7-11 (trigonal-bipyramidal Si-coordination polyhedra) each contain two bidentate ligands derived from an alpha-amino acid: (S)-alanine, (S)-phenylalanine, or (S)-tert-leucine. The deprotonated amino acids act as monoanionic (6) or as mono- and dianionic ligands (7-11). The experimental investigations were complemented by computational studies of the stereoisomers of 6 and 7.

  12. The relationship between gene expression of cationic and neutral amino acid transporters in the small intestine of chick embryos and chick breed, development, sex, and egg amino acid concentration.

    PubMed

    Zeng, P L; Li, X G; Wang, X Q; Zhang, D X; Shu, G; Luo, Q B

    2011-11-01

    This study was conducted to investigate the gene expression of cationic and neutral amino acid (AA) transporters in the small intestine of chick embryos with different genetic backgrounds [Wenshi Yellow-Feathered chick (WYFC) and White Recessive Rock chick (WRRC)]. The study also investigated the correlation between the abundance of AA transporter mRNA and the AA content of fertilized eggs. Intestinal samples were collected on embryonic d 9, 12, 14, 17, and 19 and the day of hatch. The results showed that, before incubation, the AA content of WRRC eggs was lower (P < 0.05) than the AA content of WYFC eggs. In WYFC, the mRNA abundance of CAT-1 [solute carrier (SLC) family 7 member 1], CAT-4 (SLC family 7 member 4), rBAT (SLC family 3 member 1), y(+)LAT-1 (SLC family 7 member 7), y(+)LAT-2 (SLC family 7 member 6), LAT-4 (SLC family 43 member 2), and SNAT-2 (SLC family 38 member 2), as detected by real-time reverse transcriptase PCR, was greater (P < 0.05) than the mRNA abundance detected in the WRRC samples. The mRNA abundance of all measured AA transporters was affected (P < 0.05) by embryonic age. Sex had the largest effect (P < 0.05) on the mRNA expression of CAT-1, CAT-4, y(+)LAT-2, and LAT-4 in WYFC and on CAT-4 and B(0)AT-1 (SLC family 6 member 19) mRNA expression in WRRC. In WYFC, only CAT-1 mRNA expression was negatively correlated (r = -0.68 to -0.84, P < 0.05) with all AA content. However, few correlations were detected between AA content and the mRNA expression of multiple transporters in WRRC. These findings provide a comprehensive profile of the temporal and spatial mRNA expression of AA transporters in the small intestine of chick embryos. Few correlations were detected between the AA content of the eggs and mRNA expression of specific AA transporters in the small intestine.

  13. Neutral and Non-Neutral Evolution of Drosophila Mitochondrial DNA

    PubMed Central

    Rand, D. M.; Dorfsman, M.; Kann, L. M.

    1994-01-01

    To test hypotheses of neutral evolution of mitochondrial DNA (mtDNA), nucleotide sequences were determined for 1515 base pairs of the NADH dehydrogenase subunit 5 (ND5) gene in the mitochondrial DNA of 29 lines of Drosophila melanogaster and 9 lines of its sibling species Drosophila simulans. In contrast to the patterns for nuclear genes, where D. melanogaster generally exhibits much less nucleotide polymorphism, the number of segregating sites was slightly higher in a global sample of nine ND5 sequences in D. melanogaster (s = 8) than in the nine lines of D. simulans (s = 6). When compared to variation at nuclear loci, the mtDNA variation in D. melanogaster does not depart from neutral expectations. The ND5 sequences in D. simulans, however, show fewer than half the number of variable sites expected under neutrality when compared to sequences from the period locus. While this reduction in variation is not significant at the 5% level, HKA tests with published restriction data for mtDNA in D. simulans do show a significant reduction of variation suggesting a selective sweep of variation in the mtDNA in this species. Tests of neutral evolution based on the ratios of synonymous and replacement polymorphism and divergence are generally consistent with neutral expectations, although a significant excess of amino acid polymorphism within both species is localized in one region of the protein. The rate of mtDNA evolution has been faster in D. melanogaster than in D. simulans and the population structure of mtDNA is distinct in these species. The data reveal how different rates of mtDNA evolution between species and different histories of neutral and adaptive evolution within species can compromise historical inferences in population and evolutionary biology. PMID:7851771

  14. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. II. The relationship between the coordination state of solvent molecules and concerted versus sequential acid dissociation.

