WorldWideScience

Sample records for active cftr-regulated anion

  1. Defective CFTR-regulated granulosa cell proliferation in polycystic ovarian syndrome.

    Science.gov (United States)

    Chen, Hui; Guo, Jing Hui; Zhang, Xiao Hu; Chan, Hsiao Chang

    2015-05-01

    Polycystic ovarian syndrome (PCOS) is one of the most frequent causes of female infertility, featured by abnormal hormone profile, chronic oligo/anovulation, and presence of multiple cystic follicles in the ovary. However, the mechanism underlying the abnormal folliculogenesis remains obscure. We have previously demonstrated that CFTR, a cAMP-dependent Cl(-) and HCO3 (-) conducting anion channel, is expressed in the granulosa cells and its expression is downregulated in PCOS rat models and human patients. In this study, we aimed to investigate the possible involvement of downregulation of CFTR in the impaired follicle development in PCOS using two rat PCOS models and primary culture of granulosa cells. Our results indicated that the downregulation of CFTR in the cystic follicles was accompanied by reduced expression of proliferating cell nuclear antigen (PCNA), in rat PCOS models. In addition, knockdown or inhibition of CFTR in granulosa cell culture resulted in reduced cell viability and downregulation of PCNA. We further demonstrated that CFTR regulated both basal and FSH-stimulated granulosa cell proliferation through the HCO3 (-)/sAC/PKA pathway leading to ERK phosphorylation and its downstream target cyclin D2 (Ccnd2) upregulation. Reduced ERK phosphorylation and CCND2 were found in ovaries of rat PCOS model compared with the control. This study suggests that CFTR is required for normal follicle development and that its downregulation in PCOS may inhibit granulosa cell proliferation, resulting in abnormal follicle development in PCOS.

  2. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis.

    Science.gov (United States)

    Song, Hyun-Ouk; Ryu, Jae-Sook

    2013-08-01

    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.

  3. Peroxidase activation of cytoglobin by anionic phospholipids: Mechanisms and consequences.

    Science.gov (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

    2016-05-01

    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.

  4. Carbon dioxide suppresses macrophage superoxide anion production independent of extracellular pH and mitochondrial activity

    NARCIS (Netherlands)

    Kuebler, Joachim F.; Kos, Marcin; Jesch, NataLie K.; Metzelder, Martin L.; van der Zee, David C.; Bax, Klaas M.; Vieten, Gertrud; Ure, Benno M.

    2007-01-01

    Background: Superoxide anions released by activated inacrophages during surgery are considered to be responsible for local cellular damage. Application of CO2 prieumoperitoneum during laparoscopy affects superoxide anion release, but the underlying mechanism remains unclear and the data reported are

  5. Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity

    OpenAIRE

    Hunter, B. M.; Hieringer, W.; Winkler, J.R.; Gray, H B; Müller, A. M.

    2016-01-01

    We synthesized nickel–iron layered double hydroxide ([NiFe]-LDH) nanosheets with different interlayer anions to probe their role in water oxidation catalysis. In alkaline electrolyte in ambient air, carbonate rapidly replaced other interlayer anions and catalytic activity was highest. Electrocatalytic water oxidation in virtually carbonate-free alkaline electrolyte revealed that activity was a function of anion basicity. Our [NiFe]-LDH nanosheets, prepared by pulsed laser ablation in liquids,...

  6. Plasma Membrane CFTR Regulates RANTES Expression via Its C-Terminal PDZ-Interacting Motif

    OpenAIRE

    Estell, Kim; Braunstein, Gavin; Tucker, Torry; Varga, Karoly; Collawn, James F.; Schwiebert, Lisa M.

    2003-01-01

    Despite the identification of 1,000 mutations in the cystic fibrosis gene product CFTR, there remains discordance between CFTR genotype and lung disease phenotype. The study of CFTR, therefore, has expanded beyond its chloride channel activity into other possible functions, such as its role as a regulator of gene expression. Findings indicate that CFTR plays a role in the expression of RANTES in airway epithelia. RANTES is a chemokine that has been implicated in the regulation of mucosal immu...

  7. Synergy of cAMP and calcium signaling pathways in CFTR regulation.

    Science.gov (United States)

    Bozoky, Zoltan; Ahmadi, Saumel; Milman, Tal; Kim, Tae Hun; Du, Kai; Di Paola, Michelle; Pasyk, Stan; Pekhletski, Roman; Keller, Jacob P; Bear, Christine E; Forman-Kay, Julie D

    2017-03-14

    Cystic fibrosis results from mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) chloride channel, leading to defective apical chloride transport. Patients also experience overactivation of inflammatory processes, including increased calcium signaling. Many investigations have described indirect effects of calcium signaling on CFTR or other calcium-activated chloride channels; here, we investigate the direct response of CFTR to calmodulin-mediated calcium signaling. We characterize an interaction between the regulatory region of CFTR and calmodulin, the major calcium signaling molecule, and report protein kinase A (PKA)-independent CFTR activation by calmodulin. We describe the competition between calmodulin binding and PKA phosphorylation and the differential effects of this competition for wild-type CFTR and the major F508del mutant, hinting at potential therapeutic strategies. Evidence of CFTR binding to isolated calmodulin domains/lobes suggests a mechanism for the role of CFTR as a molecular hub. Together, these data provide insights into how loss of active CFTR at the membrane can have additional consequences besides impaired chloride transport.

  8. Dendronized Anionic Gold Nanoparticles: Synthesis, Characterization, and Antiviral Activity.

    Science.gov (United States)

    Peña-González, Cornelia E; García-Broncano, Pilar; Ottaviani, M Francesca; Cangiotti, Michela; Fattori, Alberto; Hierro-Oliva, Margarita; González-Martín, M Luisa; Pérez-Serrano, Jorge; Gómez, Rafael; Muñoz-Fernández, M Ángeles; Sánchez-Nieves, Javier; de la Mata, F Javier

    2016-02-24

    Anionic carbosilane dendrons decorated with sulfonate functions and one thiol moiety at the focal point have been used to synthesize water-soluble gold nanoparticles (AuNPs) through the direct reaction of dendrons, gold precursor, and reducing agent in water, and also through a place-exchange reaction. These nanoparticles have been characterized by NMR spectroscopy, TEM, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, elemental analysis, and zeta-potential measurements. The interacting ability of the anionic sulfonate functions was investigated by EPR spectroscopy with copper(II) as a probe. Different structures and conformations of the AuNPs modulate the availability of sulfonate and thiol groups for complexation by copper(II). Toxicity assays of AuNPs showed that those produced through direct reaction were less toxic than those obtained by ligand exchange. Inhibition of HIV-1 infection was higher in the case of dendronized AuNPs than in dendrons.

  9. Activation/driving force relationships for cyclopropylcarbinyl --> homoallyl-type rearrangements of radical anions.

    Science.gov (United States)

    Chahma, M'hamed; Li, Xiangzhong; Phillips, J Paige; Schwartz, Phillip; Brammer, Larry E; Wang, Yonghui; Tanko, James M

    2005-04-21

    By using direct and indirect electrochemical methods, rate constants (ko) for cyclopropane ring opening of radical anions derived from the one-electron reduction of trans-1-benzoyl-2-phenylcyclopropane, trans-1-benzoyl-2-vinylcyclopropane, 2-methylenecyclopropyl phenyl ketone, spiro[anthracene-9,1'-cyclopropan-10-one], 3-cyclopropylcyclohex-2-en-1-one, and 3-(1-methylcyclopropyl)cyclohex-2-en-1-one were determined. Qualitatively, rate constants for ring opening of these (and other cyclopropyl- and cyclobutyl-containing radical anions) can be rationalized on the basis of the thermodynamic stability of the radical anion, the ability of substituents on the cyclopropyl group to stabilize the radical portion of the distonic radical anion, and the stability of the enolate portion of the distonic radical anion. On the basis of this notion, a thermochemical cycle for estimating deltaG(o) for ring opening was presented. For simple cyclopropyl-containing ketyl anions, a reasonable correlation between log(ko) and deltaG(o) was found, and stepwise dissociative electron transfer theory was applied to rationalize the results. Activation energies calculated with density functional theory (UB3LYP/6-31+G*) correlate reasonably well with measured log(ko). The derived log(ko) and deltaG(o) and log(ko) vs E(a) plots provide the basis for a "calibration curve" to predict rate constants for ring opening of radical anions derived from carbonyl compounds, in general.

  10. Swelling-Activated Anion Channels Are Essential for Volume Regulation of Mouse Thymocytes

    Directory of Open Access Journals (Sweden)

    Ravshan Z. Sabirov

    2011-12-01

    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.

  11. In vitro inhibition of superoxide anion production and superoxide dismutase activity by zinc in human spermatozoa.

    Science.gov (United States)

    Gavella, M; Lipovac, V; Vucić, M; Sverko, V

    1999-08-01

    The in vitro effect of zinc on superoxide anion (O2-) generation and on SOD-like activity in spermatozoa of infertile men was investigated. The formation of superoxide anion was stimulated by NADPH and the level of superoxide anion was measured by the reduction of ferricytochrome c. Both Percoll-isolated (n = 14) and washed spermatozoa (n = 14) exposed to 1 mmol/L zinc (60 min, 37 degrees C), released less (p zinc-untreated spermatozoa. These results implicate a possible role for zinc as a scavenger of excessive superoxide anions produced by defective spermatozoa in semen after ejaculation. Additionally, zinc was found to dose-dependently inhibit superoxide dismutase (SOD)-like activity of spermatozoa in vitro. The inhibition of SOD-like activity by an equal concentration of zinc (1 mmol/L) was less pronounced in oligospermic (p zinc to inhibit SOD-like activity may be relevant to the physiological function of spermatozoa in fertilization. The evidence that zinc may elicit an inhibition of both superoxide anion production and SOD-like activity in human spermatozoa, indicate the existence of novel, zinc-related mechanism(s) involved in the oxidative events occurring after ejaculation, with a possible modulatory effect on germ cell function.

  12. Absorption of the selenite anion from aqueous solutions by thermally activated layered double hydroxide.

    Science.gov (United States)

    Liu, Rui; Frost, Ray L; Martens, Wayde N

    2009-03-01

    The presence of selenite or selenate in potable water is a health hazard especially when consumed over a long period of time. Its removal from potable water is of importance. This paper reports technology for the removal of selenite from water through the use of thermally activated layered double hydroxides. Mg/Al hydrotalcites with selenite in the interlayer were prepared at different times from 0.5 to 20 h through ion exchange. X-ray diffraction of the MgAlSeO3 hydrotalcites indicates that the selenite anion entered the interlayer spacing of Mg/Al hydrotalcite and MgAlSeO3 hydrotalcite was formed. Raman spectra proved the presence of selenite anion in the hydrotalcite interlayer as the counter anion. The band intensity and width of MgAlSeO3 hydrotalcite in the region of 3800-3000 cm(-1) increase with the adsorption of selenite by the Mg/Al hydrotalcite. The characteristic bands of free selenite anions in the MgAlSeO3 hydrotalcites are located between the region between 850 and 800 cm(-1). The Raman spectra of the lower wave number region of 550-500 cm(-1) show a shift toward higher wave numbers with adsorption of the selenite. An estimation of the amount of selenite anion removed by the thermally activated layered double hydroxide was obtained through the measurement of the intensity of the selenite Raman bands at 814 and 835 cm(-1) resulting from the amount of selenite anion remaining in solution. Thermally activated LDHs provide a mechanism for removing selenite anions from aqueous solutions.

  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

    2007-01-01

    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. How Phosphorylation and ATPase Activity Regulate Anion Flux though the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR).

    Science.gov (United States)

    Zwick, Matthias; Esposito, Cinzia; Hellstern, Manuel; Seelig, Anna

    2016-07-08

    The cystic fibrosis transmembrane conductance regulator (CFTR, ABCC7), mutations of which cause cystic fibrosis, belongs to the ATP-binding cassette (ABC) transporter family and works as a channel for small anions, such as chloride and bicarbonate. Anion channel activity is known to depend on phosphorylation by cAMP-dependent protein kinase A (PKA) and CFTR-ATPase activity. Whereas anion channel activity has been extensively investigated, phosphorylation and CFTR-ATPase activity are still poorly understood. Here, we show that the two processes can be measured in a label-free and non-invasive manner in real time in live cells, stably transfected with CFTR. This study reveals three key findings. (i) The major contribution (≥90%) to the total CFTR-related ATP hydrolysis rate is due to phosphorylation by PKA and the minor contribution (≤10%) to CFTR-ATPase activity. (ii) The mutant CFTR-E1371S that is still conductive, but defective in ATP hydrolysis, is not phosphorylated, suggesting that phosphorylation requires a functional nucleotide binding domain and occurs in the post-hydrolysis transition state. (iii) CFTR-ATPase activity is inversely related to CFTR anion flux. The present data are consistent with a model in which CFTR is in a closed conformation with two ATPs bound. The open conformation is induced by ATP hydrolysis and corresponds to the post-hydrolysis transition state that is stabilized by phosphorylation and binding of chloride channel potentiators.

  15. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-).

