Sample records for acid anion pair

  1. Amino acid anions in organic ionic compounds. An ab initio study of selected ion pairs. (United States)

    Benedetto, A; Bodo, E; Gontrani, L; Ballone, P; Caminiti, R


    The combination of amino acids in their deprotonated and thus anionic form with a choline cation gives origin to a new and potentially important class of organic ionic compounds. A series of such neutral ion pairs has been investigated by first principle methods. The results reveal intriguing structural motives as well as regular patterns in the charge distribution and predict a number of vibrational and optical properties that could guide the experimental investigation of these compounds. The replacement of choline with its phosphocholine analogue causes the spontaneous reciprocal neutralization of cations and anions, taking place through the transfer of a proton between the two ions. Systems of this kind, therefore, provide a wide and easily accessible playground to probe the ionic/polar transition in organic systems, while the easy transfer of H(+) among neutral and ionic species points to their potential application as proton conductors. The analysis of the ab initio data highlights similarities as well as discrepancies from the rigid-ions force-field picture and suggests directions for the improvement of empirical models.

  2. Anions in Nucleic Acid Crystallography. (United States)

    D'Ascenzo, Luigi; Auffinger, Pascal


    Nucleic acid crystallization buffers contain a large variety of chemicals fitting specific needs. Among them, anions are often solely considered for pH-regulating purposes and as cationic co-salts while their ability to directly bind to nucleic acid structures is rarely taken into account. Here we review current knowledge related to the use of anions in crystallization buffers along with data on their biological prevalence. Chloride ions are frequently identified in crystal structures but display low cytosolic concentrations. Hence, they are thought to be distant from nucleic acid structures in the cell. Sulfate ions are also frequently identified in crystal structures but their localization in the cell remains elusive. Nevertheless, the characterization of the binding properties of these ions is essential for better interpreting the solvent structure in crystals and consequently, avoiding mislabeling of electron densities. Furthermore, understanding the binding properties of these anions should help to get clues related to their potential effects in crowded cellular environments.

  3. Ursodeoxycholic acid and superoxide anion

    Institute of Scientific and Technical Information of China (English)

    Predrag Ljubuncic; Omar Abu-Salach; Arieh Bomzon


    AIM: To investigate the ability of ursodeoxycholic acid (UDCA) to scavenge superoxide anion (O2-).METHODS: We assessed the ability of UDCA to scavenge (O2-) generated by xanthine-xanthine oxidase (X-XO) in a cell-free system and its effect on the rate of O2--induced ascorbic acid (AA) oxidation in hepatic post-mitochondrial supernatants.RESULTS: UDCA at a concentration as high as 1 mmol/Ldid not impair the ability of the X-XO system to generate O2-, but could scavenge O2- at concentrations of 0.5 and 1 mmol/L, and decrease the rate of AA oxidation at a concentration of 100 μmol/L.CONCLUSION: UDCA can scavenge O2-, an action that may be beneficial to patients with primary biliary cirrhosis.

  4. Paired-ion electrospray ionization--triple quadrupole tandem mass spectrometry for quantification of anionic surfactants in waters. (United States)

    Santos, Inês C; Guo, Hongyue; Mesquita, Raquel B R; Rangel, António O S S; Armstrong, Daniel W; Schug, Kevin A


    A new paired ion electrospray ionization tandem mass spectrometry method for determination of anionic surfactants in water samples was developed. In this method, dicationic ion-pairing reagents were complexed with monoanionic analytes to facilitate analyte detection in positive mode electrospray ionization - mass spectrometry. Single ion monitoring and selected reaction monitoring on a triple quadrupole instrument were performed and compared. Four dicationic reagents were tested for the determination of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBS), and stearic acid (SA), among other common anions. The obtained limits of detection were compared with those from previous literature. Solid phase extraction using a C18 cartridge was performed in order to eliminate matrix interferences. A literature review was compiled for the methods published between 2010 and 2015 for determination of anionic surfactants. The optimized method was more sensitive than previously developed methods with LOD values of 2.35, 35.4, 37.0, 1.68, and 0.675 pg for SDS, SA, DBS, PFOS, and PFOA, respectively. The developed method was effectively applied for the determination of anionic surfactants in different water samples such as bottled drinking water, cooking water, tap water, and wastewater.

  5. Survey of organic acid eluents for anion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Book, D.E.


    Of all the potential eluents surveyed (including aromatic, sulfonic, phosphonic, among other acids), only the carboxylic acids and the nitrophenols are recommended as eluents for anion chromatography. The concentration of the eluent should be in the range 5 x 10/sup -5/ to 1 x 10/sup -3/ M. The eluent should have the same charge as inorganic anions, a higher charge than organic acid samples. Choice of eluents for separation of halides, chloride and sulfate, multivalent inorganic anions, small alkyl acids, and aromatic acids is discussed. (DLC)

  6. Anion pairs in room temperature ionic liquids predicted by molecular dynamics simulation, verified by spectroscopic characterization

    Energy Technology Data Exchange (ETDEWEB)

    Schwenzer, Birgit; Kerisit, Sebastien N.; Vijayakumar, M.


    Molecular-level spectroscopic analyses of an aprotic and a protic room-temperature ionic liquid, BMIM OTf and BMIM HSO4, respectively, have been carried out with the aim of verifying molecular dynamics simulations that predict anion pair formation in these fluid structures. Fourier-transform infrared spectroscopy, Raman spectroscopy and nuclear magnetic resonance spectroscopy of various nuclei support the theoretically-determined average molecular arrangements.

  7. Isoprene, sulphoxy radical-anions and acidity

    Directory of Open Access Journals (Sweden)

    K. J. Rudziński


    Full Text Available Transformation of isoprene coupled with autoxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over broad range of solution acidities (pH=3–9 to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the autoxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene – sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=162.9, sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=164.9, sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl ester (m/z=178.9, sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl ester (m/z=180.9 – was indicated by mass spectroscopic analysis of post-reaction mixtures. The results of experiments were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions – the scavenging of sulphoxy radicals by isoprene, the formation of sulphoxy radicals during further reactions of isoprene radicals, and the autoxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. Interaction of isoprene with sulphur(IV species and oxygen can possibly result in formation of new organosulphate components of atmospheric aerosols and waters, and influence distribution of reactive sulphur and oxygen species in isoprene-emitting organisms exposed to SIV pollutants.

  8. Anion-Channel Blockers Inhibit S-Type Anion Channels and Abscisic Acid Responses in Guard Cells. (United States)

    Schwartz, A.; Ilan, N.; Schwarz, M.; Scheaffer, J.; Assmann, S. M.; Schroeder, J. I.


    The effects of anion-channel blockers on light-mediated stomatal opening, on the potassium dependence of stomatal opening, on stomatal responses to abscisic acid (ABA), and on current through slow anion channels in the plasma membrane of guard cells were investigated. The anion-channel blockers anthracene-9-carboxylic acid (9-AC) and niflumic acid blocked current through slow anion channels of Vicia faba L. guard cells. Both 9-AC and niflumic acid reversed ABA inhibition of stomatal opening in V. faba L. and Commelina communis L. The anion-channel blocker probenecid also abolished ABA inhibition of stomatal opening in both species. Additional tests of 9-AC effects on stomatal aperture in Commelina revealed that application of this anion-channel blocker allowed wide stomatal opening under low (1 mM) KCI conditions and increased the rate of stomatal opening under both low and high (100 mM) KCI conditions. These results indicate that anion channels can function as a negative regulator of stomatal opening, presumably by allowing anion efflux and depolarization, which prohibits ion up-take in guard cells. Furthermore, 9-AC prevented ABA induction of stomatal closure. A model in which ABA activation of anion channels contributes a rate-limiting mechanism during ABA-induced stomatal closure and inhibition of stomatal opening is discussed.

  9. Molecular dynamics simulation of anionic clays containing glutamic acid (United States)

    Xu, Qian; Ni, Zheming; Yao, Ping; Li, Yuan


    Supra-molecular structure of glutamic acid intercalated ZnAl layered double hydroxides (Glu-ZnAl-LDH) was modeled by molecular dynamics (MD) methods. Hydrogen bonding, hydration and swelling properties of Glu-LDH have been investigated. For Nw layers and anions. When A-W type H-bonds gradually reached a saturation state, water molecules continued to form hydrogen bonds with the hydroxyls of the layers. The L-W type H-bonds gradually substituted the L-A type H-bonds and Glu anions moved to the center of an interlayer and then separated with the layers. Last, a well-ordered structural water layer was formed on the surface hydroxyls of Glu-LDH. The lower releasing content of Glu-LDH maybe was influenced by the lower balance hydration energy and existence of L-A type H-bonds in high water content.

  10. Adsorption and desorption dynamics of citric acid anions in soil

    KAUST Repository

    Oburger, E.


    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal uptake. Little is known about the interaction dynamics of organic acid anions with the soil matrix and the potential impact of adsorption and desorption processes on the functional significance of these effects. The aim of this study was to characterize experimentally the adsorption and desorption dynamics of organic acid anions in five agricultural soils differing in iron and aluminium oxide contents and using citrate as a model carboxylate. Results showed that both adsorption and desorption processes were fast in all soils, reaching a steady state within approximately 1 hour. However, for a given total soil citrate concentration (ct) the steady state was critically dependent on the starting conditions of the experiment, whether most of the citrate was initially present in solution (cl) or held on the solid phase (cs). Specifically, desorption-led processes resulted in significantly smaller steady-state solution concentrations than adsorption-led processes, indicating that hysteresis occurred. As it is not possible to distinguish between different adsorption and desorption pools in soil experimentally, a new dynamic hysteresis model that relies only on measured soil solution concentrations was developed. The model satisfactorily explained experimental data and was able to predict dynamic adsorption and desorption behaviour. To demonstrate its use, we applied the model to two relevant situations involving exudation and microbial degradation. The study highlighted the complex nature of citrate adsorption and desorption dynamics in soil. We conclude that existing models need to incorporate both temporal and hysteresis components to describe realistically the role and fate of organic acids in soil processes. © 2011 The

  11. Separation of multiply charged anions by capillary electrophoresis using alkyl phosphonium pairing agents. (United States)

    Feng, Qing; Wanigasekara, Eranda; Breitbach, Zachary S; Armstrong, Daniel W


    Two newly developed UV transparent phosphonium-based cationic reagents were evaluated as background electrolyte additives for capillary electrophoresis for the separation of multiply charged anions, including several complex anions. These cationic reagents showed moderate suppression of the electroosmotic flow, interacted with the analytes to improve their separation and often improved the peak shape. The effects of the additives and their concentration on the separation were studied, as well as the buffer type, pH, and voltage. The dicationic reagent effectively separated eight divalent anions within 17 min and the tetracationic reagent best separated nine trivalent anions, as well as a mixture of all the anions.

  12. Determination of UV active inorganic anions in potable and high salinity water by ion pair reversed phase liquid chromatography. (United States)

    Sadiq Khan, Sadaf; Riaz, M


    Reversed phase column was dynamically modified into anion exchange column using various types of tetraalkylammonium salts as ion pair reagents (IPRs) for the separation and quantification of toxic anions such as nitrite, bromate, bromide and nitrate in potable and high salinity water. Various chromatographic parameters such as types and concentration of IPRs, concentration of organic modifier, phosphate buffer and mobile phase pH were optimized for the base-line separation of anions. The lowest detection limits (LDLs) were 0.2 for nitrate and nitrite, 0.6 µg ml(-1)for bromate and bromide respectively for potable water samples. NaCl and Na₂SO₄ were incorporated in the mobile phase for the analysis of high salinity water samples to minimize matrix interferences. This has resulted in change in elution order of anions, better tolerance of matrix anions such as chloride and sulphate. The developed method was successfully utilized for analysis of anions in potable, high salinity and sea water samples.

  13. 2-Pyrrole Carboxylic Acid Nitro-Phenylamide: New Colorimetric Sensor for Anion

    Institute of Scientific and Technical Information of China (English)

    YIN Zhen-Ming; YANG Wen-Zhi; HE Jia-Qi; ZHU Xiao-Qing; CHENG Jin-Pei


    @@ Due to the role played by anions in the field of biology and environmental chemistry, the development of selec tive and sensitive chemosensor for anion sensing is a topic of current attention. Colorimetric anion sensor, which does not require the use of a potentiostate or spectrometer to detect redox or optical perturbation, can give immediate qualitative anion sensing information by visual detection and therefore has advantages over other molecular sensors.According the anion binding ability of some pyrrolic amides reported by Schmuck and Gale, we linked the color reporter group of nitroanile to pyrrole moiety and synthesized two 2-pyrrole carboxylic acid nitro-phenylamides (1 and 2).

  14. [Determination of organic acids and inorganic anions by gradient ion chromatography]. (United States)

    Liu, Z; Liu, K; Shen, D; Song, Q; Mou, S; Feng, Y


    The chromatographic conditions for separation and detection of organic acids and inorganic anions by gradient ion chromatography with suppressed conductivity detection were studied. The optimized gradient programs were established. Ion chromatography were performed with a DX-100 chromatograph (DIONEX). The separation column is IonPac-AS11. Compared with NaHCO3/Na2CO3 and Na2B4O7, NaOH was the optimal eluent. The effect of organic modifier was also studied. Among methanol, 2-propanol and acetonitrile, methanol can make ion pairs such as malate and succinate, malonate and tartrate gaining baseline resolution. By using ion exchange separation, Cl-, NO3-, malate, succinate, malonate, tartrate, SO4(2-), oxalate were eluted between 5 mmol/L NaOH-16% CH3OH and 10 mmol/L NaOH-16% CH3OH in 25 min. A mobile phase composed of 30 mmol/L NaOH, 50% CH3OH and D.I. water was chosen to elute two groups of organic acids and inorganic anions: (1) quinate, formate, Cl-, malate, malonate, oxalate, citrate, isocitrate, aconitate; (2) lactate, Cl-, SO4(2-), tartrate, PO4(3-), citrate, isocitrate, aconitate. The detection limits (S/N = 3) were 0.1625 (quinate), 0.0691 (formate), 0.0115 (Cl-), 0.0886 (malate), 0.0591 (malonate), 0.0263 (oxalate), 0.1147 (citrate), 0.2017 (isocitrate), 0.3656 (cis-aconitate), 0.1045 (trans-aconitate), 0.1950 (lactate), 0.0729 (tartrate), 0.0224 (SO4(2-)) and 0.0692 (PO4(3-)) mg/L. The relative standard deviations were lower than 11.9% (n = 7) and the correlation coefficients ranged from 0.9212 for Cl- to 0.9999 for formate. The method was applied to determine the organic acids and inorganic anions of beverages and citric acids fermenting-medium. The results were satisfactory.

  15. Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils (United States)

    Kharaka, Y.K.; Lundegard, P.D.; Ambats, G.; Evans, William C.; Bischoff, J.L.


    Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.

  16. Separation of thorium and uranium in nitric acid solution using silica based anion exchange resin. (United States)

    Chen, Yanliang; Wei, Yuezhou; He, Linfeng; Tang, Fangdong


    To separate thorium and uranium in nitric acid solution using anion exchange process, a strong base silica-based anion exchange resin (SiPyR-N4) was synthesized. Batch experiments were conducted and the separation factor of thorium and uranium in 9M nitric acid was about 10. Ion exchange chromatography was applied to separate thorium and uranium in different ratios. Uranium could be eluted by 9M nitric acid and thorium was eluted by 0.1M nitric acid. It was proved that thorium and uranium can be separated and recovered successfully by this method.

  17. Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces. (United States)

    Zhao, Yingjie; Cotelle, Yoann; Avestro, Alyssa-Jennifer; Sakai, Naomi; Matile, Stefan


    Here we provide experimental evidence for anion-π catalysis of enamine chemistry and for asymmetric anion-π catalysis. A proline for enamine formation on one side and a glutamic acid for nitronate protonation on the other side are placed to make the enamine addition to nitroolefins occur on the aromatic surface of π-acidic naphthalenediimides. With increasing π acidity of the formally trifunctional catalysts, rate and enantioselectivity of the reaction increase. Mismatched and more flexible controls reveal that the importance of rigidified, precisely sculpted architectures increases with increasing π acidity as well. The absolute configuration of stereogenic sulfoxide acceptors at the edge of the π-acidic surface has a profound influence on asymmetric anion-π catalysis and, if perfectly matched, affords the highest enantio- and diastereoselectivity.

  18. Roles of Organic Acid Anion Secretion in Aluminium Tolerance of Higher Plants

    Directory of Open Access Journals (Sweden)

    Lin-Tong Yang


    Full Text Available Approximately 30% of the world’s total land area and over 50% of the world’s potential arable lands are acidic. Furthermore, the acidity of the soils is gradually increasing as a result of the environmental problems including some farming practices and acid rain. At mildly acidic or neutral soils, aluminium(Al occurs primarily as insoluble deposits and is essentially biologically inactive. However, in many acidic soils throughout the tropics and subtropics, Al toxicity is a major factor limiting crop productivity. The Al-induced secretion of organic acid (OA anions, mainly citrate, oxalate, and malate, from roots is the best documented mechanism of Al tolerance in higher plants. Increasing evidence shows that the Al-induced secretion of OA anions may be related to the following several factors, including (a anion channels or transporters, (b internal concentrations of OA anions in plant tissues, (d temperature, (e root plasma membrane (PM H+-ATPase, (f magnesium (Mg, and (e phosphorus (P. Genetically modified plants and cells with higher Al tolerance by overexpressing genes for the secretion and the biosynthesis of OA anions have been obtained. In addition, some aspects needed to be further studied are also discussed.

  19. Roles of organic acid anion secretion in aluminium tolerance of higher plants. (United States)

    Yang, Lin-Tong; Qi, Yi-Ping; Jiang, Huan-Xin; Chen, Li-Song


    Approximately 30% of the world's total land area and over 50% of the world's potential arable lands are acidic. Furthermore, the acidity of the soils is gradually increasing as a result of the environmental problems including some farming practices and acid rain. At mildly acidic or neutral soils, aluminium (Al) occurs primarily as insoluble deposits and is essentially biologically inactive. However, in many acidic soils throughout the tropics and subtropics, Al toxicity is a major factor limiting crop productivity. The Al-induced secretion of organic acid (OA) anions, mainly citrate, oxalate, and malate, from roots is the best documented mechanism of Al tolerance in higher plants. Increasing evidence shows that the Al-induced secretion of OA anions may be related to the following several factors, including (a) anion channels or transporters, (b) internal concentrations of OA anions in plant tissues, (d) temperature, (e) root plasma membrane (PM) H(+)-ATPase, (f) magnesium (Mg), and (e) phosphorus (P). Genetically modified plants and cells with higher Al tolerance by overexpressing genes for the secretion and the biosynthesis of OA anions have been obtained. In addition, some aspects needed to be further studied are also discussed.

  20. The preferences of orientations between the Pairs of amino acids

    Institute of Scientific and Technical Information of China (English)

    Chen Ying; Wang Jun; Wang Wei


    In this work,we make an investigation on the preferences of orientations between amino acids using the orientation defined based on the local geometry of the amino acids concerned.It is found that there are common preferences of orientations (70°,30°,140°) and (110°,340°,100°) for various pairs of amino acids.Different side chains may strengthen or weaken the common preferences,which is related to the effect of packing.Some amino acids having specific local flexibility may possess some preferences of orientations besides the common ones,such as (10°,280°,210°) .Another analysis on the pairs of the amino acids with different secondary-structure preferences shows that the directional interaction may affect the distribution of orientation more effectively than the packing or local flexibility.All these results provide us some insight of the organization of amino acids in protein,and their relation with some related interactions.

  1. Analysis of trace inorganic anions in weak acid salts by single pump cycling-column-switching ion chromatography. (United States)

    Huang, Zhongping; Ni, Chengzhu; Zhu, Zhuyi; Pan, Zaifa; Wang, Lili; Zhu, Yan


    The application of ion chromatography with the single pump cycling-column-switching technique was described for the analysis of trace inorganic anions in weak acid salts within a single run. Due to the hydrogen ions provided by an anion suppressor electrolyzing water, weak acid anions could be transformed into weak acids, existing as molecules, after passing through the suppressor. Therefore, an anion suppressor and ion-exclusion column were adopted to achieve on-line matrix elimination of weak acid anions with high concentration for the analysis of trace inorganic anions in weak acid salts. A series of standard solutions consisting of target anions of various concentrations from 0.005 to 10 mg/L were analyzed, with correlation coefficients r ≥ 0.9990. The limits of detection were in the range of 0.67 to 1.51 μg/L, based on the signal-to-noise ratio of 3 and a 25 μL injection volume. Relative standard deviations for retention time, peak area, and peak height were all less than 2.01%. A spiking study was performed with satisfactory recoveries between 90.3 and 104.4% for all anions. The chromatographic system was successfully applied to the analysis of trace inorganic anions in five weak acid salts.

  2. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis. (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel


    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  3. Studies concerning the anion ex-change resins catalyzed esterification of epichlorohydrin with organic acids

    Directory of Open Access Journals (Sweden)

    E.I. Muresan


    Full Text Available The paper studies the esterification of carboxylic acids with epichlorohydrin over two macroporous strong base anion exchange resins with different polymer matrix. For both resins, the influence of reaction parameters (temperature, catalyst loading, molar ratio on the reaction rate and the yields of the two isomeric esters were investigated.

  4. Metabolism and root exudation of organic acid anions under aluminium stress

    NARCIS (Netherlands)

    Mariano, E.D.; Jorge, R.A.; Keltjens, W.G.; Menossi, M.


    Numerous plant species can release organic acid anions (OA) from their roots in response to toxic aluminium (Al) ions present in the rooting medium. Hypothetically OA complex Al in the root apoplast and/or rhizosphere and thus avoid its interaction with root cellular components and its entry in the

  5. Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid-base pairs. (United States)

    Morgan, Ian R; Di Paolo, Angela; Vidovic, Dragoslav; Fallis, Ian A; Aldridge, Simon


    A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

  6. Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization. (United States)

    Lewis, Jennifer D; Van de Vyver, Stijn; Román-Leshkov, Yuriy


    Hf-, Sn-, and Zr-Beta zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions.


    Directory of Open Access Journals (Sweden)

    D. Afzaal, M. Nisa, M. A. Khan and M. Sarwar


    Full Text Available The acid base status of a dairy cow is maintained within a narrow range. The key mechanisms involving blood, cells and lungs, perform this function. Although other minerals have an impact on acid base metabolism, the minerals used in dietary cation-anion balance (DCAB namely sodium (Na, potassium (K and chloride (Cl have the greatest effect. Hence, acid base status implicates other biological functions of dairy cows. Low DCAB prepartum reduces the incidence of milk fever and increases the productivity by simmering down the severity of hypocalcaemia. High DCAB diets have proved to increase dry mater and water intake and production and to mitigate the effects of heat stress.

  8. Preparation of a Novel Acid Doped Polyaniline Adsorbent for Removal of Anionic Pollutant from Wastewater

    Institute of Scientific and Technical Information of China (English)

    LI Jiajia; WANG Qizhao; BAI Yan; JIA Yongming; SHANG Pan; HUANG Haohao; WANG Fangping


    Polyaniline (PANI) was one of the most extensively studied adsorbents due to its low cost and good environmental stability. The objective of the current study was to improve the selective capabilities of PANI for anionic dyes. We found that the acid doped PANI prepared with hydrochloric acid and p-toluenesulfonic acid (PTSA) could selectively adsorb anionic dyes. It exhibited very good selectivity for OG dye, the mechanism was proposed based on the chemical interaction of PANI with the sulfonate group of the dyes. The effects of solution pH, initial dye concentration, and different HCl/PTSA mole ratios on the adsorption capacity of OG have been investigated. Kinetic simulations indicated that the adsorption process could be well represented by pseudo-second-order kinetic plots. The isothermal adsorption curve iftting also showed that the adsorption process could be well described by the Langmuir isothermal equation. The results showed that acid doped PANI could be employed as a promising adsorbent for anion removal from dye wastewater.

  9. Recognition of amino acids and anions by a Zn(Ⅱ)-methylazacalix[4]pyridine complex

    Institute of Scientific and Technical Information of China (English)


    As a powerful macrocyclic host molecule with unique conformation and cavity structure that are fine-tuned by the bridging nitrogen atoms, methylazacalix[4]pyridine (MACP-4) has been shown to selectively recognize Zn2+ and form stable Zn(Ⅱ)-MACP-4 complexes both in solid state and solution with an association constant up to 5.97 (logKs). The molecular recognition of Zn(Ⅱ)-MACP-4 complexes towards various amino acids and anions with different geometry was investigated by using the spectral titration methods and X-ray analysis. The Zn(Ⅱ)-MACP-4 complex was found to recognize the 17 amino acids tested with the association constant up to 3.97 (logKs). On the other hand, the Zn(Ⅱ)-MACP-4 complex selectively interacted with anions and the maximum association constant of 3.9 (logKs) was obtained.

  10. NO3− anions can act as Lewis acid in the solid state (United States)

    Bauzá, Antonio; Frontera, Antonio; Mooibroek, Tiddo J.


    Identifying electron donating and accepting moieties is crucial to understanding molecular aggregation, which is of pivotal significance to biology. Anions such as NO3− are typical electron donors. However, computations predict that the charge distribution of NO3− is anisotropic and minimal on nitrogen. Here we show that when the nitrate's charge is sufficiently dampened by resonating over a larger area, a Lewis acidic site emerges on nitrogen that can interact favourably with electron rich partners. Surveys of the Cambridge Structural Database and Protein Data Bank reveal geometric preferences of some oxygen and sulfur containing entities around a nitrate anion that are consistent with this ‘π-hole bonding' geometry. Computations reveal donor–acceptor orbital interactions that confirm the counterintuitive Lewis π–acidity of nitrate. PMID:28220788

  11. NO3- anions can act as Lewis acid in the solid state (United States)

    Bauzá, Antonio; Frontera, Antonio; Mooibroek, Tiddo J.


    Identifying electron donating and accepting moieties is crucial to understanding molecular aggregation, which is of pivotal significance to biology. Anions such as NO3- are typical electron donors. However, computations predict that the charge distribution of NO3- is anisotropic and minimal on nitrogen. Here we show that when the nitrate's charge is sufficiently dampened by resonating over a larger area, a Lewis acidic site emerges on nitrogen that can interact favourably with electron rich partners. Surveys of the Cambridge Structural Database and Protein Data Bank reveal geometric preferences of some oxygen and sulfur containing entities around a nitrate anion that are consistent with this `π-hole bonding' geometry. Computations reveal donor-acceptor orbital interactions that confirm the counterintuitive Lewis π-acidity of nitrate.

  12. Bis(imidazolium) salts derived from amino acids as receptors and transport agents for chloride anions

    NARCIS (Netherlands)

    González-Mendoza, Laura; Altava, Belén; Burguete, M.I.; Escorihuela, Jorge; Hernando, Elsa; Luis, S.V.; Quesada, Roberto; Vicent, Cristian


    The binding properties of bis(imidazolium) hosts 1a-c derived from amino acids towards different anions have been studied by 1H NMR titration experiments in 95:05 CD3CN:H2O at 303 K, ESI-MS and theoretical calculations. Among this family, the salt 1c showed a stro

  13. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions. (United States)

    Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong


    Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

  14. Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes

    CERN Document Server

    Savoie, Brett M; Miller, Thomas F


    Solid polymer electrolytes (SPE) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li-ion conductivity remains a barrier to technological viability. SPEs are designed to maximize Li-ion diffusivity relative to the anion, while maintaining sufficient salt solubility. It is thus remarkable that polyethylene oxide (PEO), the most widely used SPE, exhibits Li-ion diffusivity that is an order of magnitude smaller than that of typical counter-ions, such as TFSI, at moderate salt concentrations. Here, we show that Lewis-basic polymers like PEO intrinsically favor slow cation and rapid anion diffusion while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics (MD) simulations, Lewis-acidic polyboranes are identified that achieve up to a ten-fold increase in Li-ion diffusivity and a significant decrease in anion diffusivity, relative to PEO. The results for this new class of Lewis-acidic SPEs illustrate a general principle for incre...

  15. DFT computational study on decarboxylation mechanism of salicylic acid and its derivatives in the anionic state (United States)

    Gao, Lu; Hu, Yanying; Zhang, Huitu; Liu, Yanchun; Song, Zhidan; Dai, Yujie


    The mechanisms of the decarboxylation of salicylic acid anion and its ortho substituted derivatives in gas phase and aqueous solution have been investigated by B3LYP method of DFT theory using the 6-31++G (d,p) basis set. The decarboxylation process includes hydrogen transfers from hydroxyl to carboxyl group and from carboxyl to the α-C of the aryl ring. The mechanism suggested is a pseudo-unimolecular decomposition of the salicylic acid anion and the hydrogen transfer from carboxyl to the α-C of the aryl ring is the rate determining step. Compared with the decarboxylation process in gas phase, the energy barriers in aqueous solution approximately declined by 25%-31%with the water mediation of the hydrogen transfer from carboxyl to the α-C of the aryl ring. The effects of substituents at the ortho position on the decarboxylation process were also investigated. Both the electron donating CH3 and withdrawing group NO2 at the ortho position of carboxyl group can further reduce the reaction energy barriers of the decarboxylation of salicylic acid anions.

  16. Enhanced anion electroadsorption into carbon molecular sieve electrodes in acidic media. (United States)

    Eliad, Linoam; Salitra, Gregory; Pollak, Elad; Soffer, Abraham; Aurbach, Doron


    We previously showed that, for neutral electrolytes of small cations and relatively larger anions, it is possible to design certain pore sizes in active carbons that are large enough to electroadsorb cations but too small to allow anion electroadsorption. This situation leads to an electrical double-layer (EDL) capacitance that is significant only at potentials that are negative to the potential of zero charge (PZC); hence, much smaller capacitance is measured at potentials positive to the PZC. It was found that when the electrolyte is a strong acid (e.g., H(2)SO(4), HCl), a considerable capacitance is observed at positive potentials, even when the average pore size is too small to allow the insertion of large anions in neutral electrolyte solutions. This effect disappears when the pore size becomes considerably larger than the size of the ions. In this case, the EDL capacitance at positive potentials for both neutral and acidic solutions is comparable. The following four-step mechanism was found to comply best with the experimental data: (1) By acid catalysis, the protons form carbonium species within the conjugated carbon network. (2) The anions react with the carbonium ions, providing uncharged species in an activated state, which are chemibound as surface groups to the walls of the pores. (3) Because these surface groups are effectively much smaller in size than are the charged ions, they can migrate by chemical bond exchange within the carbon skeleton via constrictions (known to exist in microporous and molecular sieving carbons), which are too narrow to accommodate hydrated charged species. (4) Upon reaching wider spaces, the uncharged species are reionized and solvated by water molecules, which can fill small pores. The justification for the above mechanism is thoroughly discussed and demonstrated by the experimental results.

  17. Anionic magnetite nanoparticle conjugated with pyrrolidinyl peptide nucleic acid for DNA base discrimination (United States)

    Khadsai, Sudarat; Rutnakornpituk, Boonjira; Vilaivan, Tirayut; Nakkuntod, Maliwan; Rutnakornpituk, Metha


    Magnetite nanoparticles (MNPs) were surface modified with anionic poly( N-acryloyl glycine) (PNAG) and streptavidin for specific interaction with biotin-conjugated pyrrolidinyl peptide nucleic acid (PNA). Hydrodynamic size ( D h) of PNAG-grafted MNPs varied from 334 to 496 nm depending on the loading ratio of the MNP to NAG in the reaction. UV-visible and fluorescence spectrophotometries were used to confirm the successful immobilization of streptavidin and PNA on the MNPs. About 291 pmol of the PNA/mg MNP was immobilized on the particle surface. The PNA-functionalized MNPs were effectively used as solid supports to differentiate between fully complementary and non-complementary/single-base mismatch DNA using the PNA probe. These novel anionic MNPs can be efficiently applicable for use as a magnetically guidable support for DNA base discrimination.

  18. Evidence of interlipidic ion-pairing in anion-induced DNA release from cationic amphiphile-DNA complexes. Mechanistic implications in transfection. (United States)

    Bhattacharya, S; Mandal, S S


    Complex formation of DNA with a number of cationic amphiphiles has been examined using fluorescence, gel electrophoresis, and chemical nuclease digestion. Here we have addressed the status of both DNA and lipid upon complexation with each other. DNA upon binding with cationic amphiphiles changes its structure in such a way that it loses the ability to intercalate and becomes resistant to nuclease digestion. Fluorescence anisotropy measurements due to 1, 6-diphenylhexatriene (DPH) doped in cationic liposomes demonstrated that upon complexation with DNA, the resulting complexes still retain lamellar organizations with modest enhancement in thermal stabilities. The lipid-DNA complexation is most effective only when the complexation was carried out at or around the phase transition temperatures of the cationic lipid employed in the complexation with DNA. The release of DNA from cationic lipid-DNA complexes could be induced by several anionic additives. Determination of fluorescence anisotropies (due to DPH) as a function of temperature clearly demonstrates that the addition of equivalent amounts of anionic amphiphile into cationic lipid-DNA complexes leads to the ion-pairing of the amphiphiles, the melting profiles of which are virtually the same as those obtained in the absence of DNA. In this process DNA gets released from its complexes with cationic lipids and regains its natural intercalation ability, movement, and staining ability on agarose gel and also the sensitivities toward nuclease digestion. This clearly suggests that combination of ion-pairing and hydrophobic interactions between cationic and anionic amphiphiles is stronger than the electrostatic forces involved in the cationic lipid-DNA complexation. It is further revealed that the DNA release by anions is most efficient from the cationic lipid-DNA complexes at or around the Tm of the cationic lipid used in DNA complexation. This explains why more effective DNA delivery is achieved with cationic lipids

  19. Hyaluronic acid ion-pairing nanoparticles for targeted tumor therapy. (United States)

    Li, Wenhao; Yi, Xiaoli; Liu, Xing; Zhang, Zhirong; Fu, Yao; Gong, Tao


    Hyaluronic acid (HA)-based doxorubicin (DOX) nanoparticles (HA-NPs) were fabricated via ion-pairing between positively charged DOX and negatively charged HA, which displayed near-spherical shapes with an average size distribution of 180.2nm (PDI=0.184). Next, HA-NPs were encapsulated in liposomal carriers to afford HA-based DOX liposomes (HA-LPs), which also showed near-spherical morphology with an average size of 130.5nm (PDI=0.201). HA-NPs and HA-LPs displayed desirable sustained-release profiles compared to free DOX, and moreover, HA-LPs were proven to prevent premature release of DOX from HA-NPs. Cell based studies demonstrated HA-NPs and HA-LPs were selectively taken up by CD44(+) tumor cells, and DOX was released intracellularly to target the cell nuclei. Both HA-NPs and HA-LPs showed comparable levels of penetration efficiency in tumor spheroids. In vivo studies revealed that HA-NPs and HA-LPs significantly prolonged the blood circulation time of DOX, decreased accumulation in the normal tissues and enriched drugs into the tumors. Furthermore, HA-NPs and HA-LPs greatly enhanced therapeutic efficacy of DOX in tumor-bearing mice and minimized systemic toxicity against vital organs. In sum, HA-NPs and HA-LPs represent promising nanocarriers for CD44(+) tumor-targeted delivery.

  20. Solid phase extraction of lactic acid from fermentation broth by anion-exchangeable silica confined ionic liquids. (United States)

    Bi, Wentao; Zhou, Jun; Row, Kyung Ho


    Three anion-exchangeable, silica-confined ionic liquids were synthesized for solid phase extraction of lactic acid from fermentation broth, followed by high-performance liquid chromatography coupled to ultraviolet detection. By comparing the adsorption isotherms of lactic acid on different silica-confined ionic liquids, interactions between the lactic acid and sorbents were investigated. The adsorbed amounts were then fitted into different adsorption isotherm equations; finally, the Langmuir equation was selected. Then the imidazolium silica with the highest adsorption capacity of lactic acid was packed into a cartridge for solid phase extraction. The loading volume of the cartridge was optimized by the Langmuir equation and geometry. After washing with distilled water and eluting with 0.25 mol L(-1) of an HCl solution, the lactic acid was separated from interference with a recovery yield of 91.9%. Furthermore, this kind of anion-exchangeable material exhibited potential for industrial applications and separation of other anionic bioactive compounds.

  1. Organic acids and inorganic anions in Bayer liquors by ion chromatography after solid-phase extraction

    Institute of Scientific and Technical Information of China (English)

    ZHONG Fu-jin; CHEN Xiao-qing; ZHANG Shu-chao; LI Yue-ping


    A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, propionate, oxalate, succinate,glutarate, fluoride, chloride and sulfate were separated and determined in 33 min. The samples were pretreated with solid-phase extraction, which has high selectivity for removing a large number of metallic ions in the Bayer liquors, and filtered with a 0.45 μm filter membrane before being injected into the ion chromatographic system. The separation of six organic acids and three inorganic anions was achieved on an IonPac AS11-HC column with KOH as the eluent, and the detection was performed by a conductivity detection mode. No interference is found in the presence of fluorate, chlorate and sulphate when organic acids are determined. The calibration graphs of peak area for all the analytes are linear over a wide range. The relative standard derivation of the peak area of analytes is less than 2.14%. Under optimum conditions the detection ranges from 0.2 to 100.0 mg/L. The average recoveries of the added standards are between 94.3% and 102.8%.

  2. Electrochemical Behavior of Heteropoly Acid Anions Adsorbed in Electrodes Modified with Mesoporous Molecular Sieve Silica

    Institute of Scientific and Technical Information of China (English)

    Wenjiang LI; Zichen WANG; Changqing SUN; Muyu ZHAO; Youwei YAO; Aili CUI


    Heteropoly acid H4SiW12O48 (denoted as SiW12) was assembled with the mesoporous materials MCM-41 modified with 3-aminopropyltriethoxysilane (APTES) (denote MCM-41(m)). The electrochemical behavior of SiW12/MCM-41(m) complexes-based electrode indicated SiW12 anion was adsorbed by MCM-41(m). In MCM-41(m) electrode, large voltammetric waves, showing that the electrostatic bound ions adsorbed in MCM-41(m) were electrochemically active. The potential application as amperometric sensors for nitrite is anticipated.

  3. A density-functional theory study of electrochemical adsorption of sulfuric acid anions on Pt(111). (United States)

    Santana, Juan A; Cabrera, Carlos R; Ishikawa, Yasuyuki


    A density-functional theory study of the electrochemical adsorption of sulfuric acid anions was conducted at the Pt(111)/electrolyte interface over a wide range of electrode potential, including the anomalous region of the hydrogen voltammogram of this electrode. We focus on the precise nature of the binding species and their bonding to the surface, identifying the adsorbed species as a function of electrode potential. In particular, the origin of anomalous or so-called "butterfly" feature in this voltammogram between +0.30 and +0.50 V vs. the reference hydrogen electrode and the nature of the adsorbed species on the Pt(111) surface in this potential range were explicated.

  4. Determination of uranium isotopes in environmental samples by anion exchange in sulfuric and hydrochloric acid media. (United States)

    Popov, L


    Method for determination of uranium isotopes in various environmental samples is presented. The major advantages of the method are the low cost of the analysis, high radiochemical yields and good decontamination factors from the matrix elements, natural and man-made radionuclides. The separation and purification of uranium is attained by adsorption with strong base anion exchange resin in sulfuric and hydrochloric acid media. Uranium is electrodeposited on a stainless steel disk and measured by alpha spectrometry. The analytical method has been applied for the determination of concentrations of uranium isotopes in mineral, spring and tap waters from Bulgaria. The analytical quality was checked by analyzing reference materials.

  5. Metabolism and root exudation of organic acid anions under aluminium stress


    Eduardo D Mariano; Jorge, Renato A; Keltjens, Willem G.; Menossi, Marcelo


    Numerous plant species can release organic acid anions (OA) from their roots in response to toxic aluminium (Al) ions present in the rooting medium. Hypothetically OA complex Al in the root apoplast and/or rhizosphere and thus avoid its interaction with root cellular components and its entry in the root symplast. Two temporal patterns of root OA exudation are observed. In pattern I, OA release is rapidly activated after the contact of the root with Al ions while in pattern II there is a lag p...

  6. Nucleic Acid Base Analog FRET-Pair Facilitating Detailed Structural Measurements in Nucleic Acid Containing Systems

    DEFF Research Database (Denmark)

    Börjesson, Karl; Preus, Søren; El-Sagheer, Afaf;


    toward detailed studies of the inherent dynamics of nucleic acid structures. Moreover, the placement of FRET-pair chromophores inside the base stack will be a great advantage in studies where other (biomacro)molecules interact with the nucleic acid. Lastly, our study gives possibly the first truly solid...... distances covering up to more than one turn of the DNA duplex. Importantly, we show that the rigid stacking of the two base analogs, and consequently excellent control of their exact positions and orientations, results in a high control of the orientation factor and hence very distinct FRET changes...... as the number of bases separating tCO and tC(nitro) is varied. A set of DNA strands containing the FRET-pair at wisely chosen locations will, thus, make it possible to accurately distinguish distance- from orientation-changes using FRET. In combination with the good nucleobase analog properties, this points...

  7. Thermodynamics of Ion Pair Formations Between Charged Poly(Amino Acid)s. (United States)

    Petrauskas, Vytautas; Maximowitsch, Eglė; Matulis, Daumantas


    Electrostatic interactions between the positively and negatively charged amino acids in proteins play an important role in macromolecular stability, binding, and recognition. Numerous amino acids in proteins are ionizable and may exist in negatively (e.g., Glu, Asp, Cys, Tyr) or positively (e.g., Arg, Lys, His, Orn) charged form dependent on pH and their pKas. In this work, isothermal titration calorimetry was used to determine the average standard values of thermodynamic parameters (the Gibbs free energy, enthalpy, entropy, and the heat capacity) of interaction between the positively charged amino acid homopolymers (polyarginine, polylysine, and polyornithine) and the negatively charged homopolymers (polyaspartic and polyglutamic acids). These values are of potential use in the computational models of interacting proteins and other biological macromolecules. The study showed that oppositely charged poly(amino acid)s bound each other with the stoichiometry of one positive to one negative charge. Arginine bound to the negatively charged amino acids with exothermic enthalpy and higher affinity than lysine. This result also suggests that positive charges in proteins should not be considered entirely equivalent if carried by lysine or arginine. The difference in binding energy of arginine and lysine association with the negatively charged amino acids was attributed to the enthalpy of the second ionic hydrogen bond formation between the guanidine and carboxylic groups. Despite the favorable enthalpic contribution, all such ion pair formation reactions were largely entropy-driven. Consistent with previously observed ionic interactions, the positive heat capacity was always observed during the amino acid ion pair formation.

  8. Negative ion photoelectron spectroscopy of the copper-aspartic acid anion and its hydrated complexes (United States)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.; Martínez, Ana; Salpin, Jean-Yves; Schermann, Jean-Pierre


    Negative ions of copper-aspartic acid Cu(Asp)- and its hydrated complexes have been produced in the gas phase and studied by anion photoelectron spectroscopy. The vertical detachment energies (VDE) of Cu(Asp)- and Cu(Asp)-(H2O)1,2 were determined to be 1.6, 1.95, and 2.20 eV, respectively. The spectral profiles of Cu(Asp)-(H2O)1 and Cu(Asp)-(H2O)2 closely resembled that of Cu(Asp)-, indicating that hydration had not changed the structure of Cu(Asp)- significantly. The successive shifts to higher electron binding energies by the spectra of the hydrated species provided measures of their stepwise solvation energies. Density functional calculations were performed on anionic Cu(Asp)- and on its corresponding neutral. The agreement between the calculated and measured VDE values implied that the structure of the Cu(Asp)- complex originated with a zwitterionic form of aspartic acid in which a copper atom had inserted into the N-H bond.

  9. High performance ion chromatography of haloacetic acids on macrocyclic cryptand anion exchanger. (United States)

    Bruzzoniti, Maria Concetta; De Carlo, Rosa Maria; Horvath, Krisztian; Perrachon, Daniela; Prelle, Ambra; Tófalvi, Renáta; Sarzanini, Corrado; Hajós, Péter


    A new high performance ion chromatographic method has been developed for the separation of the nine chlorinated-brominated haloacetic acids (HAAs) that are the disinfection by-products of chlorination of drinking water, using a macrocycle-based adjustable-capacity anion-exchange separator column (IonPac Cryptand A1). A gradient method based on theoretical and experimental considerations has been optimized in which 10 mM NaOH-LiOH step gradient was performed at the third minute of the analysis. The optimized method allowed us to separate the nine HAAs and seven possibly interfering inorganic anions in less than 25 min with acceptable resolution. The minimum concentrations detectable for HAAs were between 8.0 (MBA) and 210 (TBA) microg L(-1), with linearity included between 0.9947 (TBA) and 0.9998 (MBA). To increase sensitivity, a 25-fold preconcentration step on a reversed phase substrate (LiChrolut EN) has been coupled. Application of this method to the analysis of haloacetic acids in real tap water samples is illustrated.

  10. Mechanism of protection of adenosine from sulphate radical anion and repair of adenosine radicals by caffeic acid in aqueous solution

    Indian Academy of Sciences (India)

    M Sudha Swaraga; L Charitha; M Adinarayana


    The photooxidation of adenosine in presence of peroxydisulphate (PDS) has been studied by spectrophotometrically measuring the absorbance of adenosine at 260 nm. The rates of oxidation of adenosine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of adenosine suggesting that caffeic acid acts as an efficient scavenger of $SO_{4}^{\\bullet-}$ and protects adenosine from it. Sulphate radical anion competes for adenosine as well as for caffeic acid. The quantum yields of photooxidation of adenosine have been calculated from the rates of oxidation of adenosine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields (exptl) and the quantum yields calculated (cal) assuming caffeic acid acting only as a scavenger of $SO_{4}^{\\bullet-}$ show that exptl values are lower than cal values. The ' values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for $SO_{4}^{\\bullet-}$ scavenging by caffeic acid, are also found to be greater than exptl values. These observations suggest that the transient adenosine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.

  11. Three ion-pair complexes containing bis(maleonitriledithiolate)copper(II) anion and substituted 2-aminopyridinium cations: Syntheses, crystal structures, and magnetic properties (United States)

    Liu, Yin; Ou, Shu-Hua; Li, Jin-Ni; Liao, Xiao-Lan; Zheng, Xiao-Xu; Luo, Cui-Ping; Yang, Le-Min; Zhou, Jia-Rong; Ni, Chun-Lin


    Three new ion-pair complexes, [2-ClBz-2‧-NH2Py]2[Cu(mnt)2](1), [2-Cl-4-ClBz-2-NH2Py]2[Cu(mnt)2](2) and [2-Cl-4-BrBz-2‧-NH2Py]2[Cu(mnt)2]·C2H5OH(3) ([2-Cl-4-RBz-2‧-NH2Py]+ = 1-(2‧-chloro-4‧-Rbenzyl)-2-aminopyridinium, R = H, Cl, Br; mnt2- = maleonitriledithiolate), were synthesized and characterized by elemental analyses, IR, UV-visible, single crystal X-ray diffraction and magnetic measurements. Both 1 and 2 crystallize in the monoclinic space group P2(1)/c, and the [Cu(mnt)2]2- anions and the cations form a 1D network structure through the N-HṡṡṡN hydrogen bonds. While the anions in 3 form a ladder-like chain through the C-HṡṡṡN interactions between the [Cu(mnt)2]2- anions and CH3CH2OH molecules. Some weak interactions such as πṡṡṡπ, CuṡṡṡN, ClṡṡṡC, and C-HṡṡṡCl, O-HṡṡṡCl, C-HṡṡṡS, N-HṡṡṡO, N-HṡṡṡN and C-HṡṡṡN hydrogen bonds in three molecular solids generate further a 3D network structure. The magnetic measurement reveals that 1 shows a very weak ferromagnetic interaction, and 2 exhibits a transition from ferromagnetic to antiferromagnetic coupling about 15 K, while 3 shows an antiferromagnetic coupling feature with θ = -12.51 K when the temperature is lowered.

  12. Capillary ion electrophoresis of inorganic anions and uric acid in human saliva using a polyvinyl alcohol coated capillary column and hexamethonium chloride as additive of background electrolyte. (United States)

    Mori, Masanobu; Yamamoto, Tsukasa; Kaseda, Maki; Yamada, Sachiko; Itabashi, Hideyuki


    A combination of polyvinyl alcohol chemically coated capillary (PVA capillary) and background electrolyte (BGE) with ion-pair reagent (hexamethonium dichloride, HMC) was used on capillary ion electrophoresis-UV detection (CIE-UV) for analysis of Br⁻, I⁻, NO₂⁻, NO₃⁻, SCN⁻ and uric acid in human saliva. The PVA capillary prepared in our laboratory minimized electro-osmotic flow (EOF) at the BGE in pH 3-10, and did not affect the UV detection at 210 nm by the PVA-layer on capillary wall. Therefore, use of the PVA capillary was suitable for sensitive UV detection for analyte anions, as well as suppression of protein adsorption. In this study, we optimized the BGE of 10 mM phosphate plus 10 mM HMC with applying a voltage of -15 kV. HMC as an additive to BGE could manipulate the electrophoretic mobility of anions, without electrostatic adsorption to the PVA capillary. The CIE-UV could separate and determine analyte anions in human saliva containing proteins by the direct injection without pretreatments such as dilution or deproteinization within 13 min. The relative standard deviations (n=10) were ranged of 0.5-1.6% in migration times, 2.2-6.8% in peak heights and 2.8-8.4% in peak areas. The limits of detection (S/N=3) were ranged of 3.42-6.87 μM. The peak height of anions in this system was gradually decreased through the successive injections of saliva samples, but the problem was successfully solved by periodically conditioning the PVA capillary. The quantifiability of anions in human saliva samples by the CIE-UV was evaluated through the recoveries by standard addition methods and comparison of other representative analytical methods, as well as identification by ion chromatography (IC). From the anion analyses in 12 different saliva samples, the CIE-UV demonstrated that can obtain obvious differences in concentrations of SCN⁻ between of smoker and non-smoker and those of uric acid between male and female with satisfactory results.

  13. Cryogenic neon matrix-isolation FTIR spectroscopy of evaporated ionic liquids: geometrical structure of cation-anion 1:1 pair in the gas phase. (United States)

    Akai, Nobuyuki; Parazs, David; Kawai, Akio; Shibuya, Kazuhiko


    Low-temperature infrared spectra of thermally evaporated ionic liquids, 1-ethyl- and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and bis(trifluoromethanesulfonyl)amide have been measured in a cryogenic Ne matrix. The experimental IR spectrum of bis(trifluoromethanesulfonyl)amide can be reproduced theoretically by not B3LYP/6-31G* but MP2/6-31G* calculation, which suggests that the vibrational analysis for ionic liquids composed of bis(trifluoromethanesulfonyl)imide anion would be more successfully performed using the MP2 calculation. By comparison of the matrix-isolation spectra of the ionic liquids with the MP2 calculation, their geometrical structures in the gas phase are determined to be of C(2-position)-H(+)...N(-) interaction structure, which corresponds to the geometry of the energetically second-lowest ion-pair structure. The present study may provide a valuable clue to understand a vaporization mechanism of ionic liquid.

  14. Enhanced conductivity detection of common inorganic anions in electrostatic ion chromatography using water eluent

    Institute of Scientific and Technical Information of China (English)

    Daisuke KOZAKI; Chao-Hong SHI; Kazuhiko TANAKA; Nobutake NAKATANI


    To enhance the conductivity detection sensitivity of common anions (Na-anions) in electrostatic ion chromatography (EIC) by elution with water,a conductivity enhancement column packed with strong acid cation exchange resin in the H-form was inserted between an octadecyl silane (ODS)-silica separation column modified with zwitterionic surfactant ( CHAPS:3- { ( 3-cholamidopropyl ) -dimethylammonio } propanesulfonate ) and a conductivity detector.Specifically,the Na-anion pairing is converted to H-anion pairing after the EIC separation and then detected sensitively by the conductivity detector.The effects of conductivity enhancement and suppression in the EIC by the enhanced conductivity detection were characterized for the common strong acid anions such as SO42-,Cl-,NO3-,I- and ClO4- and weak acid anions such as F-,NO2-,HCOO-,CH3COO- and HCO3-.For the conductivity enhancement effect in the EIC,it is found that the conductivity of measured for all strong acid anions (Na-anions) was enhanced acording to the theoretical conductivity predicted for H-anions and that of the measured for weak acid anions was suppressed depending on their pKa of H-anions.For the calibration linearity in the EIC,the strong acid anions were linear (r2 =0.99 - 1.00) because the degree of dissociation is almost 1.0 over all the concentration range and that of the weak acid anions was non-linear because the degree of dissociation decreased by increasing the concentration of the weak acid anions.In conclusion,the EIC by enhanced conductivity detection was recognized to be useful only for the strong acid anions in terms of conductivity detection and calibration linearity.

  15. L(+-Lactic acid recovery from cassava bagasse based fermented medium using anion exchange resins

    Directory of Open Access Journals (Sweden)

    Rojan P. John


    Full Text Available The properties of the ion exchange resins, Amberlite IRA 402, a strong anion exchange resin and IRA 67, a weak anion exchange resin were determined to evaluate their comparative suitability for lactic acid recovery from fermented cassava bagasse. Data on binding capacities and recovery proved that weak base resin in chloride form was the most favourable ones for lactic acid recovery from aqueous solutions and fermentation media. Fermented media obtained through simultaneous saccharification and fermentation of cassava bagasse starch hydrolysate based medium were used for lactic acid recovery study using weak base resin column. Amberlite IRA 67 had much more efficiency than Amberlite IRA 402 to recover lactic acid. Like in other reports, due to the presence of nutrients and ions other than lactate, the binding capacity was slightly lesser while using fermented media (~93% instead of aqueous lactic acid solutions (~98%.As propriedades das resinas de troca iônica, da Amberlite IRA 402, uma resina de troca aniônica forte, e da IRA 67, uma resina de troca aniônica fraca, foram determinadas para se avaliar a adequabilidade comparativa delas à obtenção de ácido lático de bagaço de mandioca fermentado. Dados sobre a capacidade de ligação e sobre a obtenção provaram que a resina de base fraca na forma de cloreto era a mais adequada para a obtenção de ácido lático em soluções aquosas e meios de fermentação. Os meios de fermentação obtidos da sacarificação e da fermentação simultâneas de meios baseados hidrolisados de fécula de bagaço de mandioca foram usados para o estudo da obtenção de ácido lático usando uma coluna de resina de base fraca. A Amberlite IRA 67 mostrou-se muito mais eficaz do que a Amberlite IRA 402 para a obtenção de ácido lático. Como em outros relatórios, devido à presença de nutrientes e íons que não lactatos, a capacidade de ligação foi ligeiramente inferior enquanto se utilizavam meios

  16. Application of partially fluorinated carboxylic acids as ion-pairing reagents in LC/ESI-MS. (United States)

    Yamamoto, Eiichi; Ishihama, Yasushi; Asakawa, Naoki


    This report describes the application of partially fluorinated carboxylic acids as ion-pairing reagents for basic analytes in high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (LC/ESI-MS) in positive-ion mode. Partially fluoridated carboxylic acids such as difluoroacetic acid, 3,3,3-trifluoropropionic acid and 3,3,3-trifluoromethyl-2-trifluoromethylpropionic acid functioned as volatile paired-ion similarly as trifluoroacetic acid (TFA). These acids provided basic analytes larger retention factor (k) compared to acetic acid or formic acid in LC. The ESI-MS signal strength of analytes with these acids were higher than that of TFA and was analogous to that of acetic acid or formic acid. The performances of partially fluorinated carboxylic acids in LC and ESI-MS for basic analytes were analyzed by multivariate statistical analysis using physicochemical descriptors of acids. Equations obtained in the analysis enabled us the quantitative evaluation of the performance of fluorinated carboxylic acids as ion-pair reagents for basic analytes in LC/ESI-MS.


    Institute of Scientific and Technical Information of China (English)

    Chao Long; Quan-xing Zhang; Ai-min Li; Jin-long Chen


    The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, ptoluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy,and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.

  18. Simultaneous determination of three chloroacetic acids, three herbicides, and 12 anions in water by ion chromatography. (United States)

    Luo, Ximing; Chen, Liang; Zhao, Yanqing


    An ion chromatography method was developed for the simultaneous detection of three soluble herbicides (glyphosate, bentazone and picloram), three chlorine disinfection byproducts (monochloroacetic acid, dichloroacetic acid and trichloroacetic acid) and 12 anions in water (Cl(-), Br(-), SO4(2-), CO3(2-), ClO3(-), ClO4(-), BrO3(-), PO4(3-), NO2(-), NO3(-), CH3COO(-) and COO(-)). High linearity (r(2) > 0.996) was observed for all target analytes for each respective concentration range. The limit of detection and limit of quantitation were between 0.21-0.85 and 0.06-25.46 μg/L, respectively. However, the interference effect of Cl(-), NO3(-) , SO4 (2-) and CO3(2-) on some target analytes must be considered during the analysis. Sample pre-treatment by a hydrogen column (H-column) required to reduce the negative effect of CO3(2-). Additionally, sample pre-treatment by a sliver-hydrogen column (Ag-H-column) is required when Cl(-) > 100 mg/L and SO4(2-) 100 mg/L and SO4(2-) > 50 mg/L. When Cl(-) > 100 mg/L, SO4(2-) > 50 mg/L and CO3(2-) > 20 mg/L, the sample pre-treatment by either an Ag-H-Ba-column or an Ag-H-column and Ba-column is required to minimize interference.

  19. Scale-free behaviour of amino acid pair interactions in folded proteins

    DEFF Research Database (Denmark)

    Petersen, Steffen B.; Neves-Petersen, Maria Teresa; Mortensen, Rasmus J.


    that they are in buried a-helices or b-strands, in a spatial distance of 3.8–4.3A° and in a sequence distance .4 residues. We speculate that the scale free organization of the amino acid pair interactions in the 8D protein structure combined with the clear dominance of pairs of Ala, Ile, Leu and Val is important......The protein structure is a cumulative result of interactions between amino acid residues interacting with each other through space and/or chemical bonds. Despite the large number of high resolution protein structures, the ‘‘protein structure code’’ has not been fully identified. Our manuscript...... presents a novel approach to protein structure analysis in order to identify rules for spatial packing of amino acid pairs in proteins. We have investigated 8706 high resolution non-redundant protein chains and quantified amino acid pair interactions in terms of solvent accessibility, spatial and sequence...


    Institute of Scientific and Technical Information of China (English)

    TAOZuyi; WANGChangshou


    The general procedure based on the potentiometric titration has developed.According to the procedure,the rational equilibrium constants of the ion exchange reactions RH/Na,RH/Ca,RH/Sr,RH/Ba for the weak acid cation exchange resin D725 and ROH/Cl for the weak base anion exchange resin D705 have been determined.

  1. Lysozyme stability and amyloid fibrillization dependence on Hofmeister anions in acidic pH. (United States)

    Poniková, Slavomíra; Antošová, Andrea; Demjén, Erna; Sedláková, Dagmar; Marek, Jozef; Varhač, Rastislav; Gažová, Zuzana; Sedlák, Erik


    We have explored an effect of Hofmeister anions, Na2SO4, NaCl, NaBr, NaNO3, NaSCN and NaClO4, on stability and amyloid fibrillization of hen egg white lysozyme at pH 2.7. The stability of the protein was analyzed by differential scanning calorimetry. The Hofmeister effect of the anions was assessed by the parameter dT trs/d[anion] (T trs, transition temperature). We show that dT trs/d[anion] correlates with anion surface tension effects and anion partition coefficients indicating direct interactions between anions and lysozyme. The kinetic of amyloid fibrillization of lysozyme was followed by Thioflavin T (ThT) fluorescence. Negative correlation between dT trs/d[anion] and the nucleation rate of fibrillization in the presence of monovalent anions indicates specific effect of anions on fibrillization rate of lysozyme. The efficiency of monovalent anions to accelerate fibrillization correlates with inverse Hofmeister series. The far-UV circular dichroism spectroscopy and atomic force microscopy findings show that conformational properties of fibrils depend on fibrillization rate. In the presence of sodium chloride, lysozyme forms typical fibrils with elongated structure and with the secondary structure of the β-sheet. On the other hand, in the presence of both chaotropic perchlorate and kosmotropic sulfate anions, the fibrils form clusters with secondary structure of β-turn. Moreover, the acceleration of fibril formation is accompanied by decreased amount of the formed fibrils as indicated by ThT fluorescence. Taken together, our study shows Hofmeister effect of monovalent anions on: (1) lysozyme stability; (2) ability to accelerate nucleation phase of lysozyme fibrillization; (3) amount, and (4) conformational properties of the formed fibrils.

  2. Solvation free energies in [bmim]-based ionic liquids: Anion effect toward solvation of amino acid side chain analogues (United States)

    Latif, Muhammad Alif Mohammad; Micaêlo, Nuno; Abdul Rahman, Mohd Basyaruddin


    Stochastic molecular dynamics simulations were performed to investigate the solvation free energy of 15 neutral amino acid side chain analogues in aqueous and five, 1-butyl-3-methylimidazolium ([BMIM])-based ionic liquids. The results in aqueous were found highly correlated with previous experimental and simulation data. Meanwhile, [BMIM]-based RTILs showed better solvation thermodynamics than water to an extent that they were capable of solvating molecules immiscible in water. Non-polar analogues showed stronger solvation in hydrophobic RTIL anions such as [PF6]- and [Tf2N]- while polar analogues showed stronger solvation in the more hydrophilic RTIL anions such as [Cl]-, [TfO]- and [BF4]-.

  3. Selenium speciation in urine by ion-pairing chromatography with perfluorinated carboxylic acids and ICP-MS detection

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Bendahl, L.; Sidenius, U.;


    Five aqueous standards, selenomethionine (SeMet), methylselenomethionine (MeSeMet), methylselenocysteine (MeSeCys), selenogammaaminobutyric acid (SeGaba) and the trimethylselenonium ion (TMSe), were separated in ion-pairing chromatographic systems based on perfluorinated carboxylic acids...... in methanol. Two different perfluorinated carboxylic acids, heptafluorobutanoic acid (HFBA) and nonafluoropentanoic acid (NFPA), were used as ion-pairing agents in the separation. The selectivities of the ion-pairing agents were different. The separation was performed on a microbore column, which...