    PubMed

    Maurer, Patrick; Thomas, Vibin; Iftimie, Radu

    2011-03-01

    We investigate the role played by the coordination state of pre-existing water wires during the dissociation of moderately strong acids by means of first-principles molecular dynamics calculations. By preparing 2,4,6-tricyanophenol (calc. pKa∼0.5) in two different initial states, we are able to observe sequential as well as concerted trajectories of dissociation: On one hand, equilibrium dissociation takes place on a ∼50 ps timescale; proton conduction occurs through three-coordinated water wires in this case, by means of sequential Grotthus hopping. On the other hand, by preparing 2,4,6-tricyanophenol in a hydration state inherited from that of equilibrated phenol (calc. pKa=7.6), the moderately strong acid finds itself in a presolvated state from which dissociation can take place on a ∼1 ps timescale. In this case, concerted dissociation trajectories are observed, which consist of proton translocation through two intervening, four-coordinated, water molecules in 0.1-1.0 ps. The present results suggest that, in general, the mechanism of proton translocation depends on how the excess proton is injected into a hydrogen bond network. In particular, if the initial conditions favour proton release to a fourfold H-bonded water molecule, proton translocation by as much as 6-8 Å can take place on a sub-picosecond timescale.

  15. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. II. The relationship between the coordination state of solvent molecules and concerted versus sequential acid dissociation

    NASA Astrophysics Data System (ADS)

    Maurer, Patrick; Thomas, Vibin; Iftimie, Radu

    2011-03-01

    We investigate the role played by the coordination state of pre-existing water wires during the dissociation of moderately strong acids by means of first-principles molecular dynamics calculations. By preparing 2,4,6-tricyanophenol (calc. pKa˜0.5) in two different initial states, we are able to observe sequential as well as concerted trajectories of dissociation: On one hand, equilibrium dissociation takes place on a ˜50 ps timescale; proton conduction occurs through three-coordinated water wires in this case, by means of sequential Grotthus hopping. On the other hand, by preparing 2,4,6-tricyanophenol in a hydration state inherited from that of equilibrated phenol (calc. pKa = 7.6), the moderately strong acid finds itself in a presolvated state from which dissociation can take place on a ˜1 ps timescale. In this case, concerted dissociation trajectories are observed, which consist of proton translocation through two intervening, four-coordinated, water molecules in 0.1-1.0 ps. The present results suggest that, in general, the mechanism of proton translocation depends on how the excess proton is injected into a hydrogen bond network. In particular, if the initial conditions favour proton release to a fourfold H-bonded water molecule, proton translocation by as much as 6-8 Å can take place on a sub-picosecond timescale.

  16. Biological neutralization and biosorption of dyes of alkaline textile industry wastewater.

    PubMed

    Jain, Rakeshkumar M; Mody, Kalpana H; Keshri, Jitendra; Jha, Bhavanath

    2014-07-15

    The present work was aimed to secure biological neutralization and biosorption of dyes of an alkaline textile industrial effluent (ATIE) using an alkaliphilic bacterium, Enterococcus faecalis strain R-16 isolated from Gujarat coast. The isolate was capable and competent to bring down the pH of ATIE from 12.1 to 7.0 within 2 h in the presence of carbon and nitrogen sources. Carboxylic group concentration (CGC), NMR and FT-IR analysis revealed production of carboxylic acid as a result of neutralization. The unconventional carbon and nitrogen sources like Madhuca indica flowers or sugar cane bagasse supported the growth of bacterium with effective neutralization and biosorption of dyes from ATIE. The process proved to be efficient, inexpensive and eco-friendly as compared to conventional chemical neutralization process.