    Science.gov (United States)

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian

    2015-12-01

    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. Tilting and Tumbling in Transmembrane Anion Carriers: Activity Tuning through n‐Alkyl Substitution

    OpenAIRE

    Edwards, Sophie J.; Marques, Igor; Dias, Christopher M.; Tromans, Robert A.; Lees, Nicholas R; Félix, Vítor; Valkenier, Hennie; Davis, Anthony P

    2016-01-01

    Abstract Anion transport by synthetic carriers (anionophores) holds promise for medical applications, especially the treatment of cystic fibrosis. Among the factors which determine carrier activity, the size and disposition of alkyl groups is proving remarkably important. Herein we describe a series of dithioureidodecalin anionophores, in which alkyl substituents on one face are varied from C0 to C10 in two‐carbon steps. Activities increase then decrease as the chain length grows, peaking qui...

  18. Feijoa sellowiana Berg fruit juice: anti-inflammatory effect and activity on superoxide anion generation.

    Science.gov (United States)

    Monforte, Maria T; Fimiani, Vincenzo; Lanuzza, Francesco; Naccari, Clara; Restuccia, Salvatore; Galati, Enza M

    2014-04-01

    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.

  19. Allosteric Activation of the Phosphoinositide Phosphatase Sac1 by Anionic Phospholipids

    Science.gov (United States)

    2012-01-01

    Sac family phosphoinositide phosphatases comprise an evolutionarily conserved family of enzymes in eukaryotes. Our recently determined crystal structure of the Sac phosphatase domain of yeast Sac1, the founding member of the Sac family proteins, revealed a unique conformation of the catalytic P-loop and a large positively charged groove at the catalytic site. We now report a unique mechanism for the regulation of its phosphatase activity. Sac1 is an allosteric enzyme that can be activated by its product phosphatidylinositol or anionic phospholipid phosphatidylserine. The activation of Sac1 may involve conformational changes of the catalytic P-loop induced by direct binding with the regulatory anionic phospholipids in the large cationic catalytic groove. These findings highlight the fact that lipid composition of the substrate membrane plays an important role in the control of Sac1 function. PMID:22452743

  20. Effect of anions on the oxidation of organic compounds with ultrasonically activated persulfate

    Science.gov (United States)

    Sizykh, M. R.; Batoeva, A. A.

    2016-06-01

    The effect of anions typically present in natural and waste waters on the oxidation of the azo dye methyl orange with persulfate activated with high-frequency ultrasound was studied. At a chloride concentration of 1 mmol/L, the rate constant of substrate oxidation increased 1.5-fold, but further increase in the chloride content retarded the process. The addition of nitrates, carbonates, and hydrogen carbonates to the solution inhibited the process (NO 3 - natural surface water from Lake Baikal.

  1. Plasmodium induces swelling-activated ClC-2 anion channels in the host erythrocyte

    OpenAIRE

    Huber, Stephan M.; Duranton, Christophe; Henke, Guido; Van De Sand, Claudia; Heussler, Volker; Shumilina, Ekaterina; Sandu, Ciprian D.; Tanneur, Valerie; Brand, Verena; Kasinathan, Ravi S.; Lang, Karl S; Peter G Kremsner; Hübner, Christian A; Marco B Rust; Dedek, Karin

    2004-01-01

    Intraerythrocytic growth of the human malaria parasite Plasmodium falciparum depends on delivery of nutrients. Moreover, infection challenges cell volume constancy of the host erythrocyte requiring enhanced activity of cell volume regulatory mechanisms. Patch clamp recording demonstrated inwardly and outwardly rectifying anion channels in infected but not in control erythrocytes. The molecular identity of those channels remained elusive. We show here for one channel type that voltage dependen...

  2. Plasmodium induces swelling-activated ClC-2 anion channels in the host erythrocyte

    OpenAIRE

    Huber, Stephan M.; Duranton, Christophe; Henke, Guido; Van De Sand, Claudia; Heussler, Volker; Shumilina, Ekaterina; Sandu, Ciprian D.; Tanneur, Valerie; Brand, Verena; Kasinathan, Ravi S.; Lang, Karl S; Peter G Kremsner; Christian A. Hübner; Rust, Marco B.; Dedek, Karin

    2004-01-01

    Intraerythrocytic growth of the human malaria parasite Plasmodium falciparum depends on delivery of nutrients. Moreover, infection challenges cell volume constancy of the host erythrocyte requiring enhanced activity of cell volume regulatory mechanisms. Patch clamp recording demonstrated inwardly and outwardly rectifying anion channels in infected but not in control erythrocytes. The molecular identity of those channels remained elusive. We show here for one channel type that voltage dependen...

  3. Superoxide anion production and superoxide dismutase and catalase activities in Coxiella burnetii.

    OpenAIRE

    Akporiaye, E T; Baca, O G

    1983-01-01

    Coxiella burnetii was examined for superoxide anion (O2-) production and superoxide dismutase and catalase activities. The organism generated O2- at pH 4.5 but not at pH 7.4. The rickettsia displayed superoxide dismutase activity distinguishable from that of the host cell (L-929 mouse fibroblast). Catalase activity was maximal at pH 7.0 and diminished at pH 4.5. These enzymes may account, in part, for the ability of this obligate intracellular parasite to survive within phagocytes.

  4. Activation of Methane Promoted by Adsorption of CO on Mo2 C2 (-) Cluster Anions.

    Science.gov (United States)

    Liu, Qing-Yu; Ma, Jia-Bi; Li, Zi-Yu; Zhao, Chongyang; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui

    2016-05-04

    Atomic clusters are being actively studied for activation of methane, the most stable alkane molecule. While many cluster cations are very reactive with methane, the cluster anions are usually not very reactive, particularly for noble metal free anions. This study reports that the reactivity of molybdenum carbide cluster anions with methane can be much enhanced by adsorption of CO. The Mo2 C2 (-) is inert with CH4 while the CO addition product Mo2 C3 O(-) brings about dehydrogenation of CH4 under thermal collision conditions. The cluster structures and reactions are characterized by mass spectrometry, photoelectron spectroscopy, and quantum chemistry calculations, which demonstrate that the Mo2 C3 O(-) isomer with dissociated CO is reactive but the one with non-dissociated CO is unreactive. The enhancement of cluster reactivity promoted by CO adsorption in this study is compared with those of reported systems of a few carbonyl complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Methane Activation by Tantalum Carbide Cluster Anions Ta2C4().

    Science.gov (United States)

    Li, Hai-Fang; Zhao, Yan-Xia; Yuan, Zhen; Liu, Qing-Yu; Li, Zi-Yu; Li, Xiao-Na; Ning, Chuan-Gang; He, Sheng-Gui

    2017-02-02

    Methane activation by transition metals is of fundamental interest and practical importance, as this process is extensively involved in the natural gas conversion to fuels and value-added chemicals. While single-metal centers have been well recognized as active sites for methane activation, the active center composed of two or more metal atoms is rarely addressed and the detailed reaction mechanism remains unclear. Here, by using state-of-the-art time-of-flight mass spectrometry, cryogenic anion photoelectron imaging spectroscopy, and quantum-chemical calculations, the cooperation of the two Ta atoms in a dinuclear carbide cluster Ta2C4(-) for methane activation has been identified. The C-H bond activation takes place predominantly around one Ta atom in the initial stage of the reaction and the second Ta atom accepts the delivered H atom from the C-H bond cleavage. The well-resolved vibrational spectra of the cryogenically cooled anions agree well with theoretical simulations, allowing the clear characterization of the structure of Ta2C4(-) cluster. The reactivity comparison between Ta2C4(-) cluster and the carbon-less analogues (Ta2C3(-) and Ta2C2(-)) demonstrated that the cooperative effect of the two metal atoms can be well tuned by the carbon ligands in terms of methane activation and transformation.

  6. An anionic defensin from Plutella xylostella with potential activity against Bacillus thuringiensis.

    Science.gov (United States)

    Xu, X-X; Zhang, Y-Q; Freed, S; Yu, J; Gao, Y-F; Wang, S; Ouyang, L-N; Ju, W-Y; Jin, F-L

    2016-12-01

    Insect defensins, are cationic peptides that play an important role in immunity against microbial infection. In the present study, an anionic defensin from Plutella xylostella, (designated as PxDef) was first cloned and characterized. Amino acid sequence analysis showed that the mature peptide owned characteristic six-cysteine motifs with predicted isoelectric point of 5.57, indicating an anionic defensin. Quantitative real-time polymerase chain reaction analysis showed that PxDef was significantly induced in epidermis, fat body, midgut and hemocytes after injection of heat-inactivated Bacillus thuringiensis, while such an induction was delayed by the injection of live B. thuringiensis in the 4th instar larvae of P. xylostella. Knocking down the expression of nuclear transcription factor Dorsal in P. xylostella by RNA interference significantly decreased the mRNA level of PxDef, and increased the sensitivity of P. xylostella larvae to the infection by live B. thuringiensis. The purified recombinant mature peptide (PxDef) showed higher activity against Gram-positive bacteria, with the minimum inhibition concentrations of 1.6 and 2.6 µM against B. thuringiensis and Bacillus subtilis, respectively. To our knowledge, this is the first report about an anionic PxDef, which may play an important role in the immune system of P. xylostella against B. thuringiensis.

  7. Schisandrin A and B induce organic anion transporting polypeptide 1B1 transporter activity.

    Science.gov (United States)

    Guo, Cheng-Xian; Deng, Sheng; Yin, Ji-Ye; Liu, Zhao-Qian; Zhang, Wei; Zhou, Hong-Hao

    2015-01-01

    Organic anion transporting polypeptide 1B1 (OATP1B1) is the most important transporter in the organic anion transporting polypeptide family. OATP1B1 plays an important role in the hepatic uptake of many endogenous compounds and xenobiotics, including many clinical drugs. At present, the combinational usage of Chinese traditional herbal medicines and conventional chemical pharmaceuticals may affect the activity of enzymes and transporters activity and cause absorption of their substrates and metabolic changes. In this study, we aimed to investigate the effect of schisandrin A, schisandrin B and tanshinone IIA, which were extracted from medicinal plants, on OATP1B1 activity. HepG2 cells are used as in vitro models for OATP1B1 activity studies. A combination of 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl-tertazolium bromide (MTT) assays, real-time RT-PCR, and transporter activity analysis were employed. We found that schisandrin A and B increased OATP1B1 mRNA levels by 1.81-fold (p Schisandrin A of 1 μM and 10 μM and schisandrin B of 10 μM significantly increased the uptake of [3H] estrone-3-sulfate (p schisandrin A and B induced OATP1B1 expression and increased its transporter activity in HepG2 cells.

  8. Ultrafast dynamics and anionic active states of the flavin cofactor in cryptochrome and photolyase.

    Science.gov (United States)

    Kao, Ya-Ting; Tan, Chuang; Song, Sang-Hun; Oztürk, Nuri; Li, Jiang; Wang, Lijuan; Sancar, Aziz; Zhong, Dongping

    2008-06-18

    We report here our systematic studies of the dynamics of four redox states of the flavin cofactor in both photolyases and insect type 1 cryptochromes. With femtosecond resolution, we observed ultrafast photoreduction of oxidized state flavin adenine dinucleotide (FAD) in subpicosecond and of neutral radical semiquinone (FADH(*)) in tens of picoseconds through intraprotein electron transfer mainly with a neighboring conserved tryptophan triad. Such ultrafast dynamics make these forms of flavin unlikely to be the functional states of the photolyase/cryptochrome family. In contrast, we find that upon excitation the anionic semiquinone (FAD(*-)) and hydroquinone (FADH(-)) have longer lifetimes that are compatible with high-efficiency intermolecular electron transfer reactions. In photolyases, the excited active state (FADH(-)*) has a long (nanosecond) lifetime optimal for DNA-repair function. In insect type 1 cryptochromes known to be blue-light photoreceptors the excited active form (FAD(*-)*) has complex deactivation dynamics on the time scale from a few to hundreds of picoseconds, which is believed to occur through conical intersection(s) with a flexible bending motion to modulate the functional channel. These unique properties of anionic flavins suggest a universal mechanism of electron transfer for the initial functional steps of the photolyase/cryptochrome blue-light photoreceptor family.

  9. Determination of anionic surface active agents using silica coated magnetite nanoparticles modified with cationic surfactant aggregates.

    Science.gov (United States)

    Pena-Pereira, Francisco; Duarte, Regina M B O; Trindade, Tito; Duarte, Armando C

    2013-07-19

    The development of a novel methodology for extraction and preconcentration of the most commonly used anionic surface active agents (SAAs), linear alkylbenzene sulfonates (LAS), is presented herein. The present method, based on the use of silica-magnetite nanoparticles modified with cationic surfactant aggregates, was developed for determination of C10-C13 LAS homologues. The proposed methodology allowed quantitative recoveries of C10-C13 LAS homologues by using a reduced amount of magnetic nanoparticles. Limits of detection were in the range 0.8-1.9μgL(-1) for C10-C13 LAS homologues, while the repeatability, expressed as relative standard deviation (RSD), ranged from 2.0 to 3.9% (N=6). Finally, the proposed method was successfully applied to the analysis of a variety of natural water samples.