  4. Gluconic acid production in bioreactor with immobilized glucose oxidase plus catalase on polymer membrane adjacent to anion-exchange membrane. (United States)

    Godjevargova, Tzonka; Dayal, Rajeshwar; Turmanova, Sevdalina


    Gluconic acid was obtained in the permeate side of the bioreactor with glucose oxidase (GOD) immobilized onto anion-exchange membrane (AEM) of low-density polyethylene grafted with 4-vinylpiridine. The electric resistance of the anion-exchange membranes was increased after the enzyme immobilization on the membrane. The gluconic acid productions were relatively low with the GOD immobilized by any method on the AEM. To increase the enzyme reaction efficiency, GOD was immobilized on membrane of AN copolymer (PAN) adjacent to an anion-exchange membrane in bioreactor. Uses of anion-exchange membrane led to selective removal of the gluconic acid from the glucose solution and reduce the gluconic acid inhibition. The amount of gluconic acid obtained in the permeate side of the bioreactor with the GOD immobilized on the PAN membrane adjacent to the AEM under electrodialysis was about 30 times higher than that obtained with enzyme directly bound to the AEM. The optimal substrate concentration in the feed side was found to be about 1 g/l. Further experiments were carried out with the co-immobilized GOD plus Catalase (CAT) on the PAN membrane adjacent to the AEM to improve the efficiency of the immobilize system. The yield of this process was at least 95%. The storage stability of the co-immobilized GOD and CAT was studied (lost 20% of initial activity for 90 d). The results obtained clearly showed the higher potential of the dual membrane bioreactor with GOD plus CAT bound to ultrafiltration polymer membrane adjacent to the AEM. Storage stability of GOD activity in GOD plus CAT immobilized on PAN//AEM membranes and on AEM.

  5. Increasing Hydrogen Density with the Cation-Anion Pair BH4−-NH4+ in Perovskite-Type NH4Ca(BH43

    Directory of Open Access Journals (Sweden)

    Pascal Schouwink


    Full Text Available A novel metal borohydride ammonia-borane complex Ca(BH42·NH3BH3 is characterized as the decomposition product of the recently reported perovskite-type metal borohydride NH4Ca(BH43, suggesting that ammonium-based metal borohydrides release hydrogen gas via ammonia-borane-complexes. For the first time the concept of proton-hydride interactions to promote hydrogen release is applied to a cation-anion pair in a complex metal hydride. NH4Ca(BH43 is prepared mechanochemically from Ca(BH42 and NH4Cl as well as NH4BH4 following two different protocols, where the synthesis procedures are modified in the latter to solvent-based ball-milling using diethyl ether to maximize the phase yield in chlorine-free samples. During decomposition of NH4Ca(BH43 pure H2 is released, prior to the decomposition of the complex to its constituents. As opposed to a previously reported adduct between Ca(BH42 and NH3BH3, the present complex is described as NH3BH3-stuffed α-Ca(BH42.

  6. Phase behavior and properties of salt-free cationic/anionic surfactant mixtures of oleic acid and stearic acid

    Institute of Scientific and Technical Information of China (English)

    ZHAO DianYing; LI HongGuang; SONG AiXin; HAO JingCheng


    Cationic base surfactant,tetradecyltrimethylammonium hydroxide (TTAOH),can be obtained through anion exchange from tetradecyltrimethylammonium bromide (TTABr).Salt-free cationic and anionic (catanionic) surfactant mixtures were studied by mixing TTAOH with oleic acid (OA) or stearic acid (SA) in water.The phase behavior of TTAOH/OA/H_2O is compared with that of TTAOH/SA/H_2O.It was found that the phase behavior of TTAOH/OA/H_2O and TTAOH/SA/H_2O system differs from each other due to the existence of the unsaturated double carbon bond (C=C) in OA.At fixed total surfactant concentration (25 mg/mL) of TTAOHIONH_2O system at 25℃,one can observe an isotropic L_1 phase,and a L_1/L_α two-phase region with increasing OA content.The volume of top turbid L.phase increases while the bottom phase changes gradually from transparently clear to a bit turbid until a single L_α-phase is reached.Finally at high OA concentration,excess OA is separated from the bulk aqueous solutions.TTAOH/SA/H_2O system usually forms white precipitating at 25℃ due to the high chain melting temperature of SA.When heated to 60℃,however,the state of samples changes.At fixed total surfactant concentration of 25 mg/mL,an isotropic L1 phase and a milk-white or bluish La-phase are observed with increasing SA concentration.Transparent thin layers which are strongly birefringent form at the tops of some samples within the L_α-phase region.Finally,at high SA concentration,excess SA is separated from the bulk aqueous solutions.In addition to phase behavior study,we also measured the conductivity of TTAOH/OA/H_2O system at 25℃ and TTAOH/SA/H_2O system at 60℃,respectively.Surface tension and rheological measurements were also performed on typical samples.

  7. Organic Anion Transporting Polypeptides Contribute to the Disposition of Perfluoroalkyl Acids in Humans and Rats. (United States)

    Zhao, Wen; Zitzow, Jeremiah D; Weaver, Yi; Ehresman, David J; Chang, Shu-Ching; Butenhoff, John L; Hagenbuch, Bruno


    Perfluoroalkyl sulfonates (PFSAs) such as perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) have very long serum elimination half-lives in humans, and preferentially distribute to serum and liver. The enterohepatic circulation of PFHxS and PFOS likely contributes to their extended elimination half-lives. We previously demonstrated that perfluorobutane sulfonate (PFBS), PFHxS, and PFOS are transported into hepatocytes both in a sodium-dependent and a sodium-independent manner. We identified Na(+)/taurocholate cotransporting polypeptide (NTCP) as the responsible sodium-dependent transporter. Furthermore, we demonstrated that the human apical sodium-dependent bile salt transporter (ASBT) contributes to the intestinal reabsorption of PFOS. However, so far no sodium-independent uptake transporters for PFSAs have been identified in human hepatocytes or enterocytes. In addition, perfluoroalkyl carboxylates (PFCAs) with 8 and 9 carbons were shown to preferentially distribute to the liver of rodents; however, no rat or human liver uptake transporters are known to transport these PFCAs. Therefore, we tested whether PFBS, PFHxS, PFOS, and PFCAs with 7-10 carbons are substrates of organic anion transporting polypeptides (OATPs). We used CHO and HEK293 cells to demonstrate that human OATP1B1, OATP1B3, and OATP2B1 can transport PFBS, PFHxS, PFOS, and the 2 PFCAs (C8 and C9). In addition, we show that rat OATP1A1, OATP1A5, OATP1B2, and OATP2B1 transport all 3 PFSAs. In conclusion, our results suggest that besides NTCP and ASBT, OATPs also are capable of contributing to the enterohepatic circulation and extended human serum elimination half-lives of the tested perfluoroalkyl acids.

  8. Lewis pair polymerization by classical and frustrated Lewis pairs: Acid, base and monomer scope and polymerization mechanism

    KAUST Repository

    Zhang, Yuetao


    Classical and frustrated Lewis pairs (LPs) of the strong Lewis acid (LA) Al(C 6F 5) 3 with several Lewis base (LB) classes have been found to exhibit exceptional activity in the Lewis pair polymerization (LPP) of conjugated polar alkenes such as methyl methacrylate (MMA) as well as renewable α-methylene-γ-butyrolactone (MBL) and γ-methyl- α-methylene-γ-butyrolactone (γ-MMBL), leading to high molecular weight polymers, often with narrow molecular weight distributions. This study has investigated a large number of LPs, consisting of 11 LAs as well as 10 achiral and 4 chiral LBs, for LPP of 12 monomers of several different types. Although some more common LAs can also be utilized for LPP, Al(C 6F 5) 3-based LPs are far more active and effective than other LA-based LPs. On the other hand, several classes of LBs, when paired with Al(C 6F 5) 3, can render highly active and effective LPP of MMA and γ-MMBL; such LBs include phosphines (e.g., P tBu 3), chiral chelating diphosphines, N-heterocyclic carbenes (NHCs), and phosphazene superbases (e.g., P 4- tBu). The P 4- tBu/Al(C 6F 5) 3 pair exhibits the highest activity of the LP series, with a remarkably high turn-over frequency of 9.6 × 10 4 h -1 (0.125 mol% catalyst, 100% MMA conversion in 30 s, M n = 2.12 × 10 5 g mol -1, PDI = 1.34). The polymers produced by LPs at RT are typically atactic (P γMMBL with ∼47% mr) or syndio-rich (PMMA with ∼70-75% rr), but highly syndiotactic PMMA with rr ∼91% can be produced by chiral or achiral LPs at -78 °C. Mechanistic studies have identified and structurally characterized zwitterionic phosphonium and imidazolium enolaluminates as the active species of the current LPP system, which are formed by the reaction of the monomer·Al(C 6F 5) 3 adduct with P tBu 3 and NHC bases, respectively. Kinetic studies have revealed that the MMA polymerization by the tBu 3P/ Al(C 6F 5) 3 pair is zero-order in monomer concentration after an initial induction period, and the polymerization

  9. Ferrocene-based Lewis acids and Lewis pairs: Synthesis and structural characterization

    Indian Academy of Sciences (India)

    Pagidi Sudhakar; Pakkirisamy Thilagar


    Optically active Lewis acids and Lewis pairs were synthesized and characterized by multinuclear NMR, UV/Vis spectroscopy and elemental analysis. Optical rotation measurements were carried out and the absolute configuration of the new chiral molecules confirmed by single crystal X-ray diffraction.

  10. Study on the Retention Behavior of Aromatic Carboxylic and Sulfonic acid on a New Anion Exchange Column

    Institute of Scientific and Technical Information of China (English)

    SHI,Ya-Li; CAI,Ya-Qi; MOU,Shi-Fen


    Ion chromatography (IC) has gradually developed into a preferred method for the determination of inorganic anions. And in recent years some low molecular aliphatic acid can be also separated in the ion exchange column with the development of stationary phase. But for the determination of aromatic ionic compounds there are some problems. The aromatic anions show enhanced retention due to interaction with the π electrons of the aromatic backbone. Although the addition of an organic modifier can alleviate the difficulty, it is not the ultimate solution.IonPac AS20 column was developed using a unique polymer bonding technology and its substrate coating is aliphatic backbone. The polymer is completely free of any π electron-containing substituents in the AS20 column. In this paper, the retention behavior of aromatic carboxylic and sulfonic acid on two hydroxide-selective columns,IonPac AS11-HC, AS16, and the new column AS20 was also studied. The result showed that the retentions of ten compounds on three columns were different with each other because of their different column characteristics.Among them 4-chlorobenzene sulfonic acid, 3,5-dihydric benzoic acid and salicylic acid obviously exhibited the weakest retention on the IonPac AS20. It was showed that π-π bond function between anion and stationary phases was weakened in AS20 column because its polymer was completely free of any π electron-containing substituents.So in this paper the AS20 was selected as an analytical column to separate ten aromatic ionic compounds, fumaric acid with conjugate bond included. The retention behavior, separation of the ten compounds and effect of temperature on their retention in the anion-exchange column AS20 (2 mm) were studied. The result showed that those compounds could be separated with each other when running in gradient program and the organic modifier was unnecessary during the separation. So it is showed that AS20 column can be used as a separating column because its

  11. Production of 61Cu using natural cobalt target and its separation using ascorbic acid and common anion exchange resin. (United States)

    Das, Sujata Saha; Chattopadhyay, Sankha; Barua, Luna; Das, Malay Kanti


    (61)Cu was produced by (nat)Co(α, xn)(61)Cu reaction. (61)Cu production yield was 89.5 MBq/μAh (2.42 mCi/μAh) at the end of irradiation (EOI). A simple radiochemical separation method using anion exchange resin and ascorbic acid has been employed to separate the product radionuclide from inactive target material and co-produced non-isotopic impurities. The radiochemical separation yield was about 90%. Radiochemical purity of (61)Cu was >99% 1 h after EOI. Final product was suitable for making complex with N(2)S(2) type of ligands.

  12. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate

    Indian Academy of Sciences (India)

    G P Panigrahi; Jagannath Panda


    Kinetics of oxidation of N-methyl and N-ethyl aniline by peroxomono-phosphoric acid (PMPA) in aqueous and 5% (v/v) acetonitrile medium respectively have been studied in presence of anionic micelles of sodium lauryl sulphate (SLS) at different H. Oxidation rate of both the substrates increases up to a certain [SLS] much below the critical micellar concentration (cmc) after which the rate is retarded. Kinetic data have been used to compute the binding constants of both substrate and oxidant with the micelle. A scheme explaining the kinetic data has been proposed.

  13. Hydrogen bonding: a channel for protons to transfer through acid-base pairs. (United States)

    Wu, Liang; Huang, Chuanhui; Woo, Jung-Je; Wu, Dan; Yun, Sung-Hyun; Seo, Seok-Jun; Xu, Tongwen; Moon, Seung-Hyeon


    Different from H(3)O(+) transport as in the vehicle mechanism, protons find another channel to transfer through the poorly hydrophilic interlayers in a hydrated multiphase membrane. This membrane was prepared from poly(phthalazinone ether sulfone kentone) (SPPESK) and H(+)-form perfluorosulfonic resin (FSP), and poorly hydrophilic electrostatically interacted acid-base pairs constitute the interlayer between two hydrophilic phases (FSP and SPPESK). By hydrogen bonds forming and breaking between acid-base pairs and water molecules, protons transport directly through these poorly hydrophilic zones. The multiphase membrane, due to this unique transfer mechanism, exhibits better electrochemical performances during fuel cell tests than those of pure FSP and Nafion-112 membranes: 0.09-0.12 S cm(-1) of proton conductivity at 25 degrees C and 990 mW cm(-2) of the maximum power density at a current density of 2600 mA cm(-2) and a cell voltage of 0.38 V.

  14. Thermodynamics of the ethylene glycol pair interaction with some amino acids and benzene

    Energy Technology Data Exchange (ETDEWEB)

    Kustov, Andrey V., E-mail: [G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation); Ivanovo State University of Chemistry and Technology, Sheremetevskiy av. 7, 153012, Ivanovo (Russian Federation); Antonova, Olga A.; Smirnova, Nataliya L. [G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation); Ivanovo State University of Chemistry and Technology, Sheremetevskiy av. 7, 153012, Ivanovo (Russian Federation)


    Highlights: • Thermodynamics of amino acid solutions in highly aqueous Eg was studied at 298 and 313 K. • The pair interaction parameters were computed using the virial expansion technique. • The results were discussed in terms of solute–Eg pair interactions. - Abstract: We have studied thermodynamics of interaction of benzene and some amino acids with ethylene glycol (Eg) which is a stabilizing agent for proteins in water using calorimetric and solubility data. Enthalpic, entropic and free energy parameters in highly diluted aqueous solutions have been computed at 298 and 313 K using the virial expansion technique and compared with available literature values. The results obtained are discussed in terms of solute–solute interactions and their relation to stability of macromolecules.

  15. Novel additives for the separation of organic acids by ion-pair chromatography

    Institute of Scientific and Technical Information of China (English)


    This paper proposes the use of novel surfactant additives for the separation of organic acids by ion-pair chromatography and studies the influences of surfactants on the chromatographic separation behaviors.Researches have been carried out on both silica gel matrix and polymer supporters in order to compare the two ordinary kinds of stationary phases,and the phenomenon is similar. Separation is based on differences in the stabilities of analyte-additive complexes in solution.Retention times of analytes c...

  16. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    Energy Technology Data Exchange (ETDEWEB)

    Roman, Yuriy [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)


    The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathways for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through

  17. A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Neus Mesquida


    Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

  18. Production of {sup 61}Cu using natural cobalt target and its separation using ascorbic acid and common anion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Das, Sujata Saha; Chattopadhyay, Sankha; Barua, Luna [Radiopharmaceuticals Laboratory, Board of Radiation and Isotope Technology (BRIT), Variable Energy Cyclotron Centre (VECC), Kolkata 700064 (India); Das, Malay Kanti, E-mail: [Radiopharmaceuticals Laboratory, Board of Radiation and Isotope Technology (BRIT), Variable Energy Cyclotron Centre (VECC), Kolkata 700064 (India)


    {sup 61}Cu was produced by {sup nat}Co({alpha}, xn){sup 61}Cu reaction. {sup 61}Cu production yield was 89.5 MBq/{mu}Ah (2.42 mCi/{mu}Ah) at the end of irradiation (EOI). A simple radiochemical separation method using anion exchange resin and ascorbic acid has been employed to separate the product radionuclide from inactive target material and co-produced non-isotopic impurities. The radiochemical separation yield was about 90%. Radiochemical purity of {sup 61}Cu was >99% 1 h after EOI. Final product was suitable for making complex with N{sub 2}S{sub 2} type of ligands. - Highlights: Black-Right-Pointing-Pointer High purity, no-carrier added {sup 61}Cu produced from natural cobalt target. Black-Right-Pointing-Pointer {sup 61}Cu separated from impurities using anion exchange resin and ascorbic acid. Black-Right-Pointing-Pointer {sup 61}Cu preparation was successfully used to label N{sub 2}S{sub 2}-type of ligand.

  19. Preparation and Microbiological Evaluation of Amphiphilic Kanamycin-Lipoamino Acid Ion-Pairs

    Directory of Open Access Journals (Sweden)

    Rosario Pignatello


    Full Text Available Amphiphilic ion-pairs of kanamycin (KAN were prepared by evaporation of a water-ethanol co-solution of KAN base and a lipoamino acid bearing a 12-carbon atoms alkyl side chain (LAA12, at different molar ratios. Infrared spectroscopy confirmed the structure of ion-pairs, while differential scanning calorimetry (DSC and powder X-ray diffractometry (PXRD studies supported the formation of new saline species with a different crystalline structure than the starting components. The solubility pattern shown in a range of both aqueous and organic solvents confirmed that the ion-pairs possess an amphiphilic character. The LAA12 counter-ion showed not to improve the antibacterial activity of KAN, suggesting that such chemical strategy is not able to favor the penetration of this drug inside the bacteria cells. Nevertheless, a slight improving, i.e., a one-fold dilution, was observed in E. coli. The present study can also serve as the basis for a further evaluation of LAA ion-pairing of antibiotics, as a means to improve the loading of hydrophilic drugs into lipid-based nanocarriers.

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jie [Iowa State Univ., Ames, IA (United States)


    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.

  1. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid-base pairs. (United States)

    Baylon, Rebecca A L; Sun, Junming; Martin, Kevin J; Venkitasubramanian, Padmesh; Wang, Yong


    We report the direct conversion of mixed carboxylic acids to C-C olefins with up to 60 mol% carbon yield through cascade (cross) ketonization, (cross) aldolization and self-deoxygenation reactions. Co-feeding hydrogen provides an additional ketone hydrogenation/dehydration pathway to a wider range of olefins.

  2. Catalytic activity of thiacalix[4]arenetetrasulfonate metal complexes on modified anion-exchangers for ascorbic acid oxidation. (United States)

    Odo, Junichi; Hirashima, Tomomi; Hayashida, Tomoko; Miyauchi, Asuka; Minemoto, Mami; Iuchi, Masato; Inoguchi, Masahiko


    The catalysis of ascorbic acid (AsA) oxidation by anion-exchangers modified with metal complexes of thiacalix[4]arenetetrasulfonate (Me-TCAS[4]A-500, Me=Mn(3+), Fe(3+), Co(3+), Ce(4+), Cu(2+), Zn(2+), Ni(2+), and H2) were investigated. Me-TCAS[4]A-500 (Me=Mn(3+), Fe(3+), Ce(4+), and Cu(2+)) all exhibited the ability to catalyze the oxidative reaction of AsA to dehydroascorbic acid. However, in the presence of high concentrations of AsA, only Cu(2+)-TCAS[4]A-500 was capable of complete oxidation of the acid. Moreover, after six repeat uses, Cu(2+)-TCAS[4]A-500 maintained high and relatively constant catalytic activity. Prior treatment of glucose solutions with Cu(2+)-TCAS[4]A-500, even in the presence of high AsA concentrations, enabled the satisfactory determination of glucose without interference by AsA. Cu(2+)-TCAS[4]A-500 will therefore be applicable as an artificial substitute for ascorbate oxidase, and may be useful as a means to eliminate AsA interference during the analysis of vital compounds such as glucose and uric acid.

  3. Simultaneous determination of gallic acid and gentisic acid in organic anion transporter expressing cells by liquid chromatography-tandem mass spectrometry. (United States)

    Wang, Li; Halquist, Matthew S; Sweet, Douglas H


    In order to elucidate the role of organic anion transporters (OATs) in the renal elimination of gallic acid and gentisic acid, a new, rapid, and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been developed and validated for the simultaneous determination of gallic acid and gentisic acid in cell lysate, using Danshensu as the internal standard (IS). After a simple liquid-liquid extraction, the analytes were detected in negative ESI mode using selected reaction monitoring. The precursor-to-product ion transitions (m/z) were 169.0→125.0, 153.1→108.0, and 196.8→135.2 for gallic acid, gentisic acid, and the IS, respectively. Chromatographic separation was achieved on a C18 column using mobile phases consisting of water with 0.1% acetic acid (A) and acetonitrile with 0.05% formic acid. (B) The total run time was 3min and calibration curves were linear over the concentrations of 0.33-2400ng/mL for both compounds (r(2)>0.995). Good precision (between 3.11% and 14.1% RSD) and accuracy (between -12.7% and 11% bias) was observed for quality controls at concentrations of 0.33 (lower limit of quantification), 1, 50, and 2000ng/mL. The mean extraction recovery of gallic acid and gentisic acid was 80.7% and 83.5%, respectively. Results from post-column infusion and post-extraction methods indicated that the analytical method exhibited negligible matrix effects. Finally, this validated assay was successfully applied in a cellular uptake study to determine the intracellular concentrations of gallic acid and gentisic acid in OAT expressing cells.

  4. Simultaneous separation and quantitative determination of monosaccharides, uronic acids, and aldonic acids by high performance anion-exchange chromatography coupled with pulsed amperometric detection in corn stover prehydrolysates

    Directory of Open Access Journals (Sweden)

    Xing Wang


    Full Text Available A method for simultaneous separation and quantitative determination of arabinose, galactose, glucose, xylose, xylonic acid, gluconic acid, galacturonic acid, and glucuronic acid was developed by using high performance anion-exchange chromatography coupled with pulsed amperometric detection (HPAEC-PAD. The separation was performed on a CarboPacTM PA-10 column (250 mm × 2 mm with a various gradient elution of NaOH-NaOAc solution as the mobile phase. The calibration curves showed good linearity (R2 ≥ 0.9993 for the monosaccharides, uronic acids, and aldonic acids in the range of 0.1 to 12.5 mg/L. The detection limits (LODs and the quantification limits (LOQs were 4.91 to 18.75 μg/L and 16.36 to 62.50 μg/L, respectively. Relative standard deviations (RSDs of the retention times and peak areas for the seven consecutive determinations of an unknown amount of mixture were 0.15% to 0.44% and 0.22% to 2.31%, respectively. The established method was used to separate and determine four monosaccharides, two uronic acids, and two aldonic acids in the prehydrolysate from dilute acid steam-exploded corn stover within 21 min. The spiked recoveries of monosaccharides, uronic acids, and aldonic acids ranged from 91.25% to 108.81%, with RSDs (n=3 of 0.04% ~ 6.07%. This method was applied to evaluate the quantitative variation of sugar and sugar acid content in biomass prehydrolysates.

  5. Use of niflumic acid to determine the nature of the asymmetry of the human erythrocyte anion exchange system

    Energy Technology Data Exchange (ETDEWEB)

    Knauf, P.A.; Mann, N.A.


    Niflumic acid is a noncompetitive inhibitor of chloride exchange, which binds to a site different from the transport or modifier sites. When the internal Cl/sup -/ concentration is raised, at constant extracellular Cl/sup -/, the inhibitory potency of niflumic acid increases. This effect cannot be attributed to changes in membrane potential, but rather it suggests that niflumic acid binds to the anion exchange protein band 3 only when the transport site faces outward. When the chloride gradient is reversed, with Cl/sub o/ > Cl/sub i/, the inhibitory potency of niflumic acid decreases greatly, which indicates that the affinity of niflumic acid for band 3 with the transport site facing inward is almost 50 times less than when the transport site faces outward. Experiments in which Cl/sub i/ = Cl/sub o/ show no significant change in the inhibition by niflumic acid when Cl/sup -/ is lowered from 150 to 10 mM. These data suggest that the intrinsic dissociation constants for Cl/sup -/ at the two sides of the membrane are nearly equal. Thus, the chloride-loaded transport sites have an asymmetric orientation like that of the unloaded transport sites, with approx.15 times more sites facing the inside than the outside. The asymmetry reflects an approx.1.5 kcal/mol free energy difference between the inward-facing and outward-facing chloride-loaded forms of band 3. High concentrations of chloride (with Cl/sub i/ = Cl/sub o/), which partially saturate the modifier site, have no effect on niflumic acid inhibition, which indicates that chloride binds equally well to the modifier site regardless of the orientation of the transport site. 25 references, 6 figures, 3 tables.

  6. Use of niflumic acid to determine the nature of the asymmetry of the human erythrocyte anion exchange system (United States)


    Niflumic acid is a noncompetitive inhibitor of chloride exchange, which binds to a site different from the transport or modifier sites. When the internal Cl- concentration is raised, at constant extracellular Cl- , the inhibitory potency of niflumic acid increases. This effect cannot be attributed to changes in membrane potential, but rather it suggests that niflumic acid binds to the anion exchange protein band 3 only when the transport site faces outward. When the chloride gradient is reversed, with Clo greater than Cli , the inhibitory potency of niflumic acid decreases greatly, which indicates that the affinity of niflumic acid for band 3 with the transport site facing inward is almost 50 times less than when the transport site faces outward. Experiments in which Cli = Clo show no significant change in the inhibition by niflumic acid when Cl- is lowered from 150 to 10 mM. These data suggest that the intrinsic dissociation constants for Cl- at the two sides of the membrane are nearly equal. Thus, the chloride- loaded transport sites have an asymmetric orientation like that of the unloaded transport sites, with approximately 15 times more sites facing the inside than the outside. The asymmetry reflects an approximately 1.5 kcal/mol free energy difference between the inward-facing and outward-facing chloride-loaded forms of band 3. High concentrations of chloride (with Cli = Clo), which partially saturate the modifier site, have no effect on niflumic acid inhibition, which indicates that chloride binds equally well to the modifier site regardless of the orientation of the transport site. PMID:6736917

  7. An anionic two-dimensional indium carboxylate framework derived from a pseudo 3-symmetric semi-flexible tricarboxylic acid

    Indian Academy of Sciences (India)

    Pratap Vishnoi; Alok Ch Kalita; Ramaswamy Murugavel


    Hydrothermal treatment of indium(III) nitrate with a flexible pseudo 3-symmetric tricarboxylic acid at 115°C for 5 days in DMF yields a new layered anionic indium carboxylate framework, [(CH3)2 NH2)][In(L)(HCOO)(DMF)] (1) (L = 2,4,6-tris[(4′-carboxyphenoxy)methyl]-1,3,5-trimethylbenzene), existing as two-dimensional sheets. The framework solid has been characterized by elemental analysis, FT-IR spectroscopy, TGA, PXRD and single crystal X-ray diffraction studies. DMF undergoes cleavage to dimethyl ammonium and formate ions, which are incorporated in the framework. A slipped stacking of the two dimensional sheets along -axis in 1 results in a drastic decrease in the anticipated large porosity of the framework.

  8. [5-0xoproline (pyroglutamic acid) acidosis and acetaminophen- a differential diagnosis in high anion gap metabolic acidosis]. (United States)

    Weiler, Stefan; Bellmann, Romuald; Kullak-Ublick, Gerd A


    Rare cases of high anion gap metabolic acidosis during long-term paracetamol administration in therapeutic doses with causative 5-oxoproline (pyroglutamic acid} accumulation have been reported. Other concomitant risk factors such as malnutrition, alcohol abuse, renal or hepatic dysfunction, comedication with flue/oxacillin, vigabatrin, netilmicin or sepsis have been described. The etiology seems to be a drug-induced reversible inhibition of glutathione synthetase or 5-oxoprolinase leading to elevated serum and urine levels of 5-oxoproline. Other more frequent differential diagnoses, such as intoxications, ketoacidosis or lactic acidosis should be excluded. Causative substances should be stopped. 5-oxoproline concentrations in urine can be quantified to establish the diagnosis. Adverse drug reactions, which are not listed or insufficiently described in the respective Swiss product information, should be reported to the regional pharmacovigilance centres for early signal detection. 5-0 xoproline acidosis will be integrated as a potential adverse drug reaction in the Swiss product information for paracetamol.

  9. Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors

    Directory of Open Access Journals (Sweden)

    Refat M. Hassan


    Full Text Available Corrosion inhibition of aluminum (Al in hydrochloric acid by anionic polyeletrolyte pectates (PEC as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

  10. Synthesis and Crystal Structure of a Novel Ion-pair Compound Consisting of 1-(4-Bromobenzyl)pyridinium Cation and 7,7,8,8-Tetracyanoquinodimethanide Anion

    Institute of Scientific and Technical Information of China (English)

    ZHOU Hong-Bo; CHEN You-Cun


    The title compound [BrBzPy][TCNQ] (BrBzPy+=1-(4-bromobenzyl)pyridinium cation, TCNQ = 7,7,8,8-tetracyanoquinodimethanide anion) was synthesized by the reaction of [BrBzPy]Br and LiTCNQ in ethanol solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.067(3), b = 7.3089(14), c = 23.796(4) (A), β = 122.011 (9)°, V = 2074.6(7) (A)3, Z = 4, C24H15BrN5, Mr = 453.32, Dc = 1.451 g/cm3, μ = 2.002 mm-1, S = 1.047, F(000) = 916, R = 0.0398 and wR = 0.0921. The most prominent structural features are the completely segregated stacking columns of the TCNQ-anions and [BrBzPy]+ cations. In a TCNQ column, the centroid-to-centroid distances of the neighboring anions of TCNQ are 3.2693 and 4.9464 (A), respectively.

  11. Field measurement of acid gases and soluble anions in atmospheric particulate matter using a parallel plate wet denuder and an alternating filter-based automated analysis system. (United States)

    Boring, C Bradley; Al-Horr, Rida; Genfa, Zhang; Dasgupta, Pumendu K; Martin, Michael W; Smith, William F


    We present a new fully automated instrument for the measurement of acid gases and soluble anionic constituents of atmospheric particulate matter. The instrument operates in two independent parallel channels. In one channel, a wet denuder collects soluble acid gases; these are analyzed by anion chromatography (IC). In a second channel, a cyclone removes large particles and the aerosol stream is then processed by another wet denuder to remove potentially interfering gases. The particles are then collected by one of two glass fiber filters which are alternately sampled, washed, and dried. The washings are preconcentrated and analyzed by IC. Detection limits of low to subnanogram per cubic meter concentrations of most gaseous and particulate constituents can be readily attained. The instrument has been extensively field-tested; some field data are presented. Results of attempts to decipher the total anionic constitution of urban ambient aerosol by IC-MS analysis are also presented.

  12. Recovery of lactic acid from simultaneous saccharification and fermentation media using anion exchange resins. (United States)

    Moldes, A B; Alonso, J L; Parajó, J C


    The physicochemical properties (capacity, kinetics and selectivity) of the ion exchange resins Amberlite IRA900, IRA400, IRA96 and IRA67 were determined to evaluate their comparative suitability for lactic acid recovery. Both the kinetics of lactic acid sorption from aqueous solutions and the equilibrium were assessed using mathematical models, which provided a close interpretation of the experimental results. The best resins (Amberlite IRA96 and IRA67) were employed in further fixed-bed operation using aqueous lactic acid solutions as feed. In this set of experiments, parameters such as capacity, regenerant consumption, percentage of lactic acid recovery and product concentration were measured. Amberlite IRA67, a weak base resin, was selected for lactic acid recovery from SSF (simultaneous saccharification and fermentation) broths. Owing to the presence of nutrients and ions other than lactate, a slightly decreased capacity was determined when using SSF media instead aqueous lactic acid solutions, but quantitative lactic acid recoveries at constant capacities were obtained in four sequential load/regeneration cycles.

  13. Ion pair formation as a possible mechanism for the enhancement effect of lauric acid on the transdermal permeation of ondansetron. (United States)

    Dimas, Dimitrios A; Dallas, Paraskevas P; Rekkas, Dimitrios M


    Transdermal application can be an alternative drug delivery route for ondansetron, an antiemetic drug. Previous studies found that fatty acids, namely oleic and lauric, were the most effective penetration enhancers. The aim of this study was to investigate the formation of an ion pair between ondansetron and lauric acid as a possible mechanism of its enhancing action. Several techniques were used to reveal the formation of an ion pair complex. Partitioning experiments, where the n-octanol/water coefficient was measured, showed an increase in the distribution coefficient in the presence of the acid, possibly as a result of the formation of more lipophilic ion pairs between the charged molecules of ondansetron and lauric acid. Further evidence of complex formation between ondansetron and lauric acid, was gained from the 13C-nuclear magnetic resonance (13C-NMR) spectra of ondansetron, lauric acid, and their mixture (molar ratio 1:1). The NMR spectra revealed alterations to the magnetic environment of the carbon atoms adjacent to the ionized group, which are the carbonyl group of the acid and the nitrogen of the imidazole ring of ondansetron. This evidence substantiates the theory of ion pair formation. Finally, thermal analysis of the binary mixtures of ondansetron and lauric acid revealed the formation of an additional compound, with different melting point from pure ondansetron and lauric acid, which is thermodynamically favored.

  14. Acid/base bifunctional carbonaceous nanomaterial with large surface area: Preparation, characterization, and adsorption properties for cationic and anionic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Li, Kai; Ma, Chun–Fang; Ling, Yuan; Li, Meng [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Gao, Qiang, E-mail: [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Engineering Research Center of Nano-Geo Materials of Ministry of Education, China University of Geosciences, Wuhan 430074 (China); Luo, Wen–Jun, E-mail: [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China)


    Nanostructured carbonaceous materials are extremely important in the nano field, yet developing simple, mild, and “green” methods that can make such materials possess large surface area and rich functional groups on their surfaces still remains a considerable challenge. Herein, a one-pot and environment-friendly method, i.e., thermal treatment (180 °C; 18 h) of water mixed with glucose and chitosan (CTS), has been proposed. The resultant carbonaceous nanomaterials were characterized by field emitting scanning electron microscope, N{sub 2} adsorption/desorption, Fourier transform infrared spectroscope, X-ray photoelectron spectroscopy, and zeta-potential analysis. It was found that, in contrast to the conventional hydrothermally carbonized product from pure glucose, with low surface area (9.3 m{sup 2} g{sup −1}) and pore volume (0.016 cm{sup 3} g{sup −1}), the CTS-added carbonaceous products showed satisfactory textural parameters (surface area and pore volume up to 254 m{sup 2} g{sup −1} and 0.701 cm{sup 3} g{sup −1}, respectively). Moreover, it was also interestingly found that these CTS-added carbonaceous products possessed both acidic (–COOH) and basic (–NH{sub 2}) groups on their surfaces. Taking the advantages of large surface area and –COOH/–NH{sub 2} bifunctional surface, the carbonaceous nanomaterials exhibited excellent performance for adsorptions of cationic compound (i.e., methylene blue) at pH 10 and anionic compound (i.e., acid red 18) at pH 2, respectively. This work not only provides a simple and green route to prepare acid/base bifunctional carbonaceous nanomaterials with large surface area but also well demonstrates their potential for application in adsorption. - Highlights: • A simple and green method was proposed to prepare carbon nanomaterials. • The carbon product showed acid/base bifunctional surface with large surface area. • The carbon material could efficiently adsorb both cationic and anionic compounds.

  15. Nanohybrids of Mg/Al layered double hydroxide and long-chain (C18) unsaturated fatty acid anions: Structure and sorptive properties (United States)

    Long-chain (C18) unsaturated fatty acid anions, elaidate (ELA), oleate (OLE), linoleate (LINO), and linolenate (LINOLEN), were intercalated into Mg/Al (3:1) layered double hydroxide (LDH) and the resultant organo-LDH nanohybrid materials were characterized and subsequently evaluated as sorbents of s...

  16. Pentaarylfullerenes as noncoordinating cyclopentadienyl anions

    NARCIS (Netherlands)

    Bouwkamp, Marco W.; Meetsma, Auke


    The first example of an early-transition-metal complex involving a pentaarylfullerene was prepared. Instead of half-sandwich complexes, solvent separated ion pairs were obtained in which the pentaarylfullerene moiety acts as noncoordinating cyclopentadienyl anion.

  17. Amino acid sequence of anionic peroxidase from the windmill palm tree Trachycarpus fortunei. (United States)

    Baker, Margaret R; Zhao, Hongwei; Sakharov, Ivan Yu; Li, Qing X


    Palm peroxidases are extremely stable and have uncommon substrate specificity. This study was designed to fill in the knowledge gap about the structures of a peroxidase from the windmill palm tree Trachycarpus fortunei. The complete amino acid sequence and partial glycosylation were determined by MALDI-top-down sequencing of native windmill palm tree peroxidase (WPTP), MALDI-TOF/TOF MS/MS of WPTP tryptic peptides, and cDNA sequencing. The propeptide of WPTP contained N- and C-terminal signal sequences which contained 21 and 17 amino acid residues, respectively. Mature WPTP was 306 amino acids in length, and its carbohydrate content ranged from 21% to 29%. Comparison to closely related royal palm tree peroxidase revealed structural features that may explain differences in their substrate specificity. The results can be used to guide engineering of WPTP and its novel applications.

  18. Protonation Equilibria of L-Aspartic, Citric and Succinic Acids in Anionic Micellar Media

    Directory of Open Access Journals (Sweden)

    P. Srinivasa Rao


    Full Text Available The impact of sodium lauryl sulphate (SLS on the protonation equilibria of L-aspartic acid, citric acid and succinic acid has been studied in various concentrations (0.5-2.5% w/v of SLS solution maintaining an ionic strength of 0.16 mol dm-3 at 303 K. The protonation constants have been calculated with the computer program MINIQUAD75 and the best fit models have been calculated based on statistical parameters. The trend of log values of step-wise protonation constants with mole fraction of the medium has been explained based on electrostatic and non-electrostatic forces operating on the protonation equilibria. The effects of errors on the protonation constants have also been presented.

  19. A new unnatural base pair system between fluorophore and quencher base analogues for nucleic acid-based imaging technology. (United States)

    Kimoto, Michiko; Mitsui, Tsuneo; Yamashige, Rie; Sato, Akira; Yokoyama, Shigeyuki; Hirao, Ichiro


    In the development of orthogonal extra base pairs for expanding the genetic alphabet, we created novel, unnatural base pairs between fluorophore and quencher nucleobase analogues. We found that the nucleobase analogue, 2-nitropyrrole (denoted by Pn), and its 4-substitutions, such as 2-nitro-4-propynylpyrrole (Px) and 4-[3-(6-aminohexanamido)-1-propynyl]-2-nitropyrrole (NH(2)-hx-Px), act as fluorescence quenchers. The Pn and Px bases specifically pair with their pairing partner, 7-(2,2'-bithien-5-yl)imidazo[4,5-b]pyridine (Dss), which is strongly fluorescent. Thus, these unnatural Dss-Pn and Dss-Px base pairs function as reporter-quencher base pairs, and are complementarily incorporated into DNA by polymerase reactions as a third base pair in combination with the natural A-T and G-C pairs. Due to the static contact quenching, the Pn and Px quencher bases significantly decreased the fluorescence intensity of Dss by the unnatural base pairings in DNA duplexes. In addition, the Dss-Px pair exhibited high efficiency and selectivity in PCR amplification. Thus, this new unnatural base pair system would be suitable for detection methods of target nucleic acid sequences, and here we demonstrated the applications of the Dss-Pn and Dss-Px pairs as molecular beacons and in real-time PCR. The genetic alphabet expansion system with the replicable, unnatural fluorophore-quencher base pair will be a useful tool for sensing and diagnostic applications, as well as an imaging tool for basic research.

  20. Design and synthesis of novel tweezer anion receptors based on deoxycholic acid

    Institute of Scientific and Technical Information of China (English)

    Xing Li Liu; Zhi Gang Zhao; Shu Hua Chen


    A novel type of molecular tweezer receptors based on deoxycholic acid has been designed and synthesized and their binding properties were examined by UV-vis spectral titration. These molecular tweezers showed a high selectivity toward F- over Cl-,Br-, I-, AcO-, H2PO4-.

  1. Anion-exchange high-performance liquid chromatography with post-column detection for the analysis of phytic acid and other inositol phosphates (United States)

    Rounds, M. A.; Nielsen, S. S.; Mitchell, C. A. (Principal Investigator)


    The use of gradient anion-exchange HPLC, with a simple post-column detection system, is described for the separation of myo-inositol phosphates, including "phytic acid" (myo-inositol hexaphosphate). Hexa-, penta-, tetra-, tri- and diphosphate members of this homologous series are clearly resolved within 30 min. This method should facilitate analysis and quantitation of "phytic acid" and other inositol phosphates in plant, food, and soil samples.

  2. The volume-regulated anion channel (LRRC8) in nodose neurons is sensitive to acidic pH. (United States)

    Wang, Runping; Lu, Yongjun; Gunasekar, Susheel; Zhang, Yanhui; Benson, Christopher J; Chapleau, Mark W; Sah, Rajan; Abboud, François M


    The leucine rich repeat containing protein 8A (LRRC8A), or SWELL1, is an essential component of the volume-regulated anion channel (VRAC) that is activated by cell swelling and ionic strength. We report here for the first time to our knowledge its expression in a primary cell culture of nodose ganglia neurons and its localization in the soma, neurites, and neuronal membrane. We show that this neuronal VRAC/SWELL1 senses low external pH (pHo) in addition to hypoosmolarity. A robust sustained chloride current is seen in 77% of isolated nodose neurons following brief exposures to extracellular acid pH. Its activation involves proton efflux, intracellular alkalinity, and an increase in NOX-derived H2O2. The molecular identity of both the hypoosmolarity-induced and acid pHo-conditioned VRAC as LRRC8A (SWELL1) was confirmed by Cre-flox-mediated KO, shRNA-mediated knockdown, and CRISPR/Cas9-mediated LRRC8A deletion in HEK cells and in primary nodose neuronal cultures. Activation of VRAC by low pHo reduces neuronal injury during simulated ischemia and N-methyl-D-aspartate-induced (NMDA-induced) apoptosis. These results identify the VRAC (LRRC8A) as a dual sensor of hypoosmolarity and low pHo in vagal afferent neurons and define the mechanisms of its activation and its neuroprotective potential.

  3. The volume-regulated anion channel (LRRC8) in nodose neurons is sensitive to acidic pH (United States)

    Wang, Runping; Lu, Yongjun; Gunasekar, Susheel; Zhang, Yanhui; Benson, Christopher J.; Chapleau, Mark W.; Sah, Rajan; Abboud, François M.


    The leucine rich repeat containing protein 8A (LRRC8A), or SWELL1, is an essential component of the volume-regulated anion channel (VRAC) that is activated by cell swelling and ionic strength. We report here for the first time to our knowledge its expression in a primary cell culture of nodose ganglia neurons and its localization in the soma, neurites, and neuronal membrane. We show that this neuronal VRAC/SWELL1 senses low external pH (pHo) in addition to hypoosmolarity. A robust sustained chloride current is seen in 77% of isolated nodose neurons following brief exposures to extracellular acid pH. Its activation involves proton efflux, intracellular alkalinity, and an increase in NOX-derived H2O2. The molecular identity of both the hypoosmolarity-induced and acid pHo–conditioned VRAC as LRRC8A (SWELL1) was confirmed by Cre-flox–mediated KO, shRNA-mediated knockdown, and CRISPR/Cas9-mediated LRRC8A deletion in HEK cells and in primary nodose neuronal cultures. Activation of VRAC by low pHo reduces neuronal injury during simulated ischemia and N-methyl-D-aspartate–induced (NMDA-induced) apoptosis. These results identify the VRAC (LRRC8A) as a dual sensor of hypoosmolarity and low pHo in vagal afferent neurons and define the mechanisms of its activation and its neuroprotective potential. PMID:28289711

  4. Dysfunction of organic anion transporting polypeptide 1a1 alters intestinal bacteria and bile acid metabolism in mice.

    Directory of Open Access Journals (Sweden)

    Youcai Zhang

    Full Text Available Organic anion transporting polypeptide 1a1 (Oatp1a1 is predominantly expressed in liver and is able to transport bile acids (BAs in vitro. Male Oatp1a1-null mice have increased concentrations of taurodeoxycholic acid (TDCA, a secondary BA generated by intestinal bacteria, in both serum and livers. Therefore, in the present study, BA concentrations and intestinal bacteria in wild-type (WT and Oatp1a1-null mice were quantified to investigate whether the increase of secondary BAs in Oatp1a1-null mice is due to alterations in intestinal bacteria. The data demonstrate that Oatp1a1-null mice : (1 have similar bile flow and BA concentrations in bile as WT mice; (2 have a markedly different BA composition in the intestinal contents, with a decrease in conjugated BAs and an increase in unconjugated BAs; (3 have BAs in the feces that are more deconjugated, desulfated, 7-dehydroxylated, 3-epimerized, and oxidized, but less 7-epimerized; (4 have 10-fold more bacteria in the small intestine, and 2-fold more bacteria in the large intestine which is majorly due to a 200% increase in Bacteroides and a 30% reduction in Firmicutes; and (5 have a different urinary excretion of bacteria-related metabolites than WT mice. In conclusion, the present study for the first time established that lack of a liver transporter (Oatp1a1 markedly alters the intestinal environment in mice, namely the bacteria composition.

  5. Short chain aliphatic acid anions in oil field waters and their contribution to the measured alkalinity (United States)

    Willey, L.M.; Kharaka, Y.K.; Presser, T.S.; Rapp, J.B.; Barnes, I.


    High alkalinity values found in some formation waters from Kettleman North Dome oil field are due chiefly to acetate and propionate ions, with some contribution from higher molecular weight organic acid ions. Some of these waters contain no detectable bicarbonate alkalinity. For waters such as these, high supersaturation with respect to calcite will be incorrectly indicated by thermodynamic calculations based upon carbonate concentrations inferred from traditional alkalinity measurements. ?? 1975.

  6. Inhibitory effect of caffeic acid on human organic anion transporters hOAT1 and hOAT3: a novel candidate for food-drug interaction. (United States)

    Uwai, Yuichi; Ozeki, Yukihiro; Isaka, Tomonori; Honjo, Hiroaki; Iwamoto, Kikuo


    Several kinds of food have been shown to influence the absorption and metabolism of drugs, although there is little information about their effect on the renal excretion of drugs. In this study, we performed uptake experiments using Xenopus laevis oocytes to assess the inhibitory effects of chlorogenic acid, caffeic acid and quinic acid, which are contained in coffee, fruits and vegetables, on human organic anion transporters hOAT1 and hOAT3; these transporters mediate renal tubular uptake of anionic drugs from blood. Injection of hOAT1 and hOAT3 cRNA into oocytes stimulated uptake of typical substrates of hOAT1 and hOAT3 (p-aminohippurate and estrone sulfate, respectively); among the three compounds tested, caffeic acid most strongly inhibited these transporters. The apparent 50% inhibitory concentrations of caffeic acid were estimated to be 16.6 µM for hOAT1 and 5.4 µM for hOAT3. Eadie-Hofstee plot analysis showed that caffeic acid inhibited both transporters in a competitive manner. In addition to the transport of p-aminohippurate and estrone sulfate, that of antifolates and antivirals was inhibited by caffeic acid. These findings show that caffeic acid has inhibitory potential against hOAT1 and hOAT3, suggesting that renal excretion of their substrates could be affected in patients consuming a diet including caffeic acid.

  7. Interaction of bovine serum albumin with N-acyl amino acid based anionic surfactants: Effect of head-group hydrophobicity. (United States)

    Ghosh, Subhajit; Dey, Joykrishna


    The function of a protein depends upon its structure and surfactant molecules are known to alter protein structure. For this reason protein-surfactant interaction is important in biological, pharmaceutical, and cosmetic industries. In the present work, interactions of a series of anionic surfactants having the same hydrocarbon chain length, but different amino acid head group, such as l-alanine, l-valine, l-leucine, and l-phenylalanine with the transport protein, bovine serum albumin (BSA), were studied at low surfactant concentrations using fluorescence and circular dichroism (CD) spectroscopy, and isothermal titration calorimetry (ITC). The results of fluorescence measurements suggest that the surfactant molecules bind simultaneously to the drug binding site I and II of the protein subdomain IIA and IIIA, respectively. The fluorescence as well as CD spectra suggest that the conformation of BSA goes to a more structured state upon surfactant binding at low concentrations. The binding constants of the surfactants were determined by the use of fluorescence as well as ITC measurements and were compared with that of the corresponding glycine-derived surfactant. The binding constant values clearly indicate a significant head-group effect on the BSA-surfactant interaction and the interaction is mainly hydrophobic in nature.

  8. Sulphonic acid derivatives as probes of pore properties of volume-regulated anion channels in endothelial cells. (United States)

    Droogmans, G; Maertens, C; Prenen, J; Nilius, B


    1. We have used the whole-cell patch-clamp technique to study the effects of 4-sulphonic-calixarenes and some other poly-sulphonic acid agents, such as suramin and basilen blue, on volume-regulated anion channel (VRAC) currents in cultured endothelial cells (CPAE cells). 2. The 4-sulphonic-calixarenes induced a fast inhibition at positive potentials but were ineffective at negative potentials. At small positive potentials, 4-sulphonic-calix[4]arene was a more effective inhibitor than 4-sulphonic-calix[6]arene and -calix[8]arene, which became more effective at more positive potentials. 3. Also suramin and basilen blue induced a voltage dependent current inhibition, reaching a maximum around +40 mV and declining at more positive potentials. 4. The voltage dependence of inhibition was modelled by assuming that these negatively charged molecules bind to a site inside VRAC that senses a fraction delta of the applied electrical field, ranging beween 0.16 to 0.32. 4-Sulphonic-calix[4]arene, suramin and basilen blue bind and occlude VRAC at moderate potentials, but permeate the channel at more positive potentials. 4-Sulphonic-calix[6]arene and -calix[8]arene however do not permeate the channel. From the structural information of the calixarenes, we estimate a lower and upper limit of 11*12 and 17*12 A2 respectively for the cross-sectional area of the pore.

  9. Improving thermal stability and light fastness of Acid Red 114 by incorporating its anions in a ZnAl-layered double hydroxides matrix

    Institute of Scientific and Technical Information of China (English)

    Haifeng Zhu; Liren Wang; Pinggui Tang; Yongjun Feng; Dianqing Li


    Incorporation of anions of Acid Red 114 dye (1,3-naphthalenedisulfonic acid,8-[2-[3,3'-dimethyl-4'-[2-[4-[[(4-methylphenyl)sulfonyl]oxy] phenyl]diazenyl] [1,1'-biphenyl]-4-yl]diazenyl]-7-hydroxy-,disodium salt) (denoted as NPDA) into ZnAl-layered double hydroxides (LDHs) has been carried out by an anionexchange method in an effort to improve their thermal stability and light fastness.After intercalation of NPDA anions,the interlayer distance of the LDHs increases from 0.87 to 2.18nm,confirming their incorporation into the interlayer galleries of the LDHs host.Infrared spectroscopy and thermogravimetric analysis revealed the presence of host-guest interactions between LDHs layers and NPDA anions.The thermal stability of NPDA and ZnAl-NPDA-LDHs was compared by thermogravimetric-differential thermal analysis,UV-visible spectroscopy and infrared spectroscopy.It was found that the thermal stability of NPDA anions was markedly improved by incorporation into the ZnAl-LDHs matrix,while the light fastness was also enhanced.

  10. [Separation of zoledronic acid and its related substances by ion-pair reversed-phase high performance liquid chromatography]. (United States)

    Zhang, Xiaoqing; Jiang, Ye; Xu, Zhiru


    A rapid and simple ion-pair reversed-phase high performance liquid chromatographic method (HPLC) has been established for the routine analysis of zoledronic acid and its related substances. The chromatographic conditions were optimized based on the satisfactory separation of zoledronic acid from imidazol-1-ylacetic acid, their retention times and peak shape. The excellent separation of zoledronic acid from its related substances, including the remaining imidazol-1-ylacetic acid used in the synthesis of zoledronic acid and other impurities of oxidation and decomposition, was achieved within 9 min on a Hypersil C8 column with UV detection at 220 nm. The mobile phase was a mixture of methanol (20%) and 5 mmo/L phosphate buffer (80%) that contains 6 mmol/L tetrabutylammonium bromide. The resolution factor of zoledronic acid from its adjacent peak was more than 2.5. This is a simple and rapid method for the routine assay of zoledronic acid.

  11. The association between paired basic amino acid cleaving enzyme 4 gene haplotype and diastolic blood pressure

    Institute of Scientific and Technical Information of China (English)

    李建平; 王晓滨; 陈常忠; 徐新; 洪雪梅; 徐希平; 高炜; 霍勇


    Background In a previously identified locus linked to hypertension on chromosome 15q, we identified three blood pressure candidate genes: insulin-like growth factor 1 receptor gene (IGF1R), myocyte specific enhancer factor 2A gene (MEF2A), and paired basic amino acid cleaving enzyme 4 gene (PACE4). In this study, we tested their associations with hypertension using haplotype analysis.Methods A total of 288 unrelated individuals, including 163 high diastolic blood pressure (DBP) subjects and 125 normal DBP subjects were enrolled in this case-control study. Twenty single nucleotide polymorphisms (SNPs) in the three genes were genotyped using polymerase chain reaction followed by restriction enzyme digestion. Haplotype analysis was accomplished in the following stages: (1) pair-wise linkage disequilibrium test among SNPs on the same gene was performed to explore blocks in which recombination is very unlikely to happen; (2) Estimation-Maximization algorithm was applied to estimate haplotype frequencies in each block; (3) the chi-square test was used to examine the specific haplotype difference, and a permutation test was used to examine the overall haplotype profile difference between cases and controls in each block.Results An estimated haplotype "CCCCG" frequency in the haplotype block on the PACE4 gene was significantly higher in high DBP cases than in controls (P<0.01). The overall estimated haplotype profile in this block was also significantly different between the cases and the controls (P<0.001). This association indicates. Conclusions This study for the first time demonstrated that PACE4 gene may play an important role in the regulation of DBP. This association indicates that variations influencing DBP resides in or near this genomic region.

  12. Organic anion-transporting polypeptide 1a4 (Oatp1a4) is important for secondary bile acid metabolism. (United States)

    Zhang, Youcai; Csanaky, Iván L; Selwyn, Felcy Pavithra; Lehman-McKeeman, Lois D; Klaassen, Curtis D


    Organic anion transporting polypeptides (human: OATPs; rodent: Oatps) were thought to have important functions in bile acid (BA) transport. Oatp1a1, 1a4, and 1b2 are the three major Oatp1 family members in rodent liver. Our previous studies have characterized the BA homeostasis in Oatp1a1-null and Oatp1b2-null mice. The present study investigated the physiological role of Oatp1a4 in BA homeostasis by using Oatp1a4-null mice. Oatp1a4 expression is female-predominant in livers of mice, and thereby it was expected that female Oatp1a4-null mice will have more prominent changes than males. Interestingly, the present study demonstrated that female Oatp1a4-null mice had no significant alterations in BA concentrations in serum or liver, though they had increased mRNA of hepatic BA efflux transporters (Mrp4 and Ostα/β) and ileal BA transporters (Asbt and Ostα/β). In contrast, male Oatp1a4-null mice showed significantly altered BA homeostasis, including increased concentrations of deoxycholic acid (DCA) in serum, liver and intestinal contents. After feeding a DCA-supplemented diet, male but not female Oatp1a4-null mice had higher concentrations of DCA in serum and livers than their WT controls. This suggested that Oatp1a4 is important for intestinal absorption of secondary BAs in male mice. Furthermore, loss of Oatp1a4 function did not decrease BA accumulation in serum or livers of bile-duct-ligated mice, suggesting that Oatp1a4 is not likely a BA uptake transporter. In summary, the present study for the first time demonstrates that Oatp1a4 does not appear to mediate the hepatic uptake of BAs, but plays an important male-predominant role in secondary BA metabolism in mice.

  13. Anion-π catalysis. (United States)

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan


    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  14. Prediction of flexible/rigid regions from protein sequences using k-spaced amino acid pairs

    Directory of Open Access Journals (Sweden)

    Ruan Jishou


    Full Text Available Abstract Background Traditionally, it is believed that the native structure of a protein corresponds to a global minimum of its free energy. However, with the growing number of known tertiary (3D protein structures, researchers have discovered that some proteins can alter their structures in response to a change in their surroundings or with the help of other proteins or ligands. Such structural shifts play a crucial role with respect to the protein function. To this end, we propose a machine learning method for the prediction of the flexible/rigid regions of proteins (referred to as FlexRP; the method is based on a novel sequence representation and feature selection. Knowledge of the flexible/rigid regions may provide insights into the protein folding process and the 3D structure prediction. Results The flexible/rigid regions were defined based on a dataset, which includes protein sequences that have multiple experimental structures, and which was previously used to study the structural conservation of proteins. Sequences drawn from this dataset were represented based on feature sets that were proposed in prior research, such as PSI-BLAST profiles, composition vector and binary sequence encoding, and a newly proposed representation based on frequencies of k-spaced amino acid pairs. These representations were processed by feature selection to reduce the dimensionality. Several machine learning methods for the prediction of flexible/rigid regions and two recently proposed methods for the prediction of conformational changes and unstructured regions were compared with the proposed method. The FlexRP method, which applies Logistic Regression and collocation-based representation with 95 features, obtained 79.5% accuracy. The two runner-up methods, which apply the same sequence representation and Support Vector Machines (SVM and Naïve Bayes classifiers, obtained 79.2% and 78.4% accuracy, respectively. The remaining considered methods are

  15. Intercalation of p-methycinnamic acid anion into Zn-Al layered double hydroxide to improve UV aging resistance of asphalt

    Directory of Open Access Journals (Sweden)

    Chao Peng


    Full Text Available A UV absorber, p-methycinnamic acid (PMCA, was intercalated into Zn-Al layered double hydroxide (LDH by calcination recovery. Fourier transform infrared spectroscopy showed that the PMCA anions completely replaced the CO32− anions in the interlayer galleries of Zn-Al-LDH containing PMCA anions (Zn-Al-PMCA-LDH. X-ray diffraction and transmission electron microscopy showed that the interlayer distance increased from 0.78 nm to 1.82 nm after the substitution of PMCA anions for CO32− anions. The similar diffraction angles of the CO32− anion-containing Zn-Al-LDH (Zn-Al-CO32−-LDH and the Zn-Al-CO32−-LDH/styrene–butadiene–styrene (SBS modified asphalt implied that the asphalt molecules do not enter into the LDH interlayer galleries to form separated-phase structures. The different diffraction angles of Zn-Al-PMCA-LDH and Zn-Al-PMCA-LDH/SBS modified asphalt indicated that the asphalt molecules penetrated into the LDH interlayer galleries to form an expanded-phase structure. UV-Vis absorbance analyses showed that Zn-Al-PMCA-LDH was better able to block UV light due to the synergistic effects of PMCA and Zn-Al-LDH. Conventional physical tests and atomic force microscopy images of the SBS modified asphalt, Zn-Al-CO32−-LDH/SBS modified asphalt and Zn-Al-PMCA-LDH/SBS modified asphalt before and after UV aging indicated that Zn-Al-PMCA-LDH improved the UV aging resistance of SBS modified asphalts.

  16. A co-crystal of nonahydrated disodium(II with mixed anions from m-chlorobenzoic acid and furosemide

    Directory of Open Access Journals (Sweden)

    Bianca King London


    Full Text Available In the title compound, [Na2(H2O9](C7H4ClO2(C12H10ClN2O5S {systematic name: catena-poly[[[triaquasodium(I]-di-μ-aqua-[triaquasodium(I]-μ-aqua] 3-chlorobenzoate 4-chloro-2-[(furan-2-ylmethylamino]-5-sulfamoylbenzoate]}, both the original m-chlorobenzoic acid and furosemide exist with deprotonated carboxylates, and the sodium cations and water molecules exist in chains with stoichiometry [Na2(OH29]2+ that propagate in the [-110] direction. Each of the two independent Na+ ions is coordinated by three monodentate water molecules, two double-water bridges, and one single-water bridge. There is considerable cross-linking between the [Na2(OH29]2+ chains and to furosemide sulfonamide and carboxylate by intermolecular O—H...O hydrogen bonds. All hydrogen-bond donors participate in a complex two-dimensional array parallel to the ab plane. The furosemide NH group donates an intramolecular hydrogen bond to the carboxylate group, and the furosemide NH2 group donates an intramolecular hydrogen bond to the Cl atom and an intermolecular one to the m-chlorobenzoate O atom. The plethora of hydrogen-bond donors on the cation/water chain leads to many large rings, up to graph set R44(24, involving two chains and two furosemide anions. The chlorobenzoate is involved in only one R22(8 ring, with two water molecules cis-coordinated to Na. The furan O atom is not hydrogen bonded.

  17. Physiological and Molecular Analysis of Aluminium-Induced Organic Acid Anion Secretion from Grain Amaranth (Amaranthus hypochondriacus L. Roots

    Directory of Open Access Journals (Sweden)

    Wei Fan


    Full Text Available Grain amaranth (Amaranthus hypochondriacus L. is abundant in oxalate and can secrete oxalate under aluminium (Al stress. However, the features of Al-induced secretion of organic acid anions (OA and potential genes responsible for OA secretion are poorly understood. Here, Al-induced OA secretion in grain amaranth roots was characterized by ion charomatography and enzymology methods, and suppression subtractive hybridization (SSH together with quantitative real-time PCR (qRT-PCR was used to identify up-regulated genes that are potentially involved in OA secretion. The results showed that grain amaranth roots secrete both oxalate and citrate in response to Al stress. The secretion pattern, however, differs between oxalate and citrate. Neither lanthanum chloride (La nor cadmium chloride (Cd induced OA secretion. A total of 84 genes were identified as up-regulated by Al, in which six genes were considered as being potentially involved in OA secretion. The expression pattern of a gene belonging to multidrug and toxic compound extrusion (MATE family, AhMATE1, was in close agreement with that of citrate secretion. The expression of a gene encoding tonoplast dicarboxylate transporter and four genes encoding ATP-binding cassette transporters was differentially regulated by Al stress, but the expression pattern was not correlated well with that of oxalate secretion. Our results not only reveal the secretion pattern of oxalate and citrate from grain amaranth roots under Al stress, but also provide some genetic information that will be useful for further characterization of genes involved in Al toxicity and tolerance mechanisms.