  17. Theoretical and Electrochemical Study of the Quinone-Benzoic Acid Adduct Linked by Hydrogen Bonds DFT Study of Electronic Structure and Geometry of Neutral and Anionic Silver Clusters

    SciTech Connect

    Matulis, Vitaly E.; Ivashkevich, Oleg A.; Gurin, Valerij

    2003-12-15

    A comparative analysis of bond lengths vertical detachment energies (VDE), excitation energies of neutral clusters with geometry of anions and vertical ionization potentials of neutral clusters calculated within density functional theory (DFT) using different functionals with both effective core potential (ECP) and all-electron basis sets for silver clusters Ag n, have been carried out. DFT methods provide a good agreement between calculated and experimental data of some characteristics. The accurate prediction of all characteristics simultaneously can be achieved with all-electron DZVP basis set only. A new functional has been developed. It provides results close to experimental data using the moderate basis set. For anionic clusters Ag2?10-, the difference between calculations with this functional and experimental values of VDE and for the most stable isomers does not exceed 0.1 eV. Based on both total energy calculations and comparison of experimental and calculated photoelectron spectra, the structural assignment of clusters Ag7-, Ag9- and Ag10- has been made. The electronic structure and geometrical characteristics of the low-lying isomers has been studied.

  18. Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces

    NASA Astrophysics Data System (ADS)

    Pershina, V.; Borschevsky, A.; Iliaš, M.; Türler, A.

    2014-08-01

    With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl4, MOCl2, MCl6-, and MOCl42 with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl4, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔHsub, of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔHsub(RfCl4) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl2 on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl4 on quartz by chemical forces, formation of the MOCl2 or MOCl42- complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl4 on a chlorinated quartz surface, formation of the MCl62- surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the "one-atom-at-a-time" gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

  19. Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

    SciTech Connect

    Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; Stack, Andrew G.; van Duin, Adri C. T.; Logan, Bruce E.

    2014-11-03

    We report that the amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10–5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g–1) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g–1) had a negative rise potential (₋31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to ₋6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. In conclusion, these results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.

  20. Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

    DOE PAGES

    Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; Stack, Andrew G.; van Duin, Adri C. T.; Logan, Bruce E.

    2014-11-03

    We report that the amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10–5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g–1) had a positive rise potential of 59 ± 4 mV in themore » LC solution, whereas the carbon with the highest concentration (0.36 mmol g–1) had a negative rise potential (₋31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to ₋6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. In conclusion, these results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.« less

  1. Effect of strong acid functional groups on electrode rise potential in capacitive mixing by double layer expansion.

    PubMed

    Hatzell, Marta C; Raju, Muralikrishna; Watson, Valerie J; Stack, Andrew G; van Duin, Adri C T; Logan, Bruce E

    2014-12-01

    The amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10(–5)) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g(–1)) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g(–1)) had a negative rise potential (−31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to −6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. These results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons. PMID:25365360

  2. Neutral beam monitoring

    DOEpatents

    Fink, Joel H.

    1981-08-18

    Method and apparatus for monitoring characteristics of a high energy neutral beam. A neutral beam is generated by passing accelerated ions through a walled cell containing a low energy neutral gas, such that charge exchange neutralizes the high energy ion beam. The neutral beam is monitored by detecting the current flowing through the cell wall produced by low energy ions which drift to the wall after the charge exchange. By segmenting the wall into radial and longitudinal segments various beam conditions are further identified.

  3. Metal-organic coordination architectures of azole heterocycle ligands bearing acetic acid groups: Synthesis, structure and magnetic properties

    SciTech Connect

    Hu Bowen; Zhao Jiongpeng; Yang Qian; Hu Tongliang; Du Wenping; Bu Xianhe

    2009-10-15

    Four new coordination complexes with azole heterocycle ligands bearing acetic acid groups, [Co(L{sup 1}){sub 2}]{sub n} (1), [CuL{sup 1}N{sub 3}]{sub n} (2), [Cu(L{sup 2}){sub 2}.0.5C{sub 2}H{sub 5}OH.H{sub 2}O]{sub n} (3) and [Co(L{sup 2}){sub 2}]{sub n} (4) (here, HL{sup 1}=1H-imidazole-1-yl-acetic acid, HL{sup 2}=1H-benzimidazole-1-yl-acetic acid) have been synthesized and structurally characterized. Single-crystal structure analysis shows that 3 and 4 are 2D complexes with 4{sup 4}-sql topologies, while another 2D complex 1 has a (4{sup 3}){sub 2}(4{sup 6})-kgd topology. And 2 is a 3D complex composed dinuclear mu{sub 1,1}-bridging azido Cu{sup II} entities with distorted rutile topology. The magnetic properties of 1 and 2 have been studied. - Graphical Abstract: The synthesis, crystal structure, and magnetic properties of the new coordination complexes with azole heterocycle ligands bearing acetic acid groups are reported.