  10. THE STUDY OF THE BIOLOGICAL ACTIVITY OF SOME COBALT(III DIOXIMATES WITH FLUORINE CONTAINING ANIONS

    Directory of Open Access Journals (Sweden)

    Eduard Coropceanu

    2008-12-01

    Full Text Available It was elaborated the methodology of synthesizing a series of new dioximates of Co(III with the general formula [Co(DioxH2(L2]X⋅nH2O, where DioxH – the dioxime anione: dimethylglyoxime (DH2, 1,2-cyclohexanedionedioxime (NioxH2; L - thiocarbamide (Thio, pyridine (Py, aniline (An, sulphanilamide (Sam;X - [BF4]-, [ZrF6]2-, [TiF6]2-, whose structures have been studied with the help of contemporary physical methods: spectroscopy IR, UV-Vis, RMN 1H, 19F, X-ray analysis. There were elaborated optimal conditions of using cobalt dioximates with fluorine in order to intensify the biosynthesis of amylases and lipases by Aspergillus and Rhizopus strains, respectively. The tested compounds increase the lipolytic activity of Rhizopus arrhisus micromycetes.

  11. H-ras transformation sensitizes volume-activated anion channels and increases migratory activity of NIH3T3 fibroblasts

    DEFF Research Database (Denmark)

    Schneider, Linda; Klausen, Thomas K; Stock, Christian;

    2008-01-01

    The expression of the H-ras oncogene increases the migratory activity of many cell types and thereby contributes to the metastatic behavior of tumor cells. Other studies point to an involvement of volume-activated anion channels (VRAC) in (tumor) cell migration. In this paper, we tested whether...... VRACs are required for the stimulation of cell migration upon expression of the H-ras oncogene. We compared VRAC activation and migration of wild-type and H-ras-transformed NIH3T3 fibroblasts by means of patch-clamp techniques and time-lapse video microscopy. Both cell types achieve the same degree...... of VRAC activation upon maximal stimulation, induced by reducing extracellular osmolarity from 300 to 190 mOsm/l. However, upon physiologically relevant reductions in extracellular osmolarity (275 mOsm/l), the level of VRAC activation is almost three times higher in H-ras-transformed compared to wild...

  12. Interaction between zwitterionic surface activity ionic liquid and anionic surfactant: Na(+)-driven wormlike micelles.

    Science.gov (United States)

    Wang, Xiaoqing; Wang, Ruitao; Zheng, Yan; Sun, Limei; Yu, Li; Jiao, Jingjing; Wang, Rui

    2013-02-14

    The physicochemical properties of the mixed zwitterionic surface activity ionic liquid/anionic surfactant (N-alkyl-N'-carboxymethyl imidazolium inner salts/sodium dodecyl sulfate, [N-C(12), N'-CO(2)-Im]/SDS) at various molar ratios (R(1) = C([N-C(12),N'-CO(2)-Im])/(C([N-C(12),N'-CO(2)-Im]) + C(SDS)) were investigated by surface tension and steady-state fluorescence measurements. The results show that the mixed [N-C(12), N'-CO(2)-Im]/SDS system has a much lower cmc value and higher surface activity than individual surfactant. Compared with the mixed zwitterionic betaine surfactant/SDS system, the mixture studied exhibits a stronger synergism, i.e., more negative interaction parameters (β(m) and β(σ)). Through addition of NaCl, the wormlike micelles (WMs) could be formed in a [N-C(12), N'-CO(2)-Im]/SDS system. Steady and dynamic rheology was employed to characterize the WMs with different surfactant ratio (R(1)), NaCl concentration, and temperature. An optimal composition, viz., C(T) = 60 mM, R(1) = 0.45, and C(NaCl) = 0.10 M, was detected to form the strongest and longest wormlike micelles. Compared with the WMs formed by a traditional zwitterionic C(12) betaine/anionic surfactant mixture (e.g., laurylamidopropyl betaine/SDS), the WMs studied have a stronger network structure, which is expected to have potential applications in some fields, such as in nanomaterials synthesis, personal care products, and flooding liquid for tertiary oil recovery.

  13. Glial and Neuronal Glutamate Transporters Differ in the Na+ Requirements for Activation of the Substrate-Independent Anion Conductance

    Directory of Open Access Journals (Sweden)

    Christopher B. Divito

    2017-05-01

    Full Text Available Excitatory amino acid transporters (EAATs are secondary active transporters of L-glutamate and L- or D-aspartate. These carriers also mediate a thermodynamically uncoupled anion conductance that is gated by Na+ and substrate binding. The activation of the anion channel by binding of Na+ alone, however, has only been demonstrated for mammalian EAAC1 (EAAT3 and EAAT4. To date, no difference has been observed for the substrate dependence of anion channel gating between the glial, EAAT1 and EAAT2, and the neuronal isoforms EAAT3, EAAT4 and EAAT5. Here we describe a difference in the Na+-dependence of anion channel gating between glial and neuronal isoforms. Chloride flux through transporters without glutamate binding has previously been described as substrate-independent or “leak” channel activity. Choline or N-methyl-D-glucamine replacement of external Na+ ions significantly reduced or abolished substrate-independent EAAT channel activity in EAAT3 and EAAT4 yet has no effect on EAAT1 or EAAT2. The interaction of Na+ with the neuronal carrier isoforms was concentration dependent, consistent with previous data. The presence of substrate and Na+-independent open states in the glial EAAT isoforms is a novel finding in the field of EAAT function. Our results reveal an important divergence in anion channel function between glial and neuronal glutamate transporters and highlight new potential roles for the EAAT-associated anion channel activity based on transporter expression and localization in the central nervous system.

  14. Predicting competitive adsorption behavior of major toxic anionic elements onto activated alumina: a speciation-based approach.

    Science.gov (United States)

    Su, Tingzhi; Guan, Xiaohong; Tang, Yulin; Gu, Guowei; Wang, Jianmin

    2010-04-15

    Toxic anionic elements such as arsenic, selenium, and vanadium often co-exist in groundwater. These elements may impact each other when adsorption methods are used to remove them. In this study, we investigated the competitive adsorption behavior of As(V), Se(IV), and V(V) onto activated alumina under different pH and surface loading conditions. Results indicated that these anionic elements interfered with each other during adsorption. A speciation-based model was developed to quantify the competitive adsorption behavior of these elements. This model could predict the adsorption data well over the pH range of 1.5-12 for various surface loading conditions, using the same set of adsorption constants obtained from single-sorbate systems. This model has great implications in accurately predicting the field capacity of activated alumina under various local water quality conditions when multiple competitive anionic elements are present.

  15. Predicting competitive adsorption behavior of major toxic anionic elements onto activated alumina: A speciation-based approach

    Energy Technology Data Exchange (ETDEWEB)

    Su Tingzhi [Department of Civil, Architectural and Environmental Engineering, Missouri University of Science and Technology, 1870 Miner Circle, Rolla, MO 65401 (United States); College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Guan Xiaohong [School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150001 (China); Tang Yulin [Department of Civil, Architectural and Environmental Engineering, Missouri University of Science and Technology, 1870 Miner Circle, Rolla, MO 65401 (United States); College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Gu Guowei [College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Wang Jianmin, E-mail: wangjia@mst.edu [Department of Civil, Architectural and Environmental Engineering, Missouri University of Science and Technology, 1870 Miner Circle, Rolla, MO 65401 (United States)

    2010-04-15

    Toxic anionic elements such as arsenic, selenium, and vanadium often co-exist in groundwater. These elements may impact each other when adsorption methods are used to remove them. In this study, we investigated the competitive adsorption behavior of As(V), Se(IV), and V(V) onto activated alumina under different pH and surface loading conditions. Results indicated that these anionic elements interfered with each other during adsorption. A speciation-based model was developed to quantify the competitive adsorption behavior of these elements. This model could predict the adsorption data well over the pH range of 1.5-12 for various surface loading conditions, using the same set of adsorption constants obtained from single-sorbate systems. This model has great implications in accurately predicting the field capacity of activated alumina under various local water quality conditions when multiple competitive anionic elements are present.

  16. Ground state destabilization by anionic nucleophiles contributes to the activity of phosphoryl transfer enzymes.

    Directory of Open Access Journals (Sweden)

    Logan D Andrews

    2013-07-01

    Full Text Available Enzymes stabilize transition states of reactions while limiting binding to ground states, as is generally required for any catalyst. Alkaline Phosphatase (AP and other nonspecific phosphatases are some of Nature's most impressive catalysts, achieving preferential transition state over ground state stabilization of more than 10²²-fold while utilizing interactions with only the five atoms attached to the transferred phosphorus. We tested a model that AP achieves a portion of this preference by destabilizing ground state binding via charge repulsion between the anionic active site nucleophile, Ser102, and the negatively charged phosphate monoester substrate. Removal of the Ser102 alkoxide by mutation to glycine or alanine increases the observed Pi affinity by orders of magnitude at pH 8.0. To allow precise and quantitative comparisons, the ionic form of bound P(i was determined from pH dependencies of the binding of Pi and tungstate, a P(i analog lacking titratable protons over the pH range of 5-11, and from the ³¹P chemical shift of bound P(i. The results show that the Pi trianion binds with an exceptionally strong femtomolar affinity in the absence of Ser102, show that its binding is destabilized by ≥10⁸-fold by the Ser102 alkoxide, and provide direct evidence for ground state destabilization. Comparisons of X-ray crystal structures of AP with and without Ser102 reveal the same active site and P(i binding geometry upon removal of Ser102, suggesting that the destabilization does not result from a major structural rearrangement upon mutation of Ser102. Analogous Pi binding measurements with a protein tyrosine phosphatase suggest the generality of this ground state destabilization mechanism. Our results have uncovered an important contribution of anionic nucleophiles to phosphoryl transfer catalysis via ground state electrostatic destabilization and an enormous capacity of the AP active site for specific and strong recognition of the

  17. 1,1-Diphenyl-2-picrylhydrazyl radical and superoxide anion scavenging activity of Rhizophora mangle (L. bark

    Directory of Open Access Journals (Sweden)

    Janet Calero Sánchez

    2010-01-01

    Full Text Available Background: Rhizophora mangle (L. produce a variety of substances that possesses pharmacological actions. Although it shown antioxidant properties in some assays, there is no available information about its effect on some free radical species. So the objective of the present research is to evaluate the DPPH radical and superoxide anion scavenging properties of R. mangle extract and its polyphenol fraction. Methods: Rhizophora mangle (L. bark aqueous extract and its major constituent, polyphenols fraction, were investigated for their antioxidant activities employing 2 in vitro assay systems: 1,1-diphenyl-2-picrylhydrazyl (DPPH and superoxide anion radicals scavenging. Results: IC 50 for DPPH radical-scavenging activity was 6.7 μg tannins/mL for extract and 7.6 μg tannins/mL for polyphenolic fraction. The extract showed better activity than its fraction (P < 0.05 in the DPPH radicals reducing power. Polyphenolic fraction exhibited better superoxide anion scavenging ability (IC 50 = 21.6 μg tannins/mL than the extract (IC 50 = 31.9 μg tannins/mL. Antioxidant activities of both samples increased with the rise of tannins concentration. The comparison of regression lines showed significant differences (P < 0.05 between extract and its polyphenolic fraction in both assays, indicating that extract was more effective in DPPH radical scavenging than its fraction at tannin concentrations below the crossing point of both lines, while that fraction was more effective than extract inhibiting the superoxide anions generation. Conclusions: R. mangle aqueous extract showed a potent antioxidant activity, achieved by the scavenging ability observed against DPPH radicals and superoxide anions. Regarding its polyphenolic composition, the antioxidant effects observed in this study are due, most probably, to the presence of polyphenolic compounds.

  18. Superoxide anion radicals induce IGF-1 resistance through concomitant activation of PTP1B and PTEN.

    Science.gov (United States)

    Singh, Karmveer; Maity, Pallab; Krug, Linda; Meyer, Patrick; Treiber, Nicolai; Lucas, Tanja; Basu, Abhijit; Kochanek, Stefan; Wlaschek, Meinhard; Geiger, Hartmut; Scharffetter-Kochanek, Karin

    2015-01-01

    The evolutionarily conserved IGF-1 signalling pathway is associated with longevity, metabolism, tissue homeostasis, and cancer progression. Its regulation relies on the delicate balance between activating kinases and suppressing phosphatases and is still not very well understood. We report here that IGF-1 signalling in vitro and in a murine ageing model in vivo is suppressed in response to accumulation of superoxide anions (O2∙-) in mitochondria, either by chemical inhibition of complex I or by genetic silencing of O2∙--dismutating mitochondrial Sod2. The O2∙--dependent suppression of IGF-1 signalling resulted in decreased proliferation of murine dermal fibroblasts, affected translation initiation factors and suppressed the expression of α1(I), α1(III), and α2(I) collagen, the hallmarks of skin ageing. Enhanced O2∙- led to activation of the phosphatases PTP1B and PTEN, which via dephosphorylation of the IGF-1 receptor and phosphatidylinositol 3,4,5-triphosphate dampened IGF-1 signalling. Genetic and pharmacologic inhibition of PTP1B and PTEN abrogated O2∙--induced IGF-1 resistance and rescued the ageing skin phenotype. We thus identify previously unreported signature events with O2∙-, PTP1B, and PTEN as promising targets for drug development to prevent IGF-1 resistance-related pathologies.