  18. Physiological and Molecular Analysis of Aluminium-Induced Organic Acid Anion Secretion from Grain Amaranth (Amaranthus hypochondriacus L.) Roots. (United States)

    Fan, Wei; Xu, Jia-Meng; Lou, He-Qiang; Xiao, Chuan; Chen, Wei-Wei; Yang, Jian-Li


    Grain amaranth (Amaranthus hypochondriacus L.) is abundant in oxalate and can secrete oxalate under aluminium (Al) stress. However, the features of Al-induced secretion of organic acid anions (OA) and potential genes responsible for OA secretion are poorly understood. Here, Al-induced OA secretion in grain amaranth roots was characterized by ion charomatography and enzymology methods, and suppression subtractive hybridization (SSH) together with quantitative real-time PCR (qRT-PCR) was used to identify up-regulated genes that are potentially involved in OA secretion. The results showed that grain amaranth roots secrete both oxalate and citrate in response to Al stress. The secretion pattern, however, differs between oxalate and citrate. Neither lanthanum chloride (La) nor cadmium chloride (Cd) induced OA secretion. A total of 84 genes were identified as up-regulated by Al, in which six genes were considered as being potentially involved in OA secretion. The expression pattern of a gene belonging to multidrug and toxic compound extrusion (MATE) family, AhMATE1, was in close agreement with that of citrate secretion. The expression of a gene encoding tonoplast dicarboxylate transporter and four genes encoding ATP-binding cassette transporters was differentially regulated by Al stress, but the expression pattern was not correlated well with that of oxalate secretion. Our results not only reveal the secretion pattern of oxalate and citrate from grain amaranth roots under Al stress, but also provide some genetic information that will be useful for further characterization of genes involved in Al toxicity and tolerance mechanisms.

  19. Enthalpic Pair Interaction of Rubidium Chloride with α-Amino Acid in Water at 298.15K

    Institute of Scientific and Technical Information of China (English)

    胡满成; 杨茜; 蒋育澄; 夏树屏


    The mixing enthalpies of aqueous heavy rare alkali metal chloride RbC1 solutions with aqueous α-amino acid (Loglycine, L-alanine and α-aminobutyric acid) solutions, as well as the dilution enthalpies of RbC1 and α-amino acid solutions in pure water had been measured at 298.15K. The transfer enthalpies of RbCI from pure water to aqueous α-amino acid solutions could be obtained from these data. The enthalpic pair interaction parameters of RbC1 with α-amino acid in water have been evaluated according to the McMillan-Mayer theory and discussed in terms of the electrostatic interaction, structure interaction and Savage-wood group additivity mode.

  20. A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal$-$Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Jacob A. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Petersen, Brenna M. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Kormos, Attila [Hungarian Academy of Sciences, Budapest (Hungary); Echeverría, Elena [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy; Chen, Yu-Sheng [Univ. of Chicago, Argonne, IL (United States). ChemMatCARS, Center for Advanced Radiation Sources; Zhang, Jian [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry


    Here, we describe a new strategy to generate non-coordinating anions using zwitterionic metal–organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]$-$) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition of aldehydes with dienes. Lastly, this work paves a new way to design functional MOFs for tunable chemical catalysis.

  1. Anion Recognition Triggered Nanoribbon-Like Self-Assembly: A Fluorescent Chemosensor for Nitrate in Acidic Aqueous Solution and Living Cells. (United States)

    Yang, Yaping; Chen, Shiyan; Ni, Xin-Long


    A water-soluble π-conjugated bispyridinium phenylenevinylene-based fluorogenic probe has been developed as a novel fluorescent chemosensor for highly selective, sensitive, and rapid detection of NO3(-) anion in acidic aqueous media. This system self-assembles to a nanoribbon as a result of ionic interaction. The positively charged chemosensor generates a nearly instantaneous significant fluorescence signal (475 vs 605 nm) in response to NO3(-) in the green/yellow spectral region, with a large Stokes shift (130 nm). The fluorescence changes can be attributed to the self-aggregation of the sensor triggered by ionic interaction, which occurs as a consequence of the subtle cooperation of electrostatic ionic bonding, van der Waals forces, and π-stacking of the π-conjugated aromatic moieties. Importantly, this chemosensor has been employed for the first time for the fluorescence detection of intracellular NO3(-) anion in cultured cells.

  2. Flow-injection Chemiluminescence Sensor for the Determination of Gallic Acid by Immobilizing Luminol and Periodate on Anion-exchange Resin

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Si-Chun(张四纯); ZHOU,Guo-Jun(周国俊); JU,Huang-Xian(鞠熀先)


    A novel chemihuminescence (CL) sensor for the determination of gallic acid combined with flow injection analysis was developed by electrostatically immobilizing luminol and periodate on anion-exchange resins respectively. Gallic acid was sensed by its enhancing effect on the weak CL reaction between luminol and periodate, which were eluted from the ion exchang ecolumn.The possible reaction mechanism of the CL system was suggested and discussed. The response of the sensor to gallic acid concentration was linear over the range of 8.0 × 10-9-1.0 × 10-6 mol/L with a detection limit of 6.5 × 10-9 mol/L (3σσ). The relative standard deviation (RSD) for 7 repetitive determinations of gallic acid (1.0 × 10-7 moL/L) was 1.8%. The sensor could be used for over 400 times determination with a good reproducibility.

  3. RNAHelix: computational modeling of nucleic acid structures with Watson-Crick and non-canonical base pairs (United States)

    Bhattacharyya, Dhananjay; Halder, Sukanya; Basu, Sankar; Mukherjee, Debasish; Kumar, Prasun; Bansal, Manju


    Comprehensive analyses of structural features of non-canonical base pairs within a nucleic acid double helix are limited by the availability of a small number of three dimensional structures. Therefore, a procedure for model building of double helices containing any given nucleotide sequence and base pairing information, either canonical or non-canonical, is seriously needed. Here we describe a program RNAHelix, which is an updated version of our widely used software, NUCGEN. The program can regenerate duplexes using the dinucleotide step and base pair orientation parameters for a given double helical DNA or RNA sequence with defined Watson-Crick or non-Watson-Crick base pairs. The original structure and the corresponding regenerated structure of double helices were found to be very close, as indicated by the small RMSD values between positions of the corresponding atoms. Structures of several usual and unusual double helices have been regenerated and compared with their original structures in terms of base pair RMSD, torsion angles and electrostatic potentials and very high agreements have been noted. RNAHelix can also be used to generate a structure with a sequence completely different from an experimentally determined one or to introduce single to multiple mutation, but with the same set of parameters and hence can also be an important tool in homology modeling and study of mutation induced structural changes.

  4. A randomized controlled study on the effects of acetate-free biofiltration on organic anions and acid-base balance in hemodialysis patients. (United States)

    Sánchez-Canel, Juan J; Hernández-Jaras, Julio; Pons-Prades, Ramón


    Metabolic acidosis correction is achieved by the transfer of bicarbonate and other buffer anions in dialysis. The aim of this study was to evaluate changes in the main anions of intermediary metabolism on standard hemodiafiltration (HDF) and on acetate-free biofiltration (AFB). A prospective, in-center, crossover study was carried out with 22 patients on maintenance dialysis. Patients were randomly assigned to start with 12 successive sessions of standard HDF with bicarbonate (34 mmol/L) and acetate dialysate (3 mmol/L) or 12 successive sessions of AFB without base in the dialysate. Acetate increased significantly during the standard HDF session from 0.078 ± 0.062 mmol/L to 0.156 ± 0.128 mmol/L (P anions (OA) were higher in HDF compared to AFB (P < 0.05). AFB achieves an optimal control of acid-base equilibrium through a bicarbonate substitution fluid. It also prevents hyperacetatemia and restores internal homeostasis with less production of intermediary metabolites.

  5. cis-Diaquabis(di-2-pyrimidinyl sulfide- K2N,N) Cobalt(II) Ditetrafluoridoborate: Lone Pair-aromatic and Anion-П Interactions in the Self-assembly of Coordination Complex%cis-Diaquabis(di-2-pyrimidinyl sulfide- K2N,N) Cobalt(II) Ditetrafluoridoborate: Lone Pair-aromatic and Anion-П Interactions in the Self-assembly of Coordination Complex

    Institute of Scientific and Technical Information of China (English)


    The title complex, [Co(DprS)2(H20)2]2(BF4)4 (DprS is di-2-pyrimidinyl sulfide), was obtained and characterized by elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P21/c with a = 11.742(1), b = 22,439(2), c = 20.538(2) A, β = 109.713(5)°, Z = 4, V = 5094.3(3)A, Dc = 1.692, μ = 0.929 mm-I, F(000) = 2600, R = 0.0756 and wR = 0.1929. The asymmetric unit of the title complex is comprised of two isomeric cobalt(II) centers (Co(l) and Co(2)) with a cis-[Co(DprS)2(H20)2]2+ moiety. Each Co(II) center exhibits a similar distorted N402-octahedral coordination geometry surrounded by a pair of DprS in a N,N'-chelate mode and two aqua ligands in a cis-relationship. Unconventional S-π(pyrimidinyl), N-π(pyrimidinyl), and anion(BF4)...π(pyrimidinyl) are found to combine with the C-H-.-F and O-H...F interactions to stabilize a whole three-dimensional framework with the mononuclear units (Co(l) and Co(2)). The ligand conformation will be also discussed.

  6. Fluoro- and perfluoralkylsulfonylpentafluoroanilides: synthesis and characterization of NH acids for weakly coordinating anions and their gas-phase and solution acidities. (United States)

    Kögel, Julius F; Linder, Thomas; Schröder, Fabian G; Sundermeyer, Jörg; Goll, Sascha K; Himmel, Daniel; Krossing, Ingo; Kütt, Karl; Saame, Jaan; Leito, Ivo


    Fluoro- and perfluoralkylsulfonyl pentafluoroanilides [HN(C6F5)(SO2X); X = F, CF3, C4F9, C8F17] are a class of imides with two different strongly electron-withdrawing substituents attached to a nitrogen atom. They are NH acids, the unsymmetrical hybrids of the well-known symmetrical bissulfonylimides and bispentafluorophenylamine. The syntheses, the structures of these perfluoroanilides, their solvates, and some selected lithium salts give rise to a structural variety beyond the symmetrical parent compounds. The acidities of representative subsets of these novel NH acids have been investigated experimentally and quantum-chemically and their gas-phase acidities (GAs) are reported, as well as the pKa values of these compounds in acetonitrile (MeCN) and DMSO solution. In quantum chemical investigations with the vertical and relaxed COSMO cluster-continuum models (vCCC/rCCC), the unusual situation is encountered that the DMSO-solvated acid Me2SO-H-N(SO2CF3)2, optimized in the gas phase (vCCC model), dissociates to Me2SO-H(+)-N(SO2CF3)2(-) during structural relaxation and full optimization with the solvation model turned on (rCCC model). This proton transfer underlines the extremely high acidity of HN(SO2CF3)2. The importance of this effect is studied computationally in DMSO and MeCN solution. Usually this effect is less pronounced in MeCN and is of higher importance in the more basic solvent DMSO. Nevertheless, the neglect of the structural relaxation upon solvation causes typical changes in the computational pKa values of 1 to 4 orders of magnitude (4-20 kJ mol(-1)). The results provide evidence that the published experimental DMSO pKa value of HN(SO2CF3)2 should rather be interpreted as the pKa of a Me2SO-H(+)-N(SO2CF3)2(-) contact ion pair.

  7. Analysis of the impacts of major anion variations on surface water acidity particularly with regard to conifer harvesting: case studies from Wales and Northern England

    Directory of Open Access Journals (Sweden)

    C. Neal


    Full Text Available Data on the water quality of streams draining a range of acidic and acid sensitive, mainly afforested, upland catchments in mid- and north-Wales and northern-England are described to investigate the acidification effects of conifer harvesting in relation to natural variability. Most sites show a large range in pH and major cation and major anion concentrations. The waters draining from the smaller catchments are more acidic and aluminium bearing reflecting a higher proportion of runoff from the acidic soils in each area. However, there is often a less acidic component of runoff under base-flow conditions due to ground-water contributions particularly within the larger streams. Higher concentrations of nitrate occur for sites which have been felled although declines in concentration occur several years after felling. Multiple regression analysis reveals the importance of cation exchange and within catchment acidification associated with sulphate and nitrate generation. Sulphate also has a component associated with weathering but the patterns vary from catchment to catchment. Analysis of the influence of changing anion concentrations associated with tree harvesting reveals that the acidification induced by increases in nitrate can be offset or reversed by the lowering of chloride and sulphate concentrations due to decreased atmospheric scavenging by the vegetation, reduced evapotranspiration and increased surface runoff diluting the acidity generated. It is concluded that contemporary UK forestry guidelines with an emphasis on phased harvesting of catchments over several years and careful harvesting methodologies can alleviate most problems of stream acidification associated with felling activities and in some cases can reverse the acidification pattern.

  8. Application of dissolvable layered double hydroxides as sorbent in dispersive solid-phase extraction and extraction by co-precipitation for the determination of aromatic acid anions. (United States)

    Tang, Sheng; Lee, Hian Kee


    Three types of magnesium-aluminum layered double hydroxides were synthesized and employed as solid-phase extraction (SPE) sorbents to extract several aromatic acids (protocatechuic acid, mandelic acid, phthalic acid, benzoic acid, and salicylic acid) from aqueous samples. An interesting feature of these sorbents is that they dissolve when the pH of the solution is lower than 4. Thus, the analyte elution step, as needed in conventional sorbent-based extraction, was obviated by dissolving the sorbent in acid after extraction and separation from the sample solution. The extract was then directly injected into a high-performance liquid chromatography-ultraviolet detection system for analysis. In the key adsorption process, both dispersive SPE and co-precipitation extraction with the sorbents were conducted and experimental parameters such as pH, temperature, and extraction time were optimized. The results showed that both extraction methods provided low limits of detection (0.03-1.47 μg/L) and good linearity (r(2) > 0.9903). The optimized extraction conditions were applied to human urine and sports drink samples. This new and interesting extraction approach was demonstrated to be a fast and efficient procedure for the extraction of organic anions from aqueous samples.

  9. Response surface methodology to optimize gradient ion chromatographic separation of inorganic anions and organic acids in tobacco leaves

    Institute of Scientific and Technical Information of China (English)

    Rui Qi Wang; Na Ni Wang; Jia Jie Zhang; Yan Zhu


    The separation optimization of nine organic and inorganic anions in tobacco leaves using gradient ion chromatography by response surface methodology was investigated. In order to achieve this goal the usefulness of the chromatographic response function (CRF) for the evaluation of the two different chromatographic performance goals (resolution and analysis time) was tested. The experiments were performed according to a Box-Behnken design response surface experimental design.


    Institute of Scientific and Technical Information of China (English)

    Xin-tao Shuai; Zbigniew; Jedlinski, Qiang Luo; Nozirow Farhod


    A novel kind of copolymer with ABA-type block structure was synthesized by anionic ring-opening polymerization of β-butyrolactone (β-BL) in the presence of a PEG-based dicarboxylates as macroinitiators which were prepared by the esterification of aliphatic cyclic anhydride and poly(ethylene glycol) (PEG) oligomers (Mn = 2000, 4000 and 6000) and conversion of potassium dicarboxylates. The resultant copolymers as well as the intermediates were characterized by IR, 1H-NMR and GPC.

  11. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid–base pairs

    Energy Technology Data Exchange (ETDEWEB)

    Baylon, Rebecca A. L.; Sun, Junming; Martin, Kevin J.; Venkitasubramanian, Padmesh; Wang, Yong


    Dwindling petroleum reserves combined with increased energy demand and political factors encouraging an increase in energy independence have led to a large amount of research on sustainable alternatives. To this end, biomass conversion has been recognized as themost readily viable technology to produce biofuel concerning our reliance on liquid fuels for transportation and has the advantage of being easily integrated into our heavy use of combustion engines. The interest in biomass conversion has also resulted in reduced costs and a greater abundance of bio-oil, a mixture of hundreds of oxygenates including alcohols, aldehydes, carboxylic acids, and ketones. However, the presence of carboxylic acids in bio-oil derived from lignocellulose pyrolysis leads to low pH, instability, and corrosiveness. In addition, carboxylic acids (i.e. acetic acid) can also be produced via fermentation of sugars. This can be accomplished by a variety of homoacetogenic microorganisms that can produce acetic acid with 100% carbon yield.

  12. Resonance energies of the allyl cation and allyl anion: contribution by resonance and inductive effects toward the acidity and hydride abstraction enthalpy of propene. (United States)

    Barbour, Josiah B; Karty, Joel M


    Density functional theory was employed to calculate the acidities and hydride abstraction enthalpies of propene (3) and propane (4), along with their vinylogues (5 and 6, respectively). The same reaction enthalpies were calculated for the propene vinylogues in which the terminal vinyl group was rotated perpendicular to the rest of the conjugated system (7). The contribution by resonance and inductive effects toward the acidity and hydride abstraction enthalpy of each vinylogue of 5 (n = 1-3) was computed and extrapolated to n = 0 (the parent propene system). The resonance energies of the allyl cation and anion were determined to be about 20-22 and 17-18 kcal/mol, respectively. Comparisons are made to resonance energies calculated using other methodologies.

  13. Molecular physiology of the insect K-activated amino acid transporter 1 (KAAT1) and cation-anion activated amino acid transporter/channel 1 (CAATCH1) in the light of the structure of the homologous protein LeuT. (United States)

    Castagna, M; Bossi, E; Sacchi, V F


    K-activated amino acid transporter 1 (KAAT1) and cation-anion-activated amino acid transporter/channel 1 (CAATCH1) are amino acid cotransporters, belonging to the Na/Cl-dependent neurotransmitter transporter family (also called SLC6/NSS), that have been cloned from Manduca sexta midgut. They have been thoroughly studied by expression in Xenopus laevis oocytes, and structure/function analyses have made it possible to identify the structural determinants of their cation and amino acid selectivity. About 40 mutants of these proteins have been studied by measuring amino acid uptake and current/voltage relationships. The results obtained since the cloning of KAAT1 and CAATCH1 are here discussed in the light of the 3D model of the first crystallized member of the family, the leucine transporter LeuT.

  14. Growth inhibition of fungus Phycomyces blakesleeanus by anion channel inhibitors anthracene-9-carboxylic and niflumic acid attained through decrease in cellular respiration and energy metabolites. (United States)

    Stanić, Marina; Križak, Strahinja; Jovanović, Mirna; Pajić, Tanja; Ćirić, Ana; Žižić, Milan; Zakrzewska, Joanna; Cvetić Antić, Tijana; Todorović, Nataša; Živić, Miroslav


    Increasing resistance of fungal strains to known fungicides has prompted identification of new candidates for fungicides among substances previously used for other purposes. We have tested the effects of known anion channel inhibitors anthracene-9-carboxylic (A9C) and niflumic acid (NFA) on growth, energy metabolism and anionic current of mycelium of fungus Phycomyces blakesleeanus. Both inhibitors significantly decreased growth and respiration of mycelium, but complete inhibition was only achieved by 100 or 500 µM NFA, for growth and respiration, respectively. A9C had no effect on respiration of human NCI-H460 cell line, and very little effect on cucumber root sprout clippings, which nominates this inhibitor for further investigation as a potential new fungicide. Effects of A9C and NFA on respiration of isolated mitochondria of P. blakesleeanus were significantly smaller, which indicates that their inhibitory effect on respiration of mycelium is indirect. NMR spectroscopy showed that both A9C and NFA decrease the levels of ATP and polyphosphates in the mycelium of P. blakesleanus, but only A9C caused intracellular acidification. Outwardly rectifying, fast inactivating instantaneous anionic current (ORIC) was also reduced to 33±5% and 21±3% of its pre-treatment size by A9C and NFA, respectively, but only in the absence of ATP. It can be assumed from our results that the regulation of ORIC is tightly linked to cellular energy metabolism in P. blakesleeanus, and the decrease in ATP and polyphosphate levels could be a direct cause of growth inhibition.

  15. Determination of ellagic acid in oak leaves and in sheep ruminal fluid by ion-pair RP-HPLC. (United States)

    del Moral, P García; Arín, M J; Resines, J A; Díez, M T


    An isocratic ion-pair high-performance liquid chromatography (IP-RP-HPLC) method with UV detection was developed to identify and quantify ellagic acid (EA). This phenolic compound is widely distributed in the plants and is often present in the diet of ruminants. The method was validated and validation parameters were: linearity range 5-100 mg/L; correlation coefficient, 0.9995; mean recoveries (99.94 and 101.07%) and detection limit 1.4 mg/L. Method was applied for the determination of ellagic acid in oak leaves and in ruminal fluid from to a vitro ruminal system. The proposed method proved to be rapid and accurate and can be successfully used in ruminant nutrition studies.

  16. Light-emitting self-assembled peptide nucleic acids exhibit both stacking interactions and Watson-Crick base pairing (United States)

    Berger, Or; Adler-Abramovich, Lihi; Levy-Sakin, Michal; Grunwald, Assaf; Liebes-Peer, Yael; Bachar, Mor; Buzhansky, Ludmila; Mossou, Estelle; Forsyth, V. Trevor; Schwartz, Tal; Ebenstein, Yuval; Frolow, Felix; Shimon, Linda J. W.; Patolsky, Fernando; Gazit, Ehud


    The two main branches of bionanotechnology involve the self-assembly of either peptides or DNA. Peptide scaffolds offer chemical versatility, architectural flexibility and structural complexity, but they lack the precise base pairing and molecular recognition available with nucleic acid assemblies. Here, inspired by the ability of aromatic dipeptides to form ordered nanostructures with unique physical properties, we explore the assembly of peptide nucleic acids (PNAs), which are short DNA mimics that have an amide backbone. All 16 combinations of the very short di-PNA building blocks were synthesized and assayed for their ability to self-associate. Only three guanine-containing di-PNAs—CG, GC and GG—could form ordered assemblies, as observed by electron microscopy, and these di-PNAs efficiently assembled into discrete architectures within a few minutes. The X-ray crystal structure of the GC di-PNA showed the occurrence of both stacking interactions and Watson-Crick base pairing. The assemblies were also found to exhibit optical properties including voltage-dependent electroluminescence and wide-range excitation-dependent fluorescence in the visible region.

  17. Ion-pair mediated transport of small model peptides in liquid phase micro extraction under acidic conditions. (United States)

    Reubsaet, J Léon E; Paulsen, Jonas V


    This paper discusses the behaviour of five small model peptides in a three phase (aqueous donor-organic-aqueous acceptor) liquid phase micro extraction system in relation to their physico-chemical properties (charge, hydrophobicity). It is proved that for all peptides transport over the organic phase is mediated by aliphatic sulphonic acids. Heptane-1-sulphonic acid gave the best overall recoveries. It appeared that peptides with hydrophobic properties (IPI) and a high number of positive charges (KYK) show good recoveries and are enriched in the acceptor phase. Variation in the pH (1.6-4.4) of the donor phase shows that there are peptide-dependent optimal pH-values for their recovery. Increasing pH in the acceptor phase shows that in most cases the recovery decreases due to decreased ion-pair mediated membrane transport. For KYK the partition between the organic phase and the aqueous acceptor-phase is also driven by the solubility in the aqueous acceptor phase. Increase of the ion strength of the acceptor phase did not affect the recovery of the peptides. Except for KYK, which showed decreased recovery when the ion strength increased. Another finding is that delocalisation of positive charge causes bad recovery, probably due to incomplete ion-pair-peptide complex formation.

  18. Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography I. Matrix elimination by ion-exclusion chromatography. (United States)

    Vermeiren, Koen


    Since years, ion exclusion chromatography (ICE) has been the standard method to separate strong acid analyte anions from concentrated weak acid matrices such as hydrofluoric acid (HF). In this work, the commercially available IonPac ICE-AS 1 column was used to separate trace levels of chloride, nitrate, sulfate and phosphate from HF solutions at 20% (w/w). The efficiency of the separation was studied in more detail using techniques such as ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP-OES) and ICP-mass spectrometry (ICP-MS). For 20% (w/w) HF solutions and at a water carrier flow-rate of 0.50 ml/min, the cut window was set from 8.5 to 14.5 min. Under these conditions, analyte recoveries of better than 90% were obtained for chloride, nitrate and sulfate, but only about 75% for phosphate. The HF rejection efficiency was better than 99.9%. It was found that the ICP techniques, measuring total element levels and not species, yielded significantly higher recoveries for phosphorus and sulfur compared to IC. Evidence will be given that part of the added phosphorus (approximately 15% for an addition of 10 mg PO4/kg) is present as mono-fluorophosphoric acid (H2FPO3). In the case of sulfate, the difference between IC and ICP-MS could be attributed to an important matrix effect from the residual HF concentration.

  19. The roles of entropy and enthalpy in stabilizing ion-pairs at transition states in zeolite acid catalysis. (United States)

    Gounder, Rajamani; Iglesia, Enrique


    Acidic zeolites are indispensable catalysts in the petrochemical industry because they select reactants and their chemical pathways based on size and shape. Voids of molecular dimensions confine reactive intermediates and transition states that mediate chemical reactions, stabilizing them by van der Waals interactions. This behavior is reminiscent of the solvation effects prevalent within enzyme pockets and has analogous consequences for catalytic specificity. Voids provide the "right fit" for certain transition states, reflected in their lower free energies, thus extending the catalytic diversity of zeolites well beyond simple size discrimination. This catalytic diversity is even more remarkable because acid strength is essentially unaffected by confinement among known crystalline aluminosilicates. In this Account, we discuss factors that determine the "right fit" for a specific chemical reaction, exploring predictive criteria that extend the prevailing discourse based on size and shape. We link the structures of reactants, transition states, and confining voids to chemical reactivity and selectivity. Confinement mediates enthalpy-entropy compromises that determine the Gibbs free energies of transition states and relevant reactants; these activation free energies determine turnover rates via transition state theory. At low temperatures (400-500 K), dimethyl ether carbonylation occurs with high specificity within small eight-membered ring (8-MR) voids in FER and MOR zeolite structures, but at undetectable rates within larger voids (MFI, BEA, FAU, and SiO(2)-Al(2)O(3)). More effective van der Waals stabilization within 8-MR voids leads to lower ion-pair enthalpies but also lower entropies; taken together, carbonylation activation free energies are lower within 8-MR voids. The "right fit" is a "tight fit" at low temperatures, a consequence of how temperature appears in the defining equation for Gibbs free energy. In contrast, entropy effects dominate in high

  20. Distance-dependent proton transfer along water wires connecting acid-base pairs

    NARCIS (Netherlands)

    Cox, M.J.; Timmer, R.L.A.; Bakker, H.J.; Park, S.; Agmon, N.


    We report time-resolved mid-IR kinetics for the ultrafast acid−base reaction between photoexcited 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS), and acetate at three concentrations (0.5, 1.0, and 2.0 M) and three temperatures (5, 30, and 65 °C) in liquid D2O. The observed proton-trans

  1. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids. (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean


    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  2. Corynebacterium jeikeium jk0268 constitutes for the 40 amino acid long PorACj, which forms a homooligomeric and anion-selective cell wall channel.

    Directory of Open Access Journals (Sweden)

    Narges Abdali

    Full Text Available Corynebacterium jeikeium, a resident of human skin, is often associated with multidrug resistant nosocomial infections in immunodepressed patients. C. jeikeium K411 belongs to mycolic acid-containing actinomycetes, the mycolata and contains a channel-forming protein as judged from reconstitution experiments with artificial lipid bilayer experiments. The channel-forming protein was present in detergent treated cell walls and in extracts of whole cells using organic solvents. A gene coding for a 40 amino acid long polypeptide possibly responsible for the pore-forming activity was identified in the known genome of C. jeikeium by its similar chromosomal localization to known porH and porA genes of other Corynebacterium strains. The gene jk0268 was expressed in a porin deficient Corynebacterium glutamicum strain. For purification temporarily histidine-tailed or with a GST-tag at the N-terminus, the homogeneous protein caused channel-forming activity with an average conductance of 1.25 nS in 1M KCl identical to the channels formed by the detergent extracts. Zero-current membrane potential measurements of the voltage dependent channel implied selectivity for anions. This preference is according to single-channel analysis caused by some excess of cationic charges located in the channel lumen formed by oligomeric alpha-helical wheels. The channel has a suggested diameter of 1.4 nm as judged from the permeability of different sized hydrated anions using the Renkin correction factor. Surprisingly, the genome of C. jeikeium contained only one gene coding for a cell wall channel of the PorA/PorH type found in other Corynebacterium species. The possible evolutionary relationship between the heterooligomeric channels formed by certain Corynebacterium strains and the homooligomeric pore of C. jeikeium is discussed.

  3. Molecular structure investigation of neutral, dimer and anion forms of 3,4-pyridinedicarboxylic acid: A combined experimental and theoretical study (United States)

    Karabacak, Mehmet; Bilgili, Sibel; Atac, Ahmet


    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.

  4. Selective recognition of sulfate anions in a 95% ethanol solvent with a simple neutral salicylaldehyde dansyl hydrazine Schiff base tuned by Brønsted-Lowry acid-base reaction (United States)

    Wei, Gao-Ning; Zhang, Jing-Li; Jia, Cang; Fan, Wei-Zhen; Lin, Li-Rong


    A new Schiff base compound, 5-(dimethylamino)-N‧-(2-hydroxybenzylidene)naphthalene-1-sulfonohydrazide (R), has been synthesized, characterized, and employed as a selective fluorescence receptor for the recognition of sulfate anions. UV-vis absorption, fluorescence emission, 1H NMR spectra and DFT calculation studies on the system have been carried out to determine the nature of the interactions between R and anions. The results reveal that the deprotonation of the phenol without the need of a strong base leads to the formation of a hydrogen-bonding complex with a sbnd SO2sbnd NHsbnd group, which is responsible for the spectra changes. The deprotonation process for the selectivity recognition of sulfate can be tuned by the Brønsted-Lowry acid-base reaction in nonaqueous solutions, revealing that suitable phenolic hydroxyl acidity is the key factor for anion recognition selectivity.

  5. Absorption Behavior of Anion Exchange Resin to Minimal Plutonium in 3 to 4 mol/L Nitric Acid Medium

    Institute of Scientific and Technical Information of China (English)


    <正>The acidity of liquor in the process of plutonium purification using extraction method is 3 to 4 mol/L and liquor contains minimal plutonium of certain concentration, the reclamation of plutonium is usually

  6. Biomarkers for the activation of calcium metabolism in dairy cows: elevation of tartrate-resistant acid phosphatase activity by lowering dietary cation-anion difference is associated with the prevention of milk fever. (United States)

    Kurosaki, Naotoshi; Yamato, Osamu; Sato, Jun; Naito, Yoshihisa; Mori, Fuminobu; Imoto, Seiichi; Maede, Yoshimitsu


    In our previous study, it was demonstrated that the administration of anion salts, which slightly lower the dietary cation-anion difference (DCAD), in the prepartum period is safe and effective for preventing milk fever in multiparous cows. In the present study, several biomarkers, which might show activation of Ca metabolism, were analyzed using stored samples in the previous study to investigate the mechanism of the preventive effect on milk fever by lowering DCAD. Changes in bone-specific alkaline phosphatase activity, osteocalcin and insulin-like growth factor I concentrations in serum were almost the same among the three groups of multiparous cows with or without the oral administration of anion salts, while the levels of these serum biomarkers in the group of primiparous cows (heifer group) were much higher compared with those in the three multiparous groups throughout the experimental period. Urinary deoxypyridinoline excretion was not a useful biomarker for dairy cows because it hardly changed during the peripartum period in all groups. However, serum tartrate-resistant acid phosphatase (TRAP) activity, which is known as a biomarker of osteoclast activity, was well associated with the administration of anion salts lowering DCAD because among the three multiparous groups, only the group of multiparous cows fed the anion salts (anion group) showed an increased level, which rose to the level in the heifer group, and was markedly higher than those in the other control groups of multiparous cows. The increased activity of serum TRAP in the anion group suggested that Ca in the plasma pool was mobilized smoothly from bone-bound Ca via mature osteoclasts at parturition, which might be due to prior activation under mild acidosis induced by slightly lowering DCAD. Therefore, TRAP was the best biomarker to monitor the activation of Ca metabolism in dairy cows fed anion salts.

  7. Incorporating significant amino acid pairs and protein domains to predict RNA splicing-related proteins with functional roles. (United States)

    Hsu, Justin Bo-Kai; Huang, Kai-Yao; Weng, Tzu-Ya; Huang, Chien-Hsun; Lee, Tzong-Yi


    Machinery of pre-mRNA splicing is carried out through the interaction of RNA sequence elements and a variety of RNA splicing-related proteins (SRPs) (e.g. spliceosome and splicing factors). Alternative splicing, which is an important post-transcriptional regulation in eukaryotes, gives rise to multiple mature mRNA isoforms, which encodes proteins with functional diversities. However, the regulation of RNA splicing is not yet fully elucidated, partly because SRPs have not yet been exhaustively identified and the experimental identification is labor-intensive. Therefore, we are motivated to design a new method for identifying SRPs with their functional roles in the regulation of RNA splicing. The experimentally verified SRPs were manually curated from research articles. According to the functional annotation of Splicing Related Gene Database, the collected SRPs were further categorized into four functional groups including small nuclear Ribonucleoprotein, Splicing Factor, Splicing Regulation Factor and Novel Spliceosome Protein. The composition of amino acid pairs indicates that there are remarkable differences among four functional groups of SRPs. Then, support vector machines (SVMs) were utilized to learn the predictive models for identifying SRPs as well as their functional roles. The cross-validation evaluation presents that the SVM models trained with significant amino acid pairs and functional domains could provide a better predictive performance. In addition, the independent testing demonstrates that the proposed method could accurately identify SRPs in mammals/plants as well as effectively distinguish between SRPs and RNA-binding proteins. This investigation provides a practical means to identifying potential SRPs and a perspective for exploring the regulation of RNA splicing.

  8. Reversible phospholipid nanogels for deoxyribonucleic acid fragment size determinations up to 1500 base pairs and integrated sample stacking. (United States)

    Durney, Brandon C; Bachert, Beth A; Sloane, Hillary S; Lukomski, Slawomir; Landers, James P; Holland, Lisa A


    Phospholipid additives are a cost-effective medium to separate deoxyribonucleic acid (DNA) fragments and possess a thermally-responsive viscosity. This provides a mechanism to easily create and replace a highly viscous nanogel in a narrow bore capillary with only a 10°C change in temperature. Preparations composed of dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) self-assemble, forming structures such as nanodisks and wormlike micelles. Factors that influence the morphology of a particular DMPC-DHPC preparation include the concentration of lipid in solution, the temperature, and the ratio of DMPC and DHPC. It has previously been established that an aqueous solution containing 10% phospholipid with a ratio of [DMPC]/[DHPC]=2.5 separates DNA fragments with nearly single base resolution for DNA fragments up to 500 base pairs in length, but beyond this size the resolution decreases dramatically. A new DMPC-DHPC medium is developed to effectively separate and size DNA fragments up to 1500 base pairs by decreasing the total lipid concentration to 2.5%. A 2.5% phospholipid nanogel generates a resolution of 1% of the DNA fragment size up to 1500 base pairs. This increase in the upper size limit is accomplished using commercially available phospholipids at an even lower material cost than is achieved with the 10% preparation. The separation additive is used to evaluate size markers ranging between 200 and 1500 base pairs in order to distinguish invasive strains of Streptococcus pyogenes and Aspergillus species by harnessing differences in gene sequences of collagen-like proteins in these organisms. For the first time, a reversible stacking gel is integrated in a capillary sieving separation by utilizing the thermally-responsive viscosity of these self-assembled phospholipid preparations. A discontinuous matrix is created that is composed of a cartridge of highly viscous phospholipid assimilated into a separation matrix

  9. Ion pairing with linoleic acid simultaneously enhances encapsulation efficiency and antibacterial activity of vancomycin in solid lipid nanoparticles. (United States)

    Kalhapure, Rahul S; Mocktar, Chunderika; Sikwal, Dhiraj R; Sonawane, Sandeep J; Kathiravan, Muthu K; Skelton, Adam; Govender, Thirumala


    Ion pairing of a fatty acid with an antibiotic may be an effective strategy for formulation optimization of a nanoantibiotic system. The aim of this study was therefore to explore the potential of linoleic acid (LA) as an ion pairing agent to simultaneously enhance encapsulation efficiency and antibacterial activity of triethylamine neutralized vancomycin (VCM) in solid lipid nanoparticles (SLNs). The prepared VCM-LA2 conjugate was characterized by Fourier transform-infrared (FT-IR) spectroscopy, logP and binding energy calculations. The shifts in the FT-IR frequencies of COOH, NH2 and CO functionalities, an increase in logP value (1.37) and a lower interaction energy between LA and VCM (-125.54 kcal/mol) confirmed the formation of the conjugate. SLNs were prepared by a hot homogenization and ultrasonication method, and characterized for size, polydispersity index (PI), zeta potential (ZP), entrapment efficiency (%EE), surface morphology and physical stability. In vitro antibacterial activity studies against Staphylococcus aureus and methicillin-resistant S. aureus (MRSA) were conducted. Size, PI and ZP for VCM-LA2_SLNs were 102.7±1.01, 0.225±0.02 and -38.8±2.1 (mV) respectively. SLNs were also stable at 4 °C for 3 months. %EE for VCM-HCl_SLNs and VCM-LA2_SLNs were 16.81±3.64 and 70.73±5.96 respectively, indicating a significant improvement in encapsulation of the drug through ion pairing with LA. Transmission electron microscopy images showed spherical nanoparticles with sizes in the range of 95-100 nm. After 36 h, VCM-HCl showed no activity against MRSA. However, the minimum inhibitory concentration for VCM-HCl_SLNs and VCM-LA2_SLNs were 250 and 31.25 μg/ml respectively against S. aureus, while against MRSA it was 500 and 15.62 μg/ml respectively. This confirms the enhanced antibacterial activity of VCM-LA2_SLNs over VCM-HCl_SLNs. These findings therefore suggest that VCM-LA2_SLNs is a promising nanoantibiotic system for effective treatment against both

  10. Stability of gas-phase tartaric acid anions investigated by quantum chemistry, mass spectrometry, and infrared spectroscopy. (United States)

    Tonner, Ralf; Schwerdtfeger, Peter; May, Amanda L; Steill, Jeffrey D; Berden, Giel; Oomens, Jos; Campagna, Shawn R; Compton, Robert N


    In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway (O(2)C-CH(OH)-CH(OH)-CO(2))(2-) → (O(2)C-CH(OH)-CH(OH))(•-) + CO(2) + e(-) explaining the observed gas-phase instability of this dianion. Further theoretical data were collected for the bare dianion, this molecule complexed to water, sodium, and a proton, in both the meso and l forms as well as for the uncomplexed radical anion and neutral diradical. The calculations suggest that the l-tartrate dianion is more thermodynamically stable than the dianion of the meso stereoisomer and that either dianion can be further stabilized by association with a separate species that can help to balance the charge of the molecular complex. Mass spectrometry was then used to measure the energy needed to initiate collisionally induced dissociation of the racemic tartrate dianion and for the proton and sodium adducts of both the racemic and meso form of this molecule. Infrared action spectra of the dianion stereoisomers complexed with sodium were also acquired to determine the influence of the metal ion on the vibrations of the dianions and validate the computationally predicted structures. These experimental data support the theoretical conclusions and highlight the instability of the bare tartrate dianion. From the experimental work, it could also be concluded that the pathway leading to dissociation is under kinetic control because the sodium adduct of the racemic stereoisomer dissociated at lower collisional energy, although it was calculated to be more stable, and that decomposition proceeded via C-C bond dissociation as computationally predicted. Taken together, these data provide insight into the gas-phase stability of the tartrate dianion and highlight the role of adducts in

  11. Reducing Dietary Cation-Anion Difference on Acid-Base Balance, Plasma Minerals Level and Anti-Oxidative Stress of Female Goats

    Institute of Scientific and Technical Information of China (English)

    WU Wen-xuan; YANG Yi; ZHANG Ji-kun; LI Sheng-li


    Reducing dietary cation-anion difference (DCAD) has been proved an effective way to prevent milk fever in dairy cows. Based on the similar physiological gastro-intestinal tract anatomy and metabolic process between female goats and dairy cows, this study was conducted to evaluate the effects of varying DCAD on fluid acid-base status, plasma minerals concentration and anti-oxidative stress capacity of female goats. Urinary pH, plasma Ca, P and Mg;and anti-oxidative stress indices of total superoxide dismutase (T-SOD), hydrogen peroxide (H2O2), glutathione peroxidase (GSH-Px) and malondialdehyde (MDA) were determined to evaluate the effect. Forty-eight Guizhou black female goats ((15±1.9) mon of old, (22.3±3.75) kg of BW) were randomly allocated to 4 blocks of 12 goats each and were fed 1 of 4 diets differed in DCAD level (calculated as Na+K-Cl-S, mEq kg-1 DM). Levels of DCAD were preliminarily designed to be control (+150 mEq kg-1 DM, CON), high DCAD (+300 mEq kg-1 DM, HD), low DCAD (0 mEq kg-1 DM, LD) and negative DCAD (-150 mEq kg-1 DM, ND), respectively. A commercial anionic salts (Animate) and sodium bicarbonate (NaHCO3) were supplemented to reduce and increase DCAD level, respectively. There was no difference in dry matter intake for 4 groups of goats. Urine pH was aggressively decreased (P0.05) plasma Mg level. There was no significant (P>0.05) difference in plasma GSH-Px activity and H2O2, but anionic salts supplementation in LD and ND significantly increased (P<0.05) plasma T-SOD activity and tended to reduce MDA (P<0.1) over HD and CON. Results from this study indicated that reducing DCAD could decrease urine pH and increase plasma Ca concentration of female goats. Additionally, reducing DCAD was helpful to enhance anti-oxidative stress capability of female goats.

  12. Analysis of nucleic acids by capillary ion-pair reversed-phase HPLC coupled to negative-ion electrospray ionization mass spectrometry. (United States)

    Huber, C G; Krajete, A


    Ion-pair reversed-phase high-performance liquid chromatography was successfully coupled to negative-ion electrospray ionization mass spectrometry by using 60 × 0.20 mm i.d. capillary columns packed with 2.3-μm micropellicular, octadecylated poly(styrene/divinylbenzene) particles as stationary phase and gradients of acetonitrile in 50 mM aqueous triethylammonium bicarbonate as mobile phase. Systematic variation of the eluent composition, such as concentration of ion-pair reagent, anion in the ion-pair reagent, solution pH, and acetonitrile concentration led to the conclusion that most parameters have opposite effects on chromatographic and mass spectrometric performances. The use of acetonitrile as sheath liquid enabled the rapid and highly efficient separation and detection of phosphorylated and nonphosphorylated oligonucleotides ranging in size from 8 to 40 nucleotides. High-quality full-scan mass spectra showing little cation adduction were acquired from which the molecular masses of the separated oligonucleotides were calculated with an accuracy of 0.011%. With calibration curves being linear over at least 2 orders of magnitude, the lower limits of detection for a oligodeoxythymidine 16-mer were 104 fmol with full scan and 710 amol with selected-ion-monitoring data acquisition. The potential of ion-pair reversed-phase high-performance liquid chromatography-electrospray ionization mass spectrometry was demonstrated for mixed-sequence oligomers by the characterization of a reaction mixture from solid-phase synthesis of a 40-mer oligonucleotide.

  13. Bound anionic states of adenine

    Energy Technology Data Exchange (ETDEWEB)

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H


    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  14. Water-miscible cooling lubricants - determination of anorganic anions and carboxylic acids using capillary zone electrophoresis; Wassermischbare Kuehlschmierstoffe - Bestimmung von anorganischen Anionen und Carbonsaeuren mittels der Kapillarzonenelektrophorese

    Energy Technology Data Exchange (ETDEWEB)

    Schubert, B.A. [Fachbereich 8, Analytische Chemie II, Universitaet-GH Siegen (Germany); Dengel, H.S. [Fachbereich 8, Analytische Chemie II, Universitaet-GH Siegen (Germany); Hohaus, E. [Fachbereich 8, Analytische Chemie II, Universitaet-GH Siegen (Germany); Maurer, W. [Fachbereich 8, Analytische Chemie II, Universitaet-GH Siegen (Germany); Riepe, W. [Fachbereich 13, Analytische Chemie, Universitaet-GH Paderborn (Germany)


    A procedure is presented which allows the quantitative determination for most of the essentiell inorganic anions besides several carbonic acids (oxalic-, citric-, malonic-, tartaric-, formic-, succinic- and adipinic acid) in concentrates and industrial application emulsions of watermiscible cooling lubricants either free of mineral oil or oleiferous. The method used is based on capillary zones electrophoresis (CZE) using indirect UV-detection. The quantification of these substances regarding a qualiy surveillance of lubricants for manufacturers and a control of possible toxicological infleunces in working places is easily performed in spite of the complex matrix of the lubricants. Only a simple dilution is necessary. Analytical chemcial parameters such as accuracy, precision and recovery rate for concentrates and emulsions in industrial use for 1995/96 reveal sufficient universal application of the presented method for general purpose analyzing cooling lubricants. (orig.) [Deutsch] Es wird ein Verfahren vorgestellt, mit dem in Konzentraten und Emulsionen von wassermischbaren mineraloelfreien und mineraloelhaltigen Kuehlschmierstoffen (KSS) neben den wesentlichen anorganischen Anionen (Thiosulfat, Bromid, Chlorid, Sulfat, Nitrit, Nitrat, Perchlorat, Chlorat, Phosphonat, Fluorid, Phosphat) Carbonsaeuren (Oxal-, Citronen-, Malon-, Wein-, Ameisen-, Bernstein- und Adipinsaeure) mit Hilfe der Kapillarzonenelektrophorese (CZE) und indirekter UV-Detektion quantitativ bestimmt werden koennen. Die Quantifizierung dieser Substanzen im Rahmen von Qualitaetssicherungs- und Arbeitsschutzmassnahmen in KSS ist trotz der komplexen Matrix der KSS ohne eine aufwendige Probenvorbereitung moeglich. Ein einfacher Verduennungsschritt der Proben genuegt. Die analytischen Verfahrenskenngroessen Richtigkeit, Praezision, Wiederfindung sowie die Untersuchungsergebnisse fuer KSS-Konzentrate einiger Hersteller aus den Produktionsjahren 1995/96 werden vorgestellt. (orig.)

  15. Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: roles of particle size and acid anion in iron dissolution. (United States)

    Rubasinghege, Gayan; Lentz, Robert W; Scherer, Michelle M; Grassian, Vicki H


    A number of recent studies have shown that iron dissolution in Fe-containing dust aerosol can be linked to source material (mineral or anthropogenic), mineralogy, and iron speciation. All of these factors need to be incorporated into atmospheric chemistry models if these models are to accurately predict the impact of Fe-containing dusts into open ocean waters. In this report, we combine dissolution measurements along with spectroscopy and microscopy to focus on nanoscale size effects in the dissolution of Fe-containing minerals in low-pH environments and the importance of acid type, including HNO(3), H(2)SO(4), and HCl, on dissolution. All of these acids are present in the atmosphere, and dust particles have been shown to be associated with nitrate, sulfate, and/or chloride. These measurements are done under light and dark conditions so as to simulate and distinguish between daytime and nighttime atmospheric chemical processing. Both size (nano- versus micron-sized particles) and anion (nitrate, sulfate, and chloride) are found to play significant roles in the dissolution of alpha-FeOOH under both light and dark conditions. The current study highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

  16. Tunable electronic interactions between anions and perylenediimide. (United States)

    Goodson, Flynt S; Panda, Dillip K; Ray, Shuvasree; Mitra, Atanu; Guha, Samit; Saha, Sourav


    Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

  17. Hydrothermal Synthesis, Crystal Structure, and Characterization of a Novel Terbium(Ⅲ) Coordination Polymer Bridged by 5-Sulfoisophthalate Trivalent Anions

    Institute of Scientific and Technical Information of China (English)


    Hydrothermal reaction of terbium( Ⅲ ) chloride with 5-sulfoisophthalic acid monosodium salt and 1, 10-phenanthroline(phen) at 415 K resulted in the formation of a novel coordination polymer, [Tb(sip) (phen) (H2O)]n( sip = 5-sulfoisophthalate trivalent anion) with a three-dimensional network structure. Each centrosymmetrically related pair of terbium ions are linked by two sip anions, forming a binuclear unit, and each binuclear unit links to four adjacent tetranuclear units, extending a two-dimensional hybrid layer at crystallographic bc plane. On the other hand,every three-terbium ion is connected by three sip anions, generating a trinuclear ring, and the trinuclear ring connects six neighboring trinuclear rings to produce another two-dimensional layer at crystallographic ab plane. Moreover, each sip anion acts as a pentadentate bridge, interconnecting two different types of layers to yield a novel three-dimensional framework.

  18. Stereoselective Michael Addition of Glycine Anions to Chiral Fischer Alkenylcarbene Complexes. Asymmetric Synthesis of beta-Substituted Glutamic Acids. (United States)

    Ezquerra, Jesús; Pedregal, Concepción; Merino, Isabel; Flórez, Josefa; Barluenga, José; García-Granda, Santiago; Llorca, María-Amparo


    The reaction of lithium enolates of achiral N-protected glycine esters with chiral alkoxyalkenylcarbene complexes of chromium provided the corresponding Michael adducts with either high anti or syn selectivity depending on the nature of the nitrogen protecting group, and high diastereofacial selectivity when carbene complexes containing the (-)-8-phenylmenthyloxy group were employed. Subsequent oxidation of the metal-carbene moiety followed by deprotection of the amine group and hydrolysis of both carboxylic esters afforded enantiomerically enriched 3-substituted glutamic acids of natural as well as unnatural stereochemistry. Alternatively, when the deprotection step was performed previously to the oxidation, cyclic aminocarbene complexes were formed, which finally led to optically active 3-substituted pyroglutamic acids.

  19. Electron paramagnetic resonance study of hydrogen peroxide/ascorbic acid ratio as initiator redox pair in the inulin-gallic acid molecular grafting reaction. (United States)

    Arizmendi-Cotero, Daniel; Gómez-Espinosa, Rosa María; Dublán García, Octavio; Gómez-Vidales, Virginia; Dominguez-Lopez, Aurelio


    Gallic acid (GA) was grafted onto inulin using the free radicals method, generated by the hydrogen peroxide/ascorbic acid (H2O2/AA) redox pair. Molar ratios of H2O2/AA at 9, 20, 39 and 49 were evaluated by Electron Paramagnetic Resonance in order to find the effect of the oxidation of the inulin and the efficiency in the inulin-gallic acid grafting (IGA). The highest concentration of the inulin macro-radical was obtained with H2O2/AA molar ratios of 20 and 49 with the removal of a hydrogen atom from a methyl group of the inulin fructose monomers. The highest grafting ratio (30.4 mg GA eq/g IGA) was obtained at 9 M of H2O2/AA. UV-Vis, FT-IR-ATR and XDR results confirmed a successful IGA grafting. The efficiency of the grafting reaction depends on the concentration of the macro-radical, it depends on the molar ratio of H2O2/AA, being affected by simultaneous reactions between components of the mixture (H2O2, AA, inulin, GA and eventually atmospheric oxygen) as well.

  20. Theoretical studies on the anionic association of phenol and its derivatives in acetonitrile (United States)

    Wiśniewska, Marta; Makowski, Mariusz


    The potentials of mean force (PMF) were determined for homoconjugated systems of anionic complexes composed of phenol and its derivatives with their conjugate anionic bases in acetonitrile (ACN). For each acid-base pair studied, a series of umbrella-sampling molecular dynamics simulations using the AMBER force field with explicit solvent was carried out; the respective PMF was calculated using the Weighted Histogram Analysis Method (WHAM). Subsequently, association equilibrium constants were calculated by numerical integration of the PMF profiles. The PMF curves had a typical shape, i.e., a very deep and narrow contact-minimum, a desolvation maximum, and a shallow solvent-separated minimum. All pairs formed complexes in solution, which was confirmed by the presence of contact minima corresponding to the existence of hydrogen bonds in the PMF curves. The calculated association constants in acetonitrile were subsequently compared with experimentally obtained values for the same solvent. Ab initio methods at the RHF level (utilizing the Gaussian 6-31++G** basis set) enabled the in vacuo calculation of energies and Gibbs free energies of interaction for each phenol derivative and anionic base pair along with a molecule of acetonitrile; this allowed the contribution of the solvent molecule to the PMF to be assessed. It was found that the interaction energies of anionic bases in acetonitrile are stronger than their related neutral phenol derivatives.

  1. Effect of dietary cation-anion difference on ruminal metabolism, total apparent digestibility, blood and renal acid-base regulation in lactating dairy cows. (United States)

    Martins, C M M R; Arcari, M A; Welter, K C; Gonçalves, J L; Santos, M V


    The present study aimed to evaluate the effect of dietary cation-anion difference (DCAD) on ruminal fermentation, total apparent digestibility, blood and renal metabolism of lactating dairy cows. Sixteen Holstein cows were distributed in four contemporary 4×4 Latin Square designs, which consisted of four periods of 21 days and four treatments according to DCAD: +290; +192; +98 and -71 milliequivalent (mEq)/kg dry matter (DM). Ruminal pH and concentrations of acetic and butyric acid increased linearly according to the increase of DCAD. Similarly, NDF total apparent digestibility linearly increased by 6.38% when DCAD increased from -71 to 290 mEq/kg DM [Y=65.90 (SE=2.37)+0.0167 (SE=0.0068)×DCAD (mEq/kg DM)]. Blood pH was also increased according to DCAD, which resulted in reduction of serum concentrations of Na, K and ionic calcium (iCa). To maintain the blood acid-base homeostasis, renal metabolism played an important role in controlling serum concentrations of Na and K, since the Na and K urinary excretion increased linearly by 89.69% and 46.06%, respectively, from -71 to 290 mEq/kg DM. Changes in acid-base balance of biological fluids may directly affect the mineral composition of milk, as milk concentrations of Na, K, iCa and chlorides were reduced according to blood pH increased. Thus, it can be concluded that the increase of DCAD raises the pH of ruminal fluid, NDF total apparent digestibility, and blood pH, and decreases the milk concentration of cationic minerals, as well as the efficiency of Na utilization to milk production.

  2. Adsorption affinity of anions on metal oxyhydroxides (United States)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.


    The dependences of anion (phosphate, carbonate, sulfate, chromate, oxalate, tartrate, and citrate) adsorption affinity anions from geometric characteristics, acid-base properties, and complex forming ability are generalized. It is shown that adsorption depends on the nature of both the anions and the ionic medium and adsorbent. It is established that anions are generally grouped into the following series of adsorption affinity reduction: PO{4/3-}, CO{3/2-} > C2O{4/2-}, C(OH)(CH2)2(COO){3/3-}, (CHOH)2(COO){2/2-} > CrO{4/2-} ≫ SO{4/2-}.

  3. Synthesis of Hydrophobically Modified Poly(acrylic acid) Gels and Interaction of the Gels with Cationic/Anionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    TIAN,Qin(田琴); TANG,Xiao-Zhen(唐小真); ZHUANG,Dong-Qing(庄东青); ZHANG,Yun-Xiang(章云祥)


    Poly( acrylic acid) (PAA) gel network with only chemical crosslinking and hydrophobically modified PAA (HM-PAA)gels with both chemical and physical crosslinking were synthesized by radical polymerization in tert-butanol, using ethylene glycol dimethacrylate (EGDMA) as crosslinker, and 2-(Nethylperfiuorooctanesulfoamido) ethyl methacrylate ( FMA ),stearyl acrylate (SA) or lauryl acrylate (LA) as hydrophobic comonomer respectively. The effect of the fractions and the species of the hydrophobes on swelling properties of HM-PAA gels and the interaction of gels and surfactants were studied.The results showed that the swelling ratio of HM-PAA gels exhibited a sharp decrease with increasing hydrophobic comonomer concentration, which could be ascribed to the formation of strong hydrophobic association among hydrophobic groups. It was proved that two kinds of binding mechanisms of surfactant/gel and different kinds of hydrophobic dusters existed in gels containing both physical and chemical networks.

  4. Novel use of positively charged nylon transfer membranes for trapping indoleacetic acid or other small anions during efflux from plant tissues (United States)

    Evans, M. L.; Hangarter, R. P.


    Positively charged nylon blotting membranes were used as an anion binding medium to trap [14C]indoleactic acid (IAA) as it exited cells at the basal ends of Coleus blumei L. stem and Zea mays L. coleoptile segments. Autoradiography was used to visualize where the [14C] that moved out of the cut ends was localized on the nylon membrane. Diffusion of [14C]IAA from the initial point of contact with the nylon membrane was minimal. Comparison of the autoradiograms with anatomical tissue prints of the cut ends of the segments was used to determine what tissues participate in IAA movement. The results of these initial studies were consistent with other reports suggesting that [14C]IAA movement was primarily associated with vascular tissues in both C. blumei stems and corn coleoptiles, but the resolution was not sufficient to identify which vascular tissues were involved in IAA transport. With further refinements, this technique could also be used for studying the movement of other small charged molecules through plant tissues.

  5. Reaction of sulphate radical anion (SO{sub 4}{sup {center_dot}}{sup -}) with cyanuric acid. A potential reaction for its degradation?

    Energy Technology Data Exchange (ETDEWEB)

    Manoj, P.; Varghese, R.; Manoj, V.M.; Aravindakumar, C.T. [Mahatma Gandhi University, School of Chemical Sciences, Kottayam (India)


    A novel reaction between sulfate radical anion (SO{sub 4}{sup {center_dot}}{sup -}) and cyanuric acid (CA), a non-degradable end product of the oxidative degradation of the triazine based herbicide, atrazine, is presented using laser flash photolysis and steady state radiolysis techniques at pH 5. A second order rate constant of 1.9x10{sup 7} dm{sup 3} mol{sup -1} s{sup -1} has been determined and the transient intermediate ({lambda}{sub max}=330 nm) is assigned to a radical cation of CA (CA{sup {center_dot}}{sup +}). The degradation profile indicated that about 76% of CA have been decomposed after an absorbed {gamma}-radiation dose of 18 kGy. It is therefore proposed that the reaction of SO{sub 4}{sup {center_dot}}{sup -} could be utilised for the degradation of CA in aqueous medium which is normally stable to any Advanced Oxidation Processes. (author)

  6. Chiral mobile phase in ligand-exchange chromatography of amino acids: exploring the copper(II) salt anion effect with a computational approach. (United States)

    Sardella, Roccaldo; Macchiarulo, Antonio; Carotti, Andrea; Ianni, Federica; Rubiño, Maria Eugenia García; Natalini, Benedetto


    With the use of a chiral ligand-exchange chromatography (CLEC) system operating with the O-benzyl-(S)-serine [(S)-OBS] [1,2] as the chiral mobile phase (CMP) additive to the eluent, the effect of the copper(II) anion type on retention (k) and separation (α) factors was evaluated, by rationally changing the following experimental conditions: salt concentration and temperature. The CLEC-CMP analysis was carried out on ten amino acidic racemates and with nine different cupric salts. While the group of analytes comprised both aliphatic (leucine, isoleucine, nor-leucine, proline, valine, nor-valine, and α-methyl-valine) and aromatic (1-aminoindan-1,5-dicarboxylic acid, phenylglycine, and tyrosine) species, representative organic (formate, methanesulfonate, and trifluoroacetate) and inorganic (bromide, chloride, fluoride, nitrate, perchlorate, and sulfate) Cu(II) salts were selected as the metal source into the eluent. This route of investigation was pursued with the aim of identifying analogies among the employed Cu(II) salts, by observing the variation profile of the selected chromatographic parameters, upon a change of the above experimental conditions. All the data were collected and analyzed through a statistical approach (PCA and k-means clustering) that revealed the presence of two behavioral classes of cupric salts, sharing the same variation profile for k and α values. Interestingly, this clustering can be explained in terms of ESP (electrostatic surface potential) balance (ESP(bal)) values, obtained by an ab initio calculation operated on the cupric salts. The results of this appraisal could aid the rational choice of the most suitable eluent system, to succeed in the enantioseparation of difficult-to-resolve compounds, along with the eventual scale-up to a semi-preparative level.

  7. iDNA-Prot|dis: identifying DNA-binding proteins by incorporating amino acid distance-pairs and reduced alphabet profile into the general pseudo amino acid composition.

    Directory of Open Access Journals (Sweden)

    Bin Liu

    Full Text Available Playing crucial roles in various cellular processes, such as recognition of specific nucleotide sequences, regulation of transcription, and regulation of gene expression, DNA-binding proteins are essential ingredients for both eukaryotic and prokaryotic proteomes. With the avalanche of protein sequences generated in the postgenomic age, it is a critical challenge to develop automated methods for accurate and rapidly identifying DNA-binding proteins based on their sequence information alone. Here, a novel predictor, called "iDNA-Prot|dis", was established by incorporating the amino acid distance-pair coupling information and the amino acid reduced alphabet profile into the general pseudo amino acid composition (PseAAC vector. The former can capture the characteristics of DNA-binding proteins so as to enhance its prediction quality, while the latter can reduce the dimension of PseAAC vector so as to speed up its prediction process. It was observed by the rigorous jackknife and independent dataset tests that the new predictor outperformed the existing predictors for the same purpose. As a user-friendly web-server, iDNA-Prot|dis is accessible to the public at Moreover, for the convenience of the vast majority of experimental scientists, a step-by-step protocol guide is provided on how to use the web-server to get their desired results without the need to follow the complicated mathematic equations that are presented in this paper just for the integrity of its developing process. It is anticipated that the iDNA-Prot|dis predictor may become a useful high throughput tool for large-scale analysis of DNA-binding proteins, or at the very least, play a complementary role to the existing predictors in this regard.

  8. Comparison of 5 monoclonal antibodies for immunopurification of human butyrylcholinesterase on Dynabeads: KD values, binding pairs, and amino acid sequences. (United States)

    Peng, Hong; Brimijoin, Stephen; Hrabovska, Anna; Targosova, Katarina; Krejci, Eric; Blake, Thomas A; Johnson, Rudolph C; Masson, Patrick; Lockridge, Oksana


    Human butyrylcholinesterase (HuBChE) is a stoichiometric bioscavenger of nerve agents and organophosphorus pesticides. Mass spectrometry methods detect stable nerve agent adducts on the active site serine of HuBChE. The first step in sample preparation is immunopurification of HuBChE from plasma. Our goal was to identify monoclonal antibodies that could be used to immunopurify HuBChE on Dynabeads Protein G. Mouse anti-HuBChE monoclonal antibodies were obtained in the form of ascites fluid, dead hybridoma cells stored frozen at -80 °C for 30 years, or recently frozen hybridoma cells. RNA from 4 hybridoma cell lines was amplified by PCR for determination of their nucleotide and amino acid sequences. Full-length light and heavy chains were expressed, and the antibodies purified from culture medium. A fifth monoclonal was purchased. The 5 monoclonal antibodies were compared for ability to capture HuBChE from human plasma on Dynabeads Protein G. In addition, they were evaluated for binding affinity by Biacore and ELISA. Epitope mapping by pairing analysis was performed on the Octet Red96 instrument. The 5 monoclonal antibodies, B2 12-1, B2 18-5, 3E8, mAb2, and 11D8, had similar KD values of 10(-9) M for HuBChE. Monoclonal B2 18-5 outperformed the others in the Dynabeads Protein G assay where it captured 97% of the HuBChE in 0.5 ml plasma. Pairing analysis showed that 3E8 and B2 12-1 share the same epitope, 11D8 and B2 18-5 share the same epitope, but mAb2 and B2 12-1 or mAb2 and 3E8 bind to different epitopes on HuBChE. B2 18-5 was selected for establishment of a stable CHO cell line for production of mouse anti-HuBChE monoclonal.