  4. Sulphydryl groups and iodo-(/sup 3/H)acetic acid labeling in proteolipids from Torpedo electroplax

    SciTech Connect

    Criado, M.; Aguilar, J.S.; De Robertis, E.

    1983-05-01

    Several fractions of proteolipids from Torpedo electroplax were separated by DEAE-cellulose chromatography in organic solvents, and the sulphydryl groups were determined by a spectrophotometric method. On the same fractions the covalent labeling with iodo-(/sup 3/H)acetic acid to sulphydryl groups was studied. In total proteolipids there were 30.3 nmol/mg protein of sulphydryl groups of which 20.6 nmoles were in the form of disulfide bonds and 10.9 nmol as free--SH groups. The highest content of sulphydryl groups (36.7 nmol/mg protein) was found in fraction II; while fraction I, that binds the cholinergic ligands, has a lower content (23.7 nmol/mg protein). The 42 Kdaltons polypeptide, which is the major band in Fraction II, has the strongest labeling with iodo-(/sup 3/H)acetic acid, while the 39 Kdaltons cholinergic polypeptide shows a lower labeling. The importance of proteolipids as channel-forming macromolecules is discussed in connection with the possible significance of the 42 Kdaltons polypeptide.

  5. Effect of clavulanic acid on the activities of ten beta-lactam agents against members of the Bacteroides fragilis group.

    PubMed Central

    Lamothe, F; Auger, F; Lacroix, J M

    1984-01-01

    Clavulanic acid reduced the MICs of amoxicillin, carbencillin , cefamandole, cefotaxime, ceftazidime, ceftizoxime, cephalothin, and penicillin G, but not of cefoxitin or moxalactam, against 77 isolates of the Bacteroides fragilis group, all rapidly beta-lactamase positive by the nitrocefin slide test. It had no effect on the susceptibilities of eight Bacteroides distasonis strains that were slowly beta-lactamase positive (18 h of incubation). PMID:6732233

  6. Method of purifying neutral organophosphorus extractants

    DOEpatents

    Horwitz, E. Philip; Gatrone, Ralph C.; Chiarizia, Renato

    1988-01-01

    A method for removing acidic contaminants from neutral mono and bifunctional organophosphorous extractants by contacting the extractant with a macroporous cation exchange resin in the H.sup.+ state followed by contact with a macroporous anion exchange resin in the OH.sup.- state, whereupon the resins take up the acidic contaminants from the extractant, purifying the extractant and improving its extraction capability.

  7. Apatite-forming ability of vinylphosphonic acid-based copolymer in simulated body fluid: effects of phosphate group content.

    PubMed

    Hamai, Ryo; Shirosaki, Yuki; Miyazaki, Toshiki

    2016-10-01

    Phosphate groups on materials surfaces are known to contribute to apatite formation upon exposure of the materials in simulated body fluid and improved affinity of the materials for osteoblast-like cells. Typically, polymers containing phosphate groups are organic matrices consisting of apatite-polymer composites prepared by biomimetic process using simulated body fluid. Ca(2+) incorporation into the polymer accelerates apatite formation in simulated body fluid owing because of increase in the supersaturation degree, with respect to apatite in simulated body fluid, owing to Ca(2+) release from the polymer. However, the effects of phosphate content on the Ca(2+) release and apatite-forming abilities of copolymers in simulated body fluid are rather elusive. In this study, a phosphate-containing copolymer prepared from vinylphosphonic acid, 2-hydroxyethyl methacrylate, and triethylene glycol dimethacrylate was examined. The release of Ca(2+) in Tris-NaCl buffer and simulated body fluid increased as the additive amount of vinylphosphonic acid increased. However, apatite formation was suppressed as the phosphate groups content increased despite the enhanced release of Ca(2+) from the polymer. This phenomenon was reflected by changes in the surface zeta potential. Thus, it was concluded that the apatite-forming ability of vinylphosphonic acid-2-hydroxyethyl methacrylate-triethylene glycol dimethacrylate copolymer treated with CaCl2 solution was governed by surface state rather than Ca(2+) release in simulated body fluid. PMID:27585911

  8. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    SciTech Connect

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  9. Chemical rescue, multiple ionizable groups, and general acid-base catalysis in the HDV genomic ribozyme.