  19. Calcium-calmodulin does not alter the anion permeability of the mouse TMEM16A calcium-activated chloride channel.

    Science.gov (United States)

    Yu, Yawei; Kuan, Ai-Seon; Chen, Tsung-Yu

    2014-07-01

    The transmembrane protein TMEM16A forms a Ca(2+)-activated Cl(-) channel that is permeable to many anions, including SCN(-), I(-), Br(-), Cl(-), and HCO3 (-), and has been implicated in various physiological functions. Indeed, controlling anion permeation through the TMEM16A channel pore may be critical in regulating the pH of exocrine fluids such as the pancreatic juice. The anion permeability of the TMEM16A channel pore has recently been reported to be modulated by Ca(2+)-calmodulin (CaCaM), such that the pore of the CaCaM-bound channel shows a reduced ability to discriminate between anions as measured by a shift of the reversal potential under bi-ionic conditions. Here, using a mouse TMEM16A clone that contains the two previously identified putative CaM-binding motifs, we were unable to demonstrate such CaCaM-dependent changes in the bi-ionic potential. We confirmed the activity of CaCaM used in our study by showing CaCaM modulation of the olfactory cyclic nucleotide-gated channel. We suspect that the different bi-ionic potentials that were obtained previously from whole-cell recordings in low and high intracellular [Ca(2+)] may result from different degrees of bi-ionic potential shift secondary to a series resistance problem, an ion accumulation effect, or both.

  20. Use of anion-aromatic interactions to position the general base in the ketosteroid isomerase active site.

    Science.gov (United States)

    Schwans, Jason P; Sunden, Fanny; Lassila, Jonathan K; Gonzalez, Ana; Tsai, Yingssu; Herschlag, Daniel

    2013-07-09

    Although the cation-pi pair, formed between a side chain or substrate cation and the negative electrostatic potential of a pi system on the face of an aromatic ring, has been widely discussed and has been shown to be important in protein structure and protein-ligand interactions, there has been little discussion of the potential structural and functional importance in proteins of the related anion-aromatic pair (i.e., interaction of a negatively charged group with the positive electrostatic potential on the ring edge of an aromatic group). We posited, based on prior structural information, that anion-aromatic interactions between the anionic Asp general base and Phe54 and Phe116 might be used instead of a hydrogen-bond network to position the general base in the active site of ketosteroid isomerase from Comamonas testosteroni as there are no neighboring hydrogen-bonding groups. We have tested the role of the Phe residues using site-directed mutagenesis, double-mutant cycles, and high-resolution X-ray crystallography. These results indicate a catalytic role of these Phe residues. Extensive analysis of the Protein Data Bank provides strong support for a catalytic role of these and other Phe residues in providing anion-aromatic interactions that position anionic general bases within enzyme active sites. Our results further reveal a potential selective advantage of Phe in certain situations, relative to more traditional hydrogen-bonding groups, because it can simultaneously aid in the binding of hydrophobic substrates and positioning of a neighboring general base.

  1. Anti-HIV-1 activity of anionic polymers: a comparative study of candidate microbicides

    Directory of Open Access Journals (Sweden)

    Li Yun-Yao

    2002-11-01

    Full Text Available Abstract Background Cellulose acetate phthalate (CAP in soluble form blocks coreceptor binding sites on the virus envelope glycoprotein gp120 and elicits gp41 six-helix bundle formation, processes involved in virus inactivation. CAP is not soluble at pH Methods Enzyme linked immunosorbent assays (ELISA were used to (1 study HIV-1 IIIB and BaL binding to micronized CAP; (2 detect virus disintegration; and (3 measure gp41 six-helix bundle formation. Cells containing integrated HIV-1 LTR linked to the β-gal gene and expressing CD4 and coreceptors CXCR4 or CCR5 were used to measure virus infectivity. Results 1 HIV-1 IIIB and BaL, respectively, effectively bound to micronized CAP. 2 The interaction between HIV-1 and micronized CAP led to: (a gp41 six-helix bundle formation; (b virus disintegration and shedding of envelope glycoproteins; and (c rapid loss of infectivity. Polymers other than CAP, except Carbomer 974P, elicited gp41 six-helix bundle formation in HIV-1 IIIB but only poly(napthalene sulfonate, in addition to CAP, had this effect on HIV-1 BaL. These polymers differed with respect to their virucidal activities, the differences being more pronounced for HIV-1 BaL. Conclusions Micronized CAP is the only candidate topical microbicide with the capacity to remove rapidly by adsorption from physiological fluids HIV-1 of both the X4 and R5 biotypes and is likely to prevent virus contact with target cells. The interaction between micronized CAP and HIV-1 leads to rapid virus inactivation. Among other anionic polymers, cellulose sulfate, BufferGel and aryl sulfonates appear most effective in this respect.

  2. Investigation of the adsorption of anionic surfactants at different pH values by means of active carbon and the kinetics of adsorption

    OpenAIRE

    2004-01-01

    In this study, the effect of pH on the removal of anionic surfactants, such as linear alkyl benzene sulfonate (LABS) and dodecyl benzene sulfonate (DBS) by means of adsorption by activated carbon was investigated. For this purpose activated carbon was used as adsorbent. Anionic surfactant solutions with initial pH values of 3, 6, 8 and 12 were used. The adsorption isotherms for the adsorption of anionic surfactants by active carbon at different pH were determined. These adsorption isotherms w...

  3. Calcium ion activity in physiological salt solutions: influence of anions substituted for chloride

    DEFF Research Database (Denmark)

    Christoffersen, Gert Rene Juul; Skibsted, Leif H

    1975-01-01

    of the snail, Helix pomatia: current-voltage characteristics and membrane potential are described during reduction of extracellular Cl- using different anions as substitutes. Methylsulphate is concluded to be the best substitute in this preparation. 3. The association constants for the binding of Ca2...

  4. CO2 Activation and Hydrogenation by PtHn (-) Cluster Anions.

    Science.gov (United States)

    Zhang, Xinxing; Liu, Gaoxiang; Meiwes-Broer, Karl-Heinz; Ganteför, Gerd; Bowen, Kit

    2016-08-08

    Gas phase reactions between PtHn (-) cluster anions and CO2 were investigated by mass spectrometry, anion photoelectron spectroscopy, and computations. Two major products, PtCO2 H(-) and PtCO2 H3 (-) , were observed. The atomic connectivity in PtCO2 H(-) can be depicted as HPtCO2 (-) , where the platinum atom is bonded to a bent CO2 moiety on one side and a hydrogen atom on the other. The atomic connectivity of PtCO2 H3 (-) can be described as H2 Pt(HCO2 )(-) , where the platinum atom is bound to a formate moiety on one side and two hydrogen atoms on the other. Computational studies of the reaction pathway revealed that the hydrogenation of CO2 by PtH3 (-) is highly energetically favorable.

  5. Perenosins: a new class of anion transporter with anti-cancer activity.

    Science.gov (United States)

    Van Rossom, Wim; Asby, Daniel J; Tavassoli, Ali; Gale, Philip A

    2016-03-07

    A new class of anion transporter named 'perenosins' consisting of a pyrrole linked through an imine to either an indole, benzimidazole or indazole is reported. The indole containing members of the perenosin family function as effective transmembrane Cl(-)/NO3(-) antiporters and HCl cotransporters in a manner similar to the prodigiosenes. The compounds reduce the viability of MDA-MB-231 and MCF-7.

  6. Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic clay for Friedel-Crafts type benzylation reactions

    Indian Academy of Sciences (India)

    Vasant R Choudhary; Rani Jha; Pankaj A Choudhari

    2005-11-01

    Fe-Mg-hydrotalcite (Mg/Fe = 3) anionic clay with or without calcination (at 200-800°C) has been used for the benzylation of toluene and other aromatic compounds by benzyl chloride. Hydrotalcite before and after its calcination was characterized for surface area, crystalline phases and basicity. Both the hydrotalcite, particularly after its use in the benzylation reaction, and the catalyst derived from it by its calcination at 200-800°C show high catalytic activity for the benzylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the chlorides and oxides of iron on the catalyst surface.

  7. Central functions of bicarbonate in S-type anion channel activation and OST1 protein kinase in CO 2 signal transduction in guard cell

    KAUST Repository

    Xue, Shaowu

    2011-03-18

    Plants respond to elevated CO(2) via carbonic anhydrases that mediate stomatal closing, but little is known about the early signalling mechanisms following the initial CO(2) response. It remains unclear whether CO(2), HCO(3)(-) or a combination activates downstream signalling. Here, we demonstrate that bicarbonate functions as a small-molecule activator of SLAC1 anion channels in guard cells. Elevated intracellular [HCO(3)(-)](i) with low [CO(2)] and [H(+)] activated S-type anion currents, whereas low [HCO(3)(-)](i) at high [CO(2)] and [H(+)] did not. Bicarbonate enhanced the intracellular Ca(2+) sensitivity of S-type anion channel activation in wild-type and ht1-2 kinase mutant guard cells. ht1-2 mutant guard cells exhibited enhanced bicarbonate sensitivity of S-type anion channel activation. The OST1 protein kinase has been reported not to affect CO(2) signalling. Unexpectedly, OST1 loss-of-function alleles showed strongly impaired CO(2)-induced stomatal closing and HCO(3)(-) activation of anion channels. Moreover, PYR/RCAR abscisic acid (ABA) receptor mutants slowed but did not abolish CO(2)/HCO(3)(-) signalling, redefining the convergence point of CO(2) and ABA signalling. A new working model of the sequence of CO(2) signalling events in gas exchange regulation is presented.

  8. Investigation of the adsorption of anionic surfactants at different pH values by means of active carbon and the kinetics of adsorption

    Directory of Open Access Journals (Sweden)

    SIBEL ZOR

    2004-01-01

    Full Text Available In this study, the effect of pH on the removal of anionic surfactants, such as linear alkyl benzene sulfonate (LABS and dodecyl benzene sulfonate (DBS by means of adsorption by activated carbon was investigated. For this purpose activated carbon was used as adsorbent. Anionic surfactant solutions with initial pH values of 3, 6, 8 and 12 were used. The adsorption isotherms for the adsorption of anionic surfactants by active carbon at different pH were determined. These adsorption isotherms were seen to be consistent with Freundlich’s adsorption isotherm. k and n constants were determined from Freundlich’s linear equation. Adsorption rate constants were determined from the obtained kinetic curves which were suitable for the first order of rate kinetics.

  9. Anion-π catalysis.

    Science.gov (United States)

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

    2014-02-05

    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

  10. A novel murrel Channa striatus mitochondrial manganese superoxide dismutase: gene silencing, SOD activity, superoxide anion production and expression.

    Science.gov (United States)

    Arockiaraj, Jesu; Palanisamy, Rajesh; Bhatt, Prasanth; Kumaresan, Venkatesh; Gnanam, Annie J; Pasupuleti, Mukesh; Kasi, Marimuthu

    2014-12-01

    We have reported the molecular characterization including gene silencing, superoxide activity, superoxide anion production, gene expression and molecular characterization of a mitochondrial manganese superoxide dismutase (mMnSOD) from striped murrel Channa striatus (named as CsmMnSOD). The CsmMnSOD polypeptide contains 225 amino acids with a molecular weight of 25 kDa and a theoretical isoelectric point of 8.3. In the N-terminal region, CsmMnSOD carries a mitochondrial targeting sequence and a superoxide dismutases (SOD) Fe domain (28-109), and in C-terminal region, it carries another SOD Fe domain (114-220). The CsmMnSOD protein sequence shared significant similarity with its homolog of MnSOD from rock bream Oplegnathus fasciatus (96%). The phylogenetic analysis showed that the CsmMnSOD fell in the clade of fish mMnSOD group. The monomeric structure of CsmMnSOD possesses 9 α-helices (52.4%), 3 β-sheets (8.8%) and 38.8% random coils. The highest gene expression was noticed in liver, and its expression was inducted with fungal (Aphanomyces invadans) and bacterial (Aeromonas hydrophila) infections. The gene silencing results show that the fish that received dsRNA exhibited significant (P superoxide anion production was determined by calculating the granular blood cell count during infection in murrel. It shows that the infection influenced the superoxide radical production which plays a major role in killing the pathogens. Overall, this study indicated the defense potentiality of CsmMnSOD; however, further research is necessary to explore its capability at protein level.