  9. Key Roles of Lewis Acid-base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Junming; Baylon, Rebecca A.; Liu, Changjun; Mei, Donghai; Martin, Kevin J.; Venkitasubramanian, Padmesh; Wang, Yong


    The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguously showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.

  10. Identification and characterization of anion binding sites in RNA

    Energy Technology Data Exchange (ETDEWEB)

    Kieft, Jeffrey S.; Chase, Elaine; Costantino, David A.; Golden, Barbara L. (Purdue); (Colorado)


    Although RNA molecules are highly negatively charged, anions have been observed bound to RNA in crystal structures. It has been proposed that anion binding sites found within isolated RNAs represent regions of the molecule that could be involved in intermolecular interactions, indicating potential contact points for negatively charged amino acids from proteins or phosphate groups from an RNA. Several types of anion binding sites have been cataloged based on available structures. However, currently there is no method for unambiguously assigning anions to crystallographic electron density, and this has precluded more detailed analysis of RNA-anion interaction motifs and their significance. We therefore soaked selenate into two different types of RNA crystals and used the anomalous signal from these anions to identify binding sites in these RNA molecules unambiguously. Examination of these sites and comparison with other suspected anion binding sites reveals features of anion binding motifs, and shows that selenate may be a useful tool for studying RNA-anion interactions.

  11. Indirect photometric detection of boron cluster anions electrophoretically separated in methanol. (United States)

    Vítová, Lada; Fojt, Lukáš; Vespalec, Radim


    3,5-Dinitrobenzoate and picrate are light absorbing anions pertinent to indirect photometric detection of boron cluster anions in buffered methanolic background electrolytes (BGEs). Tris(hydroxymethyl)aminomethane and morpholine have been used as buffering bases, which eliminated baseline steps, and minimized the baseline noise. In methanolic BGEs, mobilities of boron cluster anions depend on both ionic constituents of the BGE buffer. This dependence can be explained by ion pair interaction of detected anions with BGE cations, which are not bonded into ion pairs with the BGE anions. The former ion pair interaction decreases sensitivity of the indirect photometric detection.

  12. Simultaneous Determination of Eight Phenolic Acids, Five Saponins and Four Tanshinones for Quality Control of Compound Preparations Containing Danshen-Sanqi Herb-pair by HPLC-DAD (United States)

    Yao, Hong; Huang, Xiaomei; Li, Shaoguang; Wu, Youjia; Lin, Xinhua; Shi, Peiying


    Background: The herb-pair, Salviaemiltiorrhizae (Danshen, DS) and Panaxnotoginseng (Sanqi,SQ), often occurs in traditional Chinese medicine prescriptions used for the treatment of cardiovascular diseases in clinics in Asian areas. Many commercial preparations containing the DS-SQ herb-pair were produced by various manufactures with the different production process. The raw materials were from different sources, which raised a challenge to control the quality of the herb-pair medicines. Objective: In this paper, a high-performance liquid chromatography (HPLC) method was developed to simultaneously determine seventeen bioactive components, including 8 phenolic acids, 4 tanshinones, and 5 saponins, for quality control of compound preparations containing DS-SQ herb-pair. The chromatographic separation was studied on an Ultimate™ XB-C18 column (150 mm × 4.6 mmi.d., 3.5 μm) with a mobile phase composed of 0.5% aqueous acetic acid and acetonitrile using a gradient elution in 70 min. Results: The optimum detection wavelength was set at 288 nm for phenolic acids and tanshinones, and 203 nm for saponins. The method was validated sufficiently by examining the precision, recoveries, linearity, range, LOD and LOQ, and was successfully applied to quantify the seventeen compounds in five commercial preparations containing DS-SQ herb-pair. Conclusions: It is the first time to report the rapid and simultaneous analysis of the seventeen compounds with the base-line separation of peaks for ginsenoside Rg1 and Re in 70 min by routine HPLC. This HPLC method could be considered as good quality criteria to control the quality of preparations containing DS-SQ herb-pair. SUMMARY An HPLC method was originally developed to simultaneously quantify 8 phenolic acids, 4 tanshinones and 5 saponins in DS-SQ herb-pair preparations.The rapid and simultaneous analysis of the 17 compounds with the base-line separation of peaks for ginsenoside Rg1 and Re within 70 min was achieved for the first

  13. The toxicity of the quaternary ammonium compound benzalkonium chloride alone and in mixtures with other anionic compounds to bacteria in test systems with Vibrio fischeri and Pseudomonas putida. (United States)

    Sütterlin, H; Alexy, R; Kümmerer, K


    Mixtures of chemicals are present in the aquatic environment but standard testing methods assess only single compounds. One aspect of this question is the importance of the formation of ionic pairs, for example from quaternary ammonium compounds with organic anions, and the significance of the ionic pairs for bacterial toxicity in the aquatic environment. The aim of the present study was to investigate the toxicity of the cationic quaternary ammonium compound benzalkonium chloride (BAC) against aquatic bacteria in the presence of substances commonly found in wastewater, such as the anionic surfactant linear alkylbenzene sulfonate (LAS), naphthalene sulfonic acid (NSA), sodium dodecylsulfonate (SDS), and benzene sulfonic acid (BSA). The growth inhibition test with Pseudomonas putida and the Vibrio fischeri luminescent inhibition test were used to determine the toxicity of single compounds and compound mixtures. The results found in this study indicate that ion pair formation is of minor significance under the test conditions applied here.

  14. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    intrinsic factors and solvent effects is the enhanced reactivity of α-nucleophiles – nucleophiles with a lone-pair adjacent to the attacking site – referred to as the α-effect. This thesis concerns the reactivity of microsolvated anions and in particular how the presence of a single solvent molecule affects...... the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  15. Dendrimer-functionalized mesoporous silica as a reversed-phase/anion-exchange mixed-mode sorbent for solid phase extraction of acid drugs in human urine. (United States)

    Li, Yun; Yang, Jiajia; Huang, Chaonan; Wang, Longxing; Wang, Jincheng; Chen, Jiping


    A new dendrimer-functionalized mesoporous silica material based on large-pore 3D cubic Korea Advanced Institute of Science and Technology-6 (KIT-6) was synthesized by the growing of dendritic branches inside the mesopores of aminopropyl functionalized KIT-6. Detailed physical characterizations using transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis reveal that the multifunctional dendrimers have been grown successfully within the confined spaces of mesopores. Although the 3D ordered mesoporous architecture of KIT-6 was well preserved, there was a significant and continuous decrease in pore size, specific surface area (SBET) and pore volume when increasing dendrimer generation up to six. In order to get a compromise between the SBET, pore size and density of functionalities, the dendrimer-functionalized KIT-6 (DF-KIT-6) for generation 2 (SBET, 314.2 m(2) g(-1); pore size, 7.9 nm; carbon and nitrogen contents, 19.80% and 1.92%) was selected for solid phase extraction (SPE) applications. The DF-KIT-6 was then evaluated as a reversed-phase/anion-exchange mixed-mode sorbent for extraction of the selected acidic drugs (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBU), since the dendrimers contained both hydrocarbonaceous and amine functionalities. The effective parameters on extraction efficiency such as sample pH and volume, type and volume of eluent and wash solvents were optimized. Under the optimized experimental conditions, the DF-KIT-6 based SPE coupled with HPLC-UV method demonstrated good sensitivity (0.4-4.6 ng mL(-1) detection of limits) and linearity (R(2)>0.990 for 10-2000 ng mL(-1) of KEP and IBU, and 1-200 ng mL(-1) of NAP). The potential use of DF-KIT-6 sorbent for preconcentration and cleanup of acid drugs in human urine samples was also demonstrated. Satisfactory recoveries at two spiking levels (30 and 300 ng mL(-1) for KEP and IBU, 3 and 30 ng mL(-1

  16. Anion exchange membrane (United States)

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus


    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  17. Anions in Cometary Comae (United States)

    Charnley, Steven B.


    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  18. Solvent and H/D isotope effects on the proton transfer pathways in heteroconjugated hydrogen-bonded phenol-carboxylic acid anions observed by combined UV-vis and NMR spectroscopy. (United States)

    Koeppe, Benjamin; Guo, Jing; Tolstoy, Peter M; Denisov, Gleb S; Limbach, Hans-Heinrich


    Heteroconjugated hydrogen-bonded anions A···H···X(-) of phenols (AH) and carboxylic/inorganic acids (HX) dissolved in CD2Cl2 and CDF3/CDF2Cl have been studied by combined low-temperature UV-vis and (1)H/(13)C NMR spectroscopy (UVNMR). The systems constitute small molecular models of hydrogen-bonded cofactors in proteins such as the photoactive yellow protein (PYP). Thus, the phenols studied include the PYP cofactor 4-hydroxycinnamic acid methyl thioester, and the more acidic 4-nitrophenol and 2-chloro-4-nitrophenol which mimic electronically excited cofactor states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate the proton transfer pathways in a qualitative way. Dual absorption bands of the phenolic moiety indicate a double-well situation for the shortest OHO hydrogen bonds studied. Surprisingly, when the solvent polarity is low the carboxylates are protonated whereas the proton shifts toward the phenolic oxygens when the polarity is increased. This finding indicates that because of stronger ion-dipole interactions small anions are stabilized at high solvent polarity and large anions exhibiting delocalized charges at low solvent polarities. It also explains the large acidity difference of phenols and carboxylic acids in water, and the observation that this difference is strongly reduced in the interior of proteins when both partners form mutual hydrogen bonds.

  19. Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces. (United States)

    Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R; Sakai, Naomi; Matile, Stefan


    To integrate anion-π, cation-π, and ion pair-π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion-π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion-π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful.

  20. The scaled-charge additive force field for amino acid based ionic liquids

    DEFF Research Database (Denmark)

    Fileti, E. E.; Chaban, V. V.


    Ionic liquids (ILs) constitute an emerging research field. New ILs involve more and more organic and inorganic ions. Amino acid based ILs (AAILs) represent a specific interest due to their evolutional connection to proteins. We report a new non-polarizable force field (FF) for the eight AAILs...... comprising 1-ethyl-3-methylimidazolium cation and amino acid anions. The anions were obtained via deprotonation of carboxyl group. Specific cation-anion non-covalent interactions were taken into account by computing electrostatic potential for ion pairs. The van der Waals interactions were adopted from...

  1. A model for underpotential deposition in the presence of anions (United States)

    Giménez, M. C.; Ramirez-Pastor, A. J.; Leiva, E. P. M.


    A simple model to study the effect of on top coadsorption of anions in underpotential deposition is formulated. It considers a lattice-gas model with pair potential interactions between nearest neighbors. As test system, the electrodeposition of silver on gold is studied by means of grand canonical Monte Carlo simulations. The influence of anions on the adsorption isotherms is analyzed. It is found that as the interaction between silver atoms and anions increases, the monolayer adsorbs at more negative chemical potentials. For large interactions between silver atoms and anions, a expanded structure occurs for the silver monolayer.

  2. Synthesis, photophysical properties of triazolyl-donor/acceptor chromophores decorated unnatural amino acids: Incorporation of a pair into Leu-enkephalin peptide and application of triazolylperylene amino acid in sensing BSA. (United States)

    Bag, Subhendu Sekhar; Jana, Subhashis; Pradhan, Manoj Kumar


    The research in the field of design and synthesis of unnatural amino acids is growing at a fast space for the increasing demand of proteins of potential therapeutics and many other diversified novel functional applications. Thus, we report herein the design and synthesis of microenvironment sensitive fluorescent triazolyl unnatural amino acids (UNAA) decorated with donor and/or acceptor aromatic chromophores via click chemistry. The synthesized fluorescent amino acids show interesting solvatochromic characteristic and/or intramolecular charge transfer (ICT) feature as is revealed from the UV-visible, fluorescence photophysical properties and DFT/TDDFT calculation. HOMO-LUMO distribution shows that the emissive states of some of the amino acids are characterized with more significant electron redistribution between the triazolyl moiety and the aromatic chromophores linked to it leading to modulated emission property. A pair of donor-acceptor amino acid shows interesting photophysical interaction property indicating a FRET quenching event. Furthermore, one of the amino acid, triazolyl-perylene amino acid, has been exploited for studying interaction with BSA and found that it is able to sense BSA with an enhancement of fluorescence intensity. Finally, we incorporated a pair of donor/acceptor amino acids into a Leu-enkephalin analogue pentapeptide which was found to adopt predominantly type II β-turn conformation. We envisage that our investigation is of importance for the development of new fluorescent donor-acceptor unnatural amino acids a pair of which can be exploited for generating fluorescent peptidomimetic probe of interesting photophysical property for applications in studying peptide-protein interaction.

  3. Atomic-Level Organization of Vicinal Acid-Base Pairs through the Chemisorption of Aniline and Derivatives onto Mesoporous SBA15

    KAUST Repository

    Basset, Jean-Marie


    The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest for heterogeneous catalysis. Herein, we report a method to obtain a majority bifunctional acid-base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine-silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR: 2D ¹H-¹H double-quantum, ¹H-¹³C HETCOR experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si-N surface bond and confirm the design of vicinal acid-base pairs. This approach was successfully applied to the design of a series of aniline derivatives bifunctional SBA15. A correlation of the substituents effects on the aromatic ring (Hammet parameters) on the kinetics of the model reaction of Knoevenagel is observed.

  4. Descriptors for ions and ion-pairs for use in linear free energy relationships. (United States)

    Abraham, Michael H; Acree, William E


    The determination of Abraham descriptors for single ions is reviewed, and equations are given for the partition of single ions from water to a number of solvents. These ions include permanent anions and cations and ionic species such as carboxylic acid anions, phenoxide anions and protonated base cations. Descriptors for a large number of ions and ionic species are listed, and equations for the prediction of Abraham descriptors for ionic species are given. The application of descriptors for ions and ionic species to physicochemical processes is given; these are to water-solvent partitions, HPLC retention data, immobilised artificial membranes, the Finkelstein reaction and diffusion in water. Applications to biological processes include brain permeation, microsomal degradation of drugs, skin permeation and human intestinal absorption. The review concludes with a section on the determination of descriptors for ion-pairs.

  5. Extraction of lactic acid from fermentation broth with anion exchange resin%阴离子交换树脂分离提取发酵液中的乳酸

    Institute of Scientific and Technical Information of China (English)

    迟国达; 王鹏; 徐伟; 黄臣勇


    The domestic anion exchange resin 315 was selected to separate lactic acid from the fermentation broth. Adsorption isotherm, kinetics, effect of dynamic adsorption and elution on lactic acid, acetic acid, pyruvic acid and citric acid were studied. Adsorption isotherm results showed that the Freundlich isotherm e- quation agreed well with the adsorption data of organic acids on anion exchange resin 315, and the characteris- tic parameter of this equation n 〉 1. It displayed that the adsorption process belonged to favorable adsorption. Besides, the adsorption kinetics of organic acids on anion exchange resin 315 was mainly controlled by liquid film diffusion, and it accorded well with the Boyd liquid film diffusion model. The optimum dynamic adsorp- tion and elution conditions were determined: adsorption flow-rate, 1.5 BV/h; pH 1.88 ; eluent, deionized water; elution flow-rate, 1 BV/h. Under these conditions, the lactic could be well separated from the fermen- tation broth to achieve the purpose of increasing the yield of lactic acid products and improving product' purity.%为提高乳酸产品收率和纯度,实验筛选得到国产315型阴离子交换树脂,用于分离提取发酵液中乳酸,并研究其对乳酸、乙酸、丙酮酸及柠檬酸的吸附等温线、吸附动力学和动态吸附及洗脱效果.吸附等温线结果表明,315型树脂对乳酸等有机酸的吸附等温线符合Freundlich方程,特征参数n〉1,属于优惠吸附.吸附动力学研究表明,液膜扩散是吸附过程的主要控制步骤,符合Boyd液膜扩散模型.动态吸附及洗脱实验结果表明,以1.5BV/h、pH1.88上柱吸附,再用1BV/h的去离子水洗脱,可实现发酵液中乳酸的良好分离.

  6. Determination of volatile organic acids and inorganic anions in pharmaceutical wastewater by ion chromatography%离子色谱法测定制药废水中挥发性有机酸及无机阴离子

    Institute of Scientific and Technical Information of China (English)

    王强; 王路光; 王靖飞; 李洪波


    An ion chromatographic method for simultaneous determination of volatile organic acids and inorganic anions in pharmacentical wastewater was developed, using NaOH as eluent, ion exchange column for separation, and thermal conductivity detector for detection. Eight volatile organic acids and inorganic anions in pharmaceutical wastewater were separated in 28.0 min. The recoveries were 85.9%~109.5% and RSDs were 2.9%~10.9%. The method can be used for analysis of volatile organic acids and inorganic anions in wastewater in the production of penicillin and vitamin C.%建立了以NaOH为淋洗液、离子交换色谱柱为分析柱、用电导检测器进行检测的制药废水中有机酸和无机阴离子的离子色谱分析方法.结果表明,在28.0 min内可以分离出废水中8种主要挥发性有机酸与无机阴离子.方法回收率为85.9%~109.5 %,相对标准偏差为2.9%~10.9%.该法可用于青霉素生产废水、VC生产废水等制药废水中有机酸和无机阴离子的快速、准确分析,结果令人满意.

  7. Charge-Assisted Hydrogen-Bonded Networks of NH4+ and [Co(NH36]3+ with the New Linker Anion of 4-Phosphono-Biphenyl-4′-Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Christian Heering


    Full Text Available The new linker molecule 4-phosphono-biphenyl-4′-carboxylic acid (H2O3P-(C6H42-COOH, H3BPPA has been structurally elucidated in hydrogen-bonded networks with the ammonium cation NH4(H2BPPA(H3BPPA (1 and the hexaamminecobalt(III cation [Co(NH36](BPPA·4H2O (2. The protic O-H and N-H hydrogen atoms were found and refined in the low-temperature single-crystal X-ray structures. The hydrogen bonds in both structures are so-called charge-assisted; that is, the H-bond donor and/or acceptor carry positive and/or negative ionic charges, respectively. The H-bonded network in 1 consists of one formally mono-deprotonated 4-phosphonato-biphenyl-4′-carboxylic acid group; that is, a H2BPPA− anion and a neutral H3BPPA molecule, which together form a 3D hydrogen-bonded network. However, an almost symmetric resonance-assisted hydrogen bond (RAHB bond [O···H = 1.17 (3 and 1.26 (3 Å, O···H···O = 180 (3°] signals charge delocalization between the formal H2BPPA− anion and the formally neutral H3BPPA molecule. Hence, the anion in 1 is better formulated as [H2BPPA···H···H2BPPA]−. In the H-bonded network of 2 the 4-phosphonato-biphenyl-4′-carboxylic acid is triply deprotonated, BPPA3−. The [Co(NH36]3+ cation is embedded between H-bond acceptor groups, –COO− and –PO3− and H2O molecules. The incorporation of sixteen H2O molecules per unit cell makes 2 an analogue of the well-studied guanidinium sulfonate frameworks.

  8. Effect of encapsulation in the anion receptor pocket of sub-domain IIA of human serum albumin on the modulation of pKa of warfarin and structurally similar acidic guests: a possible implication on biological activity. (United States)

    Datta, Shubhashis; Halder, Mintu


    Supramolecular and bio-supramolecular host assisted pKa shift of biologically relevant acidic guests, warfarin and coumarin 343, has been monitored using both steady-state and time resolved fluorescence spectroscopy. The anion receptors present in sub-domain IIA of human serum albumin (HSA) stabilize the anionic form of the guest and thereby shift pKa towards acidic range. On the other hand, the preferential binding of the neutral form of guests in the non-polar hydrophobic cavity of β-cyclodextrin results in up-shifted pKa. This shifting of pKa of drugs like warfarin, etc., whose therapeutic activity depends on the position of the acid-base equilibrium in human system, is of great importance in pharmacokinetics. The release of the active form of such drugs from macrocyclic carrier and subsequent distribution through the carrier protein should depend on the modulation of the overall pKa window brought about by the encapsulation in these hosts. Present work also suggests that properly optimized encapsulation in appropriate receptor pocket can enhance the bioavailability of drugs. This work also opens up the possibility to use HSA as encapsulator, instead of traditional cyclodextrins or other polymeric hosts, since such system may overcome toxicity as well as biocompatibility issues.

  9. New insights into the electrochemical behavior of acid orange 7: Convergent paired electrochemical synthesis of new aminonaphthol derivatives (United States)

    Momeni, Shima; Nematollahi, Davood


    Electrochemical behavior of acid orange 7 has been exhaustively studied in aqueous solutions with different pH values, using cyclic voltammetry and constant current coulometry. This study has provided new insights into the mechanistic details, pH dependence and intermediate structure of both electrochemical oxidation and reduction of acid orange 7. Surprisingly, the results indicate that a same redox couple (1-iminonaphthalen-2(1H)-one/1-aminonaphthalen-2-ol) is formed from both oxidation and reduction of acid orange 7. Also, an additional purpose of this work is electrochemical synthesis of three new derivatives of 1-amino-4-(phenylsulfonyl)naphthalen-2-ol (3a–3c) under constant current electrolysis via electrochemical oxidation (and reduction) of acid orange 7 in the presence of arylsulfinic acids as nucleophiles. The results indicate that the electrogenerated 1-iminonaphthalen-2(1 H)-one participates in Michael addition reaction with arylsulfinic acids to form the 1-amino-3-(phenylsulfonyl)naphthalen-2-ol derivatives. The synthesis was carried out in an undivided cell equipped with carbon rods as an anode and cathode.

  10. Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism. (United States)

    Jakusová, Klaudia; Donovalová, Jana; Cigáň, Marek; Gáplovský, Martin; Garaj, Vladimír; Gáplovský, Anton


    The anion induced tautomerism of isatin-3-4-phenyl(semicarbazone) derivatives is studied herein. The interaction of F(-), AcO(-), H2PO4(-), Br(-) or HSO4(-) anions with E and Z isomers of isatin-3-4-phenyl(semicarbazone) and N-methylisatin-3-4-phenyl(semicarbazone) as sensors influences the tautomeric equilibrium of these sensors in the liquid phase. This tautomeric equilibrium is affected by (1) the inter- and intra-molecular interactions' modulation of isatinphenylsemicarbazone molecules due to the anion induced change in the solvation shell of receptor molecules and (2) the sensor-anion interaction with the urea hydrogens. The acid-base properties of anions and the difference in sensor structure influence the equilibrium ratio of the individual tautomeric forms. Here, the tautomeric equilibrium changes were indicated by "naked-eye" experiment, UV-VIS spectral and (1)H NMR titration, resulting in confirmation that appropriate selection of experimental conditions leads to a high degree of sensor selectivity for some investigated anions. Sensors' E and Z isomers differ in sensitivity, selectivity and sensing mechanism. Detection of F(-) or CH3COO(-) anions at high weakly basic anions' excess is possible.

  11. Functional expression of pig renal organic anion transporter 3 (pOAT3). (United States)

    Hagos, Yohannes; Braun, Isabella M; Krick, Wolfgang; Burckhardt, Gerhard; Bahn, Andrew


    With the cloning of pig renal organic anion transporter 1 (pOAT1) (Biochimie 84 (2002) 1219) we set up a model system for comparative studies of cloned and natively isolated membrane located transport proteins. Meanwhile, another transport protein involved in p-aminohippurate (PAH) uptake on the basolateral side of the proximal tubule cells was identified, designated organic anion transporter 3 (OAT3). To explore the contribution of pOAT1 to the PAH clearance in comparison to OAT3, it was the aim of this study to extend our model by cloning of the pig ortholog of OAT3. Sequence comparisons of human organic anion transporter 3 (hOAT3) with the expressed sequence tag (EST) database revealed a clone and partial sequence of the pig renal organic anion transporter 3 (pOAT3) ortholog. Sequencing of the entire open reading frame resulted in a protein of 543 amino acid residues encoded by 1632 base pairs (EMBL Acc. No. AJ587003). It showed high homologies of 81%, 80%, 76%, and 77% to the human, rabbit, rat, and mouse OAT3, respectively. A functional characterization of pOAT3 in Xenopus laevis oocytes yielded an apparent Km (Kt) for [3H]estrone sulfate of 7.8 +/- 1.3 microM. Moreover, pOAT3 mediated [3H]estrone sulfate uptake was almost abolished by 0.5 mM of glutarate, dehydroepiandosterone sulfate, or probenecid consistent with the hallmarks of OAT3 function.

  12. Five-State Molecular Shuttling of a Pair of [2]Rotaxanes: Distinct Outputs in Response to Acid and Base Stimuli. (United States)

    Ueda, Masahiro; Terazawa, Shoya; Deguchi, Yasuaki; Kimura, Masaki; Matsubara, Naoki; Miyagawa, Shinobu; Kawasaki, Tsuneomi; Tokunaga, Yuji


    In this study we synthesized two acid-/base-controllable [2]rotaxanes featuring aminodiazobenzene and aminocoumarin units, respectively, as chromophores and dibenzo[24]crown-8 and dibenzo[25]crown-8 units, respectively, as their macrocyclic components. Each [2]rotaxane contained N-alkylarylamine (ammonium) and N,N-dialkylamine (ammonium) centers as binding sites for their crown ether components. The absorption patterns of the chromophores were dependent on the position of the encircling macrocyclic component and the degree of protonation, with three distinct states (under acidic, neutral, and basic conditions) evident for each [2]rotaxane. The mixed [2]rotaxane system displayed stepwise and independent molecular shuttling behavior based on the degree of protonation of the amino groups in response to both the amount and strength of added acids or bases; as such, the system provided five different absorption signals as outputs that could be read using UV/Vis spectroscopy.

  13. Interactions of /sup 14/N:/sup 15/N stearic acid spin-label pairs: effects of host lipid alkyl chain length and unsaturation

    Energy Technology Data Exchange (ETDEWEB)

    Feix, J.B.; Yin, J.J.; Hyde, J.S.


    Electron-electron double resonance (ELDOR) and saturation recovery electron paramagnetic resonance (EPR) spectroscopy have been employed to examine the interactions of /sup 14/N:/sup 15/N stearic acid spin-label pairs in fluid-phase model membrane bilayers composed of a variety of phospholipids. The (/sup 14/N)-16-doxylstearate:(/sup 15/N)-16-doxylstearate (16:16) pair was utilized to measure lateral diffusion of the spin-labels, while the (/sup 14/N)-16-doxylstearate:(/sup 15/N)-5-doxylstearate (16:5) pair provided information on vertical fluctuations of the 16-doxylstearate nitroxide moiety toward the membrane surface. Three saturated host lipids of varying alkyl chain length (dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC), and distearoylphosphatidylcholine (DSPC)), an ..cap alpha..-saturated, ..beta..-unsaturated lipid (1-palmitoyl-2-oleoylphosphatidylcholine (POPC)), and phosphatidylcholine from a natural source (egg yolk phosphatidylcholine (egg PC)) were utilized as host lipids. Lateral diffusion of the stearic acid spin-labels was only slightly affected by alkyl chain length at a given reduced temperature (T/sub r/) in the saturated host lipids but was significantly decreased in POPC at the same T/sub r/. Lateral diffusion in DMPC, POPC, and egg PC was quite similar at 37/sup 0/C. A strong correlation was noted between lateral diffusion constants and rotational mobility of (/sup 14/N)-16-doxylstearate. Vertical fluctuations were likewise only slightly influenced by alklyl chain length but were strongly diminished in POPC and egg PC relative to the saturated systems. This diminution of the 16:5 interaction was observed even under conditions where no differences were discernible by conventional EPR.

  14. Can an excess electron localize on a purine moiety in the adenine-thymine Watson-Crick base pair? A computational study (United States)

    Mazurkiewicz, Kamil; Harańczyk, Maciej; Gutowski, Maciej; Rak, Janusz

    The electron affinity and the propensity to electron-induced proton transfer (PT) of hydrogen-bonded complexes between the Watson-Crick adenine-thymine pair (AT) and simple organic acid (HX), attached to adenine in the Hoogsteen-type configuration, were studied at the B3LYP/6-31+G** level. Although the carboxyl group is deprotonated at physiological pH, its neutral form, COOH, resembles the peptide bond or the amide fragment in the side chain of asparagine (Asn) or glutamine (Gln). Thus, these complexes mimic the interaction between the DNA environment (e.g., proteins) and nucleobase pairs incorporated in the biopolymer. Electron attachment is thermodynamically feasible and adiabatic electron affinities range from 0.41 to 1.28 eV, while the vertical detachment energies of the resulting anions span the range of 0.39-2.88 eV. Low-energy activation barriers separate the anionic minima: aHX(AT) from the more stable single-PT anionic geometry, aHX(AT)-SPT, and aHX(AT)-SPT from the double-PT anionic geometry, aHX(AT)-DPT. Interaction between the adenine of the Watson-Crick AT base pair with an acidic proton donor probably counterbalances the larger EA of isolated thymine, as SOMO is almost evenly delocalized over both types of nucleic bases in the aHX(AT) anions. Moreover, as a result of PT the excess electron localizes entirely on adenine. Thus, in DNA interacting with its physiological environment, damage induced by low-energy electrons could begin, contrary to the current view, with the formation of purine anions, which are not formed in isolated DNA because of the greater stability of anionic pyrimidines.0

  15. On the electronic structure of fullerene anions

    Energy Technology Data Exchange (ETDEWEB)

    Bergomi, L.; Jolicoeur, T. (CEA Centre d' Etudes de Saclay, 91 - Gif-sur-Yvette (France). Service de Physique Theorique)


    The authors study the electronic states of isolated fullerene anions C[sub 60][sup n-] (1 [<=] n [<=] 6) taking into account the effective interaction between electrons due to exchange of intramolecular phonons. If the vibronic coupling is strong enough such an effect may overwhelm Hund's rule and lead to an ordering of levels that can be interpreted as on-ball pairing, in a manner similar to the pairing in atomic nuclei. The authors suggest that such effects may be sought in solutions of fulleride ions and discuss recent experimental results.

  16. SCMCRYS: predicting protein crystallization using an ensemble scoring card method with estimating propensity scores of P-collocated amino acid pairs. (United States)

    Charoenkwan, Phasit; Shoombuatong, Watshara; Lee, Hua-Chin; Chaijaruwanich, Jeerayut; Huang, Hui-Ling; Ho, Shinn-Ying


    Existing methods for predicting protein crystallization obtain high accuracy using various types of complemented features and complex ensemble classifiers, such as support vector machine (SVM) and Random Forest classifiers. It is desirable to develop a simple and easily interpretable prediction method with informative sequence features to provide insights into protein crystallization. This study proposes an ensemble method, SCMCRYS, to predict protein crystallization, for which each classifier is built by using a scoring card method (SCM) with estimating propensity scores of p-collocated amino acid (AA) pairs (p=0 for a dipeptide). The SCM classifier determines the crystallization of a sequence according to a weighted-sum score. The weights are the composition of the p-collocated AA pairs, and the propensity scores of these AA pairs are estimated using a statistic with optimization approach. SCMCRYS predicts the crystallization using a simple voting method from a number of SCM classifiers. The experimental results show that the single SCM classifier utilizing dipeptide composition with accuracy of 73.90% is comparable to the best previously-developed SVM-based classifier, SVM_POLY (74.6%), and our proposed SVM-based classifier utilizing the same dipeptide composition (77.55%). The SCMCRYS method with accuracy of 76.1% is comparable to the state-of-the-art ensemble methods PPCpred (76.8%) and RFCRYS (80.0%), which used the SVM and Random Forest classifiers, respectively. This study also investigates mutagenesis analysis based on SCM and the result reveals the hypothesis that the mutagenesis of surface residues Ala and Cys has large and small probabilities of enhancing protein crystallizability considering the estimated scores of crystallizability and solubility, melting point, molecular weight and conformational entropy of amino acids in a generalized condition. The propensity scores of amino acids and dipeptides for estimating the protein crystallizability can aid

  17. Vesiculoviral matrix (M) protein occupies nucleic acid binding site at nucleoporin pair (Rae1∙Nup98)

    Energy Technology Data Exchange (ETDEWEB)

    Quan, Beili; Seo, Hyuk-Soo; Blobel, Günter; Ren, Yi [Rockefeller


    mRNA export factor 1 (Rae1) and nucleoporin 98 (Nup98) are host cell targets for the matrix (M) protein of vesicular stomatitis virus (VSV). How Rae1 functions in mRNA export and how M protein targets both Rae1 and Nup98 are not understood at the molecular level. To obtain structural insights, we assembled a 1:1:1 complex of M•Rae1•Nup98 and established a crystal structure at 3.15-Å resolution. We found that the M protein contacts the Rae1•Nup98 heterodimer principally by two protrusions projecting from the globular domain of M like a finger and thumb. Both projections clamp to the side of the β-propeller of Rae1, with the finger also contacting Nup98. The most prominent feature of the finger is highly conserved Methionine 51 (Met51) with upstream and downstream acidic residues. The complementary surface on Rae1 displays a deep hydrophobic pocket, into which Met51 fastens like a bolt, and a groove of basic residues on either side, which bond to the acidic residues of the finger. Notably, the M protein competed for in vitro binding of various oligonucleotides to Rae1•Nup98. We localized this competing activity of M to its finger using a synthetic peptide. Collectively, our data suggest that Rae1 serves as a binding protein for the phosphate backbone of any nucleic acid and that the finger of M mimics this ligand. In the context of mRNA export, we propose that a given mRNA segment, after having been deproteinated by helicase, is transiently reproteinated by Nup98-tethered Rae1. We suggest that such repetitive cycles provide cytoplasmic stopover sites required for ratcheting mRNA across the nuclear pore.

  18. Simultaneous Determination of Chelating Agents by Ion-Suppression and Ion-Pair Chromatography in Wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Dodi, Alain; Bouscarel, Maelle [Commissariat a l' energie atomique - C.E.A, Centre d' Etude de Cadarache, Laboratoire d' Analyses Radiochimiques et Chimiques, St Paul lez Durance (France)


    This article describes two methods for analysing chelating agents found in nuclear waste. First, ion-suppression chromatography using an anion exchange stationary phase and mobile phase consisting of a nitric acid solution and pure water gradient. UV detection was performed at 330 nm after the reaction with a post-column reagent composed of iron nitrate in perchloric acid. Secondly, ion-pair chromatography with a mobile phase consisting of a mixture of nitric acid, tetra-butyl-ammonium hydrogeno-sulphate, tetra-butyl-ammonium hydroxide and iron chloride. A reversed-phase material was used as a stationary phase and detection was performed by direct measurement of the UV absorption at 260 nm. The quantification limits were lower for ion-pair chromatography than for ion-suppression chromatography. Both methods were easy to implement and allow a multi-element separation in less than 30 min with low detection limits. (authors)

  19. Simultaneous quantification of amino acids and Amadori products in foods through ion-pairing liquid chromatography-high-resolution mass spectrometry. (United States)

    Troise, Antonio Dario; Fiore, Alberto; Roviello, Giovanni; Monti, Simona Maria; Fogliano, Vincenzo


    The formation of the Amadori products (APs) is the first key step of Maillard reaction. Only few papers have dealt with simultaneous quantitation of amino acids and corresponding APs (1-amino-1-deoxy-2-ketose). Chromatographic separation of APs is affected by several drawbacks mainly related to their poor retention in conventional reversed phase separation. In this paper, a method for the simultaneous quantification of amino acids and their respective APs was developed combining high-resolution mass spectrometry with ion-pairing liquid chromatography. The limit of detection was 0.1 ng/mL for tryptophan, valine and arginine, while the limit of quantification ranged from 2 to 5 ng/mL according to the specific sensitivity of each analyte. The relative standard deviation % was lower than 10 % and the coefficient of correlation was higher than 0.99 for each calibration curve. The method was applied to milk, milk-based products, raw and processed tomato. Among the analyzed products, the most abundant amino acid was glutamic acid (16,646.89 ± 1,385.40 µg/g) and the most abundant AP was fructosyl-arginine in tomato puree (774.82 ± 10.01 µg/g). The easiness of sample preparation coupled to the analytical performances of the proposed method introduced the possibility to use the pattern of free amino acids and corresponding APs in the evaluation of the quality of raw food as well as the extent of thermal treatments in different food products.

  20. Extractive spectrophotometric determination of sulphonamide drugs in pure and pharmaceutical preparations through ion-pair formation with molybdenum(V thiocyanate in acidic medium

    Directory of Open Access Journals (Sweden)

    Faten A. Nour El-Dien


    Full Text Available A simple and sensitive extraction-spectrophotometric method is described for the determination of sulfonamide drugs, namely sulphamethoxazole, sulphaguanidine, sulphaquinoxaline, sulphametrole and sulphadimidine, in both pure form and in the dosage forms available in Egyptian markets. The method is based on ion-pair formation between the sulphonamides and Mo(V-thiocyanate inorganic complex in a sulphuric acid medium followed by extraction of the coloured ion-pairs with 1,2-dichloroethane. The optimum conditions are established. The method permits the determination of sulphonamide drugs over the concentration range of 5–50 μg ml−1. The Sandell sensitivity (S, molar absorptivity, correlation coefficient and regression equations, and limits of detection (LOD and quantification (LOQ are calculated. The law values of standard deviation (0.09–0.38 and relative standard deviation (0.10–0.550 reflect the accuracy and precision of the proposed method. The method is applicable for the assay of the investigated drugs in different dosage forms and the results are in good agreement with those obtained by the official pharmacopeial method.

  1. Krebs cycle anions in metabolic acidosis. (United States)

    Bowling, Francis G; Morgan, Thomas J


    For many years it has been apparent from estimates of the anion gap and the strong ion gap that anions of unknown identity can be generated in sepsis and shock states. Evidence is emerging that at least some of these are intermediates of the citric acid cycle. The exact source of this disturbance remains unclear, because a great many metabolic blocks and bottlenecks can disturb the anaplerotic and cataplerotic pathways that enter and leave the cycle. These mechanisms require clarification with the use of tools such as gas chromatography-mass spectrometry.

  2. 离子对色谱分析测定双甘膦%Analysis of N-(Phosphonomethyl)iminodiacetic Acid by Ion-pair Chromatography

    Institute of Scientific and Technical Information of China (English)

    刘奎涛; 王俊东


    采用离子对色谱法,以甲醇、水为流动相,C18反相硅胶柱和紫外检测器分离测定双甘膦.结果表明,双甘膦的标准偏差为0.003,变异系数为0.307%,平均回收率为98.96%,线性相关系数r2=0.999.%The quantitative analysis of mixture of N-(phosphonomethyl)iminodiacetic acid by ion-pair chromatography using methanol-water as mobile phase, C18 silica gel column and ultraviolet detector was described in this paper. The results showed that the standard deviation for N-(phosphonomethyl)iminodiacetic acid was 0.003, the coefficient of variation was 0.307%, the average recovery was 98.96%, and the linear correlation was 0.999.

  3. Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds. (United States)

    Franken, Andreas; Carr, Michael J; Clegg, William; Kilner, Colin A; Kennedy, John D


    B(10)H(14) reacts with para-C(6)H(4)(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-COOH)](-) anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-COOH)](-) anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-COOH)](-) anion 3. Similarly, B(10)H(14) with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB(9)H(13)-6-(COOH)](-) anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(COOH)](-) anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB(9)H(9)-1-(COOH)](-) anion 6. Reduction of the [COOH] anions 3 and 6 with diisobutylaluminium hydride gives the [CH(2)OH] hydroxy anions [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) and [closo-1-CB(9)H(9)-1-(CH(2)OH)](-) 8 respectively. The [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) anion 7 can also be made via isomerisation of the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-CH(2)OH)](-) anion 9, in turn obtained from the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-CH(2)OH)](-) anion 10, which is obtained from the reaction of B(10)H(14) with terephthaldicarboxaldehyde, C(6)H(4)-para-(CHO)(2), in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CHO)](-) anion 11 and the aldehydic [closo-1-CB(9)H(9)-1-(CHO)](-) anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB(9)H(9)-1-C(6)H(4)-para-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion 13 and the [closo-1-CB(9)H(9)-1-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion respectively.

  4. Potentiometric anion selective sensors

    NARCIS (Netherlands)

    Antonisse, Martijn M.G.; Reinhoudt, David N.


    In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the transducer element and the aqu

  5. Assessment of capillary anion exchange ion chromatography tandem mass spectrometry for the quantitative profiling of the phosphometabolome and organic acids in biological extracts. (United States)

    Kvitvang, Hans F N; Kristiansen, Kåre A; Bruheim, Per


    Metabolic profiling has become an important tool in biological research, and the chromatographic separation of metabolites coupled with mass spectrometric detection is the most frequently used approach for such studies. The establishment of robust chromatographic methods for comprehensive coverage of the anionic metabolite pool is especially challenging. In this study, the development of a capillary ion exchange chromatography (capIC) - negative ESI tandem mass spectrometry (MS/MS) workflow for the quantitative profiling of the phosphometabolome (e.g., sugar phosphates and nucleotides) is presented. The chromatographic separation and MS/MS conditions were optimized, and the precision of repetitive injections and accuracy in terms of error percentage to true concentration were assessed. The precision is excellent for a capillary flow system with an average CV% of 8.5% for a 50-fmol standard injection and in the lower 2.4-4.4% range for higher concentrations (500-7,500 fmol). The limit of detection (LOD) ranges from 1 to 100 nM (5-500 fmol injected on column), and the limit of quantitation (LOQ) ranges from 1 to 500 nM (5-2,500 fmol injected on column). A fast gradient method with the injection of 50% methanol in water between analytical samples is needed to eliminate carry-over and ensure optimal re-equilibration of the column. Finally, the quantitative applicability of the system was tested on real biological matrices using the constant-volume standard addition method (SAM). Extracts of the human kidney Hek293 cell line were spiked with increasing concentrations of standards to determine the concentration of each metabolite in the sample. Forty-four metabolites were detected with an average uncertainty of 4.1%. Thus, the capIC-MS/MS method exhibits excellent selectivity, sensitivity and precision for the quantitative profiling of the phosphometabolome.

  6. Synthesis and application of coconut acid polyether carboxylate anionic-nonionic surfactant for EOR%椰油聚醚羧酸盐阴非离子驱油剂的合成及性能

    Institute of Scientific and Technical Information of China (English)

    鲍新宁; 张卫东; 沙鸥; 李应成


    In view of poor universality of conventional surfactants,anionic-nonionic surfactants of coconut acid monoethanol amide polyoxyethylene ether carboxylate with different EOs were synthesized from coco-nut acid monoethanolamide. Structure of products were characterized by IR. Interface properties of the products were investigated. When the concentration of surfactant is 0. 2% in either source well water or sewage water in Zhen 35 block of Jiangsu oil field ,interfacial tension between crude oil and water can reach 10 -3 mN/m order,which can be used to enhance oil recovery.%针对目前常规表面活性剂普适性差的问题,以椰油单乙醇酰胺为原料,制备系列椰油单乙醇酰胺聚氧乙烯醚羧酸盐阴非复合型表面活性剂;用红外光谱进行了表征。测定其界面性能,0.2%表活剂溶液能够使江苏油田真35区块原油分别与水源井水和油田处理站污水,都达到10-3 mN/m数量级的超低界面张力,满足油田驱油要求。

  7. A chemical approach for site-specific identification of NMR signals from protein side-chain NH{sub 3}{sup +} groups forming intermolecular ion pairs in protein–nucleic acid complexes

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kurtis M. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Nguyen, Dan; Esadze, Alexandre; Zandrashvili, Levani [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States); Gorenstein, David G. [University of Texas Health Science Center at Houston, Department of NanoMedicine and Biomedical Engineering and Institute of Molecular Medicine (United States); Iwahara, Junji, E-mail:, E-mail: [University of Texas Medical Branch, Department of Biochemistry and Molecular Biology, Sealy Center for Structural Biology and Molecular Biophysics (United States)


    Protein–nucleic acid interactions involve intermolecular ion pairs of protein side-chain and DNA or RNA phosphate groups. Using three protein–DNA complexes, we demonstrate that site-specific oxygen-to-sulfur substitution in phosphate groups allows for identification of NMR signals from the protein side-chain NH{sub 3}{sup +} groups forming the intermolecular ion pairs. A characteristic change in their {sup 1}H and {sup 15}N resonances upon this modification (i.e., substitution of phosphate to phosphorodithioate) can represent a signature of an intermolecular ion pair. Hydrogen-bond scalar coupling between protein side-chain {sup 15}N and DNA phosphorodithiaote {sup 31}P nuclei provides direct confirmation of the intermolecular ion pair. The same approach is likely applicable to protein–RNA complexes as well.

  8. Nucleophilic reactivities of the anions of nucleobases and their subunits. (United States)

    Breugst, Martin; Corral Bautista, Francisco; Mayr, Herbert


    The kinetics of the reactions of different heterocyclic anions derived from imidazoles, purines, pyrimidines, and related compounds with benzhydrylium ions and structurally related quinone methides have been studied in DMSO and water. The second-order rate constants (log k(2)) correlated linearly with the electrophilicity parameters E of the electrophiles according to the correlation log k(2) = s(N)(N+E) (H. Mayr, M. Patz, Angew. Chem. 1994, 106, 990-1010; Angew. Chem. Int. Ed. Engl. 1994, 33, 938-957) allowing us to determine the nucleophilicity parameters N and s(N) for these anions. In DMSO, the reactivities of these heterocyclic anions vary by more than six orders of magnitude and are comparable to carbanions, amide and imide anions, or amines. The azole anions are generally four to five orders of magnitude more reactive than their conjugate acids.

  9. Adsorption of inorganic anionic contaminants on surfactant modified minerals

    Directory of Open Access Journals (Sweden)



    Full Text Available Organo-mineral complexes were obtained by treatment of aluminosilicate minerals (zeolite, bentonite and diatomaceous earth with a primary amine (oleylamine and an alkyl ammonium salt (stearyldimethylbenzyl ammonium chloride. The modification of the zeolite surface was carried out in two steps. The first step was treatment of the zeolite with 2 M HCl. This acid treatment of the zeolite increased its affinity for neutral molecules such as surface-active amines. The second step of the modification was the adsorption of oleylamine on the acid treated zeolite. Four types of organo-mineral complexes were prepared and their anion adsorption properties were compared to those of organo-zeolite. The adsorption of sulphate, bichromate and dihydrogenphosphate anions on the organo-mineral complexes was investigated. The anion adsorption measurements showed that the most efficient adsorbent for anion water pollutants was the primary amine modified H+-form zeolite.

  10. Adsorption and Desorption Properties of Phytic Acid from Rice Bran on Anion Exchange Resin%阴离子交换树脂对米糠植酸的吸附解吸性能

    Institute of Scientific and Technical Information of China (English)

    王琳; 罗建平; 查学强; 张海林; 潘利华


    通过静态和动态试验研究了6种阴离子交换树脂对植酸的吸附与解吸性能.结果表明,D201树脂对植酸的吸附交换作用较好,且在pH值为2.2时吸附能力最强,静态吸附量达到94.54 mg/g,1.5 mol/L的NaOH溶液利于植酸解吸;Freundlich吸附等温方程可以较好地描述D201树脂对植酸的等温吸附,表明吸附在常温下进行即可;D201树脂对植酸的吸附过程符合Lagergren一级速率方程,表观吸附速率常数k与植酸起始植酸浓度呈负相关关系,与温度呈正相关关系.在D201树脂对植酸的动态吸附与解吸过程中,层析柱管径、上样液浓度、上样液流速和洗脱剂流速对吸附与解吸效果影响较大.%The absorption and desorption properties of phytic acid on anion exchange resin were investigated through static and dynamic experiments. The results showed that D201 resin had the best exchange adsorption performance among all tested resins. The static absorption capacity of D201 resin reached 94. 54 mg/g when the pH value of phytic acid solution was adjusted to 2. 2, and sodium hydroxide solution of 1. 5 mol/L was beneficial to desorption. The absorption behavior of D201 resin for phytic acid obeyed the Freundlich adsorption isotherm equation, indicating that the absorption can be performed under normal temperature. The absorption kinetic data complied with Lagergren pseudo-first-order rate equation. The apparent adsorption rate k has a negative correlation with the initial concentration of phytic acid and has a positive correlation with temperature. As far as the dynamic absorption and desorption of phytic acid on D201 resin was concerned, the effects of chromatography column diameter, sample concentration, sample flowing velocity and eluant flowing velocity were notably observed.

  11. Simultaneous determination of organic acids and inorganic anions in Danshen for injection (lyophilized powder) by ion chromatography%离子色谱法同时测定注射用丹参(冻干)中有机酸和无机阴离子

    Institute of Scientific and Technical Information of China (English)

    刘静; 李静; 聂黎行; 王钢力; 王英新; 林瑞超


    Objective: To establish an ion chromatography method for simultaneous determination of five organic acids (lactic acid, acetic acid, formic acid, succinic acid and oxalic acid) and two inorganic anions ( chloridion and nitrate) in Danshen for injection(lyophilized powder). Methods;Five organic acids and two inorganic anions were determined by anion exchange column Ion Pac ASH -HC,eluted by gradient hydroxide potassium(1 -50 mmol · L-1 ) and identified by suppressed conductivity detector ASRS 300 with self - circulation suppression mode. Results ; Good resolution can be achieved among the above mentioned five organic acids and two inorganic anions. Their linear correlations over the investigated concentration were in the range of 0. 9996 - 0. 9999 and 0. 9997 -0. 9999,while the average recoveries were 92. 4% - 105. 1% and 102. 0% - 103. 2% .respectively. Conclusion: The ion chromatography method is fast, accurate, simple, reliable and applicable for the assay and quality control of organic acids and inorganic anions in Danshen for injection(lyophilized powder).%目的:建立能够同时测定注射用丹参(冻干)中有机酸(乳酸、乙酸、甲酸、琥珀酸和草酸)和无机阴离子(氯离子和硝酸根离子)含量的离子色谱法.方法:以Ion Pac AS11-HC阴离子交换柱分离,1~50 mmol·L-1氢氧化钾溶液梯度淋洗,ASRS300型抑制器电导检测器检测,自循环抑制模式.结果:5个有机酸及2个无机阴离子基本达到分离,线性关系良好,相关系数分别在0.9996~0.9999和0.9997~0.9999,平均回收率分别在92.4%~105.1%和102.0% ~ 103.2%.结论:所建立的方法快速、准确、简便、实用,可用于注射用丹参(冻干)中有机酸和无机阴离子的含量测定和质量控制.

  12. Resonant spectra of quadrupolar anions

    CERN Document Server

    Fossez, K; Nazarewicz, W; Michel, N; Garrett, W R; Płoszajczak, M


    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as extreme halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-molecule problem using a non-adiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational ban...

  13. Formation of ion pairing as an alternative to improve encapsulation and anticancer activity of all-trans retinoic acid loaded in solid lipid nanoparticles

    Directory of Open Access Journals (Sweden)

    Carneiro G


    findings are in agreement with the data obtained in the evaluation of subdiploid DNA content and cell-cycle analysis, which showed better anticancer activity for BA-RA-loaded SLNs than TA-RA-loaded SLNs and free RA. Taken together, these findings suggest that the BA-RA-loaded SLN formulation is a promising alternative for the intravenous administration of RA in the treatment of cancer.Keywords: solid lipid nanoparticles, all-trans retinoic acid, cancer, treatment, antitumor activity, ion pairing

  14. Acid-base properties and surface complexation modeling of phosphate anion adsorption by wasted low grade iron ore with high phosphorus. (United States)

    Yuan, Xiaoli; Bai, Chenguang; Xia, Wentang; An, Juan


    The adsorption phenomena and specific reaction processes of phosphate onto wasted low grade iron ore with high phosphorus (WLGIOWHP) were studied in this work. Zeta potential and Fourier transform infrared spectroscopy (FTIR) analyses were used to elucidate the interaction mechanism between WLGIOWHP and aqueous solution. The results implied that the main adsorption mechanism was the replacement of surface hydroxyl groups by phosphate via the formation of inner-sphere complex. The adsorption process was characterized by chemical adsorption onto WLGIOWHP. The non-electrostatic model (NEM) was used to simulate the surface adsorption of phosphate onto WLGIOWHP. The total surface site density and protonation constants for NEM (N(T)=1.6×10(-4) mol/g, K(a1)=2.2×10(-4), K(a2)=6.82×10(-9)) were obtained by non-linear data fitting of acid-base titrations. In addition, the NEM was used to establish the surface adsorption complexation modeling of phosphate onto WLGIOWHP. The model successfully predicted the adsorption of phosphate onto WLGIOWHP from municipal wastewater.

  15. Adsorption and photocatalysis of nanocrystalline TiO2 particles for Reactive Red 195 removal: effect of humic acids, anions and scavengers. (United States)

    Chládková, B; Evgenidou, E; Kvítek, L; Panáček, A; Zbořil, R; Kovář, P; Lambropoulou, D


    In the present study, the coupling of adsorption capacity and photocatalytic efficiency of two different industrially produced titania catalysts was investigated and compared. The azo dye Reactive Red 195 was selected as a model compound. The tested catalysts, PK-10 and PK-180, exhibited different adsorption capacities due to their significant difference in their specific surface, but both have proven to be effective photocatalysts for photodegradation of the studied dye. PK-10 exhibited strong adsorption of the studied dye due to its high specific surface area, while the second studied catalyst, PK-180, demonstrated negligible adsorption of Reactive Red 195. The effect of the pH, the concentration of the catalyst and the initial concentration of the dye appear to affect the photocatalytic rate. The effect of the presence of humic acids and inorganic ions was also examined, while the contribution of various reactive species was indirectly evaluated through the addition of various scavengers. To evaluate the extent of mineralisation of the studied dye, total organic carbon (TOC) measurements during the experiment were also conducted. Besides total colour removal, evident reduction of TOC was also achieved using both catalysts.

  16. Pairing Learners in Pair Work Activity (United States)

    Storch, Neomy; Aldosari, Ali


    Although pair work is advocated by major theories of second language (L2) learning and research findings suggest that pair work facilitates L2 learning, what is unclear is how to best pair students in L2 classes of mixed L2 proficiency. This study investigated the nature of pair work in an English as a Foreign Language (EFL) class in a college in…

  17. Evaluation of antioxidant enzymes activities and identification of intermediate products during phytoremediation of an anionic dye (C.I. Acid Blue 92) by pennywort (Hydrocotyle vulgaris). (United States)

    Vafaei, Fatemeh; Movafeghi, Ali; Khataee, Alireza


    The potential of pennywort (Hydrocotyle vulgaris) for phytoremediation of C.I. Acid Blue 92 (AB92) was evaluated. The effects of various experimental parameters including pH, temperature, dye concentration and plant weight on dye removal efficiency were investigated. The results showed that the optimal condition for dye removal were pH 3.5 and temperature 25 degree C. Moreover, the absolute dye removal enhanced with increase in the initial dye concentration and plant weight. Pennywort showed the same removal efficiency in repeated experiments (four runs) as that obtained from the first run (a 6-day period). Therefore, the ability of the plant in consecutive removal of AB92 confirmed the biodegradation process. Accordingly, a number of produced intermediate compounds were identified. The effect of treatment on photosynthesis and antioxidant defense system including superoxide dismutase, peroxidase and catalase in plant roots and leaves were evaluated. The results revealed a reduction in photosynthetic pigments content under dye treatments. Antioxidant enzyme responses showed marked variations with respect to the plant organ and dye concentration in the liquid medium. Overall, the increase in antioxidant enzyme activity under AB92 stress in the roots was much higher than that in the leaves. Nevertheless, no significant increase in malondialdehyde content was detected in roots or leaves, implying that the high efficiency of antioxidant system in the elimination of reactive oxygen species. Based on these results, pennywort was founded to be a capable species for phytoremediation of AB92-contaminated water, may be effective for phytoremediation dye-contaminated polluted aquatic ecosystems.

  18. Anionic phospholipids modulate peptide insertion into membranes. (United States)

    Liu, L P; Deber, C M


    While the insertion of a hydrophobic peptide or membrane protein segment into the bilayer can be spontaneous and driven mainly by the hydrophobic effect, anionic lipids, which comprise ca. 20% of biological membranes, provide a source of electrostatic attractions for binding of proteins/peptides into membranes. To unravel the interplay of hydrophobicity and electrostatics in the binding of peptides into membranes, we designed peptides de novo which possess the typical sequence Lys-Lys-Ala-Ala-Ala-X-Ala-Ala-Ala-Ala-Ala-X-Ala-Ala-Trp-Ala-Ala-X-Ala-Al a-Ala-Lys-Lys-Lys-Lys-amide, where X residues correspond to "guest" residues which encompass a range of hydrophobicity (Leu, Ile, Gly, and Ser). Circular dichroism spectra demonstrated that peptides were partially (40-90%) random in aqueous buffer but were promoted to form 100% alpha-helical structures by anionic lipid micelles. In neutral lipid micelles, only the relatively hydrophobic peptides (X = L and I) spontaneously adopted the alpha-helical conformation, but when 25% of negatively charged lipids were mixed in to mimic the content of anionic lipids in biomembranes, the less hydrophobic (X = S and G) peptides then formed alpha-helical conformations. Consistent with these findings, fluorescence quenching by the aqueous-phase quencher iodide indicated that in anionic (dimyristoylphosphatidylglycerol) vesicles, the peptide Trp residue was buried in the lipid vesicle hydrophobic core, while in neutral (dimyristoylphosphatidylcholine) vesicles, only hydrophobic (X = L and I) peptides were shielded from the aqueous solution. Trp emission spectra of peptides in the presence of phospholipids doxyl-labeled at the 5-, 7-, 10-, 12-, and 16-fatty acid positions implied not only a transbilayer orientation for inserted peptides but also that mixed peptide populations (transbilayer + surface-associated) may arise. Overall results suggest that for hydrophobic peptides with segmental threshold hydrophobicity below that which

  19. Anionic surface binders

    Directory of Open Access Journals (Sweden)

    Aljaž-Rožič Mateja


    Full Text Available The MELAMIN Chemical Factory in Kočevje manufactures synthetic resins and binders for the paper industry. Binders based on AKD (alkyl ketene dimer are produced which are used for binding paper and cardboard in the range of neutral and partially basic pH. Cationic and, lately, anionic binders are mostly used for the bulk binding of paper and board. The possibility of using AKD binders on paper or board surfaces is presented. In this case partially cationic AKD binders may be applied. When optical whiteners are used, the application of AKD binders is recommended. In the case of paper it is possible to substitute acrylate binders by AKD binders. The best results are obtained when the paper is first partly treated in bulk and subsequently surface treated.

  20. Resonant spectra of quadrupolar anions (United States)

    Fossez, K.; Mao, Xingze; Nazarewicz, W.; Michel, N.; Garrett, W. R.; Płoszajczak, M.


    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-rotor problem using a nonadiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. The rotor is treated as a linear triad of point charges with zero monopole and dipole moments and nonzero quadrupole moment. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational bands could be identified above the detachment threshold. We study the evolution of a bound state of an anion as it dives into the continuum at a critical quadrupole moment and we show that the associated critical exponent is α =2 . Everything considered, quadrupolar anions represent a perfect laboratory for the studies of marginally bound open quantum systems.

  1. Direct determination of glyphosate and its major metabolite, aminomethylphosphonic acid, in fruits and vegetables by mixed-mode hydrophilic interaction/weak anion-exchange liquid chromatography coupled with electrospray tandem mass spectrometry. (United States)

    Chen, Ming-Xue; Cao, Zhao-Yun; Jiang, Yan; Zhu, Zhi-Wei


    A novel method was developed for the direct, sensitive, and rapid determination of glyphosate and its major metabolite, aminomethylphosphonic acid (AMPA), in fruit and vegetable samples by mixed-mode hydrophilic interaction/weak anion-exchange liquid chromatography (HILIC/WAX) coupled with electrospray tandem mass spectrometry (ESI-MS/MS). Homogenized samples were extracted with water, without derivatization or further clean-up, and the extracts were injected directly onto the Asahipak NH2P-50 4E column (250 mm × 4.6 mm i.d., 5 μm). The best results were obtained when the column was operated under mixed-mode HILIC/WAX elution conditions. An initial 10-min washing step with acetonitrile/water (10:90, v/v) in HILIC mode was used to remove potentially interfering compounds, and then the analytes were eluted in WAX mode with acetonitrile and water containing 0.1 molL(-1) ammonium hydroxide under gradient elution for the ESI analysis in negative ion mode. Limits of quantification of glyphosate and AMPA were 5 μgkg(-1) and 50 μgkg(-1), respectively, with limits of detection as low as 1.2 μgkg(-1) for glyphosate and 15 μgkg(-1) for AMPA. The linearity was satisfactory, with correlation coefficients (r)>0.9966. Recovery studies were carried out on spiked matrices (6 vegetables, 3 fruits) with glyphosate at four concentrations and AMPA at three concentrations. The mean recoveries for glyphosate and AMPA were 75.3-110% and 76.1-110%, respectively, with relative standard deviations in the range of 1.1-13.8%. The intra-day precision (n=7) for glyphosate and AMPA in vegetable and fruit samples spiked at an intermediate level between 5.9% and 7.5%, and the inter-day precision over 11 days (n=11) was between 7.0% and 13%.