    PubMed

    Perrotta, Anne T; Wadkins, Timothy S; Been, Michael D

    2006-07-01

    In the ribozyme from the hepatitis delta virus (HDV) genomic strand RNA, a cytosine side chain is proposed to facilitate proton transfer in the transition state of the reaction and, thus, act as a general acid-base catalyst. Mutation of this active-site cytosine (C75) reduced RNA cleavage rates by as much as one million-fold, but addition of exogenous cytosine and certain nucleobase or imidazole analogs can partially rescue activity in these mutants. However, pH-rate profiles for the rescued reactions were bell shaped, and only one leg of the pH-rate curve could be attributed to ionization of the exogenous nucleobase or buffer. When a second potential ionizable nucleobase (C41) was removed, one leg of the bell-shaped curve was eliminated in the chemical-rescue reaction. With this construct, the apparent pK(a) determined from the pH-rate profile correlated with the solution pK(a) of the buffer, and the contribution of the buffer to the rate enhancement could be directly evaluated in a free-energy or Brønsted plot. The free-energy relationship between the acid dissociation constant of the buffer and the rate constant for cleavage (Brønsted value, beta, = approximately 0.5) was consistent with a mechanism in which the buffer acted as a general acid-base catalyst. These data support the hypothesis that cytosine 75, in the intact ribozyme, acts as a general acid-base catalyst.

  10. Saxitoxins and okadaic acid group: accumulation and distribution in invertebrate marine vectors from Southern Chile.

    PubMed

    García, Carlos; Pérez, Francisco; Contreras, Cristóbal; Figueroa, Diego; Barriga, Andrés; López-Rivera, Américo; Araneda, Oscar F; Contreras, Héctor R

    2015-01-01

    Harmful algae blooms (HABs) are the main source of marine toxins in the aquatic environment surrounding the austral fjords in Chile. Huichas Island (Aysén) has an history of HABs spanning more than 30 years, but there is limited investigation of the bioaccumulation of marine toxins in the bivalves and gastropods from the Region of Aysén. In this study, bivalves (Mytilus chilenses, Choromytilus chorus, Aulacomya ater, Gari solida, Tagelus dombeii and Venus antiqua) and carnivorous gastropods (Argobuccinum ranelliformes and Concholepas concholepas) were collected from 28 sites. Researchers analysed the accumulation of STX-group toxins using a LC with a derivatisation post column (LC-PCOX), while lipophilic toxins (OA-group, azapiracids, pectenotoxins and yessotoxins) were analysed using LC-MS/MS with electrospray ionisation (+/-) in visceral (hepatopancreas) and non-visceral tissues (mantle, adductor muscle, gills and foot). Levels of STX-group and OA-group toxins varied among individuals from the same site. Among all tissue samples, the highest concentrations of STX-group toxins were noted in the hepatopancreas in V. antiqua (95 ± 0.1 μg STX-eq 100 g(-1)), T. dombeii (148 ± 1.4 μg STX-eq 100 g(-1)) and G. solida (3232 ± 5.2 μg STX-eq 100 g(-1); p < 0.05); in the adductor muscle in M. chilensis (2495 ± 6.4 μg STX-eq 100 g(-1); p < 0.05) and in the foot in C. concholepas (81 ± 0.7 μg STX-eq 100 g(-1)) and T. dombeii (114 ± 1.2 μg STX-eq 100 g(-1)). The highest variability of toxins was detected in G. solida, where high levels of carbamate derivatives were identified (GTXs, neoSTX and STX). In addition to the detected hydrophilic toxins, OA-group toxins were detected (OA and DTX-1) with an average ratio of ≈1:1. The highest levels of OA-group toxins were in the foot of C. concholepas, with levels of 400.3 ± 3.6 μg OA eq kg(-1) (p < 0.05) and with a toxic profile composed of 90% OA. A wide range of OA-group toxins was detected in M. chilensis with a

  11. Saxitoxins and okadaic acid group: accumulation and distribution in invertebrate marine vectors from Southern Chile.

    PubMed

    García, Carlos; Pérez, Francisco; Contreras, Cristóbal; Figueroa, Diego; Barriga, Andrés; López-Rivera, Américo; Araneda, Oscar F; Contreras, Héctor R