  11. Sono- and photocatalytic activities of SnO2 nanoparticles for degradation of cationic and anionic dyes

    Science.gov (United States)

    Paramarta, Valentinus; Taufik, Ardiansyah; Munisa, Lusitra; Saleh, Rosari

    2017-01-01

    The current research work focuses on the catalytic activity of SnO2 nanoparticles (NPs) against degradation of both cationic dye (methylene blue) and anionic dye (Congo-red). SnO2 NPs were synthesized under the sol-gel method and were characterized by performing X-ray diffraction, Fourier Transform Infrared Spectroscopy (FT-IR), Transmission Electron Microscopy (TEM) Brunauer-Emmet-Teller (BET) surface area analysis and UV-Vis spectroscopy. The results demonstrate that SnO2 NPs has well crystalline structure with the crystallite size of 44 nm. The degradation of dyes was studied under ambient temperature using ultrasonicator and UV light, respectively. The sono- and photocatalytic activities of SnO2 NPs on dyes were analyzed by measuring the change in absorbance of dyes under UV-spectrophotometer. The degradation of the organic dyes has been calculated by monitoring the degradation in the concentration of the dyes before and after irradiation of ultrasonic and light, respectively. The influence of other parameters such as catalyst dosage, pH and scavenger have also been investigated. The catalytic activity is enhanced in the presence of ultrasonic irradiation. The degradation of both dyes follows pseudo-first order kinetics. The reusability tests have also been done to ensure the stability of the used catalysts. A reasonable mechanism of sono- and photocatalysis with SnO2 NPs has been proposed by correlating the active radical species involved with the physical properties of the as-synthesized samples.

  12. Homocysteine enhances superoxide anion release and NADPH oxidase assembly by human neutrophils. Effects on MAPK activation and neutrophil migration.

    Science.gov (United States)

    Alvarez-Maqueda, Moisés; El Bekay, Rajaa; Monteseirín, Javier; Alba, Gonzalo; Chacón, Pedro; Vega, Antonio; Santa María, Consuelo; Tejedo, Juan R; Martín-Nieto, José; Bedoya, Francisco J; Pintado, Elisabeth; Sobrino, Francisco

    2004-02-01

    Hyperhomocysteinaemia has recently been recognized as a risk factor of cardiovascular disease. However, the action mechanisms of homocysteine (Hcy) are not well understood. Given that Hcy may be involved in the recruitment of monocytes and neutrophils to the vascular wall, we have investigated the role of Hcy in essential functions of human neutrophils. We show that Hcy increased superoxide anion (O2*-) release by neutrophils to the extracellular medium, and that this effect was inhibited by superoxide dismutase and diphenyleneiodonium (DPI), an inhibitor of NADPH oxidase activity. The enzyme from rat peritoneal macrophages displayed a similar response. These effects were accompanied by a time-dependent increased translocation of p47phox and p67phox subunits of NADPH oxidase to the plasma membrane. We also show that Hcy increased intracellular H2O2 production by neutrophils, that Hcy enhanced the activation and phosphorylation of mitogen-activated protein kinases (MAPKs), specifically p38-MAPK and ERK1/2, and that the migration of neutrophils was increased by Hcy. Present results are the first evidence that Hcy enhances the oxidative stress of neutrophils, and underscore the potential role of phagocytic cells in vascular wall injury through O2*- release in hyperhomocysteinaemia conditions.

  13. 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.

    Science.gov (United States)

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

    2007-03-01

    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.

  14. Kinetic analysis of anionic surfactant adsorption from aqueous solution onto activated carbon and layered double hydroxide with the zero length column method

    NARCIS (Netherlands)

    Schouten, Natasja; Ham, Louis G.J. van der; Euverink, Gert-Jan W.; Haan, André B. de

    2009-01-01

    Low cost adsorption technology offers high potential to clean-up laundry rinsing water. From an earlier selection of adsorbents, layered double hydroxide (LDH) and granular activated carbon (GAC) proved to be interesting materials for the removal of anionic surfactant, linear alkyl benzene sulfonate

  15. Functional, structural and phylogenetic analysis of domains underlying the Al-sensitivity of the aluminium-activated malate/anion transporter, TaALMT1

    Science.gov (United States)

    TaALMT1 (Triticum aestivum Aluminum Activated Malate Transporter) is the founding member of a novel gene family of anion transporters (ALMTs) that mediate the efflux of organic acids. A small subgroup of root-localized ALMTs, including TaALMT1, is physiologically associated with in planta aluminum (...

  16. Assessing gibberellins oxidase activity by anion exchange/hydrophobic polymer monolithic capillary liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Chen, Ming-Luan; Su, Xin; Xiong, Wei; Liu, Jiu-Feng; Wu, Yan; Feng, Yu-Qi; Yuan, Bi-Feng

    2013-01-01

    Bioactive gibberellins (GAs) play a key regulatory role in plant growth and development. In the biosynthesis of GAs, GA3-oxidase catalyzes the final step to produce bioactive GAs. Thus, the evaluation of GA3-oxidase activity is critical for elucidating the regulation mechanism of plant growth controlled by GAs. However, assessing catalytic activity of endogenous GA3-oxidase remains challenging. In the current study, we developed a capillary liquid chromatography--mass spectrometry (cLC-MS) method for the sensitive assay of in-vitro recombinant or endogenous GA3-oxidase by analyzing the catalytic substrates and products of GA3-oxidase (GA1, GA4, GA9, GA20). An anion exchange/hydrophobic poly([2-(methacryloyloxy)ethyl]trimethylammonium-co-divinylbenzene-co-ethylene glycol dimethacrylate)(META-co-DVB-co-EDMA) monolithic column was successfully prepared for the separation of all target GAs. The limits of detection (LODs, Signal/Noise = 3) of GAs were in the range of 0.62-0.90 fmol. We determined the kinetic parameters (K m) of recombinant GA3-oxidase in Escherichia coli (E. coli) cell lysates, which is consistent with previous reports. Furthermore, by using isotope labeled substrates, we successfully evaluated the activity of endogenous GA3-oxidase that converts GA9 to GA4 in four types of plant samples, which is, to the best of our knowledge, the first report for the quantification of the activity of endogenous GA3-oxidase in plant. Taken together, the method developed here provides a good solution for the evaluation of endogenous GA3-oxidase activity in plant, which may promote the in-depth study of the growth regulation mechanism governed by GAs in plant physiology.

  17. Assessing gibberellins oxidase activity by anion exchange/hydrophobic polymer monolithic capillary liquid chromatography-mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Ming-Luan Chen

    Full Text Available Bioactive gibberellins (GAs play a key regulatory role in plant growth and development. In the biosynthesis of GAs, GA3-oxidase catalyzes the final step to produce bioactive GAs. Thus, the evaluation of GA3-oxidase activity is critical for elucidating the regulation mechanism of plant growth controlled by GAs. However, assessing catalytic activity of endogenous GA3-oxidase remains challenging. In the current study, we developed a capillary liquid chromatography--mass spectrometry (cLC-MS method for the sensitive assay of in-vitro recombinant or endogenous GA3-oxidase by analyzing the catalytic substrates and products of GA3-oxidase (GA1, GA4, GA9, GA20. An anion exchange/hydrophobic poly([2-(methacryloyloxyethyl]trimethylammonium-co-divinylbenzene-co-ethylene glycol dimethacrylate(META-co-DVB-co-EDMA monolithic column was successfully prepared for the separation of all target GAs. The limits of detection (LODs, Signal/Noise = 3 of GAs were in the range of 0.62-0.90 fmol. We determined the kinetic parameters (K m of recombinant GA3-oxidase in Escherichia coli (E. coli cell lysates, which is consistent with previous reports. Furthermore, by using isotope labeled substrates, we successfully evaluated the activity of endogenous GA3-oxidase that converts GA9 to GA4 in four types of plant samples, which is, to the best of our knowledge, the first report for the quantification of the activity of endogenous GA3-oxidase in plant. Taken together, the method developed here provides a good solution for the evaluation of endogenous GA3-oxidase activity in plant, which may promote the in-depth study of the growth regulation mechanism governed by GAs in plant physiology.

  18. Adsorption of anionic, cationic and disperse dyes with activated pyrolytic tire char

    Directory of Open Access Journals (Sweden)

    Duangkamol Danwanichakul

    2015-12-01

    Full Text Available Activated pyrolytic tire char was applied as adsorbents to remove dyes from contaminated water. The method of surface treatment with ethanol solution, HCl solution and then activation with NaOH solution was proposed. After activation at 750oC, the specific surface area (SSA of activated char (AC increased from 154.7 m2 /g to 228.9 m2 /g. The pore size increased slightly from 323.4 oA to 349.3 oA and iodine number increased from 95 mg/g to 137 mg/g. AC was then utilized in the adsorption of three dyes which were acid dye (AR131, basic dye (BR18 and disperse dye (DR167 in a shaker with a speed of 75 rpm at 26oC. The initial concentration was varied to be 10 – 50 mg/L. The kinetic results were more consistent with pseudo-second-order model. Considering the adsorption rate constant, k2, it was found that kinetics for acid dye (AR131 was slower than basic dye (BR18 while kinetics for disperse dye (DR167 did not follow specific pattern since it cannot be dispersed well in water without any dispersing agent. Regarding adsorption equilibrium when the initial concentration was between 10-50 mg/L, the adsorption percentages for acid dye (AR131, basic dye (BR18 and disperse dye (DR167 were 88.2 - 100%, 100%, and 26.9 – 50.7%, respectively. In addition, the adsorption isotherms for acid dye (AR131 and basic dye (BR18 followed the Langmuir equation, whereas, that for disperse dye (DR167 was better fit with the Freundlich equation.

  19. Determination of UV active inorganic anions in potable and high salinity water by ion pair reversed phase liquid chromatography.

    Science.gov (United States)

    Sadiq Khan, Sadaf; Riaz, M

    2014-05-01

    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.

  20. Hypotonicity induced K+ and anion conductive pathways activation in eel intestinal epithelium

    DEFF Research Database (Denmark)

    Lionetto, M G; Giordano, M E; De Nuccio, F

    2005-01-01

    , the activation of 'emergency' systems of rapid cell volume regulation is fundamental in their physiology. The aim of the present work was to study the physiological response to hypotonic stress in a salt-transporting epithelium, the intestine of the euryhaline teleost Anguilla anguilla. Eel intestinal epithelium......(te)) and the short circuit current (I(sc)). This electrophysiological response correlated with a regulatory volume decrease (RVD) response, recorded by morphometrical measurement of the epithelium height. Changes in the transepithelial resistance were also observed following the hypotonicity exposure...

  1. Catalytic activity of thiacalix[4]arenetetrasulfonate metal complexes on modified anion-exchangers for ascorbic acid oxidation.

    Science.gov (United States)

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

    2013-01-01

    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.

  2. Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries.

    Science.gov (United States)

    Faria, P C C; Orfão, J J M; Pereira, M F R

    2004-04-01

    The influence of the surface chemical groups of an activated carbon on the removal of different classes of dyes is evaluated. Starting from the same material (NORIT GAC 1240 PLUS), the following treatments were carried out in order to produce a series of samples with different surface chemical properties but with no major differences in their textural properties: oxidation in the liquid phase with 6M HNO(3) and 10 M H(2)O(2) (acid materials) and heat treatment at 700 degrees C in H(2) or N(2) flow (basic materials). The specific micropores volume and mesopores surface area of the materials were obtained from N(2) adsorption equilibrium isotherms at 77K. The surface chemistry was characterised by temperature programmed desorption, by the determination of the point of zero charge (pH(pzc)) and by the evaluation of the acidity/basicity of the samples. Elemental and proximate analyses were also carried out. Equilibrium isotherms of selected dyes (an acid, a basic and a reactive dye) on the mentioned samples were obtained and the results discussed in relation to their surface chemistry. In general, the Langmuir model provided the best fit for the adsorption data. It is shown that the surface chemistry of the activated carbon plays a key role in dye adsorption performance. The basic sample obtained by thermal treatment under H(2) flow at 700 degrees C is the best material for the adsorption of all the tested dyes.

  3. Local membrane deformations activate Ca2+-dependent K+ and anionic currents in intact human red blood cells.

    Directory of Open Access Journals (Sweden)

    Agnieszka Dyrda

    Full Text Available BACKGROUND: The mechanical, rheological and shape properties of red blood cells are determined by their cortical cytoskeleton, evolutionarily optimized to provide the dynamic deformability required for flow through capillaries much narrower than the cell's diameter. The shear stress induced by such flow, as well as the local membrane deformations generated in certain pathological conditions, such as sickle cell anemia, have been shown to increase membrane permeability, based largely on experimentation with red cell suspensions. We attempted here the first measurements of membrane currents activated by a local and controlled membrane deformation in single red blood cells under on-cell patch clamp to define the nature of the stretch-activated currents. METHODOLOGY/PRINCIPAL FINDINGS: The cell-attached configuration of the patch-clamp technique was used to allow recordings of single channel activity in intact red blood cells. Gigaohm seal formation was obtained with and without membrane deformation. Deformation was induced by the application of a negative pressure pulse of 10 mmHg for less than 5 s. Currents were only detected when the membrane was seen domed under negative pressure within the patch-pipette. K(+ and Cl(- currents were strictly dependent on the presence of Ca(2+. The Ca(2+-dependent currents were transient, with typical decay half-times of about 5-10 min, suggesting the spontaneous inactivation of a stretch-activated Ca(2+ permeability (PCa. These results indicate that local membrane deformations can transiently activate a Ca(2+ permeability pathway leading to increased [Ca(2+](i, secondary activation of Ca(2+-sensitive K(+ channels (Gardos channel, IK1, KCa3.1, and hyperpolarization-induced anion currents. CONCLUSIONS/SIGNIFICANCE: The stretch-activated transient PCa observed here under local membrane deformation is a likely contributor to the Ca(2+-mediated effects observed during the normal aging process of red blood cells, and

  4. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    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. Anion conductance selectivity mechanism of the CFTR chloride channel.