  2. Selective Adsorption and Separation of Salicylic Acid and Phenol by 717 Anion Exchange Resin%717阴离子交换树脂选择吸附分离水杨酸和苯酚

    Institute of Scientific and Technical Information of China (English)

    谢祖芳; 童张法; 陈渊; 晏全; 李凤; 吴燕平


    The anion exchange resin 717 was used to selectively adsorb and separate the salicylic acid and phenol from their binary aqueous solution. The adsorption behavior of 717 resin for each adsorbate was studied via both dynamic and static methods. The effects of pH value, adsorbate concentration and adsorption time on the adsorption process were investigated, and the isotherm adsorption and adsorption kinetics were also studied.The experimental results show that the pH value of the solution plays the most important role in the adsorption and separation process. At pH of 4.5, the existence of phenol in the solution essentially does not affect the salicylic acid adsorption of the 717 resin, while when the pH is 11, the phenol can be adsorbed by 717 resin to substitute the adsorbed salicylic acid on it, which substantially decreases the salicylic acid adsorption capacity of the resin. In the pH range of 4~8, the 717 resin has very high selective adsorption ability and adsorption capacity for the salicylic acid, and its adsorption capacity for salicylic acid is more than an order of magnitude larger than that for the phenol. With such high adsorption selectivity, the 717 resin is favorable to be used for the separation salicylic acid from the binary aqueous solution of salicylic acid and phenol. The static adsorptions show that the adsorptions of salicylic acid and phenol by 717 resin are in accordance with Freundlieh isotherm model, and the adsorption kinetics data fit well with the Lagergren pseudo-first order rate equation. Dynamic adsorption of the mixed binary aqueous solution of salicylic acid and phenol by 717 resin shows that, in a column with resin of 1.5 g, the first 475 mL of the exit water after adsorption contains essentially only the phenol because almost all the salicylic acid are adsorbed by the resin. It was found that the salicylic acid adsorbed on the resin can be easily eluted by the 5%NaCl+2%NaOH solution at room temperature.%用717阴离子交

  3. Donnan membrane technique (DMT) for anion measurement. (United States)

    Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H


    Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

  4. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng


    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  5. Treatment of acute non-anion gap metabolic acidosis. (United States)

    Kraut, Jeffrey A; Kurtz, Ira


    Acute non-anion gap metabolic acidosis, also termed hyperchloremic acidosis, is frequently detected in seriously ill patients. The most common mechanisms leading to this acid-base disorder include loss of large quantities of base secondary to diarrhea and administration of large quantities of chloride-containing solutions in the treatment of hypovolemia and various shock states. The resultant acidic milieu can cause cellular dysfunction and contribute to poor clinical outcomes. The associated change in the chloride concentration in the distal tubule lumen might also play a role in reducing the glomerular filtration rate. Administration of base is often recommended for the treatment of acute non-anion gap acidosis. Importantly, the blood pH and/or serum bicarbonate concentration to guide the initiation of treatment has not been established for this type of metabolic acidosis; and most clinicians use guidelines derived from studies of high anion gap metabolic acidosis. Therapeutic complications resulting from base administration such as volume overload, exacerbation of hypertension and reduction in ionized calcium are likely to be as common as with high anion gap metabolic acidosis. On the other hand, exacerbation of intracellular acidosis due to the excessive generation of carbon dioxide might be less frequent than in high anion gap metabolic acidosis because of better tissue perfusion and the ability to eliminate carbon dioxide. Further basic and clinical research is needed to facilitate development of evidence-based guidelines for therapy of this important and increasingly common acid-base disorder.

  6. Selective recognition of sulfate anions by a cyclopeptide-derived receptor in aqueous phosphate buffer. (United States)

    Schaly, Astrid; Belda, Raquel; García-España, Enrique; Kubik, Stefan


    A cyclopeptide-based anion receptor containing alternating 6-aminopicolinic acid and substituted (4R)-4-aminoproline subunits with appended β-alanine residues binds sulfate anions in water. Importantly, appreciable sulfate binding is even observed in phosphate buffer, hence in the presence of anions of similar structure but with a different degree of protonation. The cause for the high selectivity of this receptor is related to the mode of action of the sulfate-binding protein.

  7. Microwave Assisted Synthesis of Carbamate-type Molecular Tweezers Based on Hyodeoxycholic Acid and Their Recognition on Halogen Anions%氨基甲酸酯型猪去氧胆酸分子钳的微波合成及其对卤素阴离子的识别

    Institute of Scientific and Technical Information of China (English)

    曾碧涛; 周黎军; 李相彪; 赵先明; 赵志刚


    Five novel carbamate-type molecular tweezers (4a ~ 4e) based on hyodeoxycholic acid were synthesized using hyodeoxycholic acid as spacer to bridge different aromatic amines under microwave irradiation. The structures were characterized by ' H NMR, IR, MS and elemental analysis. The recognition properties of 4 on halogen anions were investigated by UV-Vis titration method. The results showed that 4 not only formed 1 :1 complex with halogen anions, but also exhibited good selectivity for halogen anions with selective sequence of I- > Br- > Cl-.%在微波辐射条件下,以猪去氧胆酸为隔离基,芳香胺为手臂,通过三光气桥连,合成了五个新型猪去氧胆酸分子钳(4a~4e),其结构经1H NMR,IR,MS和元素分析表征.紫外光谱滴定法的研究结果表明,4对卤素阴离子均具有良好的识别能力,选择顺序依次为I-> Br-> Cl-;主客体之间形成1∶1型超分子配合物,识别作用的主要推动力为氢键.

  8. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids. (United States)

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W


    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  9. Precise, fast, and flexible determination of protein interactions by affinity capillary electrophoresis: part 3: anions. (United States)

    Xu, Yuanhong; Redweik, Sabine; El-Hady, Deia Abd; Albishri, Hassan M; Preu, Lutz; Wätzig, Hermann


    The binding of physiologically anionic species or negatively charged drug molecules to proteins is of great importance in biochemistry and medicine. Since affinity capillary electrophoresis (ACE) has already proven to be a suitable analytical tool to study the influence of ions on proteins, this technique was applied here for comprehensively studying the influence of various anions on proteins of BSA, β-lactoglobulin, ovalbumin, myoglobin, and lysozyme. The analysis was performed using different selected anions of succinate, glutamate, phosphate, acetate, nitrate, iodide, thiocyanate, and pharmaceuticals (salicylic acid, aspirin, and ibuprofen) that exist in the anionic form at physiological pH 7.4. Due to the excellent repeatability and precision of the ACE measurements, not necessarily strong but significant influences of the anions on the proteins were found in many cases. Different influences in the observed bindings indicated change of charge, mass, or conformational changes of the proteins due to the binding with the studied anions. Combining the mobility-shift and pre-equilibrium ACE modes, rapidity and reversibility of the protein-anion bindings were discussed. Further, circular dichroism has been used as an orthogonal approach to characterize the interactions between the studied proteins and anions to confirm the ACE results. Since phosphate and various anions from amino acids and small organic acids such as succinate or acetate are present in very high concentrations in the cellular environment, even weak influences are certainly relevant as well.

  10. Anion exchange polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo


    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  11. Neutral anion receptors; synthesis and evaluation as sensing molecules in chemically modified field effect transistors (CHEMFETs)

    NARCIS (Netherlands)

    Antonisse, Martijn M.G.; Snellink-Ruel, Bianca H.M.; Yigit, Isteyfo; Engbersen, Johan F.J.; Reinhoudt, David N.


    new class of anion selective receptors is based on the neutral uranylsalophene building block as Lewis acidic binding site. Additional hydrogen bond accepting or donating moieties near the anion binding site offer the possibility of varying the binding selectivity. Field effect transistors chemicall

  12. Powered Tate Pairing Computation (United States)

    Kang, Bo Gyeong; Park, Je Hong

    In this letter, we provide a simple proof of bilinearity for the eta pairing. Based on it, we show an efficient method to compute the powered Tate pairing as well. Although efficiency of our method is equivalent to that of the Tate pairing on the eta pairing approach, but ours is more general in principle.

  13. Pairings on hyperelliptic curves

    CERN Document Server

    Balakrishnan, Jennifer; Chisholm, Sarah; Eisentraeger, Kirsten; Stange, Katherine; Teske, Edlyn


    We assemble and reorganize the recent work in the area of hyperelliptic pairings: We survey the research on constructing hyperelliptic curves suitable for pairing-based cryptography. We also showcase the hyperelliptic pairings proposed to date, and develop a unifying framework. We discuss the techniques used to optimize the pairing computation on hyperelliptic curves, and present many directions for further research.

  14. Synthesis of the Anionic Fluororeceptors and Recognition Property for α,ω-Dicarboxylate

    Institute of Scientific and Technical Information of China (English)

    HE,Yong-Bing; WU,Jin-Long; MENG,Ling-Zhi; QIN,Hai-Juan


    @@ Anions, especially dicarboxylates, play an important role in chemical and biological processes,[1] dicarboxylates are critical components of numerous metabolic processes including, for instance, the citric acid and glyoxylate cycles.[1a]They also play an important role in the generation of high-energy phosphate bonds and in the biosynthesis of important intermediates.[1b] To date, several receptors containing different functional groups for selective binding of dicarboxylate anions have been reported.[2,3] However, the sensors based on the fluorescence emission for dicarboxylate anions are still rare.3 In this paper, we report the synthesis and binding properties of two new neutral anion receptors (1 and 2).

  15. Mechanical model for a collagen fibril pair in extracellular matrix. (United States)

    Chan, Yue; Cox, Grant M; Haverkamp, Richard G; Hill, James M


    In this paper, we model the mechanics of a collagen pair in the connective tissue extracellular matrix that exists in abundance throughout animals, including the human body. This connective tissue comprises repeated units of two main structures, namely collagens as well as axial, parallel and regular anionic glycosaminoglycan between collagens. The collagen fibril can be modeled by Hooke's law whereas anionic glycosaminoglycan behaves more like a rubber-band rod and as such can be better modeled by the worm-like chain model. While both computer simulations and continuum mechanics models have been investigated for the behavior of this connective tissue typically, authors either assume a simple form of the molecular potential energy or entirely ignore the microscopic structure of the connective tissue. Here, we apply basic physical methodologies and simple applied mathematical modeling techniques to describe the collagen pair quantitatively. We found that the growth of fibrils was intimately related to the maximum length of the anionic glycosaminoglycan and the relative displacement of two adjacent fibrils, which in return was closely related to the effectiveness of anionic glycosaminoglycan in transmitting forces between fibrils. These reveal the importance of the anionic glycosaminoglycan in maintaining the structural shape of the connective tissue extracellular matrix and eventually the shape modulus of human tissues. We also found that some macroscopic properties, like the maximum molecular energy and the breaking fraction of the collagen, were also related to the microscopic characteristics of the anionic glycosaminoglycan.

  16. Evolution of strategies to achieve baseline separation of ten anionic, water-soluble sulfated estrogens via achiral packed column supercritical fluid chromatography. (United States)

    Patel, M A; Hardink, M A; Wrisely, L; Riley, F W; Hudalla, C J; Ashraf-Khorassani, M; Taylor, L T


    Near baseline separation of ten sulfated sodium salts of various structurally related estrogens employing a variety of bonded stationary phase packed columns was obtained using a conventional supercritical fluid chromatograph coupled with UV detection. Critical pairs 2/3 (8,9-dehydroestrone/17β-dihydroequilin) and 6/7 (17α-estradiol or 17α-dihydroequilin/estrone), however, failed to baseline separate. In all preliminary separations, 10mM ammonium acetate and variable percentages of H2O were initially used as co-additives in conjunction with methanol as a modifier. Different modifier programs and temperatures were employed to optimize the separation in a timely manner. A 2-ethylpyridine column provided the best separation compared to bare silica, diol, and cyano-based bonded phase columns. The employment of both salt and water as additives to the methanol-modified CO2 mobile phase suggested a mixed mode separation mechanism involving both ion pairing of each anionic sulfated estrogen with ammonium ion and hydrophilic interaction facilitated by partitioning of analyte between the aqueous solvated stationary phase and the aqueous component of the mobile phase. Upon more extensive study with either iso-propylamine or formic acid-ammonium formate buffer, the critical anionic pairs were 95% baseline resolved.

  17. Amide-based Fluorescent Macrocyclic Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    ZENG, Zhen-Ya(曾振亚); XU, Kuo-Xi(徐括喜); HE, Yong-Bing(何永炳); LIU, Shun-Ying(刘顺英); WU, Jin-Long(吴进龙); WEI, Lan-Hua(隗兰华); MENG, Ling-Zhi(孟令芝)


    Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1: 1 complexes with anions by hydrogen bonding interactions. Receptor 1 bound anions in the order of F->Cl->H2PO4->CH3COO->>Br-, I- and receptor 2 showed high selectivity to F- over other anions.

  18. Investigation of Polyacrylate Anion-Exchangers for Separation of Rare Earth Element Complexes with EDTA

    Institute of Scientific and Technical Information of China (English)


    The rare earth complexes with EDTA, Ln(edta), show an unusual sequence of affinity for the anion-exchangers. The sorption and chromatographic separation of Y3+ for Nd3+ complexes with EDTA was studied by using the strongly basic gel and macroporous polyacrylate anion-exchangers, Amberlite IRA 458 and Amberlite 958, and the weakly basic gel polyacrylate anion-exchanger, Amberlite IRA-68. The investigations on sorption and separation of rare earth complexes with EDTA on the polyacrylate anion-exchangers applied mainly in the environment protection so far indicate that they can be applied in anionexchange separation of lanthanide complexes with aminopolycarboxylic acids. It was shown that the weakly basic polyacrylate gel anion-exchanger Amberlite IRA-68 is the most effective in purification of Y3+ from Nd3+ in comparison with the strongly basic anion-exchangers of this type.

  19. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions (United States)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.


    Thanks to large opposite electrostatic charges, cations and anions establish strong ionic bonds. However, applications of ionic systems - electrolytes, gas capture, solubilization, etc. - benefit from weaker non-covalent bonds. The common approaches are addition of cosolvents and delocalization of electron charge density via functionalization of ions. We report fine tuning of closest-approach distances, effective radii, and cation geometry by different anions using the semi-empirical molecular dynamics simulations. We found that long fatty acid chains employed in the tetraalkylammonium cation are largely inefficient and new substituents must be developed. The reported results foster progress of task-specific ionic liquids.

  20. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, K. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  1. Organometallic frustrated Lewis pair chemistry. (United States)

    Erker, Gerhard


    Frustrated Lewis pairs are playing an increasingly important role in organometallic chemistry. Examples are presented and discussed where organometallic systems themselves serve as the Lewis base or Lewis acid components in frustrated Lewis pair chemistry, mostly through their attached functional groups. Activation of dihydrogen takes place easily in many of these systems. This may lead to the generation of novel catalyst systems but also in many cases to the occurrence of specific reactions at the periphery of the organometallic frameworks. Increasingly, FLP reactions are used to carry out functional group conversions in organometallic systems under mild reaction conditions. The limits of typical FLP reactivity are explored with selected organometallic examples, a discussion that points toward new developments, such as the discovery of facile new 1,1-carboboration reactions. Learning more and more about the broad spectrum of frustrated Lewis pair chemistry helps us to find novel reactions and applications.

  2. Anion separation by selective crystallization of metal-organic frameworks. (United States)

    Custelcean, Radu; Haverlock, Tamara J; Moyer, Bruce A


    A novel approach for the separation of anions from aqueous mixtures was demonstrated, which involves their selective crystallization with metal-organic frameworks (MOFs) containing urea functional groups. Self-assembly of Zn2+ with the N,N'-bis(m-pyridyl)urea (BPU) linker results in the formation of one-dimensional MOFs including various anions for charge balance, which interact to different extents with the zinc nodes and the urea hydrogen-bonding groups, depending on their coordinating abilities. Thus, Cl-, Br-, I-, and SO4(2-), in the presence of BPU and Zn2+, form MOFs from water, in which the anions coordinate the zinc and are hydrogen-bonded to the urea groups, whereas NO3- and ClO4- anions either do not form MOFs or form water-soluble discrete coordination complexes under the same conditions. X-ray diffraction, FTIR, and elemental analysis of the coordination polymers precipitated from aqueous mixtures containing equivalent amounts of these anions indicated total exclusion of the oxoanions and selective crystallization of the halides in the form of solid solutions with the general composition ZnCl(x)Br(y)I(z).BPU (x + y + z = 2), with an anti-Hofmeister selectivity. The concomitant inclusion of the halides in the same structural frameworks facilitates the rationalization of the observed selectivity on the basis of the diminishing interactions with the zinc and urea acidic centers in the MOFs when going from Cl- to I-, which correlates with decreasing anionic charge density in the same order. The overall crystal packing efficiency of the coordination frameworks, which ultimately determines their solubility, also plays an important role in the anion crystallization selectivity under thermodynamic equilibration.

  3. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Michael Rajamathi; Grace S Thomas; P Vishnu Kamath


    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange properties together with surface basicity making them materials of importance for many modern applications. In this article, we discuss many different ways of making anionic clays and compare and contrast the rich diversity of this class of materials with the better-known cationic clays.

  4. Preparation and evaluation of packed capillary columns for the separation of nucleic acids by ion-pair reversed-phase high-performance liquid chromatography. (United States)

    Oberacher, H; Krajete, A; Parson, W; Huber, C G


    Oligonucleotides and double stranded DNA fragments were separated in 200 microm I.D. capillary columns packed with micropellicular, octadecylated, 2.1 microm poly(styrene-divinylbenzene) particles by ion-pair reversed-phase high-performance liquid chromatography (IP-RP-HPLC). Both the length and the diameter of the connecting capillaries (150 x 0.020 mm I.D.) as well as the detection volume (3 nl) had to be kept to a minimum in order to maintain the high efficiency of this chromatographic separation system with peak widths at half height in the range of a few seconds. Three different types of frits, namely sintered silica particles, sintered octadecylsilica particles, and monolithic poly(styrene-divinylbenzene) (PS-DVB) frits were evaluated with respect to their influence on chromatographic performance. Best performance for the separation of oligonucleotides and long DNA fragments was observed with the PS-DVB frits, whereas the short DNA fragments were optimally resolved in columns terminated by octadecylsilica frits. The maximum loading capacity of 60 x 0.20 mm I.D. columns ranged from 20 fmol (7.7 ng) for a 587 base pair DNA fragment to 500 fmol (2.4 ng) for a 16-mer oligonucleotide. Lower mass- and concentration detection limits in the low femtomol and low nanomol per liter range, respectively, make capillary IP-RP-HPLC with UV absorbance detection highly attractive for the separation and characterization of minute amounts of synthetic oligonucleotides, DNA restriction fragments, and short tandem repeat sequences amplified by polymerase chain reaction.

  5. Casimir light: photon pairs.



    Expressions are developed for weak single pair emission probability and strong emission average number of pairs. The water transparency cutoff is closely realized, showing that the fundamental time scale is even shorter.

  6. Interactions between Hofmeister anions and the binding pocket of a protein. (United States)

    Fox, Jerome M; Kang, Kyungtae; Sherman, Woody; Héroux, Annie; Sastry, G Madhavi; Baghbanzadeh, Mostafa; Lockett, Matthew R; Whitesides, George M


    This paper uses the binding pocket of human carbonic anhydrase II (HCAII, EC as a tool to examine the properties of Hofmeister anions that determine (i) where, and how strongly, they associate with concavities on the surfaces of proteins and (ii) how, upon binding, they alter the structure of water within those concavities. Results from X-ray crystallography and isothermal titration calorimetry show that most anions associate with the binding pocket of HCAII by forming inner-sphere ion pairs with the Zn(2+) cofactor. In these ion pairs, the free energy of anion-Zn(2+) association is inversely proportional to the free energetic cost of anion dehydration; this relationship is consistent with the mechanism of ion pair formation suggested by the "law of matching water affinities". Iodide and bromide anions also associate with a hydrophobic declivity in the wall of the binding pocket. Molecular dynamics simulations suggest that anions, upon associating with Zn(2+), trigger rearrangements of water that extend up to 8 Å away from their surfaces. These findings expand the range of interactions previously thought to occur between ions and proteins by suggesting that (i) weakly hydrated anions can bind complementarily shaped hydrophobic declivities, and that (ii) ion-induced rearrangements of water within protein concavities can (in contrast with similar rearrangements in bulk water) extend well beyond the first hydration shells of the ions that trigger them. This study paints a picture of Hofmeister anions as a set of structurally varied ligands that differ in size, shape, and affinity for water and, thus, in their ability to bind to—and to alter the charge and hydration structure of—polar, nonpolar, and topographically complex concavities on the surfaces of proteins.

  7. Anion binding in biological systems (United States)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.


    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  8. Anion binding in biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)


    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L{sub 3} (2p{sub 3/2}) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  9. Kinetics and mechanism of protection of thymine from sulphate radical anion under anoxic conditions

    Indian Academy of Sciences (India)

    M Sudha Swaraga; M Adinarayana


    The rates of photooxidation of thymine in presence of peroxydisulphate (PDS) have been determined by measuring the absorbance of thymine at 264 nm spectrophotometrically. The rates and the quantum yields () of oxidation of thymine by sulphate radical anion have been determined in the presence of different concentrations of caffeic acid. Increase in [caffeic acid] is found to decrease the rate of oxidation of thymine suggesting that caffeic acid acts as an efficient scavenger of SO$^{\\bullet -}_{4}$ and protects thymine from it. Sulphate radical anion competes for thymine as well as for caffeic acid. The rate constant of sulphate radical anion with caffeic acid has been calculated to be 1.24 × 1010 dm3 mol-1 s-1. The quantum yields of photooxidation of thymine have been calculated from the rates of oxidation of thymine and the light intensity absorbed by PDS at 254 nm, the wavelength at which PDS is activated to sulphate radical anion. From the results of experimentally determined quantum yields (exptl) and the quantum yields calculated (cl) assuming caffeic acid acting only as a scavenger of SO$^{\\bullet -}_{4}$ radicals show that exptl values are lower than cl values. The ' values, which are experimentally found quantum yield values at each caffeic acid concentration and corrected for SO$^{\\bullet-}_{4}$ scavenging by caffeic acid, are also found to be greater than exptl values. These observations suggest that the thymine radicals are repaired by caffeic acid in addition to scavenging of sulphate radical anions.

  10. Reducing nitrogen crossover in microbial reverse-electrodialysis cells by using adjacent anion exchange membranes and anion exchange resin

    KAUST Repository

    Wallack, Maxwell J.


    Microbial reverse electrodialysis cells (MRECs) combine power generation from salinity gradient energy using reverse electrodialysis (RED), with power generation from organic matter using a microbial fuel cell. Waste heat can be used to distill ammonium bicarbonate into high (HC) and low salt concentration (LC) solutions for use in the RED stack, but nitrogen crossover into the anode chamber must be minimized to avoid ammonia loses, and foster a healthy microbial community. To reduce nitrogen crossover, an additional low concentration (LC) chamber was inserted before the anode using an additional anion exchange membrane (AEM) next to another AEM, and filled with different amounts of anion or cation ion exchange resins. Addition of the extra AEM increased the ohmic resistance of the test RED stack from 103 Ω cm2 (1 AEM) to 295 Ω cm2 (2 AEMs). However, the use of the anion exchange resin decreased the solution resistance of the LC chamber by 74% (637 Ω cm2, no resin; 166 Ω cm2 with resin). Nitrogen crossover into the anode chamber was reduced by up to 97% using 50% of the chamber filled with an anion exchange resin compared to the control (no additional chamber). The added resistance contributed by the use of the additional LC chamber could be compensated for by using additional LC and HC membrane pairs in the RED stack.

  11. Separation of transition metals on a poly-iminodiacetic acid grafted polymeric resin column with post-column reaction detection utilising a paired emitter-detector diode system. (United States)

    Barron, Leon; O'Toole, Martina; Diamond, Dermot; Nesterenko, Pavel N; Paull, Brett


    The selectivity, retention and separation of transition metals on a short (2 mm x 50 mm) column packed with a poly-iminodiacetic acid functionalised polymer 10 microm resin (Dionex ProPac IMAC-10) are presented. This stationary phase, typically used for the separation of proteins, is composed of long chain poly-iminodiacetic acid groups grafted to a hydrophilic layer surrounding a 10 microm polymeric bead. Through the use of a combination of a multi-step pH and picolinic acid gradient, the separation of magnesium, iron, cobalt, cadmium, zinc, lead and copper was possible, followed by post-column reaction with 4-(2-pyridylazo) resorcinol (PAR) and absorbance detection at 510 nm using a novel and inexpensive optical detector, comprised of two light emitting diodes with one acting as a light source and the other as a detector. Column efficiency for selective transition metals was in excess of N=10,000, with the baseline separation of seven metal cations in <3 min possible under optimised conditions. Detection limits of between 5 and 81 microg/L were possible based upon a 50 microL injection volume.

  12. Clinical significance of the fractional excretion of anions in metabolic acidosis. (United States)

    Kim, H Y; Han, J S; Jeon, U S; Joo, K W; Earm, J H; Ahn, C; Kim, S; Lee, J S; Kim, G H


    The fractional excretion of anions has been proposed as a new index for the differential diagnosis of metabolic acidosis, identifying the properties of the conjugate base by examining the renal handling of the anion. Here, we investigated clinical significance of the fractional excretion of anions in pathophysiologic diagnosis of metabolic acidosis by measuring urine ammonium (NH4+) excretion, the ratio of A plasma anion gap/delta plasma HCO3- concentration (deltaAG/deltaHCO3-), and fractional excretion of anions in three different groups of metabolic acidosis: acid overproduction (8 patients with lactic acidosis, 8 with diabetic ketoacidosis, 3 with hippuric acidosis following glue sniffing), acid underexcretion (10 patients with chronic renal failure) and normal controls (10 normal volunteers who underwent 3-day NH4Cl loading). As expected, urine NH4+ excretion was higher in overproduction acidosis than in acid-loaded normal controls (88.1 +/- 12.3 vs. 54.0 +/- 3.7 mmol/day, p anions had no difference between overproduction acidosis and chronic renal failure (41.2 +/- 42.8% vs. 41.0 +/- 8.1%). However, the fractional excretion of anions showed significant differences between the subgroups in acid overproduction (lactic acidosis, 4.7 +/- 0.3%; diabetic ketoacidosis, 45.8 +/- 3.1%; hippuric acidosis, 126.0 +/- 14.4%; p anions and the ratio of plasma deltaAG/deltaHCO3- (r2 =-0.89, p anions may provide a useful clue to the differential diagnosis of metabolic acidosis caused by acid overproduction.

  13. pH值和阴离子对吡啶2,6-二羧酸在金纳米颗粒表面的增强拉曼散射的影响%Influence of pH Value and Anion on Surface Enhanced Raman Scattering of 2,6-Pyridinedicarboxylic Acid on Gold Nanoparticle Suface

    Institute of Scientific and Technical Information of China (English)

    罗伟琪; 成汉文; 宦双燕; 温国丽; 陈媛媛; 沈国励; 俞汝勤


    Surface enhanced Raman scattering (SERS) was used for the detection of 2 , 6-pyridinedicar boxylic acid (DPA) , a biomarker for bacterial spores. The gold nanoparticles of 60 nm diameters were immobilized on a polished Au electrode using PVP as an adhesive layer. We demonstrated that the fabricated SERS substrates were steady and highly sensitive. The influence of pH and anions about the adsorption mechanism of DPA on colloidal gold nanoparticles has been examined by SERS. The results showed that using a gold nanoparticle/polyvinylpyrrolidone/gold substrate (AuNPs/PVP/Au)for detection of DPA exhibited a maximum enhancement of SERS signal at low pH, however the SERS features and intensity of DPA were found to weaken when pH was greater than pKa2. The effect of different anions on the adsorption mechanism of this molecule was also investigated, the SERS effect on Au NPs-Au substrate had changed, since the anions may replace the partial sites of the citrate on the gold surface. Owing to the different adsorption mechanism of the three anions, the difference of SERS intensity was observed on the addition of different anions.%表面增强拉曼散射(SERS)被用于检测细菌芽抱中的一种重要的标志物吡啶2,6-羧酸(DPA).以聚乙烯吡啶烷酮(PVP)为粘合剂,将60 nm的金粒子组装到表面打磨光滑的金电极上,制备稳定、灵敏的SERS基底.通过不同pH值下吸附在金基底上的DPA的SERS特征,考察DPA分子吸附构型发生的变化,并分析酸根离子对其吸附的影响.结果表明:在强酸条件下,DPA在Au NPs/PVP/Au基底上的SERS信号能达到最大增强;当pH值大于DPA二级解离常数时,DPA的SERS特征逐渐减弱.在DPA中引入不同酸根盐时,后者会取代纳米金表面的柠檬酸根所占的部分位点,改变Au NPs-Au基底的SERS增强性能.3种酸根吸附性能不同,所以获得的光谱强度存在差异.

  14. A stabilized pairing functional

    CERN Document Server

    Erler, J; Reinhard, P --G


    We propose a modified pairing functional for nuclear structure calculations which avoids the abrupt phase transition between pairing and non-pairing states. The intended application is the description of nuclear collective motion where the smoothing of the transition is compulsory to remove singularities. The stabilized pairing functional allows a thoroughly variational formulation, unlike the Lipkin-Nogami (LN) scheme which is often used for the purpose of smoothing. First applications to nuclear ground states and collective excitations prove the reliability and efficiency of the proposed stabilized pairing.

  15. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman,; Verboom, Willem; Reinhoudt, David N.


    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  16. Impact of dietary cation anion difference in fish and pigs : a comparative study

    NARCIS (Netherlands)

    Dersjant-Li, Y.


    Dietary cation anion difference (CAD, Na + K - Cl, mEq kg -1 ) determines the pH and acid base status of a diet, consequently affecting the acid base balance in the body compartments of animals. After feeding, a low dietary CAD will contribute more acids to the animals than a high dietary

  17. Maize ZmALMT2 is a root anion transporter that mediates constitutive root malate efflux (United States)

    Aluminum (Al) toxicity is a primary limitation to crop productivity on acid soils throughout the plant. Root efflux of organic acid anions constitutes a mechanism by which plants cope with toxic aluminum (Al) ions on acid soils. In this study, we have characterized ZmALMT2 (a member of aluminum-acti...

  18. Adsorption of an anionic dispersant on lignite

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty


    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  19. Boric acid and boronic acids inhibition of pigeonpea urease. (United States)

    Reddy, K Ravi Charan; Kayastha, Arvind M


    Urease from the seeds of pigeonpea was competitively inhibited by boric acid, butylboronic acid, phenylboronic acid, and 4-bromophenylboronic acid; 4-bromophenylboronic acid being the strongest inhibitor, followed by boric acid > butylboronic acid > phenylboronic acid, respectively. Urease inhibition by boric acid is maximal at acidic pH (5.0) and minimal at alkaline pH (10.0), i.e., the trigonal planar B(OH)3 form is a more effective inhibitor than the tetrahedral B(OH)4 -anionic form. Similarly, the anionic form of phenylboronic acid was least inhibiting in nature.

  20. Formation of ternary complexes between a macrotricyclic host and hetero-guest pairs: an acid-base controlled selective complexation process. (United States)

    Han, Tao; Chen, Chuan-Feng


    A triptycene-based cylindrical macrotricyclic host can include diquat and electron-rich aromatics simultaneously to form stable ternary complexes, which is stabilized not only by a charge-transfer (CT) interaction between electron-rich and electron-deficient guests but also by the face to face pi-stacking interactions between the host and the guests. Moreover, a selective complexation process between a ternary complex containing benzidine and a binary complex can be effectively controlled by the use of acid and base.

  1. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad


    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  2. Efficient Amide Based Halogenide Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    Hong Xing WU; Feng Hua LI; Hai LIN; Shou Rong ZHU; Hua Kuan LIN


    In this paper, we present the synthesis and anion recognition properties of the amide based phenanthroline derivatives 1, 2 and 3. In all cases 1:1 receptor: anion complexes were observed. The receptors were found to be selective for fluoride and chloride respectively over other putative anionic guest species.

  3. Binding Hydrated Anions with Hydrophobic Pockets. (United States)

    Sokkalingam, Punidha; Shraberg, Joshua; Rick, Steven W; Gibb, Bruce C


    Using a combination of isothermal titration calorimetry and quantum and molecular dynamics calculations, we demonstrate that relatively soft anions have an affinity for hydrophobic concavity. The results are consistent with the anions remaining partially hydrated upon binding, and suggest a novel strategy for anion recognition.

  4. Utilization of a diol-stationary phase column in ion chromatographic separation of inorganic anions. (United States)

    Arai, Kaori; Mori, Masanobu; Kozaki, Daisuke; Nakatani, Nobutake; Itabashi, Hideyuki; Tanaka, Kazuhiko


    We describe the ion chromatographic separation of inorganic anions using a diol-stationary phase column (-CH(OH)CH(2)OH; diol-column) without charged functional groups. Anions were separated using acidic eluent as in typical anion-exchange chromatography. The retention volumes of anions on the diol-column increased with increasing H(+) concentration in the eluent. The anion-exchange capacities of diol-columns in the acidic eluent (pH 2.8) were larger than that of zwitterionic stationary phase column but smaller than that of an anion-exchange column. The separation of anions using the diol-column was strongly affected by the interaction of H(+) ions with the diol-functional groups and by the types of the eluents. In particular, the selection of the eluent was very important for controlling the retention time and resolution. Good separation was obtained using a diol-column (HILIC-10) with 5 mM phthalic acid as eluent. The limits of detection at a signal-to-noise ratio of 3 ranged from 1.2 to 2.7 μM with relative standard deviations (RSD, n=5) of 0.04-0.07% for the retention time and 0.4-2.0% for the peak areas. This method was successfully applied to the determination of H(2)PO(4)(-), Cl(-), and NO(3)(-) in a liquid fertilizer sample.

  5. Polymerization of anionic wormlike micelles. (United States)

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong


    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  6. Laser Cooling of Molecular Anions

    CERN Document Server

    Yzombard, Pauline; Gerber, Sebastian; Doser, Michael; Comparat, Daniel


    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarise the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C$\\_2^-$, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photo-detachment process is present, as well as Doppler laser cooling of trapped C$\\_2^-$, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources and antimatter physics.

  7. Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels (United States)

    Drozdov, A. D.; deClaville Christiansen, J.


    A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

  8. Matched-pair classification

    Energy Technology Data Exchange (ETDEWEB)

    Theiler, James P [Los Alamos National Laboratory


    Following an analogous distinction in statistical hypothesis testing, we investigate variants of machine learning where the training set comes in matched pairs. We demonstrate that even conventional classifiers can exhibit improved performance when the input data has a matched-pair structure. Online algorithms, in particular, converge quicker when the data is presented in pairs. In some scenarios (such as the weak signal detection problem), matched pairs can be generated from independent samples, with the effect not only doubling the nominal size of the training set, but of providing the structure that leads to better learning. A family of 'dipole' algorithms is introduced that explicitly takes advantage of matched-pair structure in the input data and leads to further performance gains. Finally, we illustrate the application of matched-pair learning to chemical plume detection in hyperspectral imagery.

  9. Hosting anions. The energetic perspective. (United States)

    Schmidtchen, Franz P


    Hosting anions addresses the widely spread molecular recognition event of negatively charged species by dedicated organic compounds in condensed phases at equilibrium. The experimentally accessible energetic features comprise the entire system including the solvent, any buffers, background electrolytes or other components introduced for e.g. analysis. The deconvolution of all these interaction types and their dependence on subtle structural variation is required to arrive at a structure-energy correlation that may serve as a guide in receptor construction. The focus on direct host-guest interactions (lock-and-key complementarity) that have dominated the binding concepts of artificial receptors in the past must be widened in order to account for entropic contributions which constitute very significant fractions of the total free energy of interaction. Including entropy necessarily addresses the ambiguity and fuzziness of the host-guest structural ensemble and requires the appreciation of the fact that most liquid phases possess distinct structures of their own. Apparently, it is the perturbation of the intrinsic solvent structure occurring upon association that rules ion binding in polar media where ions are soluble and abundant. Rather than specifying peculiar structural elements useful in anion binding this critical review attempts an illumination of the concepts and individual energetic contributions resulting in the final observation of specific anion recognition (95 references).

  10. Separation of seven arsenic species by ion-pair and ion-exchange high performance liquid chromatography

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt; Hansen, Sven Hedegaard


    Arsenite, arsenate, monomethylarsonate, dimethylarsinate, arsenobetaine, arsenocholine and the tetramethylarsonium ion were subjected to ion-exchange and ion-pair reversed phase HPLC. The ion exchange method was superior in selectivity and time of analysis for the arsenic anions. The ammonium ion...... used for the ion-pair method only resulted in separation of some of the anionic arsenic compounds. Flame atomic absorption spectrometry was used for on-line arsenic-specific detection....

  11. Comment on "Local impermeant anions establish the neuronal chloride concentration". (United States)

    Luhmann, Heiko J; Kirischuk, Sergei; Kilb, Werner


    Glykys et al. (Reports, 7 February 2014, p. 670) proposed that cytoplasmic impermeant anions and polyanionic extracellular matrix glycoproteins establish the local neuronal intracellular chloride concentration, [Cl(-)]i, and thereby the polarity of γ-aminobutyric acid type A (GABAA) receptor signaling. The experimental procedures and results in this study are insufficient to support these conclusions. Contradictory results previously published by these authors and other laboratories are not referred to.

  12. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan


    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  13. Synthesis, Crystal Structures and Properties of Tetrametallic Complexes: [M2(phen)4(FCA)2](ClO4)2o(H2O)2 (M=Zn or Co, phen= 1,10-phenanthroline, FCA =anion of 3-ferrocenyl-2-crotonic acid)

    Institute of Scientific and Technical Information of China (English)

    YANG Jia-Xiang; HU Zhang-Jun; ZHANG Ze; TIAN Yu-Peng; LIU Qing-Liang; CHANTRAPROMMA Suchada; FUN Hoong-Kun


    Two new complexes [Zn2(phen)4(FCA)2](ClO4)2·(H2O)2 (1) and [Co2(phen)4 (FCA)2](ClO4)2·(H2O)2 (2) (FCA =anion of 3-ferrocenyl-2-crotonic acid, phen= 1,10-phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV-Vis spectra, thermal analyses, and single-crystal X-ray diffraction. Two M(Ⅱ) (M=Zn or Co) ions are bridged by two FCA anions with syn-anti bridging ligands, leading to dimeric cores,[M2(phen)4(FCA)2]2+, and each M(Ⅱ) ion is six-coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ2-carboxylate oxygen atoms from two FCA groups. The M(Ⅱ)…M(Ⅱ) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2, respectively. Electrochemical properties of the complexes have been discussed.

  14. Cooper pairs and bipolarons


    Lakhno, Victor D.


    It is shown that Cooper pairs are a solution of the bipolaron problem for model Fr\\"{o}hlich Hamiltonian. The total energy of a pair for the initial Fr\\"{o}hlich Hamiltonian is found. Differences between the solutions for the model and initial two-particle problems are discussed.

  15. Cooper pairs and bipolarons (United States)

    Lakhno, Victor


    It is shown that Cooper pairs are a solution of the bipolaron problem for model Fröhlich Hamiltonian. The total energy of a pair for the initial Fröhlich Hamiltonian is found. Differences between the solutions for the model and initial two-particle problems are discussed.

  16. Stereo pairs in Astrophysics

    CERN Document Server

    Vogt, Frédéric


    Stereoscopic visualization is seldom used in Astrophysical publications and presentations compared to other scientific fields, e.g., Biochemistry, where it has been recognized as a valuable tool for decades. We put forth the view that stereo pairs can be a useful tool for the Astrophysics community in communicating a truer representation of astrophysical data. Here, we review the main theoretical aspects of stereoscopy, and present a tutorial to easily create stereo pairs using Python. We then describe how stereo pairs provide a way to incorporate 3D data in 2D publications of standard journals. We illustrate the use of stereo pairs with one conceptual and two Astrophysical science examples: an integral field spectroscopy study of a supernova remnant, and numerical simulations of a relativistic AGN jet. We also use these examples to make the case that stereo pairs are not merely an ostentatious way to present data, but an enhancement in the communication of scientific results in publications because they prov...

  17. Au pair trajectories

    DEFF Research Database (Denmark)

    Dalgas, Karina Märcher


    and dreams for the future become intertwined with their financial possibilities, limitations and responsibilities. The following three articles employ the notion of relatedness to explore the transnational and local social networks, including family relations, of which the au pairs are part. Arguing...... that Filipina au pairs see their stay abroad as an avenue of personal development and social recognition, I examine how the au pairs re-position themselves within their families at home through migration, and how they navigate between the often conflicting expectations of participation in the sociality...... important remittances back home. Their time in Denmark is also often part of long-term migration trajectories involving future stays in Scandinavia and southern Europe. Based on ten months of fieldwork among current and former au pairs in Denmark and ten weeks of fieldwork among prospective au pairs and au...

  18. Critical Schwinger Pair Production. (United States)

    Gies, Holger; Torgrimsson, Greger


    We investigate Schwinger pair production in spatially inhomogeneous electric backgrounds. A critical point for the onset of pair production can be approached by fields that marginally provide sufficient electrostatic energy for an off-shell long-range electron-positron fluctuation to become a real pair. Close to this critical point, we observe features of universality which are analogous to continuous phase transitions in critical phenomena with the pair-production rate serving as an order parameter: electric backgrounds can be subdivided into universality classes and the onset of pair production exhibits characteristic scaling laws. An appropriate design of the electric background field can interpolate between power-law scaling, essential Berezinskii-Kosterlitz-Thouless-type scaling, and a power-law scaling with log corrections. The corresponding critical exponents only depend on the large-scale features of the electric background, whereas the microscopic details of the background play the role of irrelevant perturbations not affecting criticality.

  19. Critical Schwinger pair production

    CERN Document Server

    Gies, Holger


    We investigate Schwinger pair production in spatially inhomogeneous electric backgrounds. A critical point for the onset of pair production can be approached by fields that marginally provide sufficient electrostatic energy for an off-shell long-range electron-positron fluctuation to become a real pair. Close to this critical point, we observe features of universality which are analogous to continuous phase transitions in critical phenomena with the pair-production rate serving as an order parameter: electric backgrounds can be subdivided into universality classes and the onset of pair production exhibits characteristic scaling laws. An appropriate design of the electric background field can interpolate between power-law scaling, essential BKT-type scaling and a power-law scaling with log corrections. The corresponding critical exponents only depend on the large-scale features of the electric background, whereas the microscopic details of the background play the role of irrelevant perturbations not affecting ...

  20. Lixiviação de cátions favorecida pela presença de ânions inorgânicos e ácidos orgânicos de baixa massa molecular em solos adubados com camas de aviário Cation leaching favored by inorganic anions and low molecular mass organic acids in soils fertilized with different poultry litters

    Directory of Open Access Journals (Sweden)

    Fabrício de Oliveira Gebrim


    to 1.200 mm, totaling 10 applications. Leachates were analyzed for cations (Ca, Mg, K and Na, anions (Cl-, NO3-and SO4(2- and low molecular mass organic acids by ion chromatography. Results indicate substantial base-leaching through the soil columns, particularly up to the third percolation. This was most likely a result of the presence of bases contained in the high poultry litter doses and the presence of accompanying anions (Cl-, NO3-and SO4(2-in the sandy loam soil and Cl-and NO3-in the clayey soil. Ca leaching was positively correlated with the malic and oxalic acid concentrations in the clayey soil. High acetic acid concentration in leachates of poultry litter-treated soils suggest that it may have favored base-leaching in the soil profile as a result of its action as an ion pair.

  1. Ion Pairing in Alkali Nitrate Electrolyte Solutions. (United States)

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin


    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  2. Photocatalytic Anion Oxidation and Applications in Organic Synthesis. (United States)

    Hering, Thea; Meyer, Andreas Uwe; König, Burkhard


    Ions and radicals of the same kind differ by one electron only. The oxidation of many stable inorganic anions yields their corresponding highly reactive radicals, and visible light excitable photocatalysts can provide the required oxidation potential for this transformation. Air oxygen serves as the terminal oxidant, or cheap sacrificial oxidants are used, providing a very practical approach for generating reactive inorganic radicals for organic synthesis. We discuss in this perspective several recently reported examples: Nitrate radicals are obtained by one-electron photooxidation of nitrate anions and are very reactive toward organic molecules. The photooxidation of sulfinate salts yields the much more stable sulfone radicals, which smoothly add to double bonds. A two-electron oxidation of chloride anions to electrophilic chlorine species reacting with arenes in aromatic substitutions extends the method beyond radical reactions. The chloride anion oxidation proceeds via photocatalytically generated peracidic acid as the oxidation reagent. Although the number of reported examples of photocatalytically generated inorganic radical intermediates for organic synthesis is still small, future extension of the concept to other inorganic ions as radical precursors is a clear perspective.

  3. H9N2 influenza virus acquires intravenous pathogenicity on the introduction of a pair of di-basic amino acid residues at the cleavage site of the hemagglutinin and consecutive passages in chickens

    Directory of Open Access Journals (Sweden)

    Sakoda Yoshihiro


    Full Text Available Abstract Background Outbreaks of avian influenza (AI caused by infection with low pathogenic H9N2 viruses have occurred in poultry, resulting in serious economic losses in Asia and the Middle East. It has been difficult to eradicate the H9N2 virus because of its low pathogenicity, frequently causing in apparent infection. It is important for the control of AI to assess whether the H9N2 virus acquires pathogenicity as H5 and H7 viruses. In the present study, we investigated whether a non-pathogenic H9N2 virus, A/chicken/Yokohama/aq-55/2001 (Y55 (H9N2, acquires pathogenicity in chickens when a pair of di-basic amino acid residues is introduced at the cleavage site of its HA molecule. Results rgY55sub (H9N2, which had four basic amino acid residues at the HA cleavage site, replicated in MDCK cells in the absence of trypsin after six consecutive passages in the air sacs of chicks, and acquired intravenous pathogenicity to chicken after four additional passages. More than 75% of chickens inoculated intravenously with the passaged virus, rgY55sub-P10 (H9N2, died, indicating that it is pathogenic comparable to that of highly pathogenic avian influenza viruses (HPAIVs defined by World Organization for Animal Health (OIE. The chickens inoculated with the virus via the intranasal route, however, survived without showing any clinical signs. On the other hand, an avirulent H5N1 strain, A/duck/Hokkaido/Vac-1/2004 (Vac1 (H5N1, acquired intranasal pathogenicity after a pair of di-basic amino acid residues was introduced into the cleavage site of the HA, followed by two passages by air sac inoculation in chicks. Conclusion The present results demonstrate that an H9N2 virus has the potential to acquire intravenous pathogenicity in chickens although the morbidity via the nasal route of infection is lower than that of H5N1 HPAIV.

  4. Computational design of model scaffold for anion recognition based on the 'C(α) NN' motif. (United States)

    Sheet, Tridip; Ghosh, Suvankar; Pal, Debnath; Banerjee, Raja


    The 'novel phosphate binding 'C(α) NN' motif', consisting of three consecutive amino acid residues, usually occurs in the protein loop regions preceding a helix. Recent computational and complementary biophysical experiments on a series of chimeric peptides containing the naturally occurring 'C(α) NN' motif at the N-terminus of a designed helix establishes that the motif segment recognizes the anion (sulfate and phosphate ions) through local interaction along with extension of the helical conformation which is thermodynamically favored even in a context-free, nonproteinaceous isolated system. However, the strength of the interaction depends on the amino acid sequence/conformation of the motif. Such a locally-mediated recognition of anions validates its intrinsic affinity towards anions and confirms that the affinity for recognition of anions is embedded within the 'local sequence' of the motif. Based on the knowledge gathered on the sequence/structural aspects of the naturally occurring 'C(α) NN' segment, which provides the guideline for rationally engineering model scaffolds, we have modeled a series of templates and investigated their interactions with anions using computational approach. Two of these designed scaffolds show more efficient anion recognition than those of the naturally occurring 'C(α) NN' motif which have been studied. This may provide an avenue in designing better anion receptors suitable for various biochemical applications.

  5. Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates (United States)

    Rannulu, Nalaka S.; Cole, Richard B.


    The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

  6. Expanded Bed Recovery of D-2-Chloropropionic Acid Dehalogenase Using TiO2-Densified Cellulose Anion Exchanger%使用纤维素-钛白粉复合扩张床阴离子吸附剂提取D-2-氯丙酸脱卤酶

    Institute of Scientific and Technical Information of China (English)

    雷引林; 金志华; 童微星; 姚善泾; 朱自强


    The TiO2-densified cellulose composite beads were activated by epichlorohydrin and coupled with diethylamine, to function as an anion exchanger for expanded bed chromatography. The adsorbent exhibited a favorable performance of expanded bed adsorption for proteins, and therefore was applied to the expanded bed recovery of D-2-chloropropionic acid dehalogenase directly from the unclarified homogenate of Pseudomonas sp. NT21. The binding capacity of the dehalogenase was found to be 8.54U·ml-1 adsorbent, and two active peaks were eluted respectively at 0.15mol· L-1 and 0.3mol· L-1 (NH4)2SO4. The result indicated that the overall enzyme yield was 68%,with a purification factor of 22. In comparison to other recovery processes, the yield of the expanded bed process rises at least 70%, simultaneously saving a great deal of operation time and costs.

  7. 离子对色谱法同时测定水中多种氯代酸性除草剂%Simultaneous Determination of Chlorinated Acidic Herbicides in Waters by Ion-pair Chromatography

    Institute of Scientific and Technical Information of China (English)

    李晓亚; 桂建业; 张莉; 张永涛; 李科


    建立了离子对色谱法同时测定水中DCPA二元酸、4-硝基苯酚、麦草畏、苯达松、2,4-二氯苯乙酸、2-甲基-4-氯苯氧乙酸(MCPA)、2-(4-氯苯氧基-2甲基)丙酸(MCPP)、3,5-二氯苯甲酸、2,4-滴丙酸9种氯代酸性除草剂.通过加入离子对试剂使多种极性强、保留弱的酸性除草剂在普通的反相色谱柱上同时分离.采用Shim-pack VP-ODS色谱柱,流动相为V(1-辛烷三乙磷酸铵溶液)∶V(乙腈)∶V(甲醇)=6∶3∶1,流速1.8 mL/min,不同组分全流程方法检出限范围为0.03~0.15μg/L,相对标准偏差在10%以下.建立的方法可将9种除草剂完全分离,与高效液相色谱法和气相色谱-质谱法相比,具有操作简单、分离效果好、回收率高、干扰少的优点,能够满足不同水质的检测要求.%A method for the simultaneous detection of several chlorinated acid herbicides such as dicamba and bentazon etc by ion-pair chromatography was developed. Several strongly polar and weak reserve chlorinated acid herbicides can be separated simultaneously from reversed-phase chromatography column by adding ion-pair reagent. Shim-pack VP-ODS column was used for analyte separation with ion-pair solution and the mobile phase was at a constant flow rate of 1. 8 mL/min. Extraction condition, ion-pair and the mobile phase were selected and optimized. The detection limit ranges of the method for different herbicides were 0. 03 to 0. 15 μg/L with RSD less than 10% . Comparing with high performance liquid chromatography and gas chromatography-mass spectrometry, the established method completely separates the 9 sorts of herbicides with advantages of simple operation, high separating effect, high recoveries and less interferences, which meet the requirements of all kind of water.

  8. Simultaneous detection of green tea catechins and gallic acid in human serum after ingestion of green tea tablets using ion-pair high-performance liquid chromatography with electrochemical detection. (United States)

    Narumi, Keiko; Sonoda, Jun-Ichiro; Shiotani, Keita; Shigeru, Michihiro; Shibata, Masayuki; Kawachi, Akio; Tomishige, Erisa; Sato, Keizo; Motoya, Toshiro


    We developed an analytical method for the simultaneous determination of tea catechins and gallic acid (GA) in human serum using ion-pair high-performance liquid chromatography (HPLC) with electrochemical detection. GA was measured to estimate the amount of gallate moiety produced by degradation of gallated catechins ((-)-epicatechin-3-gallate, ECG; (-)-epigallocatechin-3-gallate, EGCG). Ethyl gallate was adopted as an internal standard to correct for the extraction efficiency. To maximize extraction efficiency, a hydrophobic polytetrafluoroethylene (PTFE) filter was selected for pre-treatment prior to separation. HPLC separation was performed using a C18 reversed-phase column with a gradient mobile phase of phosphate buffer (pH 2.5) containing tetrahexylammonium hydrogensulfate as an ion-pair reagent. Using this method, (-)-epicatechin (EC), (-)-epigallocatechin (EGC), ECG, EGCG, ethyl gallate, and GA were detected as single peaks. The resolution values for target analytes were 4.0-13.0 and the mean values of the absolute recoveries of catechins and GA were 77.3-93.9%. The detection limits for catechins and GA in serum were 0.4-3.1ng/mL. The serum catechin levels of eight healthy volunteers after ingestion of a single dose of green tea tablets were measured using this method. The concentration of total catechins (free+conjugated forms) in serum peaked 60min after ingestion. From these results, this method is thought to enable the simultaneous quantification of GA, the hydrolysis product of gallated catechins, and target catechins, and to be sufficiently sensitive for pharmacokinetic studies of catechins following oral administration of green tea.

  9. Off-On-Off fluorescence behavior of an intramolecular charge transfer probe toward anions and CO2 (United States)

    Ali, Rashid; Razi, Syed S.; Shahid, Mohammad; Srivastava, Priyanka; Misra, Arvind


    The photophysical behavior of a newly developed fluorescent probe, tricyanoethylphenyl phenanthroimidazole (TCPPI) has been studied. Upon interaction of different class of anions TCPPI displayed naked-eye sensitive fluorescence "turn-on" response to detect selectively F- (0.98 μM, 18.62 ppb) and CN- (1.12 μM, 29.12 ppb) anions in acetonitrile (MeCN). Job's plot analysis revealed a 1:1 binding stoichiometry between probe and anions. The spectral data analysis and 1H NMR titration studies suggested about the affinity of F- and CN- anions with moderately acidic - NH fragment of imidazolyl unit of probe through deprotonation and H-bonding interaction. Moreover, the anion activated probe upon interaction with CO2 revived photophysical properties of probe, "On-Off-On" type fluorescence and enabled anion-induced CO2 sensing in the medium.

  10. Enhanced Anion Transport Using Some Expanded Porphyrins as Carriers. (United States)


    step, an acid catalyzed 1: 1 Schiff - base condensation between I ,8-diaminoanthracene 4 and 2,5-bis((3-ethylS_-formyl-4- methy’lpyrrol-2-yl) methyl... Schiff base "expanded porphyrin," 1, which when diprotonated effectively binds chloride anion in the solid state.8- 10 In addition, we present the results...parent, 1, is shown in Scheme 1. It involves, as the critical step, the acid catalyzed 1:1 Schiff - base condensation between 1.8-diaminoanthracene 49

  11. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  12. Separation of Y(dcta– complexes from Nd(dcta– and Sm(dcta– complexes on polyacrylate anion-exchangers

    Directory of Open Access Journals (Sweden)



    Full Text Available The formation of anion rare earth element complexes with aminopolycarboxylic acids gives new possibilities for the separation of these elements on anion-exchangers. The higher affinity of the Nd(dcta- and Sm(dcta- complexes for the anion-exchangers compared to Y(dcta- complexes indicates the possibility of yttrium purification as a macrocomponent from the former by frontal analysis. The weakly basic polyacrylate gel anion-exchanger Amberlite IRA 68 was more effective in the purification of Y(III from Nd(III and Sm(III complexes with DCTA than the strongly basic anion-exchangers of this type.

  13. Neutral, anionic, cationic, and zwitterionic diblock copolymers featuring poly(2-methoxyethyl acrylate) hydrophobic segments

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Jankova Atanasova, Katja; Hvilsted, Søren


    Amphiphilic diblock copolymers incorporating hydrophobic poly(2-methoxyethyl acrylate) (PMEA) and hydrophilic neutral poly(ethylene glycol) monomethyl ether (mPEG), anionic poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA), cationic poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), and ...

  14. Adaptive Pairing Reversible Watermarking. (United States)

    Dragoi, Ioan-Catalin; Coltuc, Dinu


    This letter revisits the pairwise reversible watermarking scheme of Ou et al., 2013. An adaptive pixel pairing that considers only pixels with similar prediction errors is introduced. This adaptive approach provides an increased number of pixel pairs where both pixels are embedded and decreases the number of shifted pixels. The adaptive pairwise reversible watermarking outperforms the state-of-the-art low embedding bit-rate schemes proposed so far.

  15. Determination of free and total myo-inositol in infant formula and adult/pediatric nutritional formula by high- performance anion exchange chromatography with pulsed amperometric detection, including a novel total extraction using microwave-assisted acid hydrolysis and enzymatic treatment: first action 2012.12. (United States)

    Ellingson, David; Pritchard, Ted; Foy, Pamela; King, Kathryn; Mitchell, Barbara; Austad, John; Winters, Doug; Sullivan, Darryl; Dowell, Dawn


    After an assessment of data generated from a single-laboratory validation study published in J. AOAC Int. 95, 1469-1478 (2012), a method for determining total myo-inositol in infant formula and adult/ pediatric nutritional formula by high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD), including extraction by using microwave-assisted acid hydrolysis and enzymatic treatment was presented for consideration by AOAC during the AOAC Annual Meeting held in Las Vegas, NV, from September 30 to October 3, 2012. The Expert Review Panel on Infant Formula and Adult Nutritionals concluded that the method met the criteria set by the standard method performance requirements (SMPRs) for the determination of free myo-inositol and approved the method as AOAC Official First Action. The method also determines total myo-inositol, but includes bound sources that the SMPRs exclude. The method involves using HPAEC-PAD for free myo-inositol and a total myo-inositol determination by two different techniques. The first technique uses the conventional acid hydrolysis with 6 h incubation in an autoclave. The second uses a microwave-assisted acid hydrolysis with enzymatic treatment that decreases the extraction time.

  16. Stereo pairs in Astrophysics (United States)

    Vogt, Frédéric; Wagner, Alexander Y.


    Stereoscopic visualization is seldom used in Astrophysical publications and presentations compared to other scientific fields, e.g., Biochemistry, where it has been recognized as a valuable tool for decades. We put forth the view that stereo pairs can be a useful tool for the Astrophysics community in communicating a truer representation of astrophysical data. Here, we review the main theoretical aspects of stereoscopy, and present a tutorial to easily create stereo pairs using Python. We then describe how stereo pairs provide a way to incorporate 3D data in 2D publications of standard journals. We illustrate the use of stereo pairs with one conceptual and two Astrophysical science examples: an integral field spectroscopy study of a supernova remnant, and numerical simulations of a relativistic AGN jet. We also use these examples to make the case that stereo pairs are not merely an ostentatious way to present data, but an enhancement in the communication of scientific results in publications because they provide the reader with a realistic view of multi-dimensional data, be it of observational or theoretical nature. In recognition of the ongoing 3D expansion in the commercial sector, we advocate an increased use of stereo pairs in Astrophysics publications and presentations as a first step towards new interactive and multi-dimensional publication methods.

  17. Water-Mediated Ion Pairing: Occurrence and Relevance

    DEFF Research Database (Denmark)

    van der Vegt, Nico F.A.; Haldrup, Kristoffer; Roke, Sylvie


    We present an overview of the studies of ion pairing in aqueous media of the past decade. In these studies, interactions between ions, and between ions and water, are investigated with relatively novel approaches, including dielectric relaxation spectroscopy, far-infrared (terahertz) absorption...... spectroscopy, femtosecond mid-infrared spectroscopy, and X-ray spectroscopy and scattering, as well as molecular dynamics simulation methods. With these methods, it is found that ion pairing is not a rare phenomenon only occurring for very particular, strongly interacting cations and anions. Instead, for many...

  18. Structure of cyano-anion ionic liquids: X-ray scattering and simulations. (United States)

    Dhungana, Kamal B; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J; Castner, Edward W


    Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN(-), SCN(-), N(CN)2 (-), C(CN)3 (-), and B(CN)4 (-). By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4 (-) anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1 (+)/B(CN)4 (-) is cationic.

  19. Specific adsorption of perchlorate anions on Pt{hkl} single crystal electrodes. (United States)

    Attard, Gary A; Brew, Ashley; Hunter, Katherine; Sharman, Jonathan; Wright, Edward


    The voltammetry of Pt{111}, Pt{100}, Pt{110} and Pt{311} single crystal electrodes as a function of perchloric acid concentration (0.05-2.00 M) has been studied in order to test the assertion made in recent reports by Watanabe et al. that perchlorate anions specifically adsorb on polycrystalline platinum. Such an assertion would have significant ramifications for our understanding of electrocatalytic processes at platinum surfaces since perchlorate anions at low pH have classically been assumed not to specifically adsorb. For Pt{111}, it is found that OHad and electrochemical oxide states are both perturbed significantly as perchloric acid concentration is increased. We suggest that this is due to specific adsorption of perchlorate anions competing with OHad for adsorption sites. The hydrogen underpotential deposition (H UPD) region of Pt{111} however remains unchanged although evidence for perchlorate anion decomposition to chloride on Pt{111} is reported. In contrast, for Pt{100} no variation in the onset of electrochemical oxide formation is found nor any shift in the potential of the OHad state which normally results from the action of specifically adsorbing anions. This suggests that perchlorate anions are non-specifically adsorbed on this plane although strong changes in all H UPD states are observed as perchloric acid concentration is increased. This manifests itself as a redistribution of charge from the H UPD state situated at more positive potential to the one at more negative potential. For Pt{110} and Pt{311}, marginal changes in the onset of electrochemical oxide formation are recorded, associated with specific adsorption of perchlorate. Specific adsorption of perchlorate anions on Pt{111} is deleterious to electrocatalytic activity in relation to the oxygen reduction reaction (ORR) as measured using a rotating disc electrode (RDE) in a hanging meniscus configuration. This study supports previous work suggesting that a large component of the ORR

  20. Generation of naphthoquinone radical anions by electrospray ionization: solution, gas-phase, and computational chemistry studies. (United States)

    Vessecchi, Ricardo; Naal, Zeki; Lopes, José N C; Galembeck, Sérgio E; Lopes, Norberto P


    Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(•-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q+15](-) was described as being a reaction between the solvent system and the radical anion, Q(•-). The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses.

  1. Vibrational Spectroscopy of Microhydrated Conjugate Base Anions

    NARCIS (Netherlands)

    Asmis, K. R.; Neumark, D. M.


    Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aeros

  2. Diazotization of the amino acid [closo-1-CB9H8-1-COOH-6-NH3] and reactivity of the [closo-1-CB9H8-1-COO-6-N2]- anion. (United States)

    Ringstrand, Bryan; Kaszynski, Piotr; Young, Victor G


    A comparative study of the reactivity of dinitrogen acids [closo-1-CB(9)H(8)-1-COOH-10-N(2)] (3[10]) and [closo-1-CB(9)H(8)-1-COOH-6-N(2)] (3[6]) was conducted by diazotization of a mixture of amino acids [closo-1-CB(9)H(8)-1-COOH-6-NH(3)] (1[6]) and [closo-1-CB(9)H(8)-1-COOH-10-NH(3)] (1[10]) with NO(+)BF(4)(-) in the presence of a heterocyclic base (pyridine, 4-methoxypyridine, 2-picoline, or quinoline). The 10-amino acid 1[10] formed an isolable stable 10-dinitrogen acid 3[10], while the 6-dinitrogen carboxylate 3[6](-) reacted in situ, giving products of N-substitution at the B6 position with the heterocyclic solvent (4[6]). The molecular and crystal structures for pyridinium acid 4[6]a were determined by X-ray crystallography. The electronic structures and reactivity of the 6-dinitrogen derivatives of the {1-CB(9)} cluster were assessed computationally at the B3LYP/6-31G(d,p) and MP2/6-31G(d,p) levels of theory and compared to those of the 10-dinitrogen, 2-dinitrogen, and 1-dinitrogen analogues.