    2015-01-01

    Harmful algae blooms (HABs) are the main source of marine toxins in the aquatic environment surrounding the austral fjords in Chile. Huichas Island (Aysén) has an history of HABs spanning more than 30 years, but there is limited investigation of the bioaccumulation of marine toxins in the bivalves and gastropods from the Region of Aysén. In this study, bivalves (Mytilus chilenses, Choromytilus chorus, Aulacomya ater, Gari solida, Tagelus dombeii and Venus antiqua) and carnivorous gastropods (Argobuccinum ranelliformes and Concholepas concholepas) were collected from 28 sites. Researchers analysed the accumulation of STX-group toxins using a LC with a derivatisation post column (LC-PCOX), while lipophilic toxins (OA-group, azapiracids, pectenotoxins and yessotoxins) were analysed using LC-MS/MS with electrospray ionisation (+/-) in visceral (hepatopancreas) and non-visceral tissues (mantle, adductor muscle, gills and foot). Levels of STX-group and OA-group toxins varied among individuals from the same site. Among all tissue samples, the highest concentrations of STX-group toxins were noted in the hepatopancreas in V. antiqua (95 ± 0.1 μg STX-eq 100 g(-1)), T. dombeii (148 ± 1.4 μg STX-eq 100 g(-1)) and G. solida (3232 ± 5.2 μg STX-eq 100 g(-1); p < 0.05); in the adductor muscle in M. chilensis (2495 ± 6.4 μg STX-eq 100 g(-1); p < 0.05) and in the foot in C. concholepas (81 ± 0.7 μg STX-eq 100 g(-1)) and T. dombeii (114 ± 1.2 μg STX-eq 100 g(-1)). The highest variability of toxins was detected in G. solida, where high levels of carbamate derivatives were identified (GTXs, neoSTX and STX). In addition to the detected hydrophilic toxins, OA-group toxins were detected (OA and DTX-1) with an average ratio of ≈1:1. The highest levels of OA-group toxins were in the foot of C. concholepas, with levels of 400.3 ± 3.6 μg OA eq kg(-1) (p < 0.05) and with a toxic profile composed of 90% OA. A wide range of OA-group toxins was detected in M. chilensis with a

  12. Amino acid-mediated impacts of elevated carbon dioxide and simulated root herbivory on aphids are neutralized by increased air temperatures.

    PubMed

    Ryalls, James M W; Moore, Ben D; Riegler, Markus; Gherlenda, Andrew N; Johnson, Scott N

    2015-02-01

    Changes in host plant quality, including foliar amino acid concentrations, resulting from global climate change and attack from multiple herbivores, have the potential to modify the pest status of insect herbivores. This study investigated how mechanically simulated root herbivory of lucerne (Medicago sativa) before and after aphid infestation affected the pea aphid (Acyrthosiphon pisum) under elevated temperature (eT) and carbon dioxide concentrations (eCO2). eT increased plant height and biomass, and eCO2 decreased root C:N. Foliar amino acid concentrations and aphid numbers increased in response to eCO2, but only at ambient temperatures, demonstrating the ability of eT to negate the effects of eCO2. Root damage reduced aboveground biomass, height, and root %N, and increased root %C and C:N, most probably via decreased biological nitrogen fixation. Total foliar amino acid concentrations and aphid colonization success were higher in plants with roots cut early (before aphid arrival) than those with roots cut late (after aphid arrival); however, this effect was counteracted by eT. These results demonstrate the importance of amino acid concentrations for aphids and identify individual amino acids as being potential factors underpinning aphid responses to eT, eCO2, and root damage in lucerne. Incorporating trophic complexity and multiple climatic factors into plant-herbivore studies enables greater insight into how plants and insects will interact in the future, with implications for sustainable pest control and future crop security.

  13. A Continuous Variation Study of Heats of Neutralization.

    ERIC Educational Resources Information Center

    Mahoney, Dennis W.; And Others

    1981-01-01

    Suggests that students study heats of neutralization of a 1 M solution of an unknown acid by 1 M solution of a strong base using the method continuous variation. Reviews results using several common acids. (SK)

  14. Affinity-Based Screening of Tetravalent Peptides Identifies Subtype-Selective Neutralizers of Shiga Toxin 2d, a Highly Virulent Subtype, by Targeting a Unique Amino Acid Involved in Its Receptor Recognition.