    Science.gov (United States)

    Linsdell, Paul

    2016-04-01

    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.

  6. Peroxynitrite mediates active site tyrosine nitration in manganese superoxide dismutase. Evidence of a role for the carbonate radical anion.

    Science.gov (United States)

    Surmeli, N Basak; Litterman, Nadia K; Miller, Anne-Frances; Groves, John T

    2010-12-08

    carbonate radical anion (•CO3(-)) in MnSOD nitration by PN. We also observed that the nitration of Tyr34 caused inactivation of the enzyme, while nitration of Tyr9 and Tyr11 did not interfere with the superoxide dismutase activity. The loss of MnSOD activity upon Tyr34 nitration implies that the responsible reagent in vivo is peroxynitrite, acting either directly or through the action of •CO3(-).

  7. Nisin Z, mutant nisin Z and lacticin 481 interactions with anionic lipids correlate with antimicrobial activity. A monolayer study

    NARCIS (Netherlands)

    Demel, Rudolf A.; Peelen, Tamara; Siezen, Roland J.; Kruijff, Ben de; Kuipers, Oscar P.

    1996-01-01

    Monomolecular layers of lipids at the air/water interface have been used as a model membrane to study membrane interactions of the lantibiotic nisin. The natural lantibiotics nisin A and nisin Z proved to have a high affinity for the anionic lipids phosphatidylglycerol and bis(phosphatidyl)glycerol

  8. Electrically-assisted delivery of an anionic protein across intact skin: cathodal iontophoresis of biologically active ribonuclease T1.

    Science.gov (United States)

    Dubey, S; Kalia, Y N

    2011-06-30

    Cathodal iontophoresis of anionic macromolecules has been considered a major challenge owing to (i) the presence of a negative charge on the skin under physiological conditions and (ii) the electroosmotic solvent flow in the (opposite) anode-to-cathode direction. Moreover, electroosmosis, and not electromigration, was considered as the likely electrotransport mechanism for high molecular weight cations. However, it was recently shown that electromigration governed anodal iontophoretic transport of Cytochrome c (12.4 kDa) and Ribonuclease A (RNAse A; 13.6 kDa). Thus, the objective of this study was to investigate the feasibility of iontophoresing a negatively charged protein, the enzyme Ribonuclease T1 (RNAse T1, 11.1 kDa), from the cathode across intact skin. Cumulative permeation and skin deposition of RNAse T1 were investigated as a function of current density (0.15, 0.3 and 0.5 mA/cm(2) applied for 8h) using porcine ear skin and quantified by an enzymatic activity assay. Although RNAse T1 permeation was dependent upon current density (22.41 ± 8.10, 76.41 ± 56.98 and 142.19 ± 62.23μg/cm(2), respectively), no such relationship was observed with respect to skin deposition (9.78 ± 2.39, 7.76 ± 4.34 and 8.70 ± 2.94 μg/cm(2), respectively). MALDI-TOF spectra and the activity assay confirmed that RNAse T1 retained structural integrity and enzymatic function post-iontophoresis. Acetaminophen iontophoresis demonstrated the anode-to-cathode directionality of electroosmotic solvent flow confirming that RNAse T1 electrotransport was due entirely to electromigration. Interestingly, despite its lower net charge and higher molecular weight, electromigration of cationic Ribonuclease A was superior to that of RNAse T1 after iontophoresis at 0.5 mA/cm(2) for 8h. These results provide further evidence that charge to mass ratio and hence electric mobility might not alone be sufficient to predict protein electrotransport across the skin; three dimensional structures and the

  9. The Influence of the Anionic Counter-Ion on the Activity of Ammonium Substituted Hoveyda-Type Olefin Metathesis Catalysts in Aqueous Media

    Science.gov (United States)

    Gułajski, Łukasz; Grela, Karol

    Polar olefin metathesis catalysts, bearing an ammonium group are presented. The electron withdrawing ammonium group not only activates the catalysts electronically, but at the same time makes the catalysts more hydrophilic. Catalysts can be therefore efficiently used not only in traditional media, such as methylene chloride and toluene, but also in technical-grade alcohols, alcohol— water mixtures and in neat water. Finally, in this overview the influence of the anionic counter-ion on the activity of ammonium substituted Hoveyda-type olefin metathesis catalysts in aqueous media is presented.

  10. Silver-free activation of ligated gold(I) chlorides: the use of [Me3NB12Cl11]- as a weakly coordinating anion in homogeneous gold catalysis.

    Science.gov (United States)

    Wegener, Michael; Huber, Florian; Bolli, Christoph; Jenne, Carsten; Kirsch, Stefan F

    2015-01-12

    Phosphane and N-heterocyclic carbene ligated gold(I) chlorides can be effectively activated by Na[Me3NB12Cl11] (1) under silver-free conditions. This activation method with a weakly coordinating closo-dodecaborate anion was shown to be suitable for a large variety of reactions known to be catalyzed by homogeneous gold species, ranging from carbocyclizations to heterocyclizations. Additionally, the capability of 1 in a previously unknown conversion of 5-silyloxy-1,6-allenynes was demonstrated.

  11. Active Hydrophilic Components of the Medicinal Herb Salvia miltiorrhiza (Danshen Potently Inhibit Organic Anion Transporters 1 (Slc22a6 and 3 (Slc22a8

    Directory of Open Access Journals (Sweden)

    Li Wang

    2012-01-01

    Full Text Available Many active components of herbal products are small organic anions, and organic anion transporters were previously demonstrated to be a potential site of drug-drug interactions. In this study, we assessed the inhibitory effects of six hydrophilic components of the herbal medicine Danshen, lithospermic acid, protocatechuic acid, rosmarinic acid, salvianolic acid A, salvianolic acid B, and tanshinol, on the function of the murine organic anion transporters, mOat1 and mOat3. All of Danshen components significantly inhibited mOat1- and mOat3-mediated substrate uptake (<0.001 with lithospermic acid (LSA, protocatechuic acid, rosmarinic acid (RMA, and salvianolic acid A (SAA producing virtually complete inhibition under test conditions. Kinetic analysis demonstrated that LSA, RMA, and SAA were competitive inhibitors. As such, values were estimated as 14.9±4.9 μM for LSA, 5.5±2.2 μM for RMA, and 4.9±2.2 μM for SAA on mOat1-mediated transport, and as 31.1±7.0 μM for LSA, 4.3±0.2 μM for RMA, and 21.3±7.7 μM for SAA on mOat3-mediated transport. These data suggest that herb-drug interactions may occur in vivo on the human orthologs of these transporters in situations of polypharmacy involving Danshen and clinical therapeutics known to be organic anion transporter substrates.

  12. A novel short anionic antibacterial peptide isolated from the skin of Xenopus laevis with broad antibacterial activity and inhibitory activity against breast cancer cell.

    Science.gov (United States)

    Li, Siming; Hao, Linlin; Bao, Wanguo; Zhang, Ping; Su, Dan; Cheng, Yunyun; Nie, Linyan; Wang, Gang; Hou, Feng; Yang, Yang

    2016-07-01

    A vastarray of bioactive peptides from amphibian skin secretions is attracting increasing attention due to the growing problem of bacteria resistant to conventional antibiotics. In this report, a small molecular antibacterial peptide, named Xenopus laevis antibacterial peptide-P1 (XLAsp-P1), was isolated from the skin of Xenopus laevis using reversed-phase high-performance liquid chromatography. The primary structure of XLAsp-P1, which has been proved to be a novel peptide by BLAST search in AMP database, was DEDDD with a molecular weight of 607.7 Da analysed by Edman degradation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/TOF-MS). The highlight of XLAsp-P1 is the strong in vitro potency against a variety of Gram-positive and Gram-negative bacteria with minimum inhibitory concentrations (MICs) starting at 10 μg/mL and potent inhibitory activity against breast cancer cell at tested concentrations from 5 to 50 μg/mL. In addition, only 6.2 % of red blood cells was haemolytic when incubated with 64 μg/mL (higher than MICs of all bacterial strain) of XLAsp-P1. The antimicrobial mechanism for this novel peptide was the destruction of the cell membrane investigated by transmission electron microscopy. All these showed that XLAsp-P1 is a novel short anionic antibacterial peptide with broad antibacterial activity and inhibitory activity against breast cancer cell.

  13. Anion exchange membrane

    Science.gov (United States)

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

    2013-05-07

    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.

  14. Anions in Cometary Comae

    Science.gov (United States)

    Charnley, Steven B.

    2011-01-01

    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.

  15. Recycling of agricultural solid waste, coir pith: removal of anions, heavy metals, organics and dyes from water by adsorption onto ZnCl2 activated coir pith carbon.

    Science.gov (United States)

    Namasivayam, C; Sangeetha, D

    2006-07-31

    The abundant lignocellulosic agricultural waste, coir pith is used to develop ZnCl(2) activated carbon and applied to the removal of toxic anions, heavy metals, organic compounds and dyes from water. Sorption of inorganic anions such as nitrate, thiocyanate, selenite, chromium(VI), vanadium(V), sulfate, molybdate, phosphate and heavy metals such as nickel(II) and mercury(II) has been studied. Removal of organics such as resorcinol, 4-nitrophenol, catechol, bisphenol A, 2-aminophenol, quinol, O-cresol, phenol and 2-chlorophenol has also been investigated. Uptake of acidic dyes such as acid brilliant blue, acid violet, basic dyes such as methylene blue, rhodamine B, direct dyes such as direct red 12B, congo red and reactive dyes such as procion red, procion orange were also examined to assess the possible use of the adsorbent for the treatment of contaminated ground water. Favorable conditions for maximum removal of all adsorbates at the adsorbate concentration of 20 mg/L were used. Results show that ZnCl(2) activated coir pith carbon is effective for the removal of toxic pollutants from water.

  16. Iodine release and recovery, influence of polyiodide anions on electrical conductivity and nonlinear optical activity in an interdigitated and interpenetrated bipillared-bilayer metal-organic framework.

    Science.gov (United States)

    Yin, Zheng; Wang, Qiang-Xin; Zeng, Ming-Hua

    2012-03-14

    {[Cu6(pybz)8(OH)2]·I5(–)·I7(–)}n (1), obtained hydrothermally by using iodine molecules as a versatile precursor template, consists of a cationic framework with two types of zigzag channels, which segregate I5(–) and I7(–) anions. The framework exhibits the first observed bipillared-bilayer structure featuring both interdigitation and interpenetration. 1 displays high framework stability in both acidic (HCl) and alkaline (NaOH) solutions. 1 slowly releases iodine in dry methanol to give [Cu6(pybz)8(OH)2](I–)2·3.5CH3OH (1′) and partially recovers iodine from cyclohexane to form [Cu6(pybz)8(OH)2](I–)2·xI2 (1″). Differences of up to 100 times in electrical conductivity and of 4 times in nonlinear optical activity (NLO) have been measured between 1 and 1′. This compound is one of few displaying multifunctionality, electrical conductivity, NLO, and crystal–crystal stability upon release and recovery of iodine. It is also unique in the iodine release from polyiodide anions in a metal–organic framework.

  17. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

    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.

  18. Study of the surface-enhanced Raman spectroscopy of residual impurities in hydroxylamine-reduced silver colloid and the effects of anions on the colloid activity.

    Science.gov (United States)

    Dong, Xiao; Gu, Huaimin; Liu, Fangfang

    2012-03-01

    The paper investigated the residual ions in hydroxylamine-reduced silver colloid (HRSC) and the relationship between the condition of HRSC and the enhanced mechanisms of this colloid. We also detected the SERS of MB and studied the effects of anions on the Raman signal. In the case of HRSC, the bands of residual ions diminish while the bands of Ag-anions increase gradually with increasing the concentrations of Cl(-) and NO(3)(-). It means the affinity of residual ions on the silver surface is weaker than that of Cl(-) and NO(3)(-) and the residual ions are replaced gradually by the added Cl(-) or NO(3)(-). The Raman signal of residual ions can be detected by treatment with anions that do not bind strongly to the silver surface, such as SO(4)(2-). The most intense band of Ag-anions bonds can be also observed when adding weakly binding anions to the colloid. However, the anions which make up the Ag-anions bonds are residual Cl(-) and the effect of weakly binding anions is only to aggregate the silver particles. Residual Cl(-) can be replaced by I(-) which has the highest affinity. From the detection of methylene blue (MB), the effects of anions on the enhancement of Raman signal are discussed in detail, and these findings could make the conditions suitable for detecting analytes in high efficiency. This study will have a profound implication to SERS users about their interpretation of SERS spectra when obtaining these anomalous bands.