  3. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood


    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  4. Liquid anion-exchange separation of vanadium from malonate media

    Energy Technology Data Exchange (ETDEWEB)

    Rao, R.R.; Khopkar, S.M. (Indian Inst. of Technology, Dept. of Chemistry, Bombay (India))


    Vanadium (IV) and (V) can be quantitatively extracted with 0.2 mol/l Amberlite LA-2 in xylene at pH 3.0 from 0.02 mol/l malonic acid, stripped with 0.5 mol/l hydrochloric acid, and determined spectrophotometrically. Five other liquid anion exchangers (Amberlite LA-1, Primene JM-T, Aliquat 336S, TOA and TIOA) were examined as possible extractants. The extraction of vanadium(IV) was found to be quantitative only with Amberlite LA-2, while that of vanadium(V) was quantitative with Amberlite LA-1 and LA-2, Primene JM-T and Aliquat 336S. Eight common solvents were tested as diluents; of these hexane, cyclohexane, benzene, and xylene were found to be satisfactory. Vanadium was separated from elements that do not form anionic complexes with malonic acid by selective extraction, from those that form weak complexes by washing the organic extract with water, and from metals that form strong malonato complexes by selective stripping with hydrochloric, nitric, or sulphuric acid. The method has been applied to the determination of vanadium in steel, coal fly ash and fuel oil. The precision of measurement is within {+-}5% and the detection limit of the method for vanadium is 0.5 mg/kg. (orig.).

  5. Co2 chemosorption by functionalized amino acid derivatives

    DEFF Research Database (Denmark)


    The absorption and desorption behaviour of carbon dioxide (CO2) using a composition comprising an ionic compound comprising a cation [A+] and an anion [B-] is described, wherein the anion [B-] is a mono-amine functionalized amino acid.......The absorption and desorption behaviour of carbon dioxide (CO2) using a composition comprising an ionic compound comprising a cation [A+] and an anion [B-] is described, wherein the anion [B-] is a mono-amine functionalized amino acid....

  6. Anion stripping as a general method to create cationic porous framework with mobile anions. (United States)

    Mao, Chengyu; Kudla, Ryan A; Zuo, Fan; Zhao, Xiang; Mueller, Leonard J; Bu, Xianhui; Feng, Pingyun


    Metal-organic frameworks (MOFs) with cationic frameworks and mobile anions have many applications from sensing, anion exchange and separation, to fast ion conductivity. Despite recent progress, the vast majority of MOFs have neutral frameworks. A common mechanism for the formation of neutral frameworks is the attachment of anionic species such as F(-) or OH(-) to the framework metal sites, neutralizing an otherwise cationic scaffolding. Here, we report a general method capable of converting such neutral frameworks directly into cationic ones with concurrent generation of mobile anions. Our method is based on the differential affinity between distinct metal ions with framework anionic species. Specifically, Al(3+) is used to strip F(-) anions away from framework Cr(3+) sites, leading to cationic frameworks with mobile Cl(-) anions. The subsequent anion exchange with OH(-) further leads to a porous network with mobile OH(-) anions. New materials prepared by anion stripping can undergo ion exchange with anionic organic dyes and also exhibit much improved ionic conductivity compared to the original unmodified MOFs.

  7. The Correlation between Dietary Cation-anion Difference and Acid-base Balance of Body Fluid in Dairy Cows%饲粮阴阳离子差与奶牛体液酸碱平衡的关联性研究

    Institute of Scientific and Technical Information of China (English)



    The present study was conducted to evaluate the correlation between dietary cation-anion difference (DCAD) and acid-base balance of body fluid. Data were obtained from 3 trials of DCAD on body fluid acid-base balance (urine pH, blood pH and blood HCO3- ) with peripartum dairy cows as the experimental animals and were analyzed using SAS software. The results showed as follows: 1) there was a marked relationship a-mong DCAD, urine pH, blood pH and blood HCO3- concentration (P 0.05); 3) there was a significant correlation between urine pH, blood pH and HCO3- concentration (P < 0.001), and between blood pH and blood HCO3- concentration (P <0. 001). These results suggest that urine pH can be used to evaluate the correlation between DCAD level and acid-base balance of body fluid of peripartum dairy cows.%本研究旨在分析饲粮阴阳离子差(dietary cation-anion difference,DCAD)与体液酸碱平衡之间的关联性.以3个DCAD水平对围产期奶牛体液酸碱平衡状态(尿液pH、血液pH及血液HCO3-)试验数据为基础,应用SAS统计软件分析.结果表明,DCAD与尿液pH、血液pH及血液HCO3-间存在极显著的相关性(P <0.001);DCAD与尿液pH、血液pH之间存在极显著的回归性(P <0.001),而与血液HCO3-间的回归性不显著(P>0.05);同时,尿液pH与血液pH及血液HCO3-,血液pH与血液HCO3-间存在极显著的相关性(P <0.001).由此可见,DCAD可影响奶牛体内酸碱平衡状态,尿液pH可用来评价DCAD水平调节围产期奶牛体液酸碱平衡状况的有效指标.

  8. Voltammetric Studies on Heteropoly Phosphotungstovanadate Anions Across the Liquid/Liquid Interface

    Institute of Scientific and Technical Information of China (English)

    LU Xiao-quan


    Electrochemical transfer behavior of VⅤW11-VⅤ3W9 heteropoly anions on the water/nitrobenzene interface was investigated by means of cyclic voltammetry. The effect of the solution acidity on the transfer behavior and the stable pH range for the heteropoly anions were studied. The stability of mixed tungstovanadate decreases with increasing the number of vanadium atoms. The main transfer species within the potential window have the negative charges of 4 and the transfer process is diffusion-controlled. The apparent transfer potential ΔwoΨ0 and the free energy ΔG0 w→otr for the heteropoly anions can be obtained from the experimental data. For the different anions, the ΔwoΨ1/2-pH relationship can be expressed as: ΔwoΨ1/2=constant-53pH.

  9. Effects of Hofmeister salt series on gluten network formation: Part II. Anion series. (United States)

    Tuhumury, H C D; Small, D M; Day, L


    Different anion salts from the Hofmeister series were used to investigate their effects on gluten network formation. The effects of these anion salts on the mixing properties of the dough and the rheological and chemical properties of gluten samples extracted from the dough with these respective salts were compared. The aim of this work was to determine how different anion salts influence the formation of the gluten structure during dough mixing. It was found that the Hofmeister anion salts affected the gluten network formation by interacting directly with specific amino acid residues that resulted in changes in gluten protein composition, specifically the percentage of the unextractable polymeric protein fractions (%UPP). These changes consequently led to remarkable differences in the mixing profiles and microstructural features of the dough, small deformation rheological properties of the gluten and a strain hardening behaviour of both dough and gluten samples.

  10. Inhibitory effects of cardols and related compounds on superoxide anion generation by xanthine oxidase. (United States)

    Masuoka, Noriyoshi; Nihei, Ken-ichi; Maeta, Ayami; Yamagiwa, Yoshiro; Kubo, Isao


    5-Pentadecatrienylresorcinol, isolated from cashew nuts and commonly known as cardol (C₁₅:₃), prevented the generation of superoxide radicals catalysed by xanthine oxidase without the inhibition of uric acid formation. The inhibition kinetics did not follow the Michelis-Menten equation, but instead followed the Hill equation. Cardol (C₁₀:₀) also inhibited superoxide anion generation, but resorcinol and cardol (C₅:₀) did not inhibit superoxide anion generation. The related compounds 3,5-dihydroxyphenyl alkanoates and alkyl 2,4-dihydroxybenzoates, had more than a C9 chain, cooperatively inhibited but alkyl 3,5-dihydroxybenzoates, regardless of their alkyl chain length, did not inhibit the superoxide anion generation. These results suggested that specific inhibitors for superoxide anion generation catalysed by xanthine oxidase consisted of an electron-rich resorcinol group and an alkyl chain having longer than C9 chain.

  11. Adsorption of Ce(Ⅳ) Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce(Ⅳ) Separation from Rare Earths(Ⅲ)

    Institute of Scientific and Technical Information of China (English)


    Ce(Ⅳ) nitrato complexes were adsorbed on two anion exchangers based on polyvinyl pyridine (PVP) and quaternized PVP incorporated into porous silica matrix. The effect of nitric acid concentration (0.5~6 mol·L-1) and temperature (278~318 K) on Ce(Ⅳ) sorption efficiency was investigated. Sorption increased with increasing nitric acid concentration, indicating that [Ce(NO3)6]2- complex is the main adsorbed Ce(Ⅳ) species. Oxidation of sorbents by adsorbed Ce(Ⅳ) species resulting in Ce(Ⅲ) release to the solution was observed. Pyridine based anion exchangers exhibited higher oxidation stability compared to the commercial strong base anion exchanger. Ce(Ⅳ) reduction was temperature dependent and obeyed pseudo-first-order reaction kinetics. Column separation of Ce(Ⅳ) from La(Ⅲ) and Y(Ⅲ) was carried out from 6 mol·L-1 nitric acid with PVP based anion exchanger. Reasonable Ce(Ⅳ) breakthrough capacity (0.7 mol·kg-1 PVP) was achieved. No remarkable decrease of capacity was observed within 3 consequent runs. In contrast, Ce(Ⅲ) leakage due to reduction decreased and breakthrough capacity slightly increased. This effect was more pronounced with increasing temperature. Regeneration with 0.1 mol·L-1 nitric acid was successful (recovery 100%±4%) and Ce solution of high purity (>99.97%) with respect to La and Y content was gained.

  12. NMR analysis of base-pair opening kinetics in DNA (United States)

    Szulik, Marta W.; Voehler, Markus; Stone, Michael P.


    Base pairing in nucleic acids plays a crucial role in their structure and function. Differences in the base pair opening and closing kinetics of individual double stranded DNA sequences or between chemically modified base pairs provide insight into the recognition of these base pairs by DNA processing enzymes. This unit describes how to quantify the kinetics for localized base pairs by observing changes in the imino proton signals by nuclear magnetic resonance spectroscopy. The determination of all relevant parameters using state of the art techniques and NMR instrumentation, including cryoprobes, is discussed. PMID:25501592

  13. 2,3-Diaminopyridinium sorbate–sorbic acid (1/1

    Directory of Open Access Journals (Sweden)

    Madhukar Hemamalini


    Full Text Available In the title molecular salt–adduct, C5H8N3+·C6H7O2−·C6H8O2, the 2,3-diaminopyridinium cation is essentially planar, with a maximum deviation of 0.013 (2 Å, and is protanated at its pyridine N atom. The sorbate anion and sorbic acid molecules exist in extended conformations. In the crystal, the protonated N atom and one of the two amino-group H atoms are hydrogen bonded to the sorbate anion through a pair of N—H...O hydrogen bonds, forming an R12(6 ring motif. The carboxyl groups of the sorbic acid molecules and the carboxylate groups of the sorbate anions are connected via O—H...O hydrogen bonds. Furthermore, the ion pairs and neutral molecules are connected via intermolecular N—H...O hydrogen bonds, forming sheets lying parallel to (100.

  14. Paired fuzzy sets

    DEFF Research Database (Denmark)

    Rodríguez, J. Tinguaro; Franco de los Ríos, Camilo; Gómez, Daniel


    In this paper we want to stress the relevance of paired fuzzy sets, as already proposed in previous works of the authors, as a family of fuzzy sets that offers a unifying view for different models based upon the opposition of two fuzzy sets, simply allowing the existence of different types...

  15. Minimal Pairs: Minimal Importance? (United States)

    Brown, Adam


    This article argues that minimal pairs do not merit as much attention as they receive in pronunciation instruction. There are other aspects of pronunciation that are of greater importance, and there are other ways of teaching vowel and consonant pronunciation. (13 references) (VWL)

  16. Simultaneous determination of 1-sulfo-cyclohexane carboxylic acid and sulfate anion in the by-products of caprolactam by high performance liquid chromatography-indirect photometric analysis%高效液相色谱-间接光度法同时检测己内酰胺副产物中1-磷酸环己烷羧酸及硫酸根离子

    Institute of Scientific and Technical Information of China (English)

    颜志祥; 段正康; 李立南; 李海涛; 陈秋云; 彭叶


    提出了一种能够同时检测具有紫外吸收(UV)的有机物和无紫外吸收的无机物含量的强阴离子交换色谱法(IEC).以检测己内酰胺副产物中的1-磺酸基环己烷羧酸(SCCA)粗盐为具体实例开展研究.强阴离子色谱柱以及UV检测器被用于同时分析SCCA和硫酸根离子.本实验基于高效液相色谱-间接光度检测法(HPLC-IPD)原理来测定SCCA和硫酸根离子,选用具有强紫外吸收能力的邻苯二甲酸作为本底试剂加入到流动相中产生信号.硫酸根离子和SCCA分别在0.10 ~ 10.0 g/L和0.50~40.0g/L范围内呈良好的线性关系,相关系数分别为0.999 14和0.999 97;加标回收率分别为98.50% ~ 101.00%和93.33% ~ 97.40%,定量限均为0.10 g/L,符合色谱检测要求.该方法具有良好的分离选择性,可用于SCCA和硫酸根离子的同时检测.%An improved anion-exchange chromatographic method was developed for simultaneous quantification of 1-sulfo-cyclohexane carboxylic acid (SCCA) and sulfate anion in the by-products of caprolactam. An strong anion chromatographic column and an ultraviolet (UV) detector were chosen for the assay of SCCA and sulfate anion. Non-chromophore-containing sulfate anion is not directly adaptable to the commonly used ultraviolet detection of high performance liquid chromatography (HPLC). This paper reports the development and validation of an HPLC assay for SCCA and sulfate anion based on indirect ultraviolet detection. An ultraviolet-absorbing reagent (the probe), phthalic acid (PA), was added to the mobile phase to induce a signal for the compound. The proposed method was qualified based on the performance criteria of repeatability, intermediate precision and linearity. The limits of detection were 1. 0 g/L for both the analytes. The linear ranges varied from 0. 50 to 40. 0 g/L for SCCA and from 0. 10 to 10.0 g/L for sulfate anion, with the correlation coefficients of 0.999 97 and 0. 999 14, and the recoveries of

  17. Excited cooper pairs

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Arrietea, M. G.; Solis, M. A.; De Llano, M. [Universidad Nacional Autonoma de Mexico, Mexico, D.F (Mexico)


    Excited cooper pairs formed in a many-fermion system are those with nonzero total center-of mass momentum (CMM). They are normally neglected in the standard Bardeen-Cooper-Schrieffer (BCS) theory of superconductivity for being too few compared with zero CMM pairs. However, a Bose-Einstein condensation picture requires both zero and nonzero CMM pairs. Assuming a BCS model interaction between fermions we determine the populations for all CMM values of Cooper pairs by actually calculating the number of nonzero-CMM pairs relative to that of zero-CMM ones in both 2D and 3D. Although this ratio decreases rapidly with CMM, the number of Cooper pairs for any specific CMM less than the maximum (or breakup of the pair) momentum turns out to be typically larger than about 95% of those with zero-CMM at zero temperature T. Even at T {approx}100 K this fraction en 2D is still as large as about 70% for typical quasi-2D cuprate superconductor parameters. [Spanish] Los pares de cooper excitados formados en un sistema de muchos electrones, son aquellos con momentos de centro de masa (CMM) diferente de cero. Normalmente estos no son tomados en cuenta en la teoria estandar de la superconductividad de Bardeen-Cooper-Schrieffer (BCS) al suponer que su numero es muy pequeno comparados con los pares de centro de masa igual a cero. Sin embargo, un esquema de condensacion Bose-Einstein requiere de ambos pares, con CMM cero y diferente de cero. Asumiendo una interaccion modelo BCS entre los fermiones, determinamos la poblacion de pares cooper con cada uno de todos los posibles valores del CMM calculando el numero de pares con momentos de centro de masa diferente de cero relativo a los pares de CMM igual a cero, en 2D y 3D. Aunque esta razon decrece rapidamente con el CMM, el numero de pares de cooper para cualquier CMM especifico menor que el momento maximo (o rompimiento de par) es tipicamente mas grande que el 95% de aquellos con CMM cero. Aun a T {approx}100 K esta fraccion en 2D es

  18. Multi-pair states in electron-positron pair creation (United States)

    Wöllert, Anton; Bauke, Heiko; Keitel, Christoph H.


    Ultra strong electromagnetic fields can lead to spontaneous creation of single or multiple electron-positron pairs. A quantum field theoretical treatment of the pair creation process combined with numerical methods provides a description of the fermionic quantum field state, from which all observables of the multiple electron-positron pairs can be inferred. This allows to study the complex multi-particle dynamics of electron-positron pair creation in-depth, including multi-pair statistics as well as momentum distributions and spin. To illustrate the potential benefit of this approach, it is applied to the intermediate regime of pair creation between nonperturbative Schwinger pair creation and perturbative multiphoton pair creation where the creation of multi-pair states becomes nonnegligible but cascades do not yet set in. Furthermore, it is demonstrated how spin and helicity of the created electrons and positrons are affected by the polarization of the counterpropagating laser fields, which induce the creation of electron-positron pairs.

  19. Peroxidase activation of cytoglobin by anionic phospholipids: Mechanisms and consequences. (United States)

    Tejero, Jesús; Kapralov, Alexandr A; Baumgartner, Matthew P; Sparacino-Watkins, Courtney E; Anthonymutu, Tamil S; Vlasova, Irina I; Camacho, Carlos J; Gladwin, Mark T; Bayir, Hülya; Kagan, Valerian E


    Cytoglobin (Cygb) is a hexa-coordinated hemoprotein with yet to be defined physiological functions. The iron coordination and spin state of the Cygb heme group are sensitive to oxidation of two cysteine residues (Cys38/Cys83) and/or the binding of free fatty acids. However, the roles of redox vs lipid regulators of Cygb's structural rearrangements in the context of the protein peroxidase competence are not known. Searching for physiologically relevant lipid regulators of Cygb, here we report that anionic phospholipids, particularly phosphatidylinositolphosphates, affect structural organization of the protein and modulate its iron state and peroxidase activity both conjointly and/or independently of cysteine oxidation. Thus, different anionic lipids can operate in cysteine-dependent and cysteine-independent ways as inducers of the peroxidase activity. We establish that Cygb's peroxidase activity can be utilized for the catalysis of peroxidation of anionic phospholipids (including phosphatidylinositolphosphates) yielding mono-oxygenated molecular species. Combined with the computational simulations we propose a bipartite lipid binding model that rationalizes the modes of interactions with phospholipids, the effects on structural re-arrangements and the peroxidase activity of the hemoprotein.

  20. Anion conductance selectivity mechanism of the CFTR chloride channel. (United States)

    Linsdell, Paul


    All ion channels are able to discriminate between substrate ions to some extent, a process that involves specific interactions between permeant anions and the so-called selectivity filter within the channel pore. In the cystic fibrosis transmembrane conductance regulator (CFTR) anion-selective channel, both anion relative permeability and anion relative conductance are dependent on anion free energy of hydration--anions that are relatively easily dehydrated tend to show both high permeability and low conductance. In the present work, patch clamp recording was used to investigate the relative conductance of different anions in CFTR, and the effect of mutations within the channel pore. In constitutively-active E1371Q-CFTR channels, the anion conductance sequence was Cl(-) > NO3(-) > Br(-) > formate > SCN(-) > I(-). A mutation that disrupts anion binding in the inner vestibule of the pore (K95Q) disrupted anion conductance selectivity, such that anions with different permeabilities showed almost indistinguishable conductances. Conversely, a mutation at the putative narrowest pore region that is known to disrupt anion permeability selectivity (F337A) had minimal effects on anion relative conductance. Ion competition experiments confirmed that relatively tight binding of permeant anions resulted in relatively low conductance. These results suggest that the relative affinity of ion binding in the inner vestibule of the pore controls the relative conductance of different permeant anions in CFTR, and that the pore has two physically distinct anion selectivity filters that act in series to control anion conductance selectivity and anion permeability selectivity respectively.

  1. Analysis of perfluoroalkyl acid precursors in paired maternal and cord serum in Beijing%北京母亲静脉血与脐带血中全氟化合物前体物质含量分析∗

    Institute of Scientific and Technical Information of China (English)

    杨琳; 李敬光; 石瑀; 王雨昕; 赵云峰; 吴永宁


    Perfluoroalkyl acids ( PFASs) precursors, as the indirect source of PFAS contamination, have been observed in environmental and human samples worldwide. In this study, 167 paired maternal and cord serum samples collected in Beijing city were analyzed for fifteen different PFAS precursors. 6∶2 fluorotelomer sulfonate (6∶2 FTS) and N⁃methyl perfluorooctanesulfonamidoacetates ( NMeFOSAA) had high detection frequencies in both maternal and cord sera ( 81% and 74%, maternal sera;90% and 67%, cord sera) , while the mean concentrations and detection frequencies of perfluorooctane sulfonamide ( FOSA ) and N⁃ethyl perfluorooctanesulfonamidoacetates ( NEtFOSAA) were lower in paired sera. The concentration ranges of 6∶2 FTS and NMeFOSAA in maternal sera were acid precursors in humans.%本文对北京市167对匹配母亲静脉血与脐带血中15种全氟化合物前体物质浓度水平与胎盘透过率进行了分析.研究结果表明,6∶2氟调聚磺酸(6∶2 FTS),N⁃甲基全氟辛基磺酰胺乙酸(NMeFOSAA)在母亲静脉血与脐带血中均以较高检出率检出(81%与74%,母亲静脉血;90%与67%,脐带血),浓度范围分别为<LOD (3.00)—203.00 pg·mL-1与<LOD (0.30)—46.79 pg·mL-1(母亲静脉血),<LOD (3.00)—252.12 pg·mL-1与<LOD (0.30)—16.00 pg·mL-1(脐带血);全氟辛基磺酰胺( FOSA ), N⁃乙基全氟辛基磺酰胺乙酸(NEt

  2. Anion photoelectron imaging spectroscopy of glyoxal (United States)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei


    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  3. Significance of anion exchange in pentachlorophenol sorption by variable-charge soils. (United States)

    Hyun, Seunghun; Lee, Linda S; Rao, P Suresh C


    Sorption data and subsequent predictive models for evaluating acidic pesticide behavior on variable-charge soils are needed to improve pesticide management and environmental stewardship. Previous work demonstrated that sorption of pentachlorophenol (PCP), a model organic acid, was adequately modeled by accounting for pH-and pKa-dependent chemical speciation and using two organic carbon-normalized sorption coefficients; one each for the neutral and anionic species. Such models do not account for organic anion interaction to positively charged surface sites, which can be significant for variable-charge minerals present in weathered soils typical of tropical and subtropical regions. The role of anion exchange in sorption of ionizable chemicals by variable-charge soils was assessed by measuring sorption of PCP by several variable-charge soils from aqueous solutions of CaCl2, CaSO4, Ca(H2PO4)2 as a function of pH. Differences in sorption from phosphate and chloride electrolyte solutions were attributed to pentachlorophenolate interactions with anion exchange sites. Suppression of PCP sorption by phosphate ranged from negligible in a soil with essentially no positively charge sites, as measured by negligible anion exchange capacity, to as much as 69% for variable-charge soils. Pentachlorophenolate exchange correlated well with the ratio of pH-dependent anion exchange capacity to net surface charge. Sorption reversibility of PCP by both CaCl2 and Ca(H2PO4)2 solutions was also demonstrated. Results for PCP clearly demonstrate that sorption to anion exchange sites in variable-charge soils should be considered in assessing pesticide mobility and that phosphate fertilizer application may increase the mobility of acidic pesticides.

  4. Two dialkylammonium salts of 2-amino-4-nitrobenzoic acid: crystal structures and Hirshfeld surface analysis

    Directory of Open Access Journals (Sweden)

    James L. Wardell


    Full Text Available The crystal structures of two ammonium salts of 2-amino-4-nitrobenzoic acid are described, namely dimethylazanium 2-amino-4-nitrobenzoate, C2H8N+·C7H5N2O4−, (I, and dibutylazanium 2-amino-4-nitrobenzoate, C8H20N+·C7H5N2O4−, (II. The asymmetric unit of (I comprises a single cation and a single anion. In the anion, small twists are noted for the carboxylate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13 and 3.71 (15°, respectively; the dihedral angle between the substituents is 7.9 (2°. The asymmetric unit of (II comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+-antiperiplanar] conformation, while one has a distinctive kink resulting in a (+-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxylate and nitro groups and the ring being 12.73 (6 and 4.30 (10°, respectively, for the first anion and 8.1 (4 and 12.6 (3°, respectively, for the second. The difference between anions in (I and (II is that in the anions of (II, the terminal groups are conrotatory, forming dihedral angles of 17.02 (8 and 19.0 (5°, respectively. In each independent anion of (I and (II, an intramolecular amino-N—H...O(carboxylate hydrogen bond is formed. In the crystal of (I, anions are linked into a jagged supramolecular chain by charge-assisted amine-N—H...O(carboxylate hydrogen bonds and these are connected into layers via charge-assisted ammonium-N—H...O(carboxylate hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N—O...π(arene and methyl-C—H...O(nitro interactions. In the crystal of (II, the anions are connected into four-ion aggregates by charge-assisted amino-N—H...O(carboxylate hydrogen bonding. The formation of ammonium-N—H...O(carboxylate hydrogen bonds, involving

  5. Transmembrane anion transport and cytotoxicity of synthetic tambjamine analogs. (United States)

    Hernando, Elsa; Soto-Cerrato, Vanessa; Cortés-Arroyo, Susana; Pérez-Tomás, Ricardo; Quesada, Roberto


    Ten synthetic analogs of the marine alkaloids tambjamines, bearing aromatic enamine moieties, have been synthesized. These compounds proved to be highly efficient transmembrane anion transporters in model liposomes. Changes in the electronic nature of the substituents of the aromatic enamine or the alkoxy group of the central pyrrole group did not affect this anionophore activity. The in vitro activity of these compounds has also been studied. They trigger apoptosis in several cancer cell lines with IC50 values in the low micromolar range as well as modify the intracellular pH, inducing the basification of acidic organelles.

  6. Molecular recognition of amino acids with some fluorescent ditopic pyrylium- and pyridinium-based crown ether receptors (United States)

    Moghimi, A.; Maddah, B.; Yari, A.; Shamsipur, M.; Boostani, M.; Fall Rastegar, M.; Ghaderi, A. R.


    The molecular recognition of L-amino acids such as asparagine, glutamine, lysine and arginine with some crownpyryliums, CP's, and a crownpyridinium compound, as receptors, were examined in methanol. 1H NMR spectroscopy was used to examine the structural stability of the receptors in the presence of the amino acids. The fluorimetric titration of the receptors by specified amino acids, other than arginine, was followed within a few minutes and the stoichiometry and stability of the resulting amino acid complexes were evaluated. The data analysis clearly demonstrated the critical role of the terminal amino group to carboxylic acid distance of amino acids for their proper fixation on the receptor molecules. Ion pairing for the two oppositely charged carboxylate anion and pyrylium (or pyridinium) cation, as well as the hydrogen bonding between crown ethers' oxygens and ammonium hydrogens are expected as the main interaction sources in the host-guest complexations.

  7. Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane (United States)

    Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie


    A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl‑/SO42‑ separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl‑/SO42‑ permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later.

  8. Stopped-Flow Spectrophotometric Study of the Kinetics and Mechanism of CO2 Uptake by cis-[Cr(C2O4(BaraNH2(OH22]+ Cation and the Acid-Catalyzed Decomposition of cis-[Cr(C2O4(BaraNH2OCO2]− Anion in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Lech Chmurzyński


    Full Text Available The kinetics of CO2 uptake by the cis-[Cr(C2O4(BaraNH2(OH22]+ complex cation and the acid hydrolysis of the cis-[Cr(C2O4(BaraNH2OCO2]− complex anion (where BaraNH2 denotes methyl 3-amino-2,3-dideoxy-b-D-arabino-hexopyranoside were studied using the stopped-flow technique. The reactions under study were investigated in aqueous solution in the 288–308 K temperature range. In the case of the reaction between CO2 and cis-[Cr(C2O4(BaraNH2(OH22]+ cation variable pH values (6.82–8.91 and the constant ionic strength of solution (H+, Na+, ClO4− = 1.0 were used. Carbon dioxide was generated by the reaction between sodium pyruvate and hydrogen peroxide. The acid hydrolysis of cis-[Cr(C2O4(BaraNH2OCO2]− was investigated for varying concentrations of H+ ions (0.01–2.7 M. The obtained results enabled the determination of the number of steps of the studied reactions. Based on the kinetic equations, rate constants were determined for each step. Finally, mechanisms for both reactions were proposed and discussed. Based on the obtained results it was concluded that the carboxylation (CO2 uptake reactions of cis-[Cr(C2O4(BaraNH2(OH22]+ and the decarboxylation (acid hydrolysis of the cis-[Cr(C2O4(BaraNH2OCO2]− are the opposite of each other.

  9. Junctionless Cooper pair transistor (United States)

    Arutyunov, K. Yu.; Lehtinen, J. S.


    Quantum phase slip (QPS) is the topological singularity of the complex order parameter of a quasi-one-dimensional superconductor: momentary zeroing of the modulus and simultaneous 'slip' of the phase by ±2π. The QPS event(s) are the dynamic equivalent of tunneling through a conventional Josephson junction containing static in space and time weak link(s). Here we demonstrate the operation of a superconducting single electron transistor (Cooper pair transistor) without any tunnel junctions. Instead a pair of thin superconducting titanium wires in QPS regime was used. The current-voltage characteristics demonstrate the clear Coulomb blockade with magnitude of the Coulomb gap modulated by the gate potential. The Coulomb blockade disappears above the critical temperature, and at low temperatures can be suppressed by strong magnetic field.

  10. Protected Flux Pairing Qubit (United States)

    Bell, Matthew; Zhang, Wenyuan; Ioffe, Lev; Gershenson, Michael


    We have studied the coherent flux tunneling in a qubit containing two submicron Josephson junctions shunted by a superinductor (a dissipationless inductor with an impedance much greater than the resistance quantum). The two low energy quantum states of this device, " open="|"> 0 and " open="|"> 1, are represented by even and odd number of fluxes in the loop, respectively. This device is dual to the charge pairing Josephson rhombi qubit. The spectrum of the device, studied by microwave spectroscopy, reflects the interference between coherent quantum phase slips in the two junctions (the Aharonov-Casher effect). The time domain measurements demonstrate the suppression of the qubit's energy relaxation in the protected regime, which illustrates the potential of this flux pairing device as a protected quantum circuit. Templeton Foundation, NSF, and ARO.

  11. CE-ESI-MS separation of divalent organic and inorganic anions using a tricationic complexing reagent. (United States)

    Gerardi, Anthony R; Lin, Xiuli; Breitbach, Zachary S; Armstrong, Daniel W; Colyer, Christa L


    A tricationic ion-pairing reagent, 1,3,5-1-butyl-3-methyl-1H-imidazol-3-ium-2,4,6-trimethylbenzene, was used to form complexes with doubly charged anions for their subsequent analysis by capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) in the positive-ion mode. This methodology offers the advantages of greater versatility and sensitivity relative to direct detection of the anions in negative-ion mode, and it can be realized by a number of possible complexation strategies, including pre-column, on-column, and post-column modes. Three model anions, sulfate [SO₄²⁻], thiosulfate [TSFA, S₂O₃²⁻], and benzenedisulfonate [BZDS, C₆H₄(SO₃)₂²⁻], were amenable to complexation with the tricationic reagent, yielding singly charged cations with greater mass-to-charge (m/z) ratios than the native analytes. By utilizing optimized parameters obtained through previous work with dicationic reagents and singly charged anions, including the CE separation buffer composition and pH, the concentration of the dicationic reagent, the mode of complexation, the nebulizing gas pressure, and the sheath liquid composition, it was possible to develop a robust CE-ESI-MS method appropriate for the analysis of divalent anions in a mixture.

  12. Anion conductance of the human red cell is carried by a maxi-anion channel

    DEFF Research Database (Denmark)

    Glogowska, Edyta; Dyrda, Agnieszka; Cueff, Anne


    Historically, the anion transport through the human red cell membrane has been perceived to be mediated by Band 3, in the two-component concept with the large electroneutral anion exchange accompanied by the conductance proper, which dominated the total membrane conductance. The status of anion...... that the diversity of anionic channel activities recorded in human erythrocytes corresponds to different kinetic modalities of a unique type of maxi-anion channel with multiple conductance levels and probably multiple gating properties and pharmacology, depending on conditions. It demonstrates the role of activator...... played by serum in the recruitment of multiple new conductance levels showing very complex kinetics and gating properties upon serum addition. These channels, which seem to be dormant under normal physiological conditions, are potentially activable and could confer a far higher anion conductance...

  13. Renal elimination of organic anions in cholestasis

    Institute of Scientific and Technical Information of China (English)

    Adriana Mónica Tortes


    The disposition of most drugs is highly dependent on specialized transporters.OAT1 and OAT3 are two organic anion transporters expressed in the basolateral membrane of renal proximal tubule cells,identified as contributors to xenobiotic and endogenous organic anion secretion.It is well known that cholestasis may cause renal damage.Impairment of kidney function produces modifications in the renal elimination of drugs.Recent studies have demonstrated that the renal abundance of OAT1 and OAT3 plays an important role in the renal elimination of organic anions in the presence of extrahepatic cholestasis.Time elapsed after obstructive cholestasis has an important impact on the regulation of both types of organic anion transporters.The renal expression of OAT1 and OAT3 should be taken into account in order to improve pharmacotherapeutic efficacy and to prevent drug toxicity during the onset of this hepatic disease.

  14. Tetrel bond of pseudohalide anions with XH3F (X = C, Si, Ge, and Sn) and its role in SN2 reaction (United States)

    Liu, Mingxiu; Li, Qingzhong; Cheng, Jianbo; Li, Wenzuo; Li, Hai-Bei


    The complexes of XH3F⋯ N3-/OCN-/SCN- (X = C, Si, Ge, and Sn) have been investigated at the MP2/aug-cc-pVTZ(PP) level. The σ-hole of X atom in XH3F acts as a Lewis acid forming a tetrel bond with pseudohalide anions. Interaction energies of these complexes vary from -8 to -50 kcal/mol, mainly depending on the nature of X and pseudohalide anions. Charge transfer from N/O/S lone pair to X-F and X-H σ* orbitals results in the stabilization of these complexes, and the former orbital interaction is responsible for the large elongation of X-F bond length and the remarkable red shift of its stretch vibration. The tetrel bond in the complexes of XH3F (X = Si, Ge, and Sn) exhibits a significant degree of covalency with XH3F distorted significantly in these complexes. A breakdown of the individual forces involved attributes the stability of the interaction to mainly electrostatic energy, with a relatively large contribution from polarization. The transition state structures that connect the two minima for CH3Br⋯ N3-complexhave been localized and characterized. The energetic, geometrical, and topological parameters of the complexes were analyzed in the different stages of the SN2 reaction N3- + CH3Br → Br- + CH3N3.

  15. Chromatographic separation of vanadium, tungsten and molybdenum with a liquid anion-exchanger. (United States)

    Fritz, J S; Topping, J J


    In acidic solution only molybdenum(VI), tungsten(VI), vanadium(V), niobium(V) and tantalum(V) form stable, anionic complexes with dilute hydrogen peroxide. This fact has been used in developing an analytical method of separating molybdenum(VI), tungsten(VI) and vanadium(V) from other metal ions and from each other. Preliminary investigations using reversed-phase paper chromatography and solvent extraction led to a reversed-phase column Chromatographic separation technique. These metal-peroxy anions are retained by a column containing a liquid anion-exchanger (General Mills Aliquat 336) in a solid support. Then molybdenum(VI), tungsten(VI) and vanadium(V) are selectively eluted with aqueous solutions containing dilute hydrogen peroxide and varying concentrations of sulphuric acid.

  16. Fluorescence-lifetime-based sensors for anions (United States)

    Teichmann, Maria; Draxler, Sonja; Kieslinger, Dietmar; Lippitsch, Max E.


    Sensing of anions has been investigated using the fluorescence decaytime as the information carrier. The sensing mechanism is based on the coextraction of an anion and a proton, and the presence of a fluorophore with a rather long fluorescence decaytime inside the membrane to act as a pH indicator. The relevant theory is discussed shortly. As an example a sensor for nitrate is shown, and the influence of ionic additives on the working function has been investigated.

  17. A new class of organocatalysts: sulfenate anions. (United States)

    Zhang, Mengnan; Jia, Tiezheng; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J


    Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst.

  18. Potentiometric response and mechanism of anionic recognition of heterocalixarene-based ion selective electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Shishkanova, T.V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)]. E-mail:; Sykora, D. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Sessler, J.L. [Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, University of Texas, Austin, TX 78712-0615 (United States); Kral, V. [Department of Analytical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)


    The ion selective electrode (ISE)-based potentiometric approach is shown to be an effective means of characterizing the anion recognition sites in the molecular receptor calix[2]pyridino[2]pyrrole (CPP). In particular, potentiometric pH-measurements involving the use of experimental PVC-membranes based on CPP revealed the existence of both mono- and diprotonated forms of the receptor under readily accessible conditions. Based on these analyses, apparent surface protonation constants for this heterocalixarene were found to lie between 8.5-8.9 (pK {sub B1}) and 3.3-3.8 (pK {sub B2}). CPP was found to interact with targeted anionic analytes based on both coulombic and hydrogen bond interactions, as inferred from varying the kinds of ionic sites present within the membrane phase. Potentiometric selectivity studies revealed that CPP preferred 'Y-shaped' anions (e.g. acetate, lactate, benzoate) over spherical anions (e.g. fluoride and chloride), fluoride over chloride within the set of spherical anions, and the ortho-isomer over the corresponding meta- and para-isomers in the case of hydroxybenzoate (salicylate and congeners). In the context of this study, the advantages of potentiometric determinations of acetylsalicylic acid using optimized PVC-membranes based on CPP relative to more conventional PVC-membrane ISEs based on traditional anion exchanger were also demonstrated.

  19. Complexation of Nitrous Oxide by Frustrated Lewis Pairs

    NARCIS (Netherlands)

    Otten, Edwin; Neu, Rebecca C.; Stephan, Douglas W.


    Frustrated Lewis pairs comprised of a basic yet sterically encumbered phosphine with boron Lewis acids bind nitrous oxide to give intact PNNOB linkages. The synthesis, structure, and bonding of these species are described.

  20. Distribution of 1-alkyl-3-methylimidazolium ions and their ion pairs between dichloromethane and water. (United States)

    Katsuta, Shoichi; Yamaguchi, Naoko; Ogawa, Ryuji; Kudo, Yoshihiro; Takeda, Yasuyuki


    The distribution behavior of the salts of a series of 1-alkyl-3-methylimidazolium cations (RMeIm(+); R = butyl, hexyl, and octyl) with tetrafluoroborate (BF(4)(-)), hexafluorophosphate (PF(6)(-)), bis(trifluoromethanesulfonyl)amide (NTf(2)(-)), and 2,4,6-trinitrophenolate (Pic(-)) anions has been investigated in a dichloromethane-water system at 25 degrees C. The distribution constants (K(D)) of the ion pairs and the transfer activity coefficients ((o)gamma(w)) of the single ions were determined. For the ion pairs with a given anion, the log K(D) value increases linearly with the number of methylene groups (N(CH2)) in the cation, which can be explained by using the regular solution theory. A similar relationship was observed between log (o)gamma(w) and N(CH2) for the free RMeIm(+) ions, and the result was discussed by decomposing the transfer activity coefficient into the Born-type electrostatic contribution and the non-electrostatic one. For the free anions and their ion pairs with a given cation, the (o)gamma(w) and K(D) values increase with increasing molar volume of the anion: i.e., BF(4)(-) ion-pair formation in water are also discussed by comparing the present results with those of tetraalkylammonium salts previously reported.

  1. Tunable separation of anions and cations by column switching in ion chromatography. (United States)

    Amin, Muhammad; Lim, Lee Wah; Takeuchi, Toyohide


    A convenient ion chromatography method has been proposed for the routine and simple determination of anions (Cl(-), SO(4)(2-) and NO(3)(-)) and/or cations (Na(+), NH(4)(+), K(+), Mg(2+) and Ca(2+)) using a single pump, a single eluent and a single detector. The present system used cation-exchange and anion-exchange columns connected in series via two 6-port switching valves or a single 10-port valve. The connection order of the ion-exchange columns could be varied by switching the valve(s). The present system therefore allowed the separation of either cations or anions in a single chromatographic run. While one ion-exchange column is being operated, the other ion-exchange column is being conditioned, i.e., the columns are always ready for analysis at any time. When 2.4mM 5-sulfosalicylic acid was used as the eluent, the three anions and the five cations could be separated on the anion-exchange column and cation-exchange column, respectively. In order to obtain the separations of the target ions, the injection valve was placed between the two columns. Complete separations of the above anions or cations were demonstrated within 10min each. The detection limits at S/N=3 were 19-50ppb (mug/l) for cations and 10-14ppb for anions. The relative standard deviations of the analyte ions were less than 1.1, 2.9 and 2.8% for retention time, peak area and peak height, respectively. This proposed technique was applied to the determination of common anions and cations in river water samples.

  2. Natural versus artificial creation of base pairs in DNA: origin of nucleobases from the perspectives of unnatural base pair studies. (United States)

    Hirao, Ichiro; Kimoto, Michiko; Yamashige, Rie


    Since life began on Earth, the four types of bases (A, G, C, and T(U)) that form two sets of base pairs have remained unchanged as the components of nucleic acids that replicate and transfer genetic information. Throughout evolution, except for the U to T modification, the four base structures have not changed. This constancy within the genetic code raises the question of how these complicated nucleotides were generated from the molecules in a primordial soup on the early Earth. At some prebiotic stage, the complementarity of base pairs might have accelerated the generation and accumulation of nucleotides or oligonucleotides. We have no clues whether one pair of nucleobases initially appeared on the early Earth during this process or a set of two base pairs appeared simultaneously. Recently, researchers have developed new artificial pairs of nucleobases (unnatural base pairs) that function alongside the natural base pairs. Some unnatural base pairs in duplex DNA can be efficiently and faithfully amplified in a polymerase chain reaction (PCR) using thermostable DNA polymerases. The addition of unnatural base pair systems could expand the genetic alphabet of DNA, thus providing a new mechanism for the generation novel biopolymers by the site-specific incorporation of functional components into nucleic acids and proteins. Furthermore, the process of unnatural base pair development might provide clues to the origin of the natural base pairs in a primordial soup on the early Earth. In this Account, we describe the development of three representative types of unnatural base pairs that function as a third pair of nucleobases in PCR and reconsider the origin of the natural nucleic acids. As researchers developing unnatural base pairs, they use repeated "proof of concept" experiments. As researchers design new base pairs, they improve the structures that function in PCR and eliminate those that do not. We expect that this process is similar to the one functioning in the

  3. Structural and Electronic Properties of Amino Acid Based Ionic Liquids: A Theoretical Study (United States)

    Wu, Yang; Zhang, Tiantian


    The gas-phase ion pairs of the ionic liquids containing 1-ethyl-3-methylimidazolium ([emim]+) and 20 natural amino acids ([AA]-) are studied at the B3LYP/6-311+G (d,p) level. The optimized structures, energies, and natural population analysis are presented and analyzed in terms of their possible correlation with the interaction energies and the H-bond separations. It is found that all the ion pairs of [emim][AA] can form strong H-bond interactions, which are dominated by the side-chain structure and the functional group of amino acid anions. The calculations indicate that an increase of the alkyl side-chain length coincides with a gradual decrease of H-bond energy, while the functional groups lead to the different localized charges on the anions, consequently affecting the electrostatic force. In addition, the intramolecular H bond in [AA]- can weaken the interaction, due to the decrease of the proton-accepting ability of the carbonyl O atoms. The H-bond chemical nature of [emim][AA] is investigated by atoms in molecules and natural bond orbital analyses. The preliminary analysis of 20 kinds of [emim][AA] ion pairs provides some initial hints as to the relationship between the interaction energy and the experimental glass transition temperature.

  4. Neutral pyrimidine C-H donor as anion receptor

    Institute of Scientific and Technical Information of China (English)

    袁迎雪; 吴娜娜; 韩逸飞; 宋相志; 王洪波


    Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and 1H NMR titration experiments. DFT calculations provided some information for anion recognition. It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl−.

  5. 饱和脂肪酸对泌乳中期热应激奶牛血液CO2、离子浓度和离子平衡的影响%Effect of supplemental saturated fatty acids on blood CO2, ions concentration and cation-anion balance of mid-lactating dairy cows during heat stress

    Institute of Scientific and Technical Information of China (English)

    王建平; 王加启; 卜登攀


    The objective of this study was to investigate the effect of supplemental saturated fatty acids on blood CO2,ions concentration and cation-anion balance of mid-lactating dairy cows under heat stress.Forty eight Chinese Holstein cows (150-210 days) were divided into three groups according to random block design with milk yield,DIM (days in milking) and parity.The animals were fed with diets contained 0,1.5% and 3.0% saturated fatty acid for group 1(control),group 2(SFA1.5) and group 3(SFA3.0),respectively.The minimum THI (temperature-humidity index) was normally more than 72 during experimental period.Blood CO2 concentration was 20.92,21.82 and 21.31 mmol/L in cows fed with control,SFA1.5 and SFA3 diet,respectively.The blood CO2 concentration was higher in SFA1.5 cows than control (P<0.05).There were no effects of treatment on ions concentration and cation-anion.The milk yield,milk fat content and total solid were improved by supplemental saturated fatty acid (P<0.05).In summary,supplemental saturated fatty acids improved milk yield and milk components and lessened blood CO2 concentration decrease in mid-lactation heat-stressed dairy cows.%选择产后150~210 d的中国荷斯坦奶牛48头,根据产奶量、分娩时间和胎次分为对照组(SFA0)、1.5%(SFA1.5)和3.0% (SFA3)饱和脂肪酸试验组,来研究饱和脂肪酸对高温环境条件下泌乳中期奶牛血液CO2、离子浓度和离子平衡的影响,旨在为合理利用饱和脂肪酸及其缓解奶牛热应激提供理论依据.结果表明,日粮添加饱和脂肪酸,奶牛血清中CO2的平均含量对照组、1.5%饱和脂肪酸组和3%饱和脂肪酸组分别为20.92,21.82和21.31 mmol/L,1.5%饱和脂肪酸组显著高于对照组(P<0.05),日粮添加饱和脂肪酸对热应激奶牛血液K、Na、Cl、Ca离子和离子平衡无显著影响,日粮添加饱和脂肪酸显著提高产奶量、乳脂和干物质含量(P<0.05).说明饱和脂肪酸具有改善热应激奶牛

  6. Multispecies pair annihilation reactions. (United States)

    Deloubrière, Olivier; Hilhorst, Henk J; Täuber, Uwe C


    We consider diffusion-limited reactions A(i)+A(j)--> (12 and d> or =2, we argue that the asymptotic density decay for such mutual annihilation processes with equal rates and initial densities is the same as for single-species pair annihilation A+A-->. In d=1, however, particle segregation occurs for all q< infinity. The total density decays according to a q dependent power law, rho(t) approximately t(-alpha(q)). Within a simplified version of the model alpha(q)=(q-1)/2q can be determined exactly. Our findings are supported through Monte Carlo simulations.

  7. Au pairs on Facebook

    DEFF Research Database (Denmark)

    Dalgas, Karina Märcher


    Ethnographers are increasingly making use of Facebook to acquire access and general acquaintance with their field of study. However, little has been written on how Facebook is used methodologically in research that does not have social media sites as the main focus of interest. This article argues...... that engagement with Facebook as a methodological tool can be useful in research among migrants in highly politicised fields. Pointing to a discursive construction of Filipina au pairs as victims of labour exploitation, the article shows how fieldwork on Facebook enables the exploration of the ways in which...... and on Facebook....

  8. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors. (United States)

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C


    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported.

  9. Frustrated Lewis Pair Behavior of Intermolecular Annine/B(C6F5)(3) Pairs

    NARCIS (Netherlands)

    Voss, Tanja; Mahdi, Tayseer; Otten, Edwin; Froehlich, Roland; Kehr, Gerald; Stephan, Douglas W.; Erker, Gerhard


    Reactions of N,N-dimethylaniline, N-isopropyl-aniline, 1,4-C6H4(CH(2)NHtBu)(2), and benzyldimethylamine with the Lewis acid B(C6F5)(3) have been studied. In the case of N,N-dirnethylaniline the combination of the Lewis acid and base forms an almost completely noninteracting frustrated Lewis pair, wh


    Zeolites are well known for their use in ion exchange and acid catalysis reactions. The use of zeolites in anion or ligand exchange reactions is less studied. The NH4+ form of zeolite Y (NY6, Faujasite) has been tested in this work to evaluate its performance for arsenic removal...

  11. A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

    NARCIS (Netherlands)

    Eker, Bilge; Yilmaz, Mahmut Deniz; Schlautmann, Stefan; Gardeniers, Johannes G.E.; Huskens, Jurriaan


    A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detecti

  12. Interactions between organic anions on multiple transporters in Caco-2 cells

    DEFF Research Database (Denmark)

    Grandvuinet, Anne Sophie; Steffansen, Bente


    -dependent bile acid transporter and the organic solute transporter α/β, and to less extent by the organic anion transporting polypeptide 2B1. However, interactions on efflux transporters were not detected, although they were expected from the literature on the investigated compounds. Biosimulation methods may...

  13. Studies of anions sorption on natural zeolites. (United States)

    Barczyk, K; Mozgawa, W; Król, M


    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  14. Searching for Pair Halos (United States)

    Fallon, Lisa; Abramowski, A.; Acero, F.; Aharonian, F.; Akhperjanian, A. G.; Anton, G.; Barres de Almeida, U.; Bazer-Bachi, A. R.; Becherini, Y.; Behera, B.; Bernlühr, K.; Bochow, A.; Boisson, C.; Bolmont, J.; Borrel, V.; Brucker, J.; Brun, F.; Brun, P.; Bühler, R.; Bulik, T.; Büsching, I.; Boutelier, T.; Chadwick, P. M.; Charbonnier, A.; Chaves, R. C. G.; Cheesebrough, A.; Conrad, J.; Chounet, L.-M.; Clapson, A. C.; Coignet, G.; Dalton, M.; Daniel, M. K.; Davids, I. D.; Degrange, B.; Deil, C.; Dickinson, H. J.; Domainko, A. Djannati-Ataü W.; Drury, L. O'c.; Dubois, F.; Dubus, G.; Dyks, J.; Dyrda, M.; Egberts, K.; Eger, P.; Espigat, P.; Fallon, L.; Farnier, C.; Fegan, S.; Feinstein, F.; Fernandes, M. V.; Fiasson, A.; Fürster, A.; Fontaine, G.; Füssling, M.; Gabici, S.; Gallant, Y. A.; Gérard, L.; Gerbig, D.; Giebels, B.; Glicenstein, J. F.; Glück, B.; Goret, P.; Güring, D.; Hampf, D.; Hauser, M.; Heinz, S.; Heinzelmann, G.; Henri, G.; Hermann, G.; Hinton, J. A.; Hoffmann, A.; Hofmann, W.; Hofverberg, P.; Holleran, M.; Hoppe, S.; Horns, D.; Jacholkowska, A.; de Jager, O. C.; Jahn, C.; Jung, I.; Katarzynski, K.; Katz, U.; Kaufmann, S.; Kerschhaggl, M.; Khangulyan, D.; Khálifi, B.; Keogh, D.; Klochkov, D.; Kluzniak, W.; Kneiske, T.; Komin, Nu.; Kosack, K.; Kossakowski, R.; Lamanna, G.; Lenain, J.-P.; Lohse, T.; Lu, C.-C.; Marandon, V.; Marcowith, A.; Masbou, J.; Mau-Rin, D.; McComb, T. J. L.; Medina, M. C.; Méhault, J.; Moderski, R.; Moulin, E.; Naumann-Godo, M.; de Naurois, M.; Nedbal, D.; Nekrassov, D.; Nguyen, N.; Nicholas, B.; Niemiec, J.; Nolan, S. J.; Ohm, S.; Olive, J.-F.; de Ona Wilhelmi, E.; Opitz, B.; Orford, K. J.; Ostrowski, M.; Panter, M.; Paz Arribas, M.; Pedaletti, G.; Pelletier, G.; Petrucci, P.-O.; Pita, S.; Pühlhofer, G.; Punch, M.; Quirrenbach, A.; Raubenheimer, B. C.; Raue, M.; Rayner, S. M.; Reimer, O.; Renaud, M.; de Los Reyes, R.; Rieger, F.; Ripken, J.; Rob, L.; Rosier-Lees, S.; Rowell, G.; Rudak, B.; Rulten, C. B.; Ruppel, J.; Ryde, F.; Sahakian, V.; Santangelo, A.; Schlickeiser, R.; Schück, F. M.; Schünwald, A.; Schwanke, U.; Schwarzburg, S.; Schwemmer, S.; Shalchi, A.; Sushch, I.; Sikora, M.; Skilton, J. L.; Sol, H.; Stawarz, L.; Steenkamp, R.; Stegmann, C.; Stinzing, F.; Szostek, A.; Tam, P. H.; Tavernet, J.-P.; Terrier, R.; Tibolla, O.; Tluczykont, M.; Valerius, K.; van Eldik, C.; Vasileiadis, G.; Venter, C.; Venter, L.; Vialle, J. P.; Viana, A.; Vincent, P.; Vivier, M.; Vülk, H. J.; Volpe, F.; Vorobiov, S.; Wagner, S. J.; Ward, M.; Zdziarski, A. A.; Zech, A.; Zechlin, H.-S.

    We have conducted a search for the giant Pair Halo structures which are inevitably formed around TeV sources due to interactions of very high energy gamma-rays with the Extragalactic Background Light (EBL). The resulting electron/positron pairs are Compton upscattered on photons of the 2.7 K Cosmic Microwave Background Radiation to produce a second generation of gamma-rays which again interact with the EBL; thus an electromagnetic cascade develops. If the magnetic fields on Mpc scales surrounding the central source are sufficiently strong (10-11 G or more), electrons are effectively isotropised before interacting with radiation fields. In this case an extended halo is produced around the source. Using H.E.S.S. observations of Active Galactic Nuclei, including data from PKS 2155-304, 1ES 1101-232 and 1ES 0229+200, we have completed a detailed analysis of these sources. I will present and discuss the astrophysical implications of these results.

  15. Laser photolysis of interaction of poly-guanylic acid (5′) with anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    马建华; 林维真; 王文峰; 韩镇辉; 姚思德; 林念芸


    The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly- guanylic acid (5′) in CH3CN-H2O (97:3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.

  16. Laser photolysis of interaction of poly-guanylic acid (5’) with anthraquinone-2-sulfonate

    Institute of Scientific and Technical Information of China (English)

    马建华; 韩镇辉; 林维真; 姚思德; 王文峰; 林念芸


    The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5’) in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.

  17. Anion-Functionalized Task-Specific Ionic Liquids: Molecular Origin of Change in Viscosity upon CO2 Capture. (United States)

    Li, Ailin; Tian, Ziqi; Yan, Tianying; Jiang, De-en; Dai, Sheng


    The structure and dynamics of a task-specific ionic liquid (TSIL), trihexyl(tetradecyl)phosphonium imidazolate, before and after absorbing CO(2) were studied with a molecular dynamics (MD) simulation. This particular ionic liquid is one of several newly discovered azole-based TSILs for equimolar CO(2) capture. Unlike other TSILs whose viscosity increases drastically upon reaction with CO(2), its viscosity decreases after CO(2) absorption. This unique behavior was confirmed in our MD simulation. We find that after CO(2) absorption the translational dynamics of the whole system is accelerated, accompanied by an accelerated rotational dynamics of the cations. Radial distribution function and spatial distribution function analyses show that the anions become asymmetric after reaction with CO(2), and this causes the imbalance of the interaction between the positive and negative regions of the ions. The interaction between the phosphorus atom of the cation and oxygen atoms of the carboxyl group on the anion is enhanced, while that between the phosphorus atom and the naked nitrogen atom of the anion is weakened. The ion-pair correlation functions further support that the weakened interaction leads to faster dissociation of cation-anion pairs, thereby causing an accelerated dynamics. Hence, the asymmetry of anions influences the dynamics of the system and affects the viscosity. This insight may help design better TSILs with decreased viscosity for CO(2) capture.

  18. Application of Acupoints in Pairs

    Institute of Scientific and Technical Information of China (English)



    @@ Application of acupoints in pairs is a kind of point association in which only a pair of compatible points is used. Based on the principle of compatibility, the author of this article often uses the "pair-point needling" to treat some common diseases, and have obtained very good therapeutic results. Some examples are introduced below.

  19. Diffractive charged meson pair production

    CERN Document Server

    Lehmann-Dronke, B; Schäfer, S; Stein, E; Schäfer, A


    We investigate the possibility to measure the nonforward gluon distribution function by means of diffractively produced charged pion and kaon pairs in polarized lepton nucleon scattering. The resulting cross sections are sizable and are dominated by the gluonic contribution. We find large spin asymmetries, both for pion pairs and for kaon pairs.

  20. Improved and selective platinum recovery from spent alpha-alumina supported catalysts using pretreated anionic ion exchange resin. (United States)

    Shams, K; Goodarzi, F


    Improved and selective recovery of platinum from a spent dehydrogenation platinum alpha-alumina supported catalyst using a strong basic ion exchange resin is reported. Platinum and other precious metal group (PMG) complexes are leached using concentrated hydrochloric acid along with about 0.20 vol.% nitric acid as an oxidizing agent from de-coked and crushed spent catalyst. Effects of hydrochloric acid concentration, time, and temperature in leaching stage are investigated. The strong basic anionic resin is treated by sodium hydroxide solution to replace chloride anion by hydroxyl group ion. The supernatant of the leaching process is passed through a fixed column of hydroxylated strong base anionic resin. The treated resin on which the platinum complex is adsorbed is dried and burned in an oxidizing atmosphere at 750-800 degrees C. The recovered gray metallic powder is mainly platinum. Results compared with those obtained from untreated anionic resin show that adsorption of platinum complexes onto the treated anionic resin is more selective and the yield of separation is considerably improved. The breakthrough curves of the pretreated anion exchanger and that of untreated exchange resin reveals that the capacity of the hyroxilated resin is decreased by about 14%. These breakthrough curves can be used for calculation of height of a practical exchange plate (HPEP) for design purposes.

  1. Inhibitory effects of chitosan on superoxide anion radicals and lipid free radicals

    Institute of Scientific and Technical Information of China (English)


    With the electron spin resonance (ESR) technique, the inhibitory effects of chitosan on superoxide anion radicals and linoleic acid lipid radicals were found. The inhibitory ratio E for these two kinds of radicals is in proportion to the concentration of chitosan. It was also observed that E for linoleic acid lipid radicals increased with the increase of the degree of deacetylation and decreased with the increase of the molecular weight of chitosan.

  2. Cotorsion Pair Extensions

    Institute of Scientific and Technical Information of China (English)

    De Xu ZHOU


    Assume that S is an almost excellent extension of R. Using functors Hom R(S,-) and -(×)R S, we establish some connections between classes of modules (L)R and (L)S, cotorsion pairs ((A)R, (A)R)and ((A)S, (B)S). If (L)S is a T-extension or (and) H-extension of (L)R, we show that (L)S is a (resp., monomorphic, epimorphic, special) preenveloping class if and only if so is (L)R. If (S, S) is a TH-extension of ((A)R,(B)R), we obtain that ((A)S,(B)S) is complete (resp., of finite type, of cofinite type, hereditary, perfect, n-tilting) if and only if so is ((A)R,(B)R).

  3. Vibrational spectroscopy of microhydrated conjugate base anions. (United States)

    Asmis, Knut R; Neumark, Daniel M


    Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aerosols, which are a central component of atmospheric and oceanic chemical cycles. In this Account, as a means of studying conjugate-base anions in water, we describe infrared multiple-photon dissociation spectroscopy on clusters in which the sulfate, nitrate, bicarbonate, and suberate anions are hydrated by a known number of water molecules. This spectral technique, used over the range of 550-1800 cm(-1), serves as a structural probe of these clusters. The experiments follow how the solvent network around the conjugate-base anion evolves, one water molecule at a time. We make structural assignments by comparing the experimental infrared spectra to those obtained from electronic structure calculations. Our results show how changes in anion structure, symmetry, and charge state have a profound effect on the structure of the solvent network. Conversely, they indicate how hydration can markedly affect the structure of the anion core in a microhydrated cluster. Some key results include the following. The first few water molecules bind to the anion terminal oxo groups in a bridging fashion, forming two anion-water hydrogen bonds. Each oxo group can form up to three hydrogen bonds; one structural result, for example, is the highly symmetric, fully coordinated SO(4)(2-)(H(2)O)(6) cluster, which only contains bridging water molecules. Adding more water molecules results in the formation of a solvent network comprising water-water hydrogen bonding in addition to hydrogen bonding to the anion. For the nitrate, bicarbonate, and suberate anions, fewer bridging sites are available, namely, three, two, and one (per carboxylate group), respectively. As a result, an earlier onset of water

  4. Multi-pair states in electron–positron pair creation

    Directory of Open Access Journals (Sweden)

    Anton Wöllert


    Full Text Available Ultra strong electromagnetic fields can lead to spontaneous creation of single or multiple electron–positron pairs. A quantum field theoretical treatment of the pair creation process combined with numerical methods provides a description of the fermionic quantum field state, from which all observables of the multiple electron–positron pairs can be inferred. This allows to study the complex multi-particle dynamics of electron–positron pair creation in-depth, including multi-pair statistics as well as momentum distributions and spin. To illustrate the potential benefit of this approach, it is applied to the intermediate regime of pair creation between nonperturbative Schwinger pair creation and perturbative multiphoton pair creation where the creation of multi-pair states becomes nonnegligible but cascades do not yet set in. Furthermore, it is demonstrated how spin and helicity of the created electrons and positrons are affected by the polarization of the counterpropagating laser fields, which induce the creation of electron–positron pairs.

  5. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  6. Templating irreversible covalent macrocyclization by using anions. (United States)

    Kataev, Evgeny A; Kolesnikov, Grigory V; Arnold, Rene; Lavrov, Herman V; Khrustalev, Victor N


    Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields.