    PubMed

    Mitsui, Takaaki; Watanabe-Takahashi, Miho; Shimizu, Eiko; Zhang, Baihao; Funamoto, Satoru; Yamasaki, Shinji; Nishikawa, Kiyotaka

    2016-09-01

    Shiga toxin (Stx), a major virulence factor of enterohemorrhagic Escherichia coli (EHEC), can be classified into two subgroups, Stx1 and Stx2, each consisting of various closely related subtypes. Stx2 subtypes Stx2a and Stx2d are highly virulent and linked with serious human disorders, such as acute encephalopathy and hemolytic-uremic syndrome. Through affinity-based screening of a tetravalent peptide library, we previously developed peptide neutralizers of Stx2a in which the structure was optimized to bind to the B-subunit pentamer. In this study, we identified Stx2d-selective neutralizers by targeting Asn16 of the B subunit, an amino acid unique to Stx2d that plays an essential role in receptor binding. We synthesized a series of tetravalent peptides on a cellulose membrane in which the core structure was exactly the same as that of peptides in the tetravalent library. A total of nine candidate motifs were selected to synthesize tetravalent forms of the peptides by screening two series of the tetravalent peptides. Five of the tetravalent peptides effectively inhibited the cytotoxicity of Stx2a and Stx2d, and notably, two of the peptides selectively inhibited Stx2d. These two tetravalent peptides bound to the Stx2d B subunit with high affinity dependent on Asn16. The mechanism of binding to the Stx2d B subunit differed from that of binding to Stx2a in that the peptides covered a relatively wide region of the receptor-binding surface. Thus, this highly optimized screening technique enables the development of subtype-selective neutralizers, which may lead to more sophisticated treatments of infections by Stx-producing EHEC. PMID:27382021

  15. Effect of the Methylation and N-H Acidic Group on the Physicochemical Properties of Imidazolium-Based Ionic Liquids.

    PubMed

    Rodrigues, Ana S M C; Rocha, Marisa A A; Almeida, Hugo F D; Neves, Catarina M S S; Lopes-da-Silva, José A; Freire, Mara G; Coutinho, João A P; Santos, Luís M N B F

    2015-07-16

    This work presents and highlights the differentiation of the physicochemical properties of the [C1Him][NTf2], [C2Him][NTf2], [(1)C1(2)C1Him][NTf2], and [(1)C4(2)C1(3)C1im][NTf2] that is related with the strong bulk interaction potential, which highlights the differentiation on the physicochemical arising from the presence of the acidic group (N-H) as well as the methylation in position 2, C(2), of the imidazolium ring. Densities, viscosities, refractive indices, and surface tensions in a wide range of temperatures, as well as isobaric heat capacities at 298.15 K, for this IL series are presented and discussed. It was found that the volumetric properties are barely affected by the geometric and structural isomerization, following a quite regular trend. A linear correlation between the glass transition temperature, Tg, and the alkyl chain size was found; however, ILs with the acidic N-H group present a significant higher Tg than the [(1)CN-1(3)C1im][NTf2] and [(1)CN(3)CNim][NTf2] series. It was found that the most viscous ILs, ([(1)C1Him][NTf2], [(1)C2Him][NTf2], and [(1)C1(2)C1Him][NTf2]) have an acidic N-H group in the imidazolium ring in agreement with the observed increase of energy barrier of flow. The methylation in position 2, C(2), as well as the N-H acidic group in the imidazolium ring contribute to a significant variation in the cation-anion interactions and their dynamics, which is reflected in their charge distribution and polarizability leading to a significant differentiation of the refractive indices, surface tension, and heat capacities. The observed differentiation of the physicochemical properties of the [(1)C1Him][NTf2], [(1)C2Him][NTf2], [(1)C1(2)C1Him][NTf2], and [(1)C4(2)C1(3)C1im][NTf2] are an indication of the stronger bulk interaction potential, which highlights the effect that arises from the presence of the acidic group (N-H) as well as the methylation in position 2 of the imidazolium ring.