  19. The activity of 3- and 7-hydroxyflavones as scavengers of superoxide radical anion generated from photo-excited riboflavin

    Energy Technology Data Exchange (ETDEWEB)

    Montana, P.; Pappano, N.; Debattista, N. [Universidad Nacional de San Luis, Area de Quimica Fisica, San Luis (Argentina); Avila, V.; Posadaz, A.; Bertolotti, S.G.; Garcia, N.A. [Universidad Nacional de Rio Cuarto, Dto. de Quimica, Rio Cuarto (Argentina)

    2003-08-01

    The visible-light irradiation of the system Riboflavin plus 3-hydroxyflavone or plus 7-hydroxyflavone, under aerobic conditions, produces a series of competitive processes that depend on the relative concentrations of the pigment and the flavones. The picture comprises photochemical mechanisms that potentially operate in nature. They mainly include the quenching of Rf singlet ({sup 1}Rf*) and triplet ({sup 3}Rf*) excited states (with bimolecular rate constants in the order of 10{sup 9} M{sup -1} s{sup -1}) and superoxide radical anion-mediated reactions. The participation of the oxidative species singlet molecular oxygen was not detected. The overall result shows chemical transformations in both Rf and 3-hydroxyflavone. No experimental evidence was found indicating any chemical reaction involving 7-hydroxyflavone. The fate of the pigment also depends on the amount of the dissolved flavonoid. At 50 mM concentrations of these compounds or higher, practically no photochemistry occurs, owing to the extensive quenching of ({sup 1}Rf*) When the concentration of the flavones is in the mM range or lower, ({sup 3}Rf*) is photogenerated. Then, the excited triplet species can be quenched mainly by the flavones through an electron-transfer process, yielding the semireduced pigment. The latter interacts with dissolved oxygen producing O{sub 2}{sup .-}, which reacts with both the pigment and 3-hydroxyflavone. In summary, 3-hydroxyflavone and 7-hydroxyflavone participate in the generation of superoxide ion in an Rf-sensitized process, and simultaneously 3-hydroxyflavone constitutes a degradable quencher of the oxidative species. (author)

  20. Male-dominant activation of rat renal organic anion transporter 1 (Oat1 and 3 (Oat3 expression by transcription factor BCL6.

    Directory of Open Access Journals (Sweden)

    Waja Wegner

    Full Text Available BACKGROUND: Organic anion transporters 1 (Oat1 and 3 (Oat3 mediate the transport of organic anions, including frequently prescribed drugs, across cell membranes in kidney proximal tubule cells. In rats, these transporters are known to be male-dominant and testosterone-dependently expressed. The molecular mechanisms that are involved in the sex-dependent expression are unknown. Our aim was to identify genes that show a sex-dependent expression and could be involved in male-dominant regulation of Oat1 and Oat3. METHODOLOGY/PRINCIPAL FINDINGS: Promoter activities of Oat1 and Oat3 were analyzed using luciferase assays. Expression profiling was done using a SurePrint G3 rat GE 8 × 60K microarray. RNA was isolated from renal cortical slices of four adult rats per sex. To filter the achieved microarray data for genes expressed in proximal tubule cells, transcription database alignment was carried out. We demonstrate that predicted androgen response elements in the promoters of Oat1 and Oat3 are not functional when the promoters were expressed in OK cells. Using microarray analyses we analyzed 17,406 different genes. Out of these genes, 56 exhibit a sex-dependent expression in rat proximal tubule cells. As genes potentially involved in the regulation of Oat1 and Oat3 expression, we identified, amongst others, the male-dominant hydroxysteroid (17-beta dehydrogenase 1 (Hsd17b1, B-cell CLL/lymphoma 6 (BCL6, and polymerase (RNA III (DNA directed polypeptide G (Polr3g. Moreover, our results revealed that the transcription factor BCL6 activates promoter constructs of Oat1 and Oat3. CONCLUSION: The results indicate that the male-dominant expression of both transporters, Oat1 and Oat3, is possibly not directly regulated by the classical androgen receptor mediated transcriptional pathway but appears to be regulated by the transcription factor BCL6.

  1. An electrochemical DNA biosensor for evaluating the effect of mix anion in cellular fluid on the antioxidant activity of CeO2 nanoparticles.

    Science.gov (United States)

    Zhai, Yanwu; Zhang, Yan; Qin, Fei; Yao, Xin

    2015-08-15

    CeO2 nanoparticles are of particular interest as a novel antioxidant for scavenging free radicals. However, some studies showed that they could cause cell damage or death by generating reactive oxygen species (ROS). Up to now, it is not well understood about these paradoxical phenomena. Therefore, many attentions have been paid to the factors that could affect the antioxidant activity of CeO2 nanoparticles. CeO2 nanoparticles would inevitably encounter body fluid environment for its potential medical application. In this work the antioxidant activity behavior of CeO2 nanoparticles is studied in simulated cellular fluid, which contains main body anions (HPO4(2-), HCO3(-), Cl(-) and SO4(2-)), by a method of electrochemical DNA biosensor. We found that in the solution of Cl(-) and SO4(2-), CeO2 nanoparticles can protect DNA from damage by hydroxyl radicals, while in the presence of HPO4(2-) and HCO3(-), CeO2 nanoparticles lose the antioxidant activity. This can be explained by the cerium phosphate and cerium carbonate formed on the surface of the nanoparticles, which interfere with the redox cycling between Ce(3+) and Ce(4+). These results not only add basic knowledge to the antioxidant activity of CeO2 nanoparticles under different situations, but also pave the way for practical applications of nanoceria. Moreover, it also shows electrochemical DNA biosensor is an effective method to explore the antioxidant activity of CeO2 nanoparticles.

  2. A superoxide anion-scavenger, 1,3-selenazolidin-4-one suppresses serum deprivation-induced apoptosis in PC12 cells by activating MAP kinase

    Energy Technology Data Exchange (ETDEWEB)

    Nishina, Atsuyoshi, E-mail: nishina@yone.ac.jp [Yonezawa Women' s Junior College, 6-15-1 Tohrimachi, Yonezawa, Yamagata 992-0025 (Japan); Kimura, Hirokazu; Kozawa, Kunihisa [Gunma Prefectural Institute of Public Health and Environmental Sciences, 378 Kamioki, Maebashi, Gunma 371-0052 (Japan); Sommen, Geoffroy [Lonza Braine SA, Chaussee de Tubize 297, B-1420 Braine l' Alleud (Belgium); Nakamura, Takao [Department of Biomedical Information Engineering, Graduate School of Medical Science, Yamagata University, Yamagata 990-9585 (Japan); Heimgartner, Heinz [University of Zuerich, Institut of Organic Chemistry, Winterthurerstrasse 190, CH-8057 Zuerich (Switzerland); Koketsu, Mamoru [Department of Materials Science and Technology, Faculty of Engineering, Gifu University, Gifu 501-1193 (Japan); Furukawa, Shoei [Laboratory of Molecular Biology, Gifu Pharmaceutical University, 5-6-1 Mitahora-higashi, Gifu 502-8585 (Japan)

    2011-12-15

    Synthetic organic selenium compounds, such as ebselen, may show glutathione peroxidase-like antioxidant activity and have a neurotrophic effect. We synthesized 1,3-selenazolidin-4-ones, new types of synthetic organic selenium compounds (five-member ring compounds), to study their possible applications as antioxidants or neurotrophic-like molecules. Their superoxide radical scavenging effects were assessed using the quantitative, highly sensitive method of real-time kinetic chemiluminescence. At 166 {mu}M, the O{sub 2}{sup -} scavenging activity of 1,3-selenazolidin-4-ones ranged from 0 to 66.2%. 2-[3-(4-Methoxyphenyl)-4-oxo-1,3-selenazolidin-2-ylidene]malononitrile (compound b) showed the strongest superoxide anion-scavenging activity among the 6 kinds of 2-methylene-1,3-selenazolidin-4-ones examined. Compound b had a 50% inhibitory concentration (IC{sub 50}) at 92.4 {mu}M and acted as an effective and potentially useful O{sub 2}{sup -} scavenger in vitro. The effect of compound b on rat pheochromocytome cell line PC12 cells was compared with that of ebselen or nerve growth factor (NGF) by use of the MTT [3-(4, 5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide] assay. When ebselen was added at 100 {mu}M or more, toxicity toward PC12 cells was evident. On the contrary, compound b suppressed serum deprivation-induced apoptosis in PC12 cells more effectively at a concentration of 100 {mu}M. The activity of compound b to phosphorylate mitogen-activated protein kinase/extracellular signal-regulated protein kinase (ERK) 1/2 (MAP kinase) in PC12 cells was higher than that of ebselen, and the former at 100 {mu}M induced the phosphorylation of MAP kinase to a degree similar to that induced by NGF. From these results, we conclude that this superoxide anion-scavenger, compound b, suppressed serum deprivation-induced apoptosis by promoting the phosphorylation of MAP kinase. -- Highlights: Black-Right-Pointing-Pointer We newly synthesized 1,3-selenazolidin-4-ones to

  3. Electrochemical Film Formation on Magnesium Metal in an Ionic Liquid That Dissolves Metal Triflate and Its Application to an Active Material with Anion Charge Carrier.

    Science.gov (United States)

    Shiga, Tohru; Kato, Yuichi; Inoue, Masae

    2016-11-16

    Irregular metallic growth at the anode during recharging of batteries can seriously influence the safety of batteries. To address this problem, we have attempted to design active anode materials with anion charge carriers and recently observed the formation and dissolution of an electrochemical film by triflate anions (CF3SO3(-)) at the surface of magnesium in an ionic liquid (IL) electrolyte of Mg(CF3SO3)2, which represents a rare anode material. The effect of heterogeneous cations on film formation was examined in this work. In an IL that dissolves NaCF3SO3, sodium ions with a lower reduction potential than Mg(2+)/Mg would not be expected to assist film formation. However, to our surprise, we discovered that some sodium ions are involved in film formation. The sodium ions are believed to act as a cross-linking point for the formation of a film network, which resulted in fairly good reversibility for film formation. In a Ce(CF3SO3)3-IL electrolyte, an electrochemically formed film free of Ce(3+) was obtained. The trivalent cerium cations were deactivated and transformed to an oxide on Mg metal. However, the reversibility of film formation in the Ce(CF3SO3)3 system did not meet the expected level. By coupling the film formation and dissolution behavior with a V2O5 cathode, a rechargeable battery was fabricated with dual ion transport species of Na(+) or Ce(3+) for the cathode and CF3SO3(-) for the anode. The unique battery with NaCF3SO3 is demonstrated to exhibit good discharge/charge performance with long-term cyclability.

  4. A dual action of saturated fatty acids on electrical activity in rat pancreatic β-cells. Role of volume-regulated anion channel and KATP channel currents.

    Science.gov (United States)

    Best, L; Jarman, E; Brown, P D

    2011-03-15

    Free fatty acids (FFAs) exert complex actions on pancreatic β-cells. Typically, an initial potentiation of insulin release is followed by a gradual impairment of β-cell function, the latter effect being of possible relevance to hyperlipidaemia in type 2 diabetes mellitus. The molecular actions of FFAs are poorly understood. The present study investigated the acute effects of saturated FFAs on electrophysiological responses of rat pancreatic β-cells. Membrane potential and KATP channel activity were recorded using the perforated patch technique. Volume-regulated anion channel (VRAC) activity was assessed from conventional whole-cell recordings. Cell volume regulation was measured using a video-imaging technique. Addition of octanoate caused a transient potentiation of glucose-induced electrical activity, followed by a gradual hyper-polarisation and a prolonged inhibition of electrical activity. Octanoate caused an initial increase in VRAC activity followed by a secondary inhibition coinciding with increased KATP channel activity. Similar effects were observed with palmitate and 2-bromopalmitate whereas butyrate was virtually ineffective. Octanoate and palmitate also exerted a dual effect on electrical activity evoked by tolbutamide. Octanoate significantly attenuated cell volume regulation in hypotonic solutions, consistent with VRAC inhibition. It is concluded that medium and long chain FFAs have a dual action on glucose-induced electrical activity in rat pancreatic β-cells: an initial stimulatory effect followed by a secondary inhibition. These effects appear to be the result of reciprocal actions on VRAC and KATP channel currents, and could contribute towards the stimulatory and inhibitory actions of FFAs on pancreatic β-cell function.

  5. In-situ anion exchange fabrication of porous ZnO/ZnSe heterostructural microspheres with enhanced visible light photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hairui, E-mail: liuhairui1@126.com [College of Physics & Electrics Engineering, Henan Normal University, Henan Key Laboratory of Photovoltaic Materials, Xinxiang 453007 (China); Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Hu, Yanchun [College of Physics & Electrics Engineering, Henan Normal University, Henan Key Laboratory of Photovoltaic Materials, Xinxiang 453007 (China); He, Xia [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); Jia, Husheng, E-mail: jia_husheng@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Liu, Xuguang; Xu, Bingshe [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China)

    2015-11-25

    Porous ZnO microspheres were fabricated by an ultrasonic irradiation technique. Subsequently, through a facile in-situ anion exchange reaction between the ZnO microsphere and sodium selenite, spherical ZnO/ZnSe heterostructures with different ratios of the two components were fabricated. The as-obtained products were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and UV–vis spectrometry. The results reveal that the secondary ZnSe nanoparticles are grown on the surface of pre-grown ZnO microspheres. Compared with pure ZnO microspheres, the ZnO/ZnSe hetero-microspheres show enhance visible-light photocatalytic activity for degradation of methylene blue (MB) and 4-nitrophenol (4-NP). The enhanced photocatalytic performance is attributed to fast separation and transport of photogenerated electrons and holes derived from the coupling effect of ZnSe and ZnO heterostructure. Photoluminescent spectra further indicate that the ZnO/ZnSe heterostructures greatly suppress the charge recombination of photogenerated electron–hole pairs, which would be beneficial to improve their photocatalytic activity. Finally, the photocatalytic mechanism of the ZnO/ZnSe heterostructures is proposed. - Graphical abstract: Porous ZnO/ZnSe heterostructures with different ratios of the two components were fabricated and present enhance visible-light photocatalytic activity for degradation of methylene blue (MB) and 4-nitrophenol (4-NP). The enhanced photocatalytic performance is attributed to fast separation and transport of photogenerated electrons and holes derived from the coupling effect of ZnSe and ZnO heterostructure. - Highlights: • Spherical ZnO/ZnSe porous composites were fabricated by in-situ anion exchange. • ZnO/ZnSe composites exhibited enhanced visible-light photocatalytic activity. • The matching band gap improves the separation of

  6. Electrostatics of cell membrane recognition: structure and activity of neutral and cationic rigid push-pull rods in isoelectric, anionic, and polarized lipid bilayer membranes.

    Science.gov (United States)

    Sakai, N; Gerard, D; Matile, S

    2001-03-21

    Design, synthesis, and structural and functional studies of rigid-rod ionophores of different axial electrostatic asymmetry are reported. The employed design strategy emphasized presence of (a) a rigid scaffold to minimize the conformational complexity, (b) a unimolecular ion-conducting pathway to minimize the suprastructural complexity and monitor the function, (c) an extended fluorophore to monitor structure, (d) variable axial rod dipole, and (e) variable terminal charges to create axial asymmetry. Studies in isoelectric, anionic, and polarized bilayer membranes confirmed a general increase in activity of uncharged rigid push-pull rods in polarized bilayers. The similarly increased activity of cationic rigid push-pull rods with an electrostatic asymmetry comparable to that of alpha-helical bee toxin melittin (positive charge near negative axial dipole terminus) is shown by fluorescence-depth quenching experiments to originate from the stabilization of transmembrane rod orientation by the membrane potential. The reduced activity of rigid push-pull rods having an electrostatic asymmetry comparable to that in alpha-helical natural antibiotics (a positive charge near the positive axial dipole terminus) is shown by structural studies to originate from rod "ejection" by membrane potentials comparable to that found in mammalian plasma membranes. This structural evidence for cell membrane recognition by asymmetric rods is unprecedented and of possible practical importance with regard to antibiotic resistance.

  7. Acute ethanol intake induces superoxide anion generation and mitogen-activated protein kinase phosphorylation in rat aorta: A role for angiotensin type 1 receptor

    Energy Technology Data Exchange (ETDEWEB)

    Yogi, Alvaro; Callera, Glaucia E. [Kidney Research Centre, Ottawa Hospital Research Institute, University of Ottawa, Ontario (Canada); Mecawi, André S. [Department of Physiology, Faculty of Medicine of Ribeirão Preto, University of São Paulo (USP), Ribeirão Preto, SP (Brazil); Batalhão, Marcelo E.; Carnio, Evelin C. [Department of General and Specialized Nursing, College of Nursing of Ribeirão Preto, USP, São Paulo (Brazil); Antunes-Rodrigues, José [Department of Physiology, Faculty of Medicine of Ribeirão Preto, University of São Paulo (USP), Ribeirão Preto, SP (Brazil); Queiroz, Regina H. [Department of Clinical, Toxicological and Food Science Analysis, Faculty of Pharmaceutical Sciences, USP, São Paulo (Brazil); Touyz, Rhian M. [Kidney Research Centre, Ottawa Hospital Research Institute, University of Ottawa, Ontario (Canada); Tirapelli, Carlos R., E-mail: crtirapelli@eerp.usp.br [Department of Psychiatric Nursing and Human Sciences, Laboratory of Pharmacology, College of Nursing of Ribeirão Preto, USP, Ribeirão Preto, SP (Brazil)

    2012-11-01

    Ethanol intake is associated with increase in blood pressure, through unknown mechanisms. We hypothesized that acute ethanol intake enhances vascular oxidative stress and induces vascular dysfunction through renin–angiotensin system (RAS) activation. Ethanol (1 g/kg; p.o. gavage) effects were assessed within 30 min in male Wistar rats. The transient decrease in blood pressure induced by ethanol was not affected by the previous administration of losartan (10 mg/kg; p.o. gavage), a selective AT{sub 1} receptor antagonist. Acute ethanol intake increased plasma renin activity (PRA), angiotensin converting enzyme (ACE) activity, plasma angiotensin I (ANG I) and angiotensin II (ANG II) levels. Ethanol induced systemic and vascular oxidative stress, evidenced by increased plasma thiobarbituric acid-reacting substances (TBARS) levels, NAD(P)H oxidase‐mediated vascular generation of superoxide anion and p47phox translocation (cytosol to membrane). These effects were prevented by losartan. Isolated aortas from ethanol-treated rats displayed increased p38MAPK and SAPK/JNK phosphorylation. Losartan inhibited ethanol-induced increase in the phosphorylation of these kinases. Ethanol intake decreased acetylcholine-induced relaxation and increased phenylephrine-induced contraction in endothelium-intact aortas. Ethanol significantly decreased plasma and aortic nitrate levels. These changes in vascular reactivity and in the end product of endogenous nitric oxide metabolism were not affected by losartan. Our study provides novel evidence that acute ethanol intake stimulates RAS activity and induces vascular oxidative stress and redox-signaling activation through AT{sub 1}-dependent mechanisms. These findings highlight the importance of RAS in acute ethanol-induced oxidative damage. -- Highlights: ► Acute ethanol intake stimulates RAS activity and vascular oxidative stress. ► RAS plays a role in acute ethanol-induced oxidative damage via AT{sub 1} receptor activation.

  8. Role of volume-regulated and calcium-activated anion channels in cell volume homeostasis, cancer and drug resistance

    DEFF Research Database (Denmark)

    Hoffmann, Else Kay; Sørensen, Belinda Halling; Sauter, Daniel Rafael Peter

    2015-01-01

    to be an essential component of both VRAC and VSOAC. Reduced VRAC and VSOAC activities are seen in drug resistant cancer cells. ANO1 is a calcium-activated chloride channel expressed on the plasma membrane of e.g. secretory epithelia. ANO1 is amplified and highly expressed in a large number of carcinomas. The gene...... functions as well as their role in cancer and drug resistance....

  9. Supramolecular electron transfer by anion binding.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; D'Souza, Francis; Sessler, Jonathan L

    2012-10-11

    Anion binding has emerged as an attractive strategy to construct supramolecular electron donor-acceptor complexes. In recent years, the level of sophistication in the design of these systems has advanced to the point where it is possible to create ensembles that mimic key aspects of the photoinduced electron-transfer events operative in the photosynthetic reaction centre. Although anion binding is a reversible process, kinetic studies on anion binding and dissociation processes, as well as photoinduced electron-transfer and back electron-transfer reactions in supramolecular electron donor-acceptor complexes formed by anion binding, have revealed that photoinduced electron transfer and back electron transfer occur at time scales much faster than those associated with anion binding and dissociation. This difference in rates ensures that the linkage between electron donor and acceptor moieties is maintained over the course of most forward and back electron-transfer processes. A particular example of this principle is illustrated by electron-transfer ensembles based on tetrathiafulvalene calix[4]pyrroles (TTF-C4Ps). In these ensembles, the TTF-C4Ps act as donors, transferring electrons to various electron acceptors after anion binding. Competition with non-redox active substrates is also observed. Anion binding to the pyrrole amine groups of an oxoporphyrinogen unit within various supramolecular complexes formed with fullerenes also results in acceleration of the photoinduced electron-transfer process but deceleration of the back electron transfer; again, this is ascribed to favourable structural and electronic changes. Anion binding also plays a role in stabilizing supramolecular complexes between sulphonated tetraphenylporphyrin anions ([MTPPS](4-): M = H(2) and Zn) and a lithium ion encapsulated C(60) (Li(+)@C(60)); the resulting ensemble produces long-lived charge-separated states upon photoexcitation of the porphyrins.

  10. Quantitative Prediction of Human Renal Clearance and Drug-Drug Interactions of Organic Anion Transporter Substrates Using In Vitro Transport Data: A Relative Activity Factor Approach.

    Science.gov (United States)

    Mathialagan, Sumathy; Piotrowski, Mary A; Tess, David A; Feng, Bo; Litchfield, John; Varma, Manthena V

    2017-04-01

    Organic anion transporters (OATs) are important in the renal secretion, and thus, the clearance, of many drugs; and their functional change can result in pharmacokinetic variability. In this study, we applied transport rates measured in vitro using OAT-transfected human embryonic kidney cells to predict human renal secretory and total renal clearance of 31 diverse drugs. Selective substrates to OAT1 (tenofovir), OAT2 (acyclovir and ganciclovir), and OAT3 (benzylpenicillin, oseltamivir acid) were used to obtain relative activity factors (RAFs) for these individual transporters by relating in vitro transport clearance (after physiologic scaling) to in vivo secretory clearance. Using the estimated RAFs (0.64, 7.3, and 4.1, respectively, for OAT1, OAT2, and OAT3, respectively) and the in vitro active clearances, renal secretory clearance and total renal clearance were predicted with average fold errors (AFEs) of 1.89 and 1.40, respectively. The results show that OAT3-mediated transport play a predominant role in renal secretion for 22 of the 31 drugs evaluated. This mechanistic static approach was further applied to quantitatively predict renal drug-drug interactions (AFE ∼1.6) of the substrate drugs with probenecid, a clinical probe OAT inhibitor. In conclusion, the proposed in vitro-in vivo extrapolation approach is the first comprehensive attempt toward mechanistic modeling of renal secretory clearance based on routinely employed in vitro cell models.

  11. Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions.

    Science.gov (United States)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-04-01

    Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from -3.4±0.3 to -4.3±0.3‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from -7.0±0.4 to -13.6±1.2‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO4(-)). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO).

  12. Local membrane deformations activate Ca2+-dependent K+ and anionic currents in intact human red blood cells

    DEFF Research Database (Denmark)

    Dyrda, Agnieszka; Cytlak, Urszula; Ciuraszkiewicz, Anna;

    2010-01-01

    -activated transient PCa observed here under local membrane deformation is a likely contributor to the Ca(2+)-mediated effects observed during the normal aging process of red blood cells, and to the increased Ca(2+) content of red cells in certain hereditary anemias such as thalassemia and sickle cell anemia....

  13. Hydrogen atom scrambling in selectively labeled anionic peptides upon collisional activation by MALDI tandem time-of-flight mass spectrometry

    DEFF Research Database (Denmark)

    Bache, Nicolai; Rand, Kasper Dyrberg; Roepstorff, Peter;

    2008-01-01

    have now measured the level of hydrogen scrambling in a deprotonated, selectively labeled peptide using MALDI tandem time-of-flight mass spectrometry. Our results conclusively show that hydrogen scrambling is prevalent in the deprotonated peptide upon collisional activation. The amide hydrogens ((1)H...

  14. Novel chlorambucil-conjugated anionic linear-globular PEG-based second-generation dendrimer: in vitro/in vivo improved anticancer activity

    Directory of Open Access Journals (Sweden)

    Assadi A

    2016-09-01

    Full Text Available Artin Assadi,1 Vahideh Sharifi Najafabadi,1 Seyed Ataollah Sadat Shandiz,2 Azadah Shayeq Boroujeni,1 Sepehr Ashrafi,1 Ali Zaman Vaziri,1 Seyedeh Masoumeh Ghoreishi,1 Mohammad Reza Aghasadeghi,3 Seyed Esmaeil Sadat Ebrahimi,4 Morteza Pirali-Hamedani,4 Mehdi Shafiee Ardestani1 1Department of Radiopharmacy, Faculty of Pharmacy, Tehran University of Medical Sciences, 2Young Researchers and Elite Club, East Tehran Branch, Islamic Azad University, 3Department of Hepatitis and AIDS, Pasteur Institute of Iran, 4Department of Medicinal Chemistry, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran Abstract: Evaluating the efficacy of anticancer drugs is an evolving and research-oriented issue. The objective of this study was to reduce the insolubility of chlorambucil (CBL in water and improve the anticancer activity of CBL in vitro and in vivo through the conjugation of CBL with anionic linear-globular dendrimer (second generation, G2. In the current study, the anticancer activity among three groups that include CBL, CBL–G2 dendrimer, and control was measured in vitro and in vivo. In vitro studies showed that G2 anionic linear-globular polyethylene-glycol-based dendrimer, which conjugated to the CBL exterior through an ester linkage, was able to significantly improve the treatment efficacy over clinical CBL alone with respect to proliferation assay, 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl-2H-tetrazolium-5-carboxanilide; half maximal inhibitory concentration