  7. An ion-exchange nanomembrane sensor for detection of nucleic acids using a surface charge inversion phenomenon. (United States)

    Senapati, Satyajyoti; Slouka, Zdenek; Shah, Sunny S; Behura, Susanta K; Shi, Zonggao; Stack, M Sharon; Severson, David W; Chang, Hsueh-Chia


    We present a novel low-cost biosensor for rapid, sensitive and selective detection of nucleic acids based on an ionic diode feature of an anion exchange nanoporous membrane under DC bias. The ionic diode feature is associated with external surface charge inversion on the positively charged anion exchange nanomembrane upon hybridization of negatively charged nucleic acid molecules to single-stranded oligoprobes functionalized on the membrane surface resulting in the formation of a cation selective monolayer. The resulting bipolar membrane causes a transition from electroconvection-controlled to water-splitting controlled ion conductance, with a large ion current signature that can be used to accurately quantify the hybridized nucleic acids. The platform is capable of distinguishing two base-pair mismatches in a 22-base pairing segment of microRNAs associated with oral cancer, as well as serotype-specific detection of dengue virus. We also show the sensor' capability to selectively capture target nucleic acids from a heterogeneous mixture. The limit of detection is 1 pM for short 27 base target molecules in a 15-min assay. Similar hybridization results are shown for short DNA molecules as well as RNAs from Brucella and Escherichia coli. The versatility and simplicity of this low-cost biosensor should enable point-of-care diagnostics in food, medical and environmental safety markets.

  8. Amphiphilic organic ion pairs in solution: a theoretical study. (United States)

    Pradines, Vincent; Poteau, Romuald; Pimienta, Veronique


    The macroscopic manifestation of hydrophobic interactions for amphiphilic organic ion pairs (tetraalkylammonium-anion) has been shown experimentally by measuring their association constants and their affinity with the organic phase. Beyond a certain size, there is a direct relation between association constants and chain lengths in tetraalkylammonium ions. We propose to cast a bridge between these results and geometrical properties considered at the level of a single ion pair by means of quantum chemistry calculations performed on model systems: trimethylalkylammonium-pentyl sulfate instead of tetraalkylammonium-dodecyl sulfate. Two limiting cases are considered: head-to-head configurations, which yield an optimal electrostatic interaction between polar heads, and parallel configurations with a balance between electrostatic and hydrophobic interactions. All properties (geometries, complexation energies, and atomic charges) were obtained at the MP2 level of calculation, with water described by a continuum model (CPCM). Dispersion forces link hydrocarbon chains of tetraalkylammonium ions and pentyl sulfate, thus yielding (for the largest ion pairs) parallel configurations favored with respect to head-to-head geometries by solute-solvent electrostatic interactions. Given the small experimental association energies, we probe the accuracy limit of the MP2 and CPCM methods. However, clear trends are obtained as a function of chain length, which agree with the experimental observations. The calculated monotonic stabilization of ion pairs when the hydrocarbon chain increases in length is discussed in terms of electrostatic interactions (between ions and between ion pairs and water), dispersion forces, and cavitation energies.

  9. (S-Alanine–(S-2-phenoxypropionic acid (1/1

    Directory of Open Access Journals (Sweden)

    Kiichi Amimoto


    Full Text Available In the title co-crystal, C3H7NO2·C9H10O3, the (S-alanine molecule exists in the zwitterionic form stabilized by two pairs of N+—H...O− hydrogen bonds and an electrostatic interaction between the ammonium center and the carboxylate anion, forming a sheet along the ab plane. The carboxyl group of the (S-2-phenoxypropionic acid molecule is connected to the top and bottom of the sheet via N+—H...O=C and O—H...O− [R22(7 graph set] hydrogen bonds, giving an (S,S-homochiral layer, in which both methyl groups of (S-alanine and the phenyl rings of (S-2-phenoxypropionic acid are oriented in the same direction along the b axis.

  10. Investigation of hybrid molecular material prepared by ionic liquid and polyoxometalate anion

    Indian Academy of Sciences (India)

    T Rajkumar; G Ranga Rao


    A solid hybrid molecular material containing 1-butyl 3-methyl imidazolium cations and Keggin anions of phosphotungstic acid has been synthesized. It is fully characterized by CHN analysis, FTIR, XRD, UV-Vis-NIR DRS, 31P MAS NMR, TGA and SEM. The FTIR spectrum of the compound shows the fingerprint vibrational bands of both Keggin molecular anions and imidazolium cations. The aromatic C-H stretch region (2700-3250 cm-1) of imidazolium cation is split due to the interaction between the ring C-H and bulky Keggin anion. The red-shift in the UV-Vis spectra and the downfield 31P MAS NMR chemical shift also confirm the electrostatic interaction between the ions in the compound. Near IR spectral region (1000-2500 nm) shows the elimination of water in the compound which is hydrophobic.

  11. Binding of a coordinatively unsaturated mercury(II) thiolate compound by carboxylate anions. (United States)

    Tang, Xiao-Yan; Zheng, Ai-Xia; Shang, Hai; Yuan, Rong-Xin; Li, Hong-Xi; Ren, Zhi-Gang; Lang, Jian-Ping


    Reactions of [Hg(Tab)2](PF6)2 (TabH = 4-(trimethylammonio)benzenethiol) (1) with acetic acid (HAc), propanoic acid (HPro), salicylic acid (HSal), benzoic acid (HBez), malonic acid (H2Mal), oxalic acid (H2Oxa), adipic acid (H2Adi), or methylimindiacetic acid (H2Meida) in the presence of Et3N gave rise to a family of mercury(II)-thiolate-carboxylate compounds, [Hg(Tab)2(Ac)](PF6) · 0.5H2O (2 · 0.5H2O), [Hg(Tab)2(Pro)](PF6) (3), [Hg(Tab)2(Sal)](PF6) · MeOH (4 · MeOH), [Hg(Tab)2(Sal)](Sal) · MeOH (5 · MeOH), [Hg(Tab)2(Bez)](PF6) · H2O (6 · H2O), [Hg(Tab)2(HMal)](Mal)0.5 H2O (7 · H2O), [{Hg(Tab)2}2(μ-Oxa)](PF6)2 H2O (8·2H2O), [{Hg(Tab)2}2(μ-Adi)](PF6)2 (9), [Hg(μ-Tab)(μ-Adi)]2n (10), and [Hg(Tab)2(Meida)] · 2.5H2O (11 · 2.5H2O). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. Each mercury(II) atom in [Hg(Tab)2](2+) dication of 2-7 is further coordinated by two oxygen atoms from one Ac(-), Pro(-), Sal(-), Bez(-), Mal(2-) or HMal(-) anion, forming a unique seesaw-shaped coordination geometry. In 8 or 9, two [Hg(Tab)2](2+) dications are connected by one bridging oxalate or adipate dianion to generate a dimeric structure with each mercury(II) center adopting a seesaw-shaped geometry. In 10, a pair of octahedrally coordinated mercury(II) atoms are bridged by two sulfur atoms of two Tab ligands to form a [Hg(μ-Tab)2Hg](4+) fragment, which is further connected to its equivalent ones via four adipate dianions, thereby forming a rare two-dimensional network. In 11, the mercury(II) atom in the [Hg(Tab)2](2+) dication is coordinated by one nitrogen and two oxygen atoms from one Meida(2-) dianion to have a rare square pyramidal geometry. The formation of 2-11 from 1 may be applicable to mimicking the interactions of the mercury(II) sites of Hg-MerR and Hg-MT with various amino acids encountered in nature.

  12. Modeling the environmental fate of perfluorooctanoic acid and perfluorooctanoate: An investigation of the role of individual species partitioning. (United States)

    Webster, Eva; Ellis, David A; Reid, Liisa K


    A multimedia multi-species environmental fate model was developed for the conjugate pair perfluorooctanoic acid (PFOA):perfluorooctanoate (PFO). The model allows assessment of the relative contribution of each individual species, in equilibrium with each other, to the overall environmental movement of the pair. The Lake Ontario (Canada/USA) watershed system was selected for this investigation and is simulated in a single-region, seven-compartment model, including a water surface microlayer, and aqueous aerosol generation and redeposition. Results indicate that in the equilibrated presence of both PFOA and PFO, the environmental fate of the pair can be accomplished by consideration of the physical properties of the neutral acid, which govern the intermedia distribution of the pair, coupled with processes of media advection, such as air or water flow. The role of the anion, while the most populous species in the aqueous phase, appears merely to be as a source of the neutral acid for subsequent partitioning. Thus, when only the bulk aqueous phase anion concentrations are of interest a multimedia fate model is not required because these concentrations are largely predictable from the magnitude of emissions to and the advection of the phase. With neutral species partitioning, all local field measurement concentrations of the conjugate pair, PFO(A), are explained by the model to within approximately an order of magnitude, with the exception of lake sediment solids. Model results indicate that bulk aqueous phase PFO acts as a net source for PFOA to the atmosphere, where it may be subject to long-range transport (LRT). Initial calculations suggest an atmospheric LRT potential for PFO(A) of thousands of kilometers, rendering it comparable to hexachlorobenzene.

  13. Theoretical and Experimental Studies on Interactions of Cationic-Anionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    王大喜; 杜永顺; 岳长涛; 侯建国; 栗秀刚; 杨文杰


    Typical cationic and anionic surfactants were chosen and their interactions were calculated by quantum chemical method. Interaction energies are -0.2378 kJ·mol-1, -3.3394 kJ·mol-1 and 0.1204 kJ·mol-1 for the molecular pairs with fluocarbon and hydrocarbon chain: C4H10/C5H12, C4F10/C5H12, and C4F10 /C5F12, respectively.When hydrophilic group with cationic and anionicions is introduced, interaction energies are -287.40kJ·mol-1,-311.18 kJ·mo1-1 and -345.83 kJ·mo1-1. The results show that there is strong static interaction between cationic and anionic surfactants. It has been predicted that mixed monolayer may be formed and surface activity is enhanced favorably, especially for mixtures of cationic and anionic surfactants with fluocarbon and hydrocarbon chains. The anionic surfactants, sodium octadecylbenzenesulfonate perfluopolyetherbenzenesulonate(ANF-I) was synthesized, mixture effects of ANF-I with sodium octadecylbenzenesulfonate or dodecyldimethyl benzylammonium bromide were studied. The results indicate that the efficiency of mixing increased and the theoretical prediction was testified. These results can provide useful information for the design of new surfactants.

  14. Pairing the Volcano

    CERN Document Server

    Ionica, Sorina


    Isogeny volcanoes are graphs whose vertices are elliptic curves and whose edges are $\\ell$-isogenies. Algorithms allowing to travel on these graphs were developed by Kohel in his thesis (1996) and later on, by Fouquet and Morain (2001). However, up to now, no method was known, to predict, before taking a step on the volcano, the direction of this step. Hence, in Kohel's and Fouquet-Morain algorithms, many steps are taken before choosing the right direction. In particular, ascending or horizontal isogenies are usually found using a trial-and-error approach. In this paper, we propose an alternative method that efficiently finds all points $P$ of order $\\ell$ such that the subgroup generated by $P$ is the kernel of an horizontal or an ascending isogeny. In many cases, our method is faster than previous methods. This is an extended version of a paper published in the proceedings of ANTS 2010. In addition, we treat the case of 2-isogeny volcanoes and we derive from the group structure of the curve and the pairing ...

  15. Formation of Carbamate Anions by the Gas-phase Reaction of Anilide Ions with CO2. (United States)

    Liu, Chongming; Nishshanka, Upul; Attygalle, Athula B


    The anilide anion (m/z 92) generated directly from aniline, or indirectly as a fragmentation product of deprotonated acetanilide, captures CO2 readily to form the carbamate anion (m/z 136) in the collision cell, when CO2 is used as the collision gas in a tandem-quadrupole mass spectrometer. The gas-phase affinity of the anilide ion to CO2 is significantly higher than that of the phenoxide anion (m/z 93), which adds to CO2 only very sluggishly. Our results suggest that the efficacy of CO2 capture depends on the natural charge density on the nitrogen atom, and relative nucleophilicity of the anilide anion. Generally, conjugate bases generated from aniline derivatives with proton affinities (PA) less than 350 kcal/mol do not tend to add CO2 to form gaseous carbamate ions. For example, the anion generated from p-methoxyaniline (PA = 367 kcal/mol) reacts significantly faster than that obtained from p-nitroaniline (PA = 343 kcal/mol). Although deprotonated p-aminobenzoic acid adds very poorly because the negative charge is now located primarily on the carboxylate group, it reacts more efficiently with CO2 if the carboxyl group is esterified. Moreover, mixture of CO2 and He as the collision gas was found to afford more efficient adduct formation than CO2 alone, or as mixtures made with nitrogen or argon, because helium acts as an effective "cooling" gas and reduces the internal energy of reactant ions.

  16. Swelling-Activated Anion Channels Are Essential for Volume Regulation of Mouse Thymocytes

    Directory of Open Access Journals (Sweden)

    Ravshan Z. Sabirov


    Full Text Available Channel-mediated trans-membrane chloride movement is a key process in the active cell volume regulation under osmotic stress in most cells. However, thymocytes were hypothesized to regulate their volume by activating a coupled K-Cl cotransport mechanism. Under the patch-clamp, we found that osmotic swelling activates two types of macroscopic anion conductance with different voltage-dependence and pharmacology. At the single-channel level, we identified two types of events: one corresponded to the maxi-anion channel, and the other one had characteristics of the volume-sensitive outwardly rectifying (VSOR chloride channel of intermediate conductance. A VSOR inhibitor, phloretin, significantly suppressed both macroscopic VSOR-type conductance and single-channel activity of intermediate amplitude. The maxi-anion channel activity was largely suppressed by Gd3+ ions but not by phloretin. Surprisingly, [(dihydroindenyloxy] alkanoic acid (DIOA, a known antagonist of K-Cl cotransporter, was found to significantly suppress the activity of the VSOR-type single-channel events with no effect on the maxi-anion channels at 10 μM. The regulatory volume decrease (RVD phase of cellular response to hypotonicity was mildly suppressed by Gd3+ ions and was completely abolished by phloretin suggesting a major impact of the VSOR chloride channel and modulatory role of the maxi-anion channel. The inhibitory effect of DIOA was also strong, and, most likely, it occurred via blocking the VSOR Cl− channels.

  17. Heterocyclic Anions of Astrobiological Interest (United States)

    Cole, Callie A.; Demarais, Nicholas J.; Yang, Zhibo; Snow, Theodore P.; Bierbaum, Veronica M.


    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N2O, O2, CO, OCS, CO2, and SO2) and other reactive species (CS2, CH3Cl, (CH3)3CCl, and (CH3)3CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  18. Heterocyclic anions of astrobiological interest

    Energy Technology Data Exchange (ETDEWEB)

    Cole, Callie A.; Demarais, Nicholas J.; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309 (United States); Yang, Zhibo [Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK 73019 (United States); Snow, Theodore P., E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Department of Astrophysical and Planetary Sciences, 391 UCB, University of Colorado, Boulder, CO 80309 (United States)


    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N{sub 2}O, O{sub 2}, CO, OCS, CO{sub 2}, and SO{sub 2}) and other reactive species (CS{sub 2}, CH{sub 3}Cl, (CH{sub 3}){sub 3}CCl, and (CH{sub 3}){sub 3}CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  19. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;


    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...... alkali metal chlorides as well as BaCl2, NaBr and (CH3CH2CH2)(4)NBr were used to investigate the effects of both the ionic charge, size and shape. In 1: 1 electrolytes using small ions only three peaks are present: a sharp cathodic peak at ca. - 0.6 V vs, SCE representing both the insertion of cations...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  20. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.;


    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  1. Donnan Membrane Technique (DMT) for Anion Measurement

    NARCIS (Netherlands)

    Alonso Vega, M.F.; Weng, L.P.; Temminghoff, E.J.M.; Riemsdijk, van W.H.


    Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl-, 1-2 days for NO3-, 1-4 days for SO42-

  2. Anionic/cationic complexes in hair care. (United States)

    O'Lenick, Tony


    The formulation of cosmetic products is always more complicated than studying the individual components in aqueous solution. This is because there are numerous interactions between the components, which make the formulation truly more than the sum of the parts. This article will look at interactions between anionic and cationic surfactants and offer insights into how to use these interactions advantageously in making formulations.

  3. Wigner photoemission time delay from endohedral anions (United States)

    Kumar, Ashish; Varma, Hari R.; Deshmukh, Pranawa C.; Manson, Steven T.; Dolmatov, Valeriy K.; Kheifets, Anatoli


    Characteristic features of Wigner photoemission time delay from endohedral anions A@C60q along with their dependence on the anion charge q are unraveled. Specifically, significant enhancement of the time delay in the innermost dipole photoionization channels near threshold is found, owing to the presence of the Coulomb confined resonances (CRs). Moreover, it is shown that interchannel coupling of the inner-shell Coulomb CRs with outer-shell photoionization channels results in resonantly enhanced time delay in the release of the outer-shell photoelectron well above, several hundreds eV, the outer-shell thresholds. It is also demonstrated that, and explained why, photoionization cross sections of the innermost subshells as well as outer subshells (near the inner-subshell threshold) depends only very weakly on the anion charge q , but the dependence of the corresponding time delays on q can be significant. Furthermore, Coulomb CRs are found to emerge in the innermost quadrupole photoionization channels as well, thereby causing considerable time delay in the quadrupole photoemission. These findings are illustrated in calculations of the photoionization of inner and outer subshells of the endohedral anions Ne@C60-1 and Ne@C60-5 that were chosen as case studies.

  4. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, Martijn M.G.; Snellink-Ruel, Bianca H.M.; Engbersen, Johan F.J.; Reinhoudt, David N.


    In PVC/NPOE ion-selective membranes of potentiometric sensors, the guest-host stoichiometry of the anion complex of H2PO4 - and F- selective uranyl salophene derivatives is 2:1. This stoichiometry is different from the stoichiometry observed in DMSO solution (1H NMR) or solid state (X-ray crystal st

  5. Synthetic cation-selective nanotube: Permeant cations chaperoned by anions (United States)

    Hilder, Tamsyn A.; Gordon, Dan; Chung, Shin-Ho


    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  6. Involvement of anion channels in mediating elicitor-induced ATP efflux in Salvia miltiorrhiza hairy roots. (United States)

    Wu, Shu-Jing; Siu, Ka-Chai; Wu, Jian-Yong


    This study examines the roles of anion channels and ATP binding cassette (ABC) protein transporters in mediating elicitor-induced ATP release in Salvia miltiorrhiza hairy root cultures. The elicitor-induced ATP release was effectively blocked by two putative membrane anion channel blockers, niflumic acid and Zn(2+), but not by a specific Cl(-) channel blocker, phenylanthranilic acid. The elicitor-induced ATP release was also significantly suppressed by two ABC inhibitors, glibenclamide and ethacrynic acid. Notable ATP release from the hairy roots was also induced by verapamil (2mM), an ABC activator in animal cells. The verapamil-induced ATP release was effectively blocked by niflumic acid, but only slightly inhibited by the ABC inhibitors. Another notable effect of verapamil was the induction of exocytosis, the secretion of vesicle-like particles to the root surface. The verapamil-induced exocytosis was not inhibited by nifulumic acid and YE did not induce the exocytosis. Overall, the results suggest a significant role of anion channels, a possible involvement of ABC proteins and no significant involvement of exocytosis in mediating the ATP efflux in hairy root cells.

  7. Multiple origins of asteroid pairs

    CERN Document Server

    Jacobson, Seth A


    Rotationally fissioned asteroids produce unbound daughter asteroids that have very similar heliocentric orbits. Backward integration of their current heliocentric orbits provides an age of closest proximity that can be used to date the rotational fission event. Most asteroid pairs follow a predicted theoretical relationship between the primary spin period and the mass ratio of the two pair members that is a direct consequence of the YORP-induced rotational fission hypothesis. If the progenitor asteroid has strength, asteroid pairs may have high mass ratios with possibly fast rotating primaries. However, secondary fission leaves the originally predicted trend unaltered. We also describe the characteristics of pair members produced by four alternative routes from a rotational fission event to an asteroid pair. Unlike direct formation from the event itself, the age of closest proximity of these pairs cannot generally be used to date the rotational fission event since considerable time may have passed.

  8. Extractive Spectrophotometric Determination of Bismuth(III in Water Using Some Ion Pairing Reagents

    Directory of Open Access Journals (Sweden)

    Abdulaziz S. Bashammakh


    Full Text Available Two novel and low cost liquid-liquid extraction methods for the separation of bismuth(III at trace level from aqueous medium have been developed. The two methods were based upon the formation of yellow colored ternary complex ion associates of tetraiodobismuth(III complex anion, BiI4- with the ion-pairing reagent 2,3,5-tetraphenyltetrazoliumchloride (Tz+.Cl– and 1, 10 phenanthroline (Phen in sulfuric acid medium. The effect of various parameters e.g. pH, organic solvent, shaking time, etc. on the preconcentration of bismuth(III from the aqueous media by the reagent was investigated. The developed colored complex ion associates [Tz+.BiI4-] and [Phen+.BiI4-] were extracted quantitatively into acetone-chloroform (1:1v/v and methyliso- butylketone (MIBK, respectively. The compositions of the formed complex ion associates [Tz+.BiI4-] and [Phen+.BiI4-] were determined by the Job's method at 500 and 490 nm, respectively. The plots of bismuth(III concentration (0-17 μg mL-1 versus absorbance of the associates at 500 and 490 nm were linear with good correlation coefficient (R2=0.998. The developed method of the ion associate [Tz+.BiI4-] two methods was applied successfully for the analysis of bismuth in water.

  9. Ácido siálico sérico, carga aniónica y agregación eritrocitaria en pacientes diabéticos e hipertensos Serum sialic acid, cellular anionic charge and erythrocyte aggregation in diabetic and hypertensive patients

    Directory of Open Access Journals (Sweden)

    Natalia Lebensohn


    Full Text Available El objetivo de este trabajo fue estudiar la relación del ácido siálico sérico (AS y la carga aniónica eritrocitaria (CAE con la agregación eritrocitaria en dos grupos de pacientes: diabéticos (DBT n= 20 e hipertensos (HTA n= 21, comparados con un grupo control (n= 20. Se trabajó con sangre anticoagulada con EDTA y suero. La agregación eritrocitaria se estudió por observación microscópica de los agregados y cuantificación a través de un parámetro de forma denominado ASP (Aggregation Shape Parameter. La CAE se determinó por unión a colorante alcian blue y el AS por método espectrofotométrico con reactivo de Erlich. Los valores de ASP y AS resultaron significativamente aumentados en los HTA y DBT respecto de los normales. Los HTA y DBT presentaron agregados amorfos, lo que se refleja en los valores alterados de ASP, significativamente mayores (p The aim of this work was to study the relationship between serum sialic acid (SSA and erythrocyte anionic charge (EAC with erythrocyte aggregation in two groups: diabetic (DBT, n=20 and hypertensive (HT, n=21 patients, compared to a control group (n=20. We worked with anticoagulated blood with EDTA and serum. The erythrocyte aggregation was studied by microscopically observing and quantifying aggregates using an ASP (Aggregate Shape Parameter. The EAC was determined by binding an Alcian blue dye to the membrane sialic acid and SSA was determined by spectrophotometric method with an Erlich reactant. The values of ASP and SSA increased significantly in HT and DBT patients compared to the control group. The HT and DBT groups showed amorphous aggregates, evident in an alteration in the values of ASP, which were significantly higher ( p< 0.005 than in healthy patients. The EAC values were much lower in HT and DBT patients than in the control group (p < 0.0001. In this work, abnormalities in the erythrocyte aggregation could be detected by the values of ASP, EAC and SSA, which might be involved

  10. Development of new chiral ligand exchange capillary electrophoresis system with amino acid ionic liquids ligands and its application in studying the kinetics of L-amino acid oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Bingbing [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); College of Food Sciences and Engineering, Shandong Agricultural University, Tai’an, Shandong 271018 (China); Mu, Xiaoyu [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Qi, Li, E-mail: [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)


    Highlights: • Novel amino acid ionic liquids with pyridinium as cations and L-lysine as anion were synthesized. • These synthesized AAILs have been explored as the ligands coordinated with Zn(II) in CLE-CE system. • The developed CLE-CE method could be used for the enantioseparation of Dns-D, L-amino acids. • The kinetic contents of L-amino acid oxidase were investigated with the proposed CLE-CE system. - Abstract: New kinds of amino acid ionic liquids (AAILs) with pyridinium as cations and L-lysine (L-Lys) as anion have been developed as the available chiral ligands coordinated with Zn(II) in chiral ligand-exchange capillary electrophoresis (CLE-CE). Four kinds of AAILs, including [1-ethylpyridinium][L-lysine], 1-butylpyridinium][L-lysine], [1-hexylpyridinium][L-lysine] and 1-[octylpyridinium][L-lysine], were successfully synthesized and characterized by nuclear magnetic resonance and mass spectrometry. Compared with other AAILs, the best chiral separation of Dns-D, L-amino acids could be achieved when [1-ethylpyridinium][L-lysine] was chosen as the chiral ligand. It has been found that after investigating the influence of key factors on the separation efficiency, such as pH of buffer solution, the ratio of Zn(II) to ligand and complex concentration, eight pairs of Dns-D, L-AAs enantiomers could be baseline separated and three pairs were partly separated under the optimum conditions. The proposed CLE-CE method also exhibited favorable quantitative analysis property of Dns-D, L-Met with good linearity (r{sup 2} = 0.998) and favorable repeatability (RSD ≤ 1.5%). Furthermore, the CLE-CE system was applied in investigating the kinetic contents of L-amino acid oxidase, which implied that the proposed system has the potential in studying the enzymatic reaction mechanism.

  11. Ionic polymer-metal composite actuators obtained from radiation-grafted cation- and anion-exchange membranes. (United States)

    Park, Jong Hyuk; Han, Man Jae; Song, Dae Seock; Jho, Jae Young


    Two series of ionic polymer-metal composites (IPMCs), one cationic and one anionic, are designed and prepared from radiation-grafted ion-exchange membranes. Through examination of the properties of the membranes synthesized from the two grafting monomers and the two base polymers, acrylic acid-grafted poly(vinylidene fluoride-co-hexafluoropropylene) and quarternized 4-vinylpyridine-grafted poly(ethylene-co-tetrafluoroethylene) with the appropriate amount of ionic groups are employed for the fabrication of cation and anion IPMCs, respectively. The bending displacement of the cation IPMC is comparable to Nafion-based IPMC under direct- and alternating-current voltage, but back-relaxation is not observed. The actuation performance of the anion IPMC is highly improved over those reported earlier in the literature for the other anion IPMCs.

  12. Recent progress and applications of ion-exclusion/ion-exchange chromatography for simultaneous determination of inorganic anions and cations. (United States)

    Nakatani, Nobutake; Kozaki, Daisuke; Mori, Masanobu; Tanaka, Kazuhiko


    One of the ultimate goals of ion chromatography is to determine both anions and cations found in samples with a single chromatographic run. In the present article, recent progress in ion-exclusion/ion-exchange chromatography for the simultaneous determinations of inorganic anions and cations are reviewed. Firstly, the principle and the control for the simultaneous separation and detection of analyte ions using ion-exclusion/cation-exchange chromatography with a weakly acidic cation-exchange column are outlined. Then, advanced chromatographic techniques in terms of analytical time, selectively and sensitivity are summarized. As a related method, ion-exclusion/anion-exchange chromatography with an anion-exchange column could be used for the simultaneous determination of inorganic nitrogen species, such as ammonium, nitrite and nitrate ions. Their usefulness and applications to water-quality monitoring and related techniques are also described.

  13. Cell cycle-dependent activity of the volume- and Ca2+-activated anion currents in Ehrlich lettre ascites cells

    DEFF Research Database (Denmark)

    Klausen, Thomas Kjaer; Bergdahl, Andreas; Christophersen, Palle


    Recent evidence implicates the volume-regulated anion current (VRAC) and other anion currents in control or modulation of cell cycle progression; however, the precise involvement of anion channels in this process is unclear. Here, Cl- currents in Ehrlich Lettre Ascites (ELA) cells were monitored...... during cell cycle progression, under three conditions: (i) after osmotic swelling (i.e., VRAC), (ii) after an increase in the free intracellular Ca2+ concentration (i.e., the Ca2+-activated Cl- current, CaCC), and (iii) under steady-state isotonic conditions. The maximal swelling-activated VRAC current......+ in the pipette), was unaltered from G0 to G1, but decreased in early S phase. A novel high-affinity anion channel inhibitor, the acidic di-aryl-urea NS3728, which inhibited both VRAC and CaCC, attenuated ELA cell growth, suggesting a possible mechanistic link between cell cycle progression and cell cycle...

  14. Mechanism of Polysulfone-Based Anion Exchange Membranes Degradation in Vanadium Flow Battery. (United States)

    Yuan, Zhizhang; Li, Xianfeng; Zhao, Yuyue; Zhang, Huamin


    The stability of hydrocarbon ion exchange membranes is one of the critical issues for a flow battery. However, the degradation mechanism of ion exchange membranes has been rarely investigated especially for anion exchange membranes. Here, the degradation mechanism of polysulfone based anion exchange membranes, carrying pyridine ion exchange groups, under vanadium flow battery (VFB) medium was investigated in detail. We find that sp(2) hybrid orbital interactions between pyridinic-nitrogen in 4,4'-bipyridine and benzylic carbon disrupt the charge state balance of pristine chloromethylated polysulfone. This difference in electronegativity inversely induces an electrophilic carbon center in the benzene ring, which can be attacked by the lone pair electron on the vanadium(V) oxygen species, further leading to the degradation of polymer backbone, while leaving the 4,4'-bipyridine ion exchange groups stable. This work represents a step toward design and construction of alternative type of chemically stable hydrocarbon ion exchange membranes for VFB.

  15. Homologue Structure of the SLAC1 Anion Channel for Closing Stomata in Leaves

    Energy Technology Data Exchange (ETDEWEB)

    Y Chen; L Hu; M Punta; R Bruni; B Hillerich; B Kloss; B Rost; J Love; S Siegelbaum; W Hendrickson


    The plant SLAC1 anion channel controls turgor pressure in the aperture-defining guard cells of plant stomata, thereby regulating the exchange of water vapour and photosynthetic gases in response to environmental signals such as drought or high levels of carbon dioxide. Here we determine the crystal structure of a bacterial homologue (Haemophilus influenzae) of SLAC1 at 1.20 {angstrom} resolution, and use structure-inspired mutagenesis to analyse the conductance properties of SLAC1 channels. SLAC1 is a symmetrical trimer composed from quasi-symmetrical subunits, each having ten transmembrane helices arranged from helical hairpin pairs to form a central five-helix transmembrane pore that is gated by an extremely conserved phenylalanine residue. Conformational features indicate a mechanism for control of gating by kinase activation, and electrostatic features of the pore coupled with electrophysiological characteristics indicate that selectivity among different anions is largely a function of the energetic cost of ion dehydration.

  16. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins. (United States)

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S


    Ionic organic contaminants (OCs) are a growing concern for water treatment and the environment and are removed inefficiently by many existing technologies. This study examined removal of anionic OCs by anion exchange resins (AXRs) as a promising alternative. Results indicate that two polystyrene AXRs (IRA910 and IRA96) have higher sorption capacities and selectivity than a polyacrylate resin (A860). For the polystyrene resins, selectivity follows: phenolates ≥ aromatic dicarboxylates > aromatic monocarboxylates > benzenesulfonate > aliphatic carboxylates. This trend can be explained based on hydration energy, the number of exchange groups, and aromaticity and hydrophobicity of the nonpolar moiety (NPM) of the anions. For A860, selectivity only varies within a narrow range (0.13-1.64). Despite the importance of the NPM of the anions, neutral solutes were sorbed much less, indicating synergistic combinations of electrostatic and nonelectrostatic interactions in the overall sorption. By conducting multiple linear regression between Abraham's descriptors and nature log of selectivity, induced dipole-related interactions and electrostatic interactions were found to be the most important interaction forces for sorption of the anions, while solute H-bond basicity has a negative effect. A predictive model was then developed for carboxylates and phenolates based on the poly parameter linear free energy relationships established for a diverse range of 16 anions and 5 neutral solutes, and was validated by accurate prediction of sorption of five test solutes within a wide range of equilibrium concentrations and that of benzoate at different pH.

  17. Anion-π interactions involving [MX(n)](m-) anions: a comprehensive theoretical study. (United States)

    Estarellas, Carolina; Quiñonero, David; Deyà, Pere M; Frontera, Antonio


    In this manuscript we perform a systematic study on the geometric and energetic features of anion-π complexes, wherein the anion is a metal complex of variable shapes and charges. Such a study is lacking in the literature. For the calculations we used the ab initio RI-MP2/def2-TZVPP level of theory. A search in the Cambridge Structural Database (CSD) provides the experimental starting point that inspired the subsequent theoretical study. The influence of [MX(n)](m-) on the anion-π interaction was analyzed in terms of energetic, geometric, and charge transfer properties and Bader's theory of "atom-in-molecules" (AIM). The binding energy depends on the coordination index, geometric features and different orientations adopted by the metallic anion. The binding mode resembling a stacking interaction for linear, trigonal planar and square-planar anions is the most favorable. For tetrahedral and octahedral anions the most favorable orientation is the one with three halogen atoms pointing to the ring.

  18. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    Energy Technology Data Exchange (ETDEWEB)

    Jonathan L. Sessler


    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  19. Three hydroxy aurone compounds as chemosensors for cyanide anions. (United States)

    Chen, Huihui; Sun, Yunhui; Zhou, Chuanjian; Cao, Duxia; Liu, Zhiqiang; Ma, Lin


    Three new 4-hydroxy aurone compounds 1-3 with dimethylamino (1), bromine (2) and cyano (3) as terminal group have been synthesized. Their photophysical properties as well as recognition properties for cyanide anions in acetonitrile and aqueous solution have also been examined. These compounds exhibit remarkable response to cyanide anions with obvious color and fluorescence change owing to hydrogen bonding reaction between cyanide anions and the O-H moiety of the sensors, which allows naked eye detection of cyanide anions.

  20. Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles. (United States)

    Pan, Bingcai; Xu, Jingsheng; Wu, Bing; Li, Zhigang; Liu, Xitong


    Here we fabricated a novel nanocomposite HZO-201, an encapsulated nanosized hydrous zirconium oxide (HZO) within a commercial porous polystyrene anion exchanger D201, for highly efficient defluoridation of water. HZO-201 exhibited much higher preference than activated alumina and D201 toward fluoride removal when competing anions (chloride, sulfate, nitrate, and bicarbonate) coexisted at relatively high levels. Fixed column adsorption indicated that the effective treatable volume of water with HZO-201 was about 7-14 times as much as with D201 irrespective of whether synthetic solution or groundwater was the feeding solution. In addition, HZO-201 could treat >3000 BV of the acidic effluent (around 3.5 mg F(-)/L) per run at pH 3.5, compared to only ∼4 BV with D201. The exhausted HZO-201 could be regenerated by NaOH solution for repeated use without any significant capacity loss. Such attractive performance of HZO-201 resulted from its specific hybrid structure, that is, the host anion exchanger D201 favors the preconcentration of fluoride ions inside the polymer based on the Donnan principle, and the encapsulated nanosized HZO exhibits preferable sequestration of fluoride through specific interaction, as further demonstrated by XPS spectra. The influence of solution pH, competitive anions, and contact time was also examined. The results suggested that HZO-201 has a great potential in efficient defluoridation of groundwater and acidic mine drainage.

  1. Bound anions differentially stabilize multiprotein complexes in the absence of bulk solvent. (United States)

    Han, Linjie; Hyung, Suk-Joon; Mayers, Jonathan J S; Ruotolo, Brandon T


    The combination of ion mobility separation with mass spectrometry is an emergent and powerful structural biology tool, capable of simultaneously assessing the structure, topology, dynamics, and composition of large protein assemblies within complex mixtures. An integral part of the ion mobility-mass spectrometry measurement is the ionization of intact multiprotein complexes and their removal from bulk solvent. This process, during which a substantial portion of protein structure and organization is likely to be preserved, imposes a foreign environment on proteins that may cause structural rearrangements to occur. Thus, a general means must be identified to stabilize protein structures in the absence of bulk solvent. Our approach to this problem involves the protection of protein complex structure through the addition of salts in solution prior to desorption/ionization. Anionic components of the added salts bind to the complex either in solution or during the electrospray process, and those that remain bound in the gas phase tend to have high gas phase acidities. The resulting 'shell' of counterions is able to carry away excess energy from the protein complex ion upon activation and can result in significant structural stabilization of the gas-phase protein assembly overall. By using ion mobility-mass spectrometry, we observe both the dissociation and unfolding transitions for four tetrameric protein complexes bound to populations of 12 different anions using collisional activation. The data presented here quantifies, for the first time, the influence of a large range of counterions on gas-phase protein structure and allows us to rank and classify counterions as structure stabilizers in the absence of bulk solvent. Our measurements indicate that tartrate, citrate, chloride, and nitrate anions are among the strongest stabilizers of gas-phase protein structure identified in this screen. The rank order determined by our data is substantially different when compared to

  2. Color Responses of a Tripodal Colorimetric Sensor toward Anions

    Institute of Scientific and Technical Information of China (English)

    WEI Lan-Hua; HE Yong-Bing; WU Jin-Long; QIN Hai-Juan; XU Kuo-Xi; MENG Ling-Zhi


    A thiourea-based tripodal colorimetric anion sensor was synthesized. Its binding abilities with AcO- and halide anions in DMSO were studied by UV-Vis spectra. The sensor showed different color responses to these anions. The association constants and different stoichiometries were deduced by nonlinear least-square curve fitting or linear fitting.

  3. Surface electrochemistry of CO on Pt(111): Anion Effects

    Energy Technology Data Exchange (ETDEWEB)

    Markovic, N.M.; Lucas, C.A.; Rodes, A.; Stamenkovic, V.; Ross, P.N.


    In-situ studies of CO adsorption by surface x-ray scattering (SXS) and Fourier transform infrared (FTIR) spectroscopy techniques are used to create the link between the macroscopic kinetic rates of CO oxidation and the microscopic level of understanding the structure/site occupancy of CO on Pt(111). A remarkable difference in activity was observed between alkaline and acid solutions. In alkaline solution the oxidation of CO proceeds at low overpotential (<0.2 V) by the surface reaction between the adsorbed CO and OH, the latter forming selectively in the hydrogen underpotential potential region at defect sites. In acid solution these sites are blocked by specific adsorption of anions, and consequently in a solution containing Br{sup -} the ignition potential is shifted positively by 0.6 V. Anions of supporting electrolytes also have dramatic effects on both the potential range of stability and the domain size of the p(2x2)-3CO structure which is formed at 0.05 V. The stability/domain size of this structure increases from KOH (ca. 30 {angstrom} between 0.05 < E < 0.3V), to HClO{sub 4} (ca. 140 {angstrom} between 0.05 < E < 0.6V) to HClO{sub 4} + Br{sup -} (ca 350 {angstrom} between 0.05 < E < 0.8V). The larger the ordered domains of the p(2x2)-CO{sub ad} structure are, the less active the surface is towards CO oxidation.

  4. Polysulfide anions II: structure and vibrational spectra of the S4(2-) and S5(2-) anions. Influence of the cations on bond length, valence, and torsion angle. (United States)

    el Jaroudi, O; Picquenard, E; Demortier, A; Lelieur, J P; Corset, J


    The influence of the cations on bond length, valence, and torsion angle of S4(2-) and S5(2-) anions was examined in a series of solid alkali tetra- and pentasulfides by relating their Raman spectra to their known X-ray structures through a force-field analysis. The IR and Raman spectra of BaS4.H2O and the Raman spectra of (NH4)2S4.nNH3, gamma-Na2S4, and delta-Na2S5 are presented. The similarity of spectra of gamma-Na2S4 with those of BaS4.H2O suggests similar structures of the S4(2-) anions in these two compounds with a torsion angle smaller than 90 degrees. The variations of SS bond length, SSS valence angle, and dihedral angle of Sn2- anions are related to the polarization of the lone pair and electronic charge of the anion by the electric field of the cations. A correlation between the torsion angle and the SSS valence angle is shown as that previously reported between the length of the bond around which the torsion takes place and the dihedral angle value. These geometry changes are explained by the hyperconjugation concept and the electron long-pair repulsion.

  5. Kramers Pairs in configuration interaction

    DEFF Research Database (Denmark)

    Avery, John Scales; Avery, James Emil


    The theory of symmetry-preserving Kramers pair creation operators is reviewed and formulas for applying these operators to configuration interaction calculations are derived. A new and more general type of symmetry-preserving pair creation operator is proposed and shown to commute with the total...

  6. Assessment Strategies for Pair Programming (United States)

    Hahn, Jan Hendrik; Mentz, Elsa; Meyer, Lukas


    Although pair programming has proved its usefulness in teaching and learning programming skills, it is difficult to assess the individual roles and abilities of students whilst programming in pairs. (Note that within this manuscript, the term assessment refers to evaluating individual student performance.) Assessing only the outcomes of a pair…


    Institute of Scientific and Technical Information of China (English)

    XuChengqian; ZhaoXiaoqun


    A new set of binary sequences-Periodic Complementary Binary Sequence Pair (PCSP)is proposed .A new class of block design-Difference Family Pair (DFP)is also proposed .The relationship between PCSP and DFP,the properties and exising conditions of PCSP and the recursive constructions for PCSP are given.


    Institute of Scientific and Technical Information of China (English)

    Xu Chengqian; Zhao Xiaoqun


    A new set of binary sequences-Periodic Complementary Binary Sequence Pair (PCSP) is proposed. A new class of block design-Difference Family Pair (DFP) is also proposed.The relationship between PCSP and DFP, the properties and existing conditions of PCSP and the recursive constructions for PCSP are given.

  9. Instability of vortex pair leapfrogging

    DEFF Research Database (Denmark)

    Tophøj, Laust; Aref, Hassan


    pairs fly off to infinity, and a "walkabout" mode, where the vortices depart from leapfrogging but still remain within a finite distance of one another. We show numerically that this transition is more gradual, a result that we relate to earlier investigations of chaotic scattering of vortex pairs [L...

  10. Stereo Pair: Patagonia, Argentina (United States)


    This view of northern Patagonia, near El Cain, Argentina shows complexly eroded volcanic terrain, with basalt mesas, sinkholes, landslide debris, playas, and relatively few integrated drainage channels. Surrounding this site (but also extending far to the east) is a broad plateau capped by basalt, the Meseta de Somuncura. Here, near the western edge of the plateau, erosion has broken through the basalt cap in a variety of ways. On the mesas, water-filled sinkholes (lower left) are most likely the result of the collapse of old lava tubes. Along the edges of the mesas (several locations) the basalt seems to be sliding away from the plateau in a series of slices. Water erosion by overland flow is also evident, particularly in canyons where vegetation blankets the drainage channels (green patterns, bottom of image). However, overland water flow does not extend very far at any location. This entire site drains to local playas, some of which are seen here (blue). While the water can reach the playas and then evaporate, what becomes of the eroded rock debris? Wind might excavate some of the finer eroded debris, but the fate of much of the missing bedrock remains mysterious.This cross-eyed stereoscopic image pair was generated using topographic data from the Shuttle Radar Topography Mission, combined with an enhanced Landsat 7 satellite color image. The topography data are used to create two differing perspectives of a single image, one perspective for each eye. In doing so, each point in the image is shifted slightly, depending on its elevation. When stereoscopically merged, the result is a vertically exaggerated view of the Earth's surface in its full three dimensions.Landsat satellites have provided visible light and infrared images of the Earth continuously since 1972. SRTM topographic data match the 30-meter (99-foot) spatial resolution of most Landsat images and provide a valuable complement for studying the historic and growing Landsat data archive. The Landsat 7

  11. Specific anion effects in Artemia salina. (United States)

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero


    The specific anion effect on the vitality of Artemia salina was investigated by measuring the Lethal Time LT50 of the crustaceans in the presence of different sodium salts solutions at room temperature and at the same ionic strength as natural seawater. Fluoride, thiocyanate and perchlorate are the most toxic agents, while chloride, bromide and sulfate are well tolerated. The rates of oxygen consumption of brine shrimps were recorded in mixed NaCl+NaF or NaCl+NaSCN solutions as a function of time. The results are discussed in terms of the Hofmeister series, and suggest that, besides the biochemical processes that involve F(-), SCN(-) and ClO4(-), the different physico-chemical properties of the strong kosmotropic and chaotropic anions may contribute in determining their strong toxicity for A. salina.

  12. Electron anions and the glass transition temperature

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo


    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32]2+ ∙ (e)2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

  13. Stability and Characteristics of the Halogen Bonding Interaction in an Anion-Anion Complex: A Computational Chemistry Study. (United States)

    Wang, Guimin; Chen, Zhaoqiang; Xu, Zhijian; Wang, Jinan; Yang, Yang; Cai, Tingting; Shi, Jiye; Zhu, Weiliang


    Halogen bonding is the noncovalent interaction between the positively charged σ-hole of organohalogens and nucleophiles. In reality, both the organohalogen and nucleophile could be deprotonated to form anions, which may lead to the vanishing of the σ-hole and possible repulsion between the two anions. However, our database survey in this study revealed that there are halogen bonding-like interactions between two anions. Quantum mechanics calculations with small model complexes composed of halobenzoates and propiolate indicated that the anion-anion halogen bonding is unstable in vacuum but attractive in solvents. Impressively, the QM optimized halogen bonding distance between the two anions is shorter than that in a neutral system, indicating a possibly stronger halogen bonding interaction, which is verified by the calculated binding energies. Furthermore, natural bond orbital and quantum theory of atoms in molecule analyses also suggested stronger anion-anion halogen bonding than that of the neutral one. Energy decomposition by symmetry adapted perturbation theory revealed that the strong binding might be attributed to large induction energy. The calculations on 4 protein-ligand complexes from PDB by the QM/MM method demonstrated that the anion-anion halogen bonding could contribute to the ligands' binding affinity up to ∼3 kcal/mol. Therefore, anion-anion halogen bonding is stable and applicable in reality.

  14. Lowest autodetachment state of the water anion (United States)

    Houfek, Karel; Čížek, Martin


    The potential energy surface of the ground state of the water anion H2O- is carefully mapped using multireference CI calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O-+H2 and OH-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The autodetachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O- + H2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slighly off the linear geometry and is separated by a saddle from the autodetachment region. The autodetachment region is directly accessible from the OH-+H asymptote. For the molecular geometries in the autodetachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  15. Politseiuuringud kooskõlastamisele / Liivia Anion

    Index Scriptorium Estoniae

    Anion, Liivia


    1. aprillil 2003. a. moodustatud uurimistööde kooskõlastamise komisjoni tegevuse eesmärk on saada ülevaade kõrgkoolides õppivate töötajate poolt politseis korraldatavatest uurimustest, kasutada saadud infot politsei kasuks ja vältida teenistujate tööd segavate uurimuste tegemist. Komisjoni liige Liivia Anion teeb ülevaate komisjoni otsustuspädevuse valdkondadest ja töökorraldusest

  16. Anion-induced increases in the rate of colchicine binding to tubulin. (United States)

    Bhattacharyya, B; Wolff, J


    The rate of binding of colchicine to tubulin to tubulin is enhanced by certain anions. Among the inorganic anions tested, only sulfate was effective. The organic anions include mostly dicarboxylic acids, among which tartrate was the most effective. This effect occurs onlt at low concentrations of colchicine (less than 0.6 X 10(-5) M). The rate increase dor sulfate and L-(+)-tartrate is ca. 2.5-fold at 1.0 mM and plateaus at a limiting value of ca. 4-fold at 100mM. The overall dissociation rate of the colchicine from the complex, which includes both the true rate of dissociation and the rate of irreversible denaturation of tubulin, is not influenced by 1.0 mM tartrate. The affinity constants for colchicine determined from the rate constants are 8.7 X 10(6) and 2.1 X 10(7) M-1 in the absence and the presence of 1.0 mM L-(+)-tartrate. The limiting value is 3.2 X 10(7) M-1. The affinity constant calculated from steady-state measurements is 3.2 X 10(6) M-1 with or without anions. The binding of other ligands like podophyllotoxin, vinblastine, and 1 -anilino-8-naphthalenesulfonate to tubulin is not affected by tartrate. No major conformational changes resulting from anion treatment could be detected by circular dichroism or intrinsic fluorescence. However, the ability of tubulin to polymerize is inhibited by L-(+)-tartrate at concentrations that increase the rate of colchicine binding. We conclude that anions must have a local effect at or near the binding site which enhances the binding rate of colchicine and which may be related to inhibition of polymerization.

  17. Influence of Aqueous Inorganic Anions on the Reactivity of Nanoparticles in TiO2 Photocatalysis. (United States)

    Farner Budarz, Jeffrey; Turolla, Andrea; Piasecki, Aleksander F; Bottero, Jean-Yves; Antonelli, Manuela; Wiesner, Mark R


    The influence of inorganic anions on the photoreactivity and aggregation of titanium dioxide nanoparticles (NPs) was assessed by dosing carbonate, chloride, nitrate, phosphate, and sulfate as potassium salts at multiple concentrations. NP stability was monitored in terms of aggregate morphology and electrophoretic mobility (EPM). Aggregate size and fractal dimension were measured over time by laser diffraction, and the isoelectric point (IEP) as a function of anion and concentration was obtained by measuring EPM versus pH. Phosphate, carbonate, and to a lesser extent, sulfate decreased the IEP of TiO2 and stabilized NP suspensions owing to specific surface interactions, whereas this was not observed for nitrate and chloride. TiO2 NPs were exposed to UV-A radiation, and the photoreactivity was assessed by monitoring the production of reactive species over time both at the NP surface (photogenerated holes) and in the bulk solution (hydroxyl radicals) by observing their reactions with the selective probe compounds iodide and terephthalic acid, respectively. The generation of photogenerated holes and hydroxyl radicals was influenced by each inorganic anion to varying degrees. Carbonate and phosphate inhibited the oxidation of iodide, and this interaction was successfully described by a Langmuir-Hinshelwood mechanism and related to the characteristics of TiO2 aggregates. Chloride and nitrate do not specifically interact with TiO2, and sulfate creates relatively weak interactions with the TiO2 surface such that no decrease in photogenerated hole reactivity was observed. A decrease in hydroxyl radical generation was observed for all inorganic anions. Quenching rate constants for the reaction of hydroxyl radicals with each inorganic anion do not provide a comprehensive explanation for the magnitude of this decrease, which arises from the interplay of several physicochemical phenomena. This work shows that the reactivity of NPs will be strongly influenced by the makeup of

  18. 并联式双梯度反相离子对液相色谱法快速检测土壤中芳磺酸%The Rapid Detection of Seven Kinds of Aromatic Sulfonic Acid in Soil by Parallel and Dual Ion-Pair RP-HPLC Gradient Elution Method

    Institute of Scientific and Technical Information of China (English)

    杨柳; 马浩; 李桂香; 贺伟; 施超欧


    Established a method for extraction and fast detection of 7 kinds of aromatic sulfonic acid ( anthraquinone 1, 5-disulfonic acid, 1-amino-8-naphthol-3, 6-disulfonic acid, 1-naphthol-4-sulfonic, anthraquinone-1, 8-disulfonic acid, 1-naphthalene sulfonic acid, 2-naphthalene sulfonic acid, 3-hydroxy-2-naphthoic acid) in soil by valve switching Ion-pair RP-HPLC with a dual system. Two columns were used in this system. When one was in the process of determination, the other one was in the process of equilibration. Thus 38�5% time was saved. Analytical columns were Dikma Diamonsil C18 (150 mm × 4�6 mm × 5 μm) , eluents were ion-pair reagent ( Tetrabutylammonium Hydrogen Sulfate ) and acetonitrile, and wave lengths were 226, 235, 258 nm. A good linear relationship was obtained for each aromatic sulfonic acid. All linear correlation coefficients were more than 0�999 9. Extracted and detected the randomly selected samples, and got each RSD of the 7 compounds less than 7% as well as the quantification limit no more than 0�181 2 μg/g. Both of the repeatability and quantification limit meet the requirements of detection.%通过阀切换并联式双系统,建立了一套测定土壤样品中7种芳磺酸的反相离子对液相色谱法。该方法采用2根色谱柱,一根色谱柱分析的同时,另一根色谱柱通过阀切换实现平衡,节约了38�5%的分析时间。方法使用 Dikma Diamonsil C18(150 mm ×4�6 mm ×5μm)色谱柱,以离子对试剂(四丁基硫酸氢铵)和乙腈为流动相,检测波长为226、235、258 nm。各组分线性关系良好,线性相关系数均在0�9999以上。随机抽取样品进行重新提取、检测,得到各组分的相对标准偏差均小于7%,且定量限最高不超过0�1812μg/g,重复性和定量限均能满足实验要求。

  19. Evaluation of the thermal effect on separation selectivity in anion-exchange processes using superheated water ion-exchange chromatography. (United States)

    Shibukawa, Masami; Taguchi, Akihiko; Suzuki, Yusuke; Saitoh, Kazunori; Hiaki, Toshihiko; Yarita, Takashi


    The thermal effect on retention and separation selectivity of inorganic anions and aromatic sulfonate ions in anion-exchange chromatography is studied on a quaternized styrene-divinylbenzene copolymer anion-exchange column in the temperature range of 40-120 °C using superheated water chromatography. The selectivity coefficient for a pair of identically charged anions approaches unity as temperature increases provided the ions have the same effective size, such that the retention of an analyte ion decreases with an increase in temperature when the analyte ion has stronger affinity for the ion-exchanger than that of the eluent counterion, whereas it increases when it has weaker affinity. The change in anion-exchange selectivity with temperature observed with superheated water chromatography has been discussed on the basis of the effect of temperature on hydration of the ions. At elevated temperatures, especially in superheated water, the electrostatic interaction or association of the ions with the fixed ion in the resin phase becomes a predominant factor resulting in a different separation selectivity from that obtained at ambient temperature.

  20. Tris-[8]annulenyl Isocyanurate Trianion Triradical and Hexa-anion from the Alkali Metal Reduction of [8]Annulenyl Isocyanate. (United States)

    Peters, Steven J; Klen, Joseph R


    The solution phase alkali metal reduction of [8]annulenyl isocyanate (C8H7NCO) yields an EPR spectrum, which reveals electron couplings to seven protons and only one nitrogen. Although this strongly suggested that the C8H7NCO anion radical was generated, experiments on the oxidized product reveal the actual reduced species to be tris-[8]annulenyl isocyanurate. Unlike the previously studied phenyl isocyanurate anion radical, the unpaired electron(s) is now localized within an [8]annulenyl moiety. Further exposure to metal results in the formation of an equilibrium mixture of trianion triradical and trianion radical species. The cyclotrimerization to form the isocyanurate is proposed to be driven by a reactive C8H7NCO dianion, which is produced from the large equilibrium disproportionation of the anion radical. Exhaustive reduction of the tris-[8]annulenyl isocyanurate with potassium in THF generates the first-ever observed hexa-anion of an isocyanurate. NMR analysis reveals that the polarity of the carbonyl bonds within this hexa-anion is augmented and is caused by the close proximity of K(+) ions, which are tightly ion paired to the three [8]annulenyl dianion rings. These preliminary studies on the reduction of C8H7NCO suggest that polymeric materials (e.g., polyisocyanates) made from this isocyanate might exhibit unique properties.

  1. Pairing correlations in exotic nuclei

    CERN Document Server

    Sagawa, H


    The BCS and HFB theories which can accommodate the pairing correlations in the ground states of atomic nuclei are presented. As an application of the pairing theories, we investigate the spatial extension of weakly bound Ne and C isotopes by taking into account the pairing correlation with the Hartree-Fock-Bogoliubov (HFB) method and a 3-body model, respectively. We show that the odd-even staggering in the reaction cross sections of $^{30,31,32}$Ne and $^{14,15,16}$C are successfully reproduced, and thus the staggering can be attributed to the unique role of pairing correlations in nuclei far from the stability line. A correlation between a one-neutron separation energy and the anti-halo effect is demonstrated for $s$- and p-waves using the HFB wave functions. We also propose effective density-dependent pairing interactions which reproduce both the neutron-neutron ($nn$) scattering length at zero density and the neutron pairing gap in uniform matter. Then, we apply these interactions to study pairing gaps in ...

  2. Anion order in perovskites: a group-theoretical analysis. (United States)

    Talanov, M V; Shirokov, V B; Talanov, V M


    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results.

  3. Modulation of FXYD interaction with Na,K-ATPase by anionic phospholipids and protein kinase phosphorylation

    DEFF Research Database (Denmark)

    Cornelius, Flemming; Mahmmoud, Yasser Ahmed


    with anionic phospholipids. Specifically, the effects of the cytoplasmic domain of FXYD10, which contains the phosphorylation sites for protein kinases, on the kinetics of the Na,K-ATPase reaction were investigated by a comparison of the reconstituted native enzyme and the enzyme where 23 C-terminal amino...... acids of FXYD10 had been cleaved by mild, controlled trypsin treatment. Several kinetic properties of the Na,K-ATPase reaction cycle as well as the FXYD-regulation of Na,K-ATPase activity were found to be affected by acidic phospholipids like PI, PS, and PG. This takes into consideration the Na+ and K......+ activation, the K+-deocclusion reaction, and the poise of the E1/E2 conformational equilibrium, whereas the ATP activation was unchanged. Anionic phospholipids increased the intermolecular cross-linking between the FXYD10 C-terminus (Cys74) and the Cys254 in the Na,K-ATPase A-domain. However, neither...

  4. Synthesis and Structure of Solvated Protons Incorporating Weakly Coordinating Anions. Precursors of Superacids

    Institute of Scientific and Technical Information of China (English)

    TSANG,Chi-Wing(曾志荣); YANG,Qing-Chuan(杨清传); MAK,Thomas C.W.(麦松威); XIE,Zuo-Wei(谢作伟)


    Six new solvated proton salts of highly halogenated carborane anions, [H(solvent)n] [carborane] (carborane = 1-R-CB11-Y5X-6 (R= H, Me; X, Y= Cl, Br, I), 1-H-CB9Br-9 ) were preparrf from the salt metathesis reaction of Ag(carborane)and HCl in high yields. Single-crystal X-ray analyses show that they are all discrete molecules in the solid-state. Tne mumher of the solvated molecules surrounding H+ ion can not be determined with the knowledge of the size and substituents of the carborane anions. Thnese salts provide convenient weighable sources of Brφnsted acid reagents having a wide range of acidities and good thermal stabilities. TGA results ubducate that the solvated molecules (water or organic molecules) in the catiobs [H(solvent)n]+ can be renoved under high temperature and high vacuum conditions to give superacidic mterials H(carborane) which can protonate olefin.

  5. Pairing Correlations at High Spins (United States)

    Ma, Hai-Liang; Dong, Bao-Guo; Zhang, Yan; Fan, Ping; Yuan, Da-Qing; Zhu, Shen-Yun; Zhang, Huan-Qiao; Petrache, C. M.; Ragnarsson, I.; Carlsson, B. G.

    The pairing correcting energies at high spins in 161Lu and 138Nd are studied by comparing the results of the cranked-Nilsson-Strutinsky (CNS) and cranked-Nilsson-Strutinsky-Bogoliubov (CNSB) models. It is concluded that the Coriolis effect rather than the rotational alignment effect plays a major role in the reduction of the pairing correlations in the high spin region. Then we proposed an average pairing correction method which not only better reproduces the experimental data comparing with the CNS model but also enables a clean-cut tracing of the configurations thus the full-spin-range discussion on the various rotating bands.

  6. Crystal structures of three anhydrous salts of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU with the ring-substituted benzoic acid analogues 4-aminobenzoic acid, 3,5-dinitrobenzoic acid and 3,5-dinitrosalicylic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith


    Full Text Available The anhydrous salts of the Lewis base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU with 4-aminobenzoic acid [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 4-aminobenzoate, C9H17N2+·C7H6NO2− (I], 3,5-dinitrobenzoic acid [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 3,5-dinitrobenzoate, C9H17N2+·C7H3N2O6−, (II] and 3,5-dinitrosalicylic acid (DNSA [1-aza-8-azoniabicyclo[5.4.0]undec-7-ene 2-hydroxy-3,5-dinitrobenzoate, C9H17N2+·C7H3N2O7−, (III] have been determined and their hydrogen-bonded structures are described. In both (II and (III, the DBU cations have a common disorder in three of the C atoms of the six-membered ring moieties [site-occupancy factors (SOF = 0.735 (3/0.265 (3 and 0.686 (4/0.314 (4, respectively], while in (III, there is additional rotational disorder in the DNSA anion, giving two sites (SOF = 0.72/0.28, values fixed for the phenol group. In the crystals of (I and (III, the cation–anion pairs are linked through a primary N—H...Ocarboxyl hydrogen bond [2.665 (2 and 2.869 (3 Å, respectively]. In (II, the ion pairs are linked through an asymmetric three-centre R12(4, N—H...O,O′ chelate association. In (I, structure extension is through amine N—H...Ocarboxyl hydrogen bonds between the PABA anions, giving a three-dimensional structure. The crystal structures of (II and (III are very similar, the cation–anion pairs being associated only through weak C—H...O hydrogen bonds, giving in both overall two-dimensional layered structures lying parallel to (001. No π–π ring associations are present in any of the structures.

  7. Preparation and Characterization of Amino Acids-Based Trimethoprim Salts

    Directory of Open Access Journals (Sweden)

    Afzal R. Mohammed


    Full Text Available Trimethoprim (TMP is a dihydrofolate reductase (DHFR inhibitor which prevents the conversion of dihydrofolic acid into tetrahydrofolic acid, resulting in the depletion of the latter and leading to bacterial death. Oral bioavailability of TMP is hindered by both its low solubility and low permeability. This study aims to prepare novel salts of TMP using anionic amino acids; aspartic and glutamic acid as counter ions in order to improve solubility and dissolution. TMP salts were prepared by lyophilisation and characterized using FT-IR spectroscopy, proton nuclear magnetic resonance (1HNMR, Differential Scanning Calorimetry (DSC and Thermogravimetric analysis (TGA. Both the amino acids formed salts with TMP in a 1:1 molar ratio and showed a 280 fold improvement in solubility. Investigation of the microbiological activity of the prepared salts against TMP sensitive Escherichia coli showed that the new salts not only retained antibacterial activity but also exhibited higher zone of inhibition which was attributed to improved physicochemical characters such as higher solubility and dissolution. The results are an important finding that could potentially impact on faster onset of antibacterial activity and reduced therapeutic dose when administered to patients. Studies are underway investigating the effect of ion-pairing TMP with amino acids on the permeability profile of the drug.

  8. Synthesis and Flotation Performance of a New Composite Fatty Acid Anionic Collophanite Collector%新型胶磷矿复合脂肪酸阴离子型捕收剂的合成与浮选性能研究

    Institute of Scientific and Technical Information of China (English)

    罗惠华; 饶欢欢; 李成秀; 陈炳炎; 刘连坤; 朱道鹏


    为了改善中低品位胶磷矿浮选指标,以正癸醇、柠檬酸及棉油脂肪酸皂反应,合成一种复合脂肪酸阴离子型捕收剂,并通过物料配比、合成温度、反应时间试验确定了合成条件。浮选试验结果表明:与棉油脂肪酸皂原料相比,在同样的用量0.6 kg/t 下,合成药剂的浮选精矿产率为81.23%、回收率为91%远高于棉油酸皂的61.74%和70.46%,且比棉油脂肪酸皂1.2 kg/t 时的精矿产率78.62%、回收率87.83%较优,选矿效率也较高;与不同捕收剂浮选试验指标对比显示,4种成熟捕收剂药剂用量在1.2 kg/t 时,精矿产率为50%~60%、回收率为56%~68%,比合成药剂0.6 kg/t 时的浮选指标较差。红外光谱分析表明:柠檬酸与正癸醇发生酯化反应生成柠檬酸正癸醇酯,该产物继续与棉油脂肪酸皂反应,生成的混合药剂分子中含有官能团为羟基、羧基、酯基。合成药剂对该四川磷矿石具有较强的捕收能力和较好的选择性,获得了满意的试验指标。%In order to improve the low-middle grade collophane flotation indexes,with decyl alco-hol,citric acid and cotton oil fatty acid soap reaction,a synthetic compound fatty acid anionic collector was synthesized,and through the ratio of materials,synthesis temperature,reaction time test the synthet-ic conditions were determined.Flotation test results show that:compared with cotton oil fatty acid soap raw material,under the same dosage of 0.6 kg/t,synthesized reagent flotation concentrate with yield of 81.23%,recovery of 91%,much higher than 61.74% and 70.46% for cotton oil fatty acid soap,and better that the concentrate yield rate of 78.62% and recovery of 87.83% on cotton oil fatty acid soap with dosage of 1.2 kg/t,with better beneficiation efficiency.compared with other flotation test index for different collector,when dosage of four kinds of mature collector is 1

  9. Sulfur Groups Improve the Performance of Triazole- and Triazolium-Based Interaction Units in Anion Binding. (United States)

    Álvarez-Pérez, Mónica; Velado, Marina; García-Puentes, Diego; Sáez, Elena; Vicent, Cristina; Fernández de la Pradilla, Roberto; Viso, Alma; de la Torre, María C; Sierra, Miguel A


    An NMR comparative study of 1,2,3-triazole and triazolium anion recognition units containing sulfoxide, sulfone, and sulfoximine groups at C4 unveils an enhancement in binding ability up to ≈1 kcal/mol in acetone-d6 correlated with a theoretical increase of H5 acidity. DFT calculations provide insight into binding modes in line with experimental data for these receptors.

  10. Frustrated Lewis pairs: Design and reactivity

    Indian Academy of Sciences (India)

    Sanjoy Mukherjee; Pakkirisamy Thilagar


    The interaction of a Lewis acid with a Lewis base results in the formation of a Lewis acid–base adduct. Understanding Lewis acids and bases is central to conceptualizing chemical interactions and constitutes a major portion of metal–ligand chemistry. Sterically encumbered/constrained Lewis pairs cannot form acid–base adducts, but such ‘Frustrated Lewis Pairs’ (FLPs), with their unquenched electronic demands can be elegantly used to simultaneously react with a third species, resulting in unusual reactivity of small molecules. Such unusual reactions, explored only in the last few years, have found several applications, e.g., heterolytic splitting of H2, activation of small molecules (CO2, N2O, etc.). FLPs have opened new opportunities in synthetic chemistry, covering organic, main group as well as transition metal chemistry. The design strategies adopted for FLP systems and their unique reactivity are discussed here.

  11. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions. (United States)

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L


    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions.

  12. Exact solution for generalized pairing


    Pan, Feng; J.P. Draayer


    An infinite dimensional algebra, which is useful for deriving exact solutions of the generalized pairing problem, is introduced. A formalism for diagonalizing the corresponding Hamiltonian is also proposed. The theory is illustrated with some numerical examples.

  13. Pairing versus quarteting coherence length

    CERN Document Server

    Delion, Doru S


    We systematically analyse the coherence length in even-even nuclei. The pairing coherence length in the spin-singlet channel for the effective density dependent delta (DDD) and Gaussian interaction is estimated. We consider in our calculations bound states as well as narrow resonances. It turns out that the pairing gaps given by the DDD interaction are similar to those of the Gaussian potential if one renormalizes the radial width to the nuclear radius. The correlations induced by the pairing interaction have in all considered cases a long range character inside the nucleus and decrease towards the surface. The mean coherence length is larger than the geometrical radius for light nuclei and approaches this value for heavy nuclei. The effect of the temperature and states in continuum is investigated. Strong shell effects are evidenced, especially for protons. We generalize this concept to quartets by considering similar relations, but between proton and neutron pairs. The quartet coherence length has a similar...

  14. Dual pairs in fluid dynamics

    CERN Document Server

    Gay-Balmaz, François


    This paper is a rigorous study of the dual pair structure of the ideal fluid and the dual pair structure for the $n$-dimensional Camassa-Holm (EPDiff) equation, including the proofs of the necessary transitivity results. In the case of the ideal fluid, we show that a careful definition of the momentum maps leads naturally to central extensions of diffeomorphism groups such as the group of quantomorphisms and the Ismagilov central extension.

  15. Feijoa sellowiana Berg fruit juice: anti-inflammatory effect and activity on superoxide anion generation. (United States)

    Monforte, Maria T; Fimiani, Vincenzo; Lanuzza, Francesco; Naccari, Clara; Restuccia, Salvatore; Galati, Enza M


    Feijoa sellowiana Berg var. coolidge fruit juice was studied in vivo for the anti-inflammatory activity by carrageenin-induced paw edema test and in vitro for the effects on superoxide anion release from neutrophils in human whole blood. The fruit juice was analyzed by the high-performance liquid chromatography method, and quercetin, ellagic acid, catechin, rutin, eriodictyol, gallic acid, pyrocatechol, syringic acid, and eriocitrin were identified. The results showed a significant anti-inflammatory activity of F. sellowiana fruit juice, sustained also by an effective antioxidant activity observed in preliminary studies on 1,1-diphenyl-2-picrylhydrazyl (DPPH) test. In particular, the anti-inflammatory activity edema inhibition is significant since the first hour (44.11%) and persists until the fifth hour (44.12%) of the treatment. The effect on superoxide anion release was studied in human whole blood, in the presence of activators affecting neutrophils by different mechanisms. The juice showed an inhibiting response on neutrophils basal activity in all experimental conditions. In stimulated neutrophils, the higher inhibition of superoxide anion generation was observed at concentration of 10(-4) and 10(-2) mg/mL in whole blood stimulate with phorbol-myristate-13-acetate (PMA; 20% and 40%) and with N-formyl-methionyl-leucyl-phenylalanine (FMLP; 15% and 48%). The significant reduction of edema and the inhibition of O2(-) production, occurring mainly through interaction with protein-kinase C pathway, confirm the anti-inflammatory effect of F. sellowiana fruit juice.

  16. Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials

    Directory of Open Access Journals (Sweden)

    Peter Hesemann


    Full Text Available The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA, mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

  17. Interaction of anions with substituted buckybowls. The anion's nature and solvent effects. (United States)

    Campo-Cacharrón, Alba; Cabaleiro-Lago, Enrique M; González-Veloso, Iván; Rodríguez-Otero, Jesús


    Complexes formed by CN-substituted corannulene and sumanene with monovalent anions have been computationally studied to evaluate the effect of anion's nature and solvent upon the interaction. The results indicate that the most stable complex arrangement corresponds in all cases to the anion located by the center of the concave face of the bowl. All complexes are remarkably stable in the gas phase, with interaction energies ranging from -47 to -24 kcal/mol depending on the anion and the bowl considered. The order of stability for the different anion complexes in the gas phase is CO2H(-) > Cl(-) > Br(-) > NO3(-) ≫ ClO4(-) > BF4(-). Regarding the bowl employed, the intensity of the interaction is largest with the sumanene derivative substituted in the C-H aromatic groups. The weakest interactions are obtained with the sumanene derivative substituted in the CH2 groups, whereas complexes with the corannulene derivative give intermediate values. NO3(-) is oriented parallel to the bowl in the most stable complexes, whereas CO2H(-) prefers being oriented perpendicular to the bowl; ClO4(-) and BF4(-) arrange themselves with three bonds pointing to the bowl. These orientations are preferred on the basis of larger electrostatic and dispersion interactions. The preference of anions for the concave face of the bowl not only is mainly related to larger electrostatic interactions but also is because dispersion and induction are larger than in other arrangements considered. The presence of solvent modeled with a continuum model has a deep impact on the interaction energies already in solvents with low dielectric constant. All complexes remain stable, though energies in water hardly reach -7 kcal/mol. Br(-) complexes are the most stable in solvent, whereas CO2H(-) ones suffer a large penalty in solvent, becoming among the least stable complexes despite being the most stable in the gas phase.

  18. Pair programming: more than just working together in pairs.

    Directory of Open Access Journals (Sweden)

    Elsa Mentz


    Full Text Available Pair programming originated in the industry where focus is placed on the development of a programme at the most costand time-effective manner, and within the parameters of quality. In this context, a specific programming code is not developed individually; rather, two people work together in order to ensure a higher quality programming code and to motivate each other to work at a faster pace. The problem with this approach was that novice programmers lacked the social skills to work in pairs as they had not been exposed to this sufficiently at tertiary level. The demand of the industry, especially in terms of programmers needing to be able to programme together, led to the incorporation of pair programming at tertiary level in the late nineties. The pedagogical principles on which any teaching-learning strategy should be built were, however, largely overlooked during this process. This article firstly looks into the semantic and ontological differences between co-operative and collaborative learning and secondly argues that pair programming, within the context of a social constructivist approach to teaching and learning, can be seen as a co-operative teaching-learning strategy. Pair programming is more than just allowing two students to work together on a programming task. The more structured way, in which pair programming needs to be implemented, concur with the principles of co-operative learning. The article concludes that the correct pedagogical application of pair programming as a co-operative teaching-learning strategy in tertiary education will result in improved learning capital.

  19. Comprehensive mechanistic study of ion pair SN2 reactions of lithium isocyanate and methyl halides (United States)

    Sun, Ying-Xin; Ren, Yi; Wong, Ning-Bew; Chu, San-Yan; Xue, Ying

    The anionic SN2 reactions NCO- + CH3X and ion pair SN2 reactions LiNCO + CH3X (X = F, Cl, Br, and I) at saturated carbon with inversion and retention mechanisms were investigated at the level of MP2/6-311+G(d,p). There are two possible reaction pathways in the anionic SN2 reactions, but eight in the ion pair SN2 reactions. Calculated results suggest that the previously reported T-shaped isomer of lithium isocyanate does not exist. All the retention pathways are not favorable based on the analysis of transition structures. Two possible competitive reaction pathways proceed via two six-member ring inversion transition structures. It is found that there are two steps in the most favorable pathway, in which less stable lithium cyanate should be formed through the isomerization of lithium isocyanate and nucleophilic site (N) subsequently attacks methyl halides from the backside. The thermodynamically and kinetically favorable methyl isocyanate is predicted as major product both in the gas phase anionic and the ion pair SN2 reactions. In addition, good correlations between the overall barriers relative to separated reactants, ?H?ovr , with geometrical looseness parameter %L? and the heterolytic cleavage energies of the C bond X and Li bond N (or Li bond O) bonds are observed for the anionic and ion pair SN2 reactions. The trend of variation of the overall barriers predicts the leaving ability of X increase in the order: F reactions of LiNCO + CH3X. The calculations in solution indicate that solvent effects will retard the rate of reactions and the predicted product, methyl isocyanate, is same as the one in the gas phase.

  20. Bridging of anions by hydrogen bonds in nest motifs and its significance for Schellman loops and other larger motifs within proteins. (United States)

    Afzal, Avid M; Al-Shubailly, Fawzia; Leader, David P; Milner-White, E James


    The nest is a protein motif of three consecutive amino acid residues with dihedral angles 1,2-αR αL (RL nests) or 1,2-αL αR (LR nests). Many nests form a depression in which an anion or δ-negative acceptor atom is bound by hydrogen bonds from the main chain NH groups. We have determined the extent and nature of this bridging in a database of protein structures using a computer program written for the purpose. Acceptor anions are bound by a pair of bridging hydrogen bonds in 40% of RL nests and 20% of LR nests. Two thirds of the bridges are between the NH groups at Positions 1 and 3 of the motif (N1N3-bridging)-which confers a concavity to the nest; one third are of the N2N3 type-which does not. In bridged LR nests N2N3-bridging predominates (14% N1N3: 75% N2N3), whereas in bridged RL nests the reverse is true (69% N1N3: 25% N2N3). Most bridged nests occur within larger motifs: 45% in (hexapeptide) Schellman loops with an additional 4 → 0 hydrogen bond (N1N3), 11% in Schellman loops with an additional 5 → 1 hydrogen bond (N2N3), 12% in a composite structure including a type 1β-bulge loop and an asx- or ST- motif (N1N3)-remarkably homologous to the N1N3-bridged Schellman loop-and 3% in a composite structure including a type 2β-bulge loop and an asx-motif (N2N3). A third hydrogen bond is a previously unrecognized feature of Schellman loops as those lacking bridged nests have an additional 4 → 0 hydrogen bond.

  1. Three carbon pairs in Si

    Energy Technology Data Exchange (ETDEWEB)

    Docaj, A. [Physics Department, Texas Tech University, Lubbock, TX 79409-1051 (United States); Estreicher, S.K., E-mail: [Physics Department, Texas Tech University, Lubbock, TX 79409-1051 (United States)


    Carbon impurities in Si are common in floating-zone and cast-Si materials. The simplest and most discussed carbon complex is the interstitial-substitutional C{sub i}C{sub s} pair, which readily forms when self-interstitials are present in the material. This pair has three possible configurations, each of which is electrically active. The less common C{sub s}C{sub s} pair has been studied in irradiated material but has also recently been seen in as-grown C-rich cast-Si, which is commonly used to fabricate solar cells. The third pair consists of two interstitial C atoms: C{sub i}C{sub i}. Although its formation probability is low for several reasons, the C{sub i}C{sub i} pair is very stable and electrically inactive. In this contribution, we report preliminary results of first-principles calculations of these three C pairs in Si. The structures, binding energies, vibrational spectra, and electrical activity are predicted.

  2. Counting pairs of faint galaxies

    CERN Document Server

    Woods, D; Richer, H B; Woods, David; Fahlman, Gregory G; Richer, Harvey B


    The number of close pairs of galaxies observed to faint magnitude limits, when compared to nearby samples, determines the interaction or merger rate as a function of redshift. The prevalence of mergers at intermediate redshifts is fundamental to understanding how galaxies evolve and the relative population of galaxy types. Mergers have been used to explain the excess of galaxies in faint blue counts above the numbers expected from no-evolution models. Using deep CFHT (I\\leq24) imaging of a ``blank'' field we find a pair fraction which is consistent with the galaxies in our sample being randomly distributed with no significant excess of ``physical'' close pairs. This is contrary to the pair fraction of 34\\%\\pm9\\% found by Burkey {\\it et al.} for similar magnitude limits and using an identical approach to the pair analysis. Various reasons for this discrepancy are discussed. Colors and morphologies of our close pairs are consistent with the bulk of them being random superpositions although, as indicators of int...

  3. Effect of ion pairing on the fluorescence of berberine, a natural isoquinoline alkaloid (United States)

    Megyesi, Mónika; Biczók, László


    Effect of association with chloride or perchlorate anions on the fluorescence properties of berberine, a cationic isoquinoline alkaloid, has been studied. Interaction with Cl - caused more efficient fluorescence quenching; it significantly accelerated the radiationless deactivation and slowed down the radiative transition. Combined analysis of spectrophotometric, steady-state and time-resolved fluorescence results provided 1.5 × 10 5 M -1 for the equilibrium constant of ion pairing with Cl - in CH 2Cl 2. Both ion pairing and enrichment of the microenvironment of berberine in ions led to excited state quenching in solvents of medium polarity, but only the latter effect was observed in the presence of perchlorates in butyronitrile.

  4. Photodissociation Efficiency Spectroscopy Study of the Rydberg Excited Ion-Pair States of Carbon Dioxide (United States)

    Feng, Qiang; Xu, Yun-Feng; Sun, Jin-Da; Tian, Shan-Xi; Shan, Xiao-Bin; Liu, Fu-Yi; Sheng, Liu-Si


    Photodissociation efficiency spectrum of anionic oxygen atom produced via ion-pair dissociations of carbon dioxide is recorded by means of the synchrotron radiation excitation (XUV photon energy 17.40-20.00 eV). The present spectrum is assigned as the Rydberg-like excited ion-pair states, i.e., Tanaka-Ogawa and Henning series, tilde C2Σg+ (CO+2) vibrational ground-state and excitation series. Three Rydberg series, npσu, npπu, and nfu, converging to tilde C2Σg+ (0, 0, 0), show the higher cross sections.

  5. All-trans retinoic acid with daunorubicin or idarubicin for risk-adapted treatment of acute promyelocytic leukaemia : a matched-pair analysis of the PETHEMA LPA-2005 and IC-APL studies

    NARCIS (Netherlands)

    Sanz, Miguel A.; Montesinos, Pau; Kim, Haesook T.; Ruiz-Argueelles, Guillermo J.; Undurraga, Maria S.; Uriarte, Maria R.; Martinez, Lem; Jacomo, Rafael H.; Gutierrez-Aguirre, Homero; Melo, Raul A. M.; Bittencourt, Rosane; Pasquini, Ricardo; Pagnano, Katia; Fagundes, Evandro M.; Vellenga, Edo; Holowiecka, Alexandra; Gonzalez-Huerta, Ana J.; Fernandez, Pascual; De la Serna, Javier; Brunet, Salut; De Lisa, Elena; Gonzalez-Campos, Jose; Ribera, Jose M.; Krsnik, Isabel; Ganser, Arnold; Berliner, Nancy; Ribeiro, Raul C.; Lo-Coco, Francesco; Lowenberg, Bob; Rego, Eduardo M.


    Front-line treatment of acute promyelocytic leukaemia (APL) consists of all-trans retinoic acid (ATRA) and anthracycline-based chemotherapy. In this setting, a comparison of idarubicin and daunorubicin has never been carried out. Two similar clinical trials using ATRA and chemotherapy for newly diag

  6. Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis (United States)

    Yonetani, Yoshiteru


    Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

  7. The analysis of cations and anions in illicit heroin using capillary electrophoresis with indirect UV detection. (United States)

    Lurie, I S


    Methodology is presented for the analysis of cations and anions in illicit heroin using CE with indirect UV detection. The cations investigated include ammonium, calcium, potassium, magnesium, and sodium; the anions included acetate, chloride, citrate, phosphate, sulfate, and tartrate. For cations, the Ion Phor run buffer (Dionex Corp., Sunnyvale, CA, U.S.A.) consisting of 4 mM copper sulfate, 4 mM formic acid, and 3 mM 18-crown-6 (pH 3.0) was used. For anions, proprietary reagents were used, including the Anitron run buffer (PE Applied Biosystems, Foster City, CA, U.S.A.) and Micro-Coat capillary charge-reversal agent (PE Applied Biosystems), which was utilized to flush the capillary prior to each analysis. Lithium nitrate was used as an internal standard; excellent long- and short-term precision in relative retention times were obtained for both cations and anions. The short-term precision in peak areas was satisfactory. For the various ions examined, a linearity range of a little less than two orders of magnitude was observed. The methodology is capable of analyzing ions down to the 10(-3)% level relative to heroin.

  8. Study on Separation of Lanthanum from Praseodymium Complexes with IMDA by Gel and Macroporous Anion-Exchangers

    Institute of Scientific and Technical Information of China (English)


    During our studies on separation of rare earth complexes with aminopolycarboxylic acids on anion-exchangers, it is found that the affinity series of these elements with IMDA (Ln3+:IMDA=1:2) for the anion-exchanger Dowex 1 in the acetate and IMDA forms is non-typical: Dy3+> Ho3+> Gd3+>Eu3+>Er3+>Y3+>Sm3+>Tm3+>Nd3+>Pr3+>>La3+. In the affinity series La3+ is characterised as the lowest affinity in omparison with other rare earth elements, which indicates possibility ofpurification of La3+ from all remaining lanthanides as well as Pr3+ in the macro-micro systems by the frontal analysis technique. In the investigations strongly basic gel anion-exchangers Dowex 1×8 (type 1) and Dowex 2×8 (type 2) and strongly basic and weakly basic macroporous anion-exchangers Dowex MSA-1 and Dowex MWA-1 were used. Macroporous ion-exchangers have a sponge-like matrix which contains pores larger than molecules in size and the exchange of large ions is faster. The studies indicate that both the gel and macroporous anion-exchangers are useful for purification of La3+ from Pr3+ complexes with iminodiacetic acid.

  9. Anionic cascade reactions. One-pot assembly of (Z-chloro-exo-methylenetetrahydrofurans from β-hydroxyketones

    Directory of Open Access Journals (Sweden)

    István E. Markó


    Full Text Available The assembly of (Z-chloro-exo-methylenetetrahydrofurans by an original and connective anionic cascade sequence is reported. Base-catalysed condensation of β-hydroxyketones with 1,1-dichloroethylene generates, in moderate to good yields, the corresponding (Z-chloro-exo-methylenetetrahydrofurans. Acidic treatment of this motif leads to several unexpected dimers, possessing unique structural features.

  10. Organic superconductors with an incommensurate anion structure

    Directory of Open Access Journals (Sweden)

    Tadashi Kawamoto and Kazuo Takimiya


    Full Text Available Superconducting incommensurate organic composite crystals based on the methylenedithio-tetraselenafulvalene (MDT-TSF series donors, where the energy band filling deviates from the usual 3/4-filled, are reviewed. The incommensurate anion potential reconstructs the Fermi surface for both (MDT-TSF(AuI20.436 and (MDT-ST(I30.417 neither by the fundamental anion periodicity q nor by 2q, but by 3q, where MDT-ST is 5H-2-(1,3-dithiol-2-ylidene-1,3-diselena-4,6-dithiapentalene, and q is the reciprocal lattice vector of the anion lattice. The selection rule of the reconstructing vectors is associated with the magnitude of the incommensurate potential. The considerably large interlayer transfer integral and three-dimensional superconducting properties are due to the direct donor–donor interactions coming from the characteristic corrugated conducting sheet structure. The materials with high superconducting transition temperature, Tc, have large ratios of the observed cyclotron masses to the bare ones, which indicates that the strength of the many-body effect is the major determinant of Tc. (MDT-TS(AuI20.441 shows a metal–insulator transition at TMI=50 K, where MDT-TS is 5H-2-(1,3-diselenol-2-ylidene-1,3,4,6-tetrathiapentalene, and the insulating phase is an antiferromagnet with a high Néel temperature (TN=50 K and a high spin–flop field (Bsf=6.9 T. There is a possibility that this material is an incommensurate Mott insulator. Hydrostatic pressure suppresses the insulating state and induces superconductivity at Tc=3.2 K above 1.05 GPa, where Tc rises to the maximum, Tcmax=4.9 K at 1.27 GPa. This compound shows a usual temperature–pressure phase diagram, in which the superconducting phase borders on the antiferromagnetic insulating phase, despite the unusual band filling.

  11. Anion complexation with cyanobenzoyl substituted first and second generation tripodal amide receptors: crystal structure and solution studies. (United States)

    Hoque, Md Najbul; Gogoi, Abhijit; Das, Gopal


    Anion complexation properties of two new tripodal amide receptors have been extensively studied here. Two tripodal receptors have been synthesized from the reaction of cyanobenzoyl acid chloride with two tri-amine building blocks such as (i) tris(2-aminoethyl)amine and (ii) tris(2-(4-aminophenoxy)ethyl)amine, which resulted in the first (L1) and second (L2) generation tripodal amides respectively. A detailed comparison of their coordination behavior with anions is also described by crystallographic and solution state experiments. The crystal structure demonstrates various types of spatial orientations of tripodal arms in two receptors and concomitantly interacts with anions distinctively. Intramolecular H-bonding between amide N–H and CO prevents opening of the receptor cavity in the crystal, which leads to a locked conformation of L1 having C(3v) symmetry and makes amide hydrogen unavailable for the anion which results in side cleft anion binding. However, in L2 we conveniently shift the anion binding sites to a distant position which increases cavity size as well as rules out any intramolecular H-bonding between amide N–H and CO. The crystal structure shows a different orientation of the arms in L2; it adopts a quasi-planar arrangement with C(2v) symmetry. In the crystal structure two arms are pointed in the same direction and while extending the contact the third arm is H-bonded with the apical N-atom through a –CN group, making a pseudo capsular cavity where the anion interacts. Most importantly spatial reorientation of the receptor L2 from a C(2v) symmetry to a folded conformation with a C(3v) symmetry was observed only in the presence of an octahedral SiF6(2-) anion and forms a sandwich type complex. Receptors L1 and L2 are explored for their solution state anion binding abilities. The substantial changes in chemical shifts were observed for the amide (-NH) and aromatic hydrogen (-CH) (especially for F(-)), indicating the role of these hydrogens in

  12. Probes for anionic cell surface detection (United States)

    Smith, Bradley D.


    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  13. Electroculture for crop enhancement by air anions (United States)

    Pohl, H. A.; Todd, G. W.


    Electroculture, the practice of applying strong electric fields or other sources of small air ions to growing plants, has potential to markedly increase crop production and to speed crop growth. The considerable evidence for its effectiveness, and the studies of the mechanisms for its actions are discussed. A mild current of air anions (4 pA/cm2) stimulates bean crop growth and also earlier blossoming and increased growth in the annual, Exacum affine (Persian violet), as well as in seedling geraniums. The present results would indicate that the growing period required until the plants reach a saleable stage of maturity can be shortened by about two weeks under greenhouse conditions.

  14. Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects. (United States)

    Hack, John; Grills, David C; Miller, John R; Mani, Tomoyasu


    Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

  15. Superconductivity: The persistence of pairs

    Energy Technology Data Exchange (ETDEWEB)

    Edelman, Alex; Littlewood, Peter


    Superconductivity stems from a weak attraction between electrons that causes them to form bound pairs and behave much like bosons. These so-called Cooper pairs are phase coherent, which leads to the astonishing properties of zero electrical resistance and magnetic flux expulsion typical of superconducting materials. This coherent state may be qualitatively understood within the Bose–Einstein condensate (BEC) model, which predicts that a gas of interacting bosons will become unstable below a critical temperature and condense into a phase of matter with a macroscopic, coherent population in the lowest energy state, as happens in 4He or cold atomic gases. The successful theory proposed by Bardeen, Cooper and Schrieffer (BCS) predicts that at the superconducting transition temperature Tc, electrons simultaneously form pairs and condense, with no sign of pairing above Tc. Theorists have long surmised that the BCS and BEC models are opposite limits of a single theory and that strong interactions or low density can, in principle, drive the system to a paired state at a temperature Tpair higher than Tc, making the transition to the superconducting state BEC-like (Fig. 1). Yet most superconductors to date are reasonably well described by BCS theory or its extensions, and there has been scant evidence in electronic materials for the existence of pairing independent of the full superconducting state (though an active debate rages over the cuprate superconductors). Writing in Nature, Jeremy Levy and colleagues have now used ingenious nanostructured devices to provide evidence for electron pairing1. Perhaps surprisingly, the material they have studied is a venerable, yet enigmatic, low-temperature superconductor, SrTiO3.

  16. Anion and cation mixed-bed ion exchange for enhanced multidimensional separations of peptides and phosphopeptides. (United States)

    Motoyama, Akira; Xu, Tao; Ruse, Cristian I; Wohlschlegel, James A; Yates, John R


    Shotgun proteomics typically uses multidimensional LC/MS/MS analysis of enzymatically digested proteins, where strong cation-exchange (SCX) and reversed-phase (RP) separations are coupled to increase the separation power and dynamic range of analysis. Here we report an on-line multidimensional LC method using an anion- and cation-exchange mixed bed for the first separation dimension. The mixed-bed ion-exchange resin improved peptide recovery over SCX resins alone and showed better orthogonality to RP separations in two-dimensional separations. The Donnan effect, which was enhanced by the introduction of fixed opposite charges in one column, is proposed as the mechanism responsible for improved peptide recovery by producing higher fluxes of salt cations and lower populations of salt anions proximal to the SCX phase. An increase in orthogonality was achieved by a combination of increased retention for acidic peptides and moderately reduced retention of neutral to basic peptides by the added anion-exchange resin. The combination of these effects led to approximately 100% increase in the number of identified peptides from an analysis of a tryptic digest of a yeast whole cell lysate. The application of the method to phosphopeptide-enriched samples increased by 94% phosphopeptide identifications over SCX alone. The lower pKa of phosphopeptides led to specific enrichment in a single salt step resolving acidic phosphopeptides from other phospho- and non-phosphopeptides. Unlike previous methods that use anion exchange to alter selectivity or enrich phosphopeptides, the proposed format is unique in that it works with typical acidic buffer systems used in electrospray ionization, making it feasible for online multidimensional LC/MS/MS applications.

  17. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lai-Sheng, E-mail: [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)


    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  18. Zero-point energy effects in anion solvation shells. (United States)

    Habershon, Scott


    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  19. Mechanistic Consequences of Composition in Acid Catalysis by Polyoxometalate Keggin Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Macht, Josef; Janik, Michael J.; Neurock, Matthew; Iglesia, Enrique


    concurrent decrease in deprotonation enthalpies (DPE), which leads to more stable anionic clusters and ion-pairs at transition states. The DPE of POM clusters influences catalytic rates less than the proton affinity of the alkene-like organic moiety at the late carbenium-ion-type transition states involved. These different sensitivities reflect the fact that weaker acids typically form anionic clusters with a higher charge density at the transition state; these clusters stabilize cationic fragments more effectively than those of stronger acids, which form more stable conjugate bases with lower charge densities. These compensation effects are ubiquitous in acid chemistry and also evident for mineral acids. The stabilization energy and the concomitant charge density and distribution in the anion, but not the acid strength (DPE), determine the kinetic tolerance of n-donors and the selectivity of reactions catalyzed by Brønsted acids.

  20. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)


    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  1. Modeling Carbon Chain Anions in L1527

    CERN Document Server

    Harada, Nanase


    The low-mass protostellar region L1527 is unusual because it contains observable abundances of unsaturated carbon-chain molecules including CnH radicals, H2Cn carbenes, cyanopolyynes, and the negative ions C4H- and C6H-, all of which are more associated with cold cores than with protostellar regions. Sakai et al. suggested that these molecules are formed in L1527 from the chemical precursor methane, which evaporates from the grains during the heat-up of the region. With the gas-phase osu.03.2008 network extended to include negative ions of the families Cn-, and CnH-, as well as the newly detected C3N-, we modeled the chemistry that occurs following methane evaporation at T~ 25-30 K. We are able to reproduce most of the observed molecular abundances in L1527 at a time of ~5000 yr. At later times, the overall abundance of anions become greater than that of electrons, which has an impact on many organic species and ions. The anion-to-neutral ratio in our calculation is in good agreement with observation for C6H-...

  2. Isatin phenylhydrazones: anion enhanced photochromic behaviour. (United States)

    Cigáň, M; Jakusová, K; Gáplovský, M; Filo, J; Donovalová, J; Gáplovský, A


    The photochemical properties of two basic easily synthesized isatin N(2)-phenylhydrazones were investigated. Contrary to the corresponding isatin N(2)-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the C=N double bond creates conditions for the formation of a simple on-off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis-Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore-inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism.

  3. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  4. Paired structures in knowledge representation

    DEFF Research Database (Denmark)

    Montero, J.; Bustince, H.; Franco de los Ríos, Camilo;


    In this position paper we propose a consistent and unifying view to all those basic knowledge representation models that are based on the existence of two somehow opposite fuzzy concepts. A number of these basic models can be found in fuzzy logic and multi-valued logic literature. Here it is clai......In this position paper we propose a consistent and unifying view to all those basic knowledge representation models that are based on the existence of two somehow opposite fuzzy concepts. A number of these basic models can be found in fuzzy logic and multi-valued logic literature. Here...... of paired structures, generated from two paired concepts together with their associated neutrality, all of them to be modeled as fuzzy sets. In this way, paired structures can be viewed as a standard basic model from which different models arise. This unifying view should therefore allow a deeper analysis...

  5. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.


    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and AcO-) to a s......The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  6. Ionic force field optimization based on single-ion and ion-pair solvation properties: going beyond standard mixing rules. (United States)

    Fyta, Maria; Netz, Roland R


    Using molecular dynamics (MD) simulations in conjunction with the SPC/E water model, we optimize ionic force-field parameters for seven different halide and alkali ions, considering a total of eight ion-pairs. Our strategy is based on simultaneous optimizing single-ion and ion-pair properties, i.e., we first fix ion-water parameters based on single-ion solvation free energies, and in a second step determine the cation-anion interaction parameters (traditionally given by mixing or combination rules) based on the Kirkwood-Buff theory without modification of the ion-water interaction parameters. In doing so, we have introduced scaling factors for the cation-anion Lennard-Jones (LJ) interaction that quantify deviations from the standard mixing rules. For the rather size-symmetric salt solutions involving bromide and chloride ions, the standard mixing rules work fine. On the other hand, for the iodide and fluoride solutions, corresponding to the largest and smallest anion considered in this work, a rescaling of the mixing rules was necessary. For iodide, the experimental activities suggest more tightly bound ion pairing than given by the standard mixing rules, which is achieved in simulations by reducing the scaling factor of the cation-anion LJ energy. For fluoride, the situation is different and the simulations show too large attraction between fluoride and cations when compared with experimental data. For NaF, the situation can be rectified by increasing the cation-anion LJ energy. For KF, it proves necessary to increase the effective cation-anion Lennard-Jones diameter. The optimization strategy outlined in this work can be easily adapted to different kinds of ions.

  7. Exlusive charmed meson pair production

    CERN Document Server

    Berezhnoy, A V


    The experimental data of BELLE Collaboration on the exclusive charmed meson pair production in the process of monophotonic $e^+e^-$-annihilation ($e^+e^-\\to \\gamma^* \\to D\\bar D$) has been studied. It has been shown that these data is described satisfactorily in the frame work of constituent quark model. Our studies have demonstrated that the central production process $e^+e^-\\to e^+e^-\\gamma\\gamma \\to e^+e^-D\\bar D +X$ and the process of monophotonic $e^+e^-$-annihilation yield comparable numbers of the charmed meson pairs.

  8. Instantons in lepton pair production

    Energy Technology Data Exchange (ETDEWEB)

    Brandenburg, A.; Ringwald, A. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Utermann, A. [Vrije Univ., Amsterdam (Netherlands). Dept. of Physics and Astronomy


    We consider QCD instanton-induced contributions to lepton pair production in hadron-hadron collisions. We relate these contributions to those known from deep inelastic scattering and demonstrate that they can be calculated reliably for sufficiently large momentum transfer. We observe that the instanton contribution to the angular distribution of the lepton pairs at finite momentum transfer strongly violates the Lam-Tung relation - a relation between coefficient functions of the angular distribution which is valid within the framework of ordinary perturbation theory. The drastic violation of this relation, as seen in experimental data, might be related to such instanton-induced effects. (Orig.)

  9. Increased anion channel activity is an unavoidable event in ozone-induced programmed cell death.

    Directory of Open Access Journals (Sweden)

    Takashi Kadono

    Full Text Available BACKGROUND: Ozone is a major secondary air pollutant often reaching high concentrations in urban areas under strong daylight, high temperature and stagnant high-pressure systems. Ozone in the troposphere is a pollutant that is harmful to the plant. PRINCIPAL FINDINGS: By exposing cells to a strong pulse of ozonized air, an acute cell death was observed in suspension cells of Arabidopsis thaliana used as a model. We demonstrated that O(3 treatment induced the activation of a plasma membrane anion channel that is an early prerequisite of O(3-induced cell death in A. thaliana. Our data further suggest interplay of anion channel activation with well known plant responses to O(3, Ca(2+ influx and NADPH-oxidase generated reactive oxygen species (ROS in mediating the oxidative cell death. This interplay might be fuelled by several mechanisms in addition to the direct ROS generation by O(3; namely, H(2O(2 generation by salicylic and abscisic acids. Anion channel activation was also shown to promote the accumulation of transcripts encoding vacuolar processing enzymes, a family of proteases previously reported to contribute to the disruption of vacuole integrity observed during programmed cell death. SIGNIFICANCE: Collectively, our data indicate that anion efflux is an early key component of morphological and biochemical events leading to O(3-induced programmed cell death. Because ion channels and more specifically anion channels assume a crucial position in cells, an understanding about the underlying role(s for ion channels in the signalling pathway leading to programmed cell death is a subject that warrants future investigation.

  10. Effects of Electrolyte Anions and pH on Adsortpion of Sulfate by Variable Charge Soils

    Institute of Scientific and Technical Information of China (English)



    The effects of three electrolyte anions,ionic strength and pH on the adsorption of sulfate by two variable charge soils,with different surface charge properties were studied.Under the conditions of the same pH and ionic strength the effect of electrolyte anions on the adsorption of sulfate was in the order of Cl->NO3->ClO4-,indicating the difference of the nature among these three anions.For ferralsol in the same concentration of chloride and perchloride solutions,the two sulfate adsorption-pH curves could intersect at certain pH value.When pH was higher than the intersecting point.more sulfate was adsorbed in the perchloride solution,while when it was lower than the intersecting point,more sulfate was adsorbed in the chloride solution.In different concentratioins of electrolyte solution,the curves of the amount of oxy-acid anion adsorbed,which changed with pH,could intersect at a certain pH,which is termed point of zero salt effect(PZSE) on adsortpion.The nature of electrolyte anions influenced obviously the appearace of PZSE for sulfate adsorption.For ferralsol the curves of adsorption converged to about pH 7 in NaCl solution seemed to intersect in NaNO3 solution and to have a typical PZSE for sulfate adsorption in NaClO4 solution,For Acrisol the three curves of adsorption were nearly parallel in NaCl and NaNO3 solutions and converged to pH 6.5 in NaClO4 solution.

  11. Extractive spectrophotometric determination of five selected drugs by ion-pair complex formation with bromothymol blue in pure form and pharmaceutical preparations

    Directory of Open Access Journals (Sweden)

    Sneha G. Nair


    Full Text Available Simple, precise, selective, and expeditious spectrophotometric methods have been developed for the determination of itopride (ITO, midodrine (MID, diclofenac (DIC, mesalamine (MES, and sumatriptan (SUM in their pure form as well as in pharmaceutical preparations. The method was based on ion-pair complex formation between the drugs and anionic dye, bromothymol blue in an acidic medium (pH 2.0–4.0. The yellow colored complexes formed were quantitatively extracted into chloroform and measured at 411, 410, 413, 412, and 414 nm wavelength for ITO, MID, DIC, MES, and SUM, respectively. Beer’s law was obeyed in the concentration range of 3.0–30 µg/mL for ITO, 1.0–20 µg/mL for MID, 1.5–40 µg/mL for DIC, 1.2–12 µg/mL for MES, and 0.5–15 µg/mL for SUM. The stoichiometry of the complexes formed between the drugs and the dye was 1:1 as determined by Job’s method of continuous variation. The association constant (KIP of the ion-pair complexes formed was evaluated using Benesi–Hildebrand equation. Limit of detection, limit of quantification, and Sandell’s sensitivity of the methods were also estimated. The proposed methods were successfully employed for the determination of these drugs in their pharmaceutical dosage forms.

  12. Effects of anionic xenobiotics on rat kidney. I--Tissue and mitochondrial respiration. (United States)

    Pritchard, J B; Krall, A R; Silverthorn, S U


    The polar 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) metabolite, 2,2-bis(p-chlorophenyl)acetic acid (DDA), and the phenoxyacetic acid herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), were previously shown to be accumulated to high levels in liver and kidney via the organic acid transport system, raising the possibility of organ-specific toxicity secondary to transport. In these studies, accumulation of DDA was shown to depress oxygen consumption by renal cortical slices at high doses (0.1 and 1mM). Isolated renal and hepatic mitochondria were uncoupled by low doses of DDA (5-10 nmoles/mg mitochondrial protein. Maximal uncoupling was seen at 50-70 nmoles/mg. 2,4-D and 2,4,5-T also produced uncoupling, but at doses of 70 nmoles/mg or higher. All agents were more effective with alpha-ketoglutarate or pyruvate-malate), all three agents also depressed State 3 (ADP-stimulated) respiration. Again, DDA was more effective than 2,4-D or 2,4,5-T. These results suggest that accumulation of these or other anionic xenobiotics may lead to toxicity in those tissues possessing the organic anion transport system.

  13. Effect of some anionic polymers on pH of triethanolamine aqueous solutions. (United States)

    Musiał, Witold; Kubis, Aleksander


    One of the suggested approaches in the management and prophylaxis of acne involves binding of free fatty acids in the form of soap with alcoholamines. Due to a possible irritating effect of alcoholamines associated with a relatively high pH of their aqueous solutions, complexation of alcoholamines with acid polymers is advocated. Triethanolamine is one of the best recognized alcoholamines. It was conventionally neutralized with Carbopols, Eudragits, alginic acid and pectin. During neutralization of polymer dispersions with triethanolamine, variations in the course of the neutralization curve have been observed among individual macromolecular compounds. The pH of 0.1 mol/l triethanolamine solution reaches 10.51, while following a complete neutralization with anionic polymers, such as Carbopols, Eudragits, alginic acid and pectin, pH ranges from 3.88 for systems neutralized with alginic acid to 8.50 for the system neutralized with Eudragit S-100. Complexation of triethanolamine with anionic polymers decreases its pH, and it is possible to find such pH range in which pH of the preparation containing the polymer and triethanolamine will correspond to the physiological pH of the skin.

  14. Electrochemical investigations of antioxidant interactions with radical anion and dianion of 1,3-dinitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Arshad, Nasima [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Janjua, Naveed Kausar [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan)], E-mail:; Ahmed, Safeer [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan); Khan, Athar Yaseen [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Skibsted, Leif H. [Food Chemistry, Department of Food Science, University of Copenhagen (Denmark)


    Interactions of five antioxidants (AO), quercetin (Q), morin (M), rutin (R), ascorbic acid (AA) and {beta}-carotene ({beta}-C) with anion radical and dianion of 1,3-dinitrobenzene (1,3-DNB) in two aprotic solvents - dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) - have been studied by cyclic voltammetry using glassy carbon electrode. Electrochemical parameters - peak potential (E{sub p}), half-wave potential (E{sub 1/2}), and peak current (i{sub p}) - for the reduction of 1,3-DNB before and after the addition of various concentrations of antioxidants, were evaluated. A gradual decrease in the oxidation peak current and finally irreversibility in 1,3-DNB radical anion and dianion systems upon the addition of antioxidant, reveals their interactions. The homogeneous bi-molecular rate constant (k{sub 2}) was determined from electrochemical data. In comparison to all other antioxidants used, enhanced homogeneous second order rate constant for the interaction of morin with 1,3-DNB anion radical and dianion, was observed. This aspect is attributable to protonation initiated by hydrogen bonding and greater acidic nature of morin.

  15. Determination of Anionic Surfactants Using Atomic Absorption Spectrometry and Anodic Stripping Voltammetry (United States)

    John, Richard; Lord, Daniel


    An experiment has been developed for our undergraduate analytical chemistry course that demonstrates the indirect analysis of anionic surfactants by techniques normally associated with metal ion determination; that is, atomic absorption spectroscopy (AAS) and anodic stripping voltammetry (ASV). The method involves the formation of an extractable complex between the synthetic surfactant anion and the bis(ethylenediamine)diaqua copper(II) cation. This complex is extracted into chloroform and then back-extracted into dilute acid. The resulting Cu(II) ions are determined by AAS and ASV. Students are required to determine the concentration of a pre-prepared "unknown" anionic surfactant solution and to collect and analyze a real sample of their choice. After the two extraction processes, students typically obtain close to 100% analytical recovery. Correlation between student AAS and ASV results is very good, indicating that any errors that occur probably result from their technique (dilutions, extractions, preparation of standards, etc.) rather than from the end analyses. The experiment is a valuable demonstration of the following analytical principles: indirect analysis; compleximetric analysis; liquid-liquid (solvent) extraction; back-extraction (into dilute acid); analytical recovery; and metal ion analysis using flame-AAS and ASV.

  16. Structural and kinetic insights reveal that the amino acid pair Gln-228/Asn-254 modulates the transfructosylating specificity of Schwanniomyces occidentalis β-fructofuranosidase, an enzyme that produces prebiotics. (United States)

    Álvaro-Benito, Miguel; Sainz-Polo, M Angela; González-Pérez, David; González, Beatriz; Plou, Francisco J; Fernández-Lobato, María; Sanz-Aparicio, Julia


    Schwanniomyces occidentalis β-fructofuranosidase (Ffase) is a GH32 dimeric enzyme that releases fructose from the nonreducing end of various oligosaccharides and essential storage fructans such as inulin. It also catalyzes the transfer of a fructosyl unit to an acceptor producing 6-kestose and 1-kestose, prebiotics that stimulate the growth of bacteria beneficial for human health. We report here the crystal structure of inactivated Ffase complexed with fructosylnystose and inulin, which shows the intricate net of interactions keeping the substrate tightly bound at the active site. Up to five subsites were observed, the sugar unit located at subsite +3 being recognized by interaction with the β-sandwich domain of the adjacent subunit within the dimer. This explains the high activity observed against long substrates, giving the first experimental evidence of the direct role of a GH32 β-sandwich domain in substrate binding. Crucial residues were mutated and their hydrolase/transferase (H/T) activities were fully characterized, showing the involvement of the Gln-228/Asn-254 pair in modulating the H/T ratio and the type β(2-1)/β(2-6) linkage formation. We generated Ffase mutants with new transferase activity; among them, Q228V gives almost specifically 6-kestose, whereas N254T produces a broader spectrum product including also neokestose. A model for the mechanism of the Ffase transfructosylation reaction is proposed. The results contribute to an understanding of the molecular basis regulating specificity among GH-J clan members, which represent an interesting target for rational design of enzymes, showing redesigned activities to produce tailor-made fructooligosaccharides.

  17. Electron pair creation by photons

    NARCIS (Netherlands)

    Holtwijk, Theodoor


    In our experiment on the creation of electron pairs a 5 MeV betatron was used as radiation source and a cloud chamber (with magnetic field) was used as detection instrument. The experimental arrangement is described in section 2.1. The cloud chamber was of the overcompression type so that the recove

  18. Pairs of dual periodic frames

    DEFF Research Database (Denmark)

    Christensen, Ole; Goh, Say Song


    is needed. The purpose of the present paper is to provide constructions of dual pairs of frames in the setting of the Hilbert space of periodic functions L2(0,2π). The frames constructed are given explicitly as trigonometric polynomials, which allows for an efficient calculation of the coefficients...

  19. Atomic force microscopy study of anion intercalation into highly oriented pyrolytic graphite

    Energy Technology Data Exchange (ETDEWEB)

    Alliata, D.; Haering, P.; Haas, O.; Koetz, R. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Siegenthaler, H. [University of Berne (Switzerland)


    In the context of ion transfer batteries, we studied highly oriented pyrolytic graphite (HOPG) in perchloric acid, as a model to elucidate the mechanism of electrochemical intercalation in graphite. Aim of the work is the local and time dependent investigation of dimensional changes of the host material during electrochemical intercalation processes on the nanometer scale. We used atomic force microscopy (AFM), combined with cyclic voltammetry, as in-situ tool of analysis during intercalation and expulsion of perchloric anions into the HOPG electrodes. According to the AFM measurements, the HOPG interlayer spacing increases by 32% when perchloric anions intercalate, in agreement with the formation of stage IV of graphite intercalation compounds. (author) 3 figs., 3 refs.

  20. Ultrafast transient optical studies of charge pair generation and recombination in poly-3-hexylthiophene(P3ht):[6,6]phenyl C61 butyric methyl acid ester (PCBM) blend films. (United States)

    Kirkpatrick, James; Keivanidis, Panagiotis E; Bruno, Annalisa; Ma, Fei; Haque, Saif A; Yarstev, Arkady; Sundstrom, Villy; Nelson, Jenny


    Charge generation and recombination are studied in blend films of poly-3-hexylthiophene (P3HT) and [6,6']phenyl C61 butyric acid methyl ester (PCBM) using ultrafast transient absorption spectroscopy. We find that the charge generation yield depends upon both blend film composition and thermal annealing. The data suggest that recombination occurs over a wide range of time scales and that, in the least favorable cases, the fastest charge recombination occurs on a time scale similar to exciton diffusion. The results are explained using a simple model that incorporates the effect of P3HT domain size on exciton diffusion and uses empirical models of recombination kinetics. We propose our method as a route to interpretation of spectroscopic data where different processes occur on similar time scales.

  1. A study of quasi reversible nitro radical anion from -nitrostyrene at wax-impregnated carbon paste electrode

    Indian Academy of Sciences (India)

    Ronald J Mascarenhas; Irishi N Namboothiri; B S Sherigara; Vijayakumar K Reddy


    A comprehensive study of the electrochemical reduction of -nitrostyrene and the corresponding heterocyclic analogue has been carried out in aprotic media using wax-impregnated carbon paste electrodes. Nitrostyrene exhibits quasi-reversible reduction process in aprotic medium at the waximpregnated carbon paste electrodes as compared to other electrodes reported in the literature. The nitroradical anion couple detected in the presence of tetrabutyl ammonium perchlorate is found to be stable only in aprotic media. Though, as reported, the pharmacological activity related to this nitro radical anion and its therapeutic value are related to the stability of the nitro radical anion, the stability itself depends on the electrode system employed. Added benzoic acid is found to bring about a positive shift in cathodic peak potential.

  2. Analysis of oxyhalide disinfection by-products and other anions of interest in drinking water by ion chromatography. (United States)

    Hautman, D P; Bolyard, M


    The US Environmental Protection Agency is developing regulations for various drinking water disinfection by-products (DBPs). This effort involves developing analytical methods for the DBPs formed as a result of different disinfection treatments and collecting occurrence data for these species. Ion chromatography is one method being used to analyze drinking water samples for the following inorganic DBPs: chlorite, chlorate and bromate. These anions, however, are difficult to separate from common interfering anions of chloride, carbonate and nitrate. A method is therefore presented by which tetraborate/boric acid is used to separate these anions. Method detection limits of the order of 10 micrograms/l, using conductivity and UV detection were obtained. Stability studies of chlorite showing the effectiveness of ethylenediamine as a preservative and summary data for an occurrence of nitrite, nitrate and the DBP precursor bromide are presented.

  3. Anion permselective membrane. [For redox fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, S.S.; Hodgdon, R.B.


    Experimental anion permeselective membranes were improved and characterized for use as separators in a chemical redox, power storage cell being developed at the NASA Lewis Research Center. The goal of minimal Fe/sup +3/ ion transfer was achieved for each candidate membrane system. Minimal membrane resistivity was demonstrated by reduction of film thickness using synthetic backing materials but usefulness of thin membranes was limited by the scarcity of compatible fabrics. The most durable and useful backing fabrics were modacrylics. One membrane, a copolymer of 4 vinylpyridine and vinyl benzylchloride was outstanding in overall electrochemical and physical properties. Long term (1000 hrs) membrane chemical and thermal durability in redox environment was shown by three candidate polymers and two membranes. The remainder had good durability at ambient temperature. Manufacturing capability was demonstrated for large scale production of membrane sheets 5.5 ft/sup 2/ in area for two candidate systems.

  4. Structural evolution of small ruthenium cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Waldt, Eugen [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Hehn, Anna-Sophia; Ahlrichs, Reinhart [Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany); Kappes, Manfred M.; Schooss, Detlef, E-mail: [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany)


    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  5. Once upon Anion: A Tale of Photodetachment (United States)

    Lineberger, W. Carl


    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  6. Advanced polymer chemistry of organometallic anions

    Energy Technology Data Exchange (ETDEWEB)

    Chamberlin, R.M.; Abney, K.D. [Los Alamos National Lab., NM (United States); Balaich, G.J.; Fino, S.A. [Air Force Academy, CO (United States)


    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes.

  7. Anion channelrhodopsins for inhibitory cardiac optogenetics (United States)

    Govorunova, Elena G.; Cunha, Shane R.; Sineshchekov, Oleg A.; Spudich, John L.


    Optical control of the heart muscle is a promising strategy for cardiology because it is more specific than traditional electrical stimulation, and allows a higher temporal resolution than pharmacological interventions. Anion channelrhodopsins (ACRs) from cryptophyte algae expressed in cultured neonatal rat ventricular cardiomyocytes produced inhibitory currents at less than one-thousandth of the light intensity required by previously available optogenetic tools, such as the proton pump archaerhodopsin-3 (Arch). Because of their greater photocurrents, ACRs permitted complete inhibition of cardiomyocyte electrical activity under conditions in which Arch was inefficient. Most importantly, ACR expression allowed precisely controlled shortening of the action potential duration by switching on the light during its repolarization phase, which was not possible with previously used optogenetic tools. Optical shortening of cardiac action potentials may benefit pathophysiology research and the development of optogenetic treatments for cardiac disorders such as the long QT syndrome. PMID:27628215

  8. Solvent extraction of beryllium from malonate solutions with liquid anion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Rao, R.R.; Khopkar, S.M.


    Beryllium was quantitatively extracted at pH 5.5-7.0 in microgram amounts with 0.06 M Aliquat 336S in xylene from 5 x 10/sup -3/ M malonic acid solution, stripped with 0.5 M hydrochloric acid, and determined spectrophotometrically at 523 nm as its complex with thorin. Those metals which could not form anionic complexes with malonic acid and were not extracted with beryllium at pH 6.5 were separated from it. Metals forming weak malonato complexes were scrubbed from the organic phase with water. The elements like bismuth, antimony, iron, uranium, gallium, and vanadium which form strong malonato complexes were separated by selective stripping with hydrochloric, sulfuric, or nitric acid. The method was extended for the analysis of beryllium in beryl and beryllium alloys. 1 figure, 6 tables.

  9. SLAH3-type anion channel expressed in poplar secretory epithelia operates in calcium kinase CPK-autonomous manner. (United States)

    Jaborsky, Mario; Maierhofer, Tobias; Olbrich, Andrea; Escalante-Pérez, María; Müller, Heike M; Simon, Judy; Krol, Elzbieta; Cuin, Tracey Ann; Fromm, Jörg; Ache, Peter; Geiger, Dietmar; Hedrich, Rainer


    Extrafloral nectaries secrete a sweet sugar cocktail that lures predator insects for protection from foraging herbivores. Apart from sugars and amino acids, the nectar contains the anions chloride and nitrate. Recent studies with Populus have identified a type of nectary covered by apical bipolar epidermal cells, reminiscent of the secretory brush border epithelium in animals. Border epithelia operate transepithelial anion transport, which is required for membrane potential and/or osmotic adjustment of the secretory cells. In search of anion transporters expressed in extrafloral nectaries, we identified PttSLAH3 (Populus tremula × Populus tremuloides SLAC1 Homologue3), an anion channel of the SLAC/SLAH family. When expressed in Xenopus oocytes, PttSLAH3 displayed the features of a voltage-dependent anion channel, permeable to both nitrate and chloride. In contrast to the Arabidopsis SLAC/SLAH family members, the poplar isoform PttSLAH3 is independent of phosphorylation activation by protein kinases. To understand the basis for the autonomous activity of the poplar SLAH3, we generated and expressed chimera between kinase-independent PttSLAH3 and kinase-dependent Arabidopsis AtSLAH3. We identified the N-terminal tail and, to a lesser extent, the C-terminal tail as responsible for PttSLAH3 kinase-(in)dependent action. This feature of PttSLAH3 may provide the secretory cell with a channel probably controlling long-term nectar secretion.

  10. Characterization and anions inhibition studies of an α-carbonic anhydrase from the teleost fish Dicentrarchus labrax. (United States)

    Ekinci, Deniz; Ceyhun, Saltuk Buğrahan; Sentürk, Murat; Erdem, Deryanur; Küfrevioğlu, Omer İrfan; Supuran, Claudiu T


    Carbonic anhydrase (CA; EC was purified from the gill of the teleost fish Dicentrarchus labrax (European seabass). The purification procedure consisted of a single step affinity chromatography on Sepharose 4B-tyrosine-sulfanilamide. The enzyme was purified 84.9-fold with a yield of 58%, and a specific activity of 838.9 U/mg proteins. It has an optimum pH at 8.0; an optimum temperature at 10°C. The kinetic parameters of this enzyme were determined for its esterase activity, with 4-nitrophenyl acetate (NPA) as substrate. The following anions, H₂NSO₃⁻, I⁻, SCN⁻, NO₃⁻, NO₂⁻, N₃⁻, Br⁻, Cl⁻, SO₄²⁻, and F⁻ showed inhibitory effects on the enzyme. Sulfamic acid, iodide, and thiocyanate exhibited the strongest inhibitory action, in the micromolar range (K(i)s of 87-187 μM). NO₃⁻, NO₂⁻ and N₃⁻ were moderate inhibitors, whereas other anions showed only weak actions. All tested anions inhibited the enzyme in a competitive manner. Our findings indicate that these anions inhibit the fish enzyme in a similar manner to other α-CAs from mammals investigated earlier, but the susceptibility to various anions differs significantly between the fish and mammalian CAs.

  11. Regulation of organic anion transport in the liver

    NARCIS (Netherlands)

    Roelofsen, H; Jansen, PLM


    In several liver diseases the biliary transport is disturbed, resulting in, for example, jaundice and cholestasis. Many of these symptoms can be attributed to altered regulation of hepatic transporters. Organic anion transport, mediated by the canalicular multispecific organic anion transporter (cmo

  12. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud


    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined...



    Sprik, M.


    By means of a fully polarizable model for the chloride ion-water interaction we show that the modelling of anion solvation suffers from a similar inconsistency as the current electron-solvent potentials. Either the bulk hydration enthalpies are correct with the first hydration shell overbound, or the potential is adapted to describe the local environment of the solute at the expense of a major loss of solvation enthalpy. It is argued that boundary effects in the simulation are at least partly...

  14. Extraction of monoclonal antibodies (IgG1) using anionic and anionic/nonionic reverse micelles. (United States)

    George, Daliya A; Stuckey, David C


    Purification schemes for antibody production based on affinity chromatography are trying to keep pace with increases in cell culture expression levels and many current research initiatives are focused on finding alternatives to chromatography for the purification of Monoclonal antibodies (MAbs). In this article, we have investigated an alternative separation technique based on liquid-liquid extraction called the reverse micellar extraction. We extracted MAb (IgG1) using reverse micelles of an anionic surfactant, sodium bis 2-ethyl-hexyl sulfosuccinate (AOT) and a combination of anionic (AOT) and nonionic surfactants (Brij-30, Tween-85, Span-85) using isooctane as the solvent system. The extraction efficiency of IgG1 was studied by varying parameters, such as pH of the aqueous phase, cation concentration, and type and surfactant concentration. Using the AOT/Isooctane reverse micellar system, we could achieve good overall extraction of IgG1 (between 80 and 90%), but only 30% of the bioactivity of IgG1 could be recovered at the end of the extraction by using its binding to affinity chromatography columns as a surrogate measure of activity. As anionic surfactants were suspected as being one of the reasons for the reduced activity, we decided to combine a nonionic surfactant with an anionic surfactant and then study its effect on the extraction efficiency and bioactivity. The best results were obtained using an AOT/Brij-30/Isooctane reverse micellar system, which gave an overall extraction above 90 and 59% overall activity recovery. An AOT/Tween-85/Isooctane reverse micellar system gave an overall extraction of between 75 and 80% and overall activity recovery of around 40-45%. The results showed that the activity recovery of IgG1 can be significantly enhanced using different surfactant combination systems, and if the recovery of IgG1 can be further enhanced, the technique shows considerable promise for the downstream purification of MAbs.

  15. Skew Pairs of Idempotents in Transformation Semigroups

    Institute of Scientific and Technical Information of China (English)



    An ordered pair (e, f) of idempotents of a regular semigroup is called a skew pair if ef is not idempotent whereas fe is idempotent. We have shown previously that there are four distinct types of skew pairs of idempotents. Here we investigate the ubiquity of such skew pairs in full transformation semigroups.

  16. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis. (United States)

    Song, Hyun-Ouk; Ryu, Jae-Sook


    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.

  17. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)


    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

  18. Regulation of renal peripheral benzodiazepine receptors by anion transport inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Basile, A.S.; Lueddens, W.M.; Skolnick, P.


    The in vitro and in vivo regulation of (/sup 3/H)Ro 5-4864 binding to peripheral benzodiazepine receptors (PBR) by ion transport/exchange inhibitors was studied in the kidney. The potencies of 9-anthroic acid, furosemide, bumetanide, hydrochlorothiazide and SITS as inhibitors of (/sup 3/H)Ro 5-4864 binding to renal membranes were consistent with their actions as anion transport inhibitors (Ki approx. = 30 - 130 In contrast, spironolactone, amiloride, acetazolamide, and ouabain were less potent (Ki=100-1000 Administration of furosemide to rats for five days resulted in a profound diuresis accompanied by a significant increase in PBR density (43%) that was apparent by the fifth day of treatment. Administration of hydrochlorothiazide or Ro 5-4864 for five days also caused diuresis and increased renal PBR density. Both the diuresis and increased density of PBR produced by Ro 5-4864 were blocked by coadministration of PK 11195, which alone had no effect on either PBR density or urine volume. The equilibrium binding constants of (/sup 3/H)Ro 5-4864 to cardiac membranes were unaffected by administration of any of these drugs. These findings suggest that renal PBR may be selectively modulated in vivo and in vitro by administration of ion transport/exchange inhibitors. 36 references, 4 tables.

  19. A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device

    Directory of Open Access Journals (Sweden)

    Jurriaan Huskens


    Full Text Available A supramolecular platform based on self-assembled monolayers (SAMs has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP and pyrophosphate, as well as dipicolinic acid (DPA which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with µM and nM detection sensitivity for ATP and DPA, respectively.

  20. Collisions of Vortex Filament Pairs (United States)

    Banica, Valeria; Faou, Erwan; Miot, Evelyne


    We consider the problem of collisions of vortex filaments for a model introduced by Klein et al. (J Fluid Mech 288:201-248, 1995) and Zakharov (Sov Phys Usp 31(7):672-674, 1988, Lect. Notes Phys 536:369-385, 1999) to describe the interaction of almost parallel vortex filaments in three-dimensional fluids. Since the results of Crow (AIAA J 8:2172-2179, 1970) examples of collisions are searched as perturbations of antiparallel translating pairs of filaments, with initial perturbations related to the unstable mode of the linearized problem; most results are numerical calculations. In this article, we first consider a related model for the evolution of pairs of filaments, and we display another type of initial perturbation leading to collision in finite time. Moreover, we give numerical evidence that it also leads to collision through the initial model. We finally study the self-similar solutions of the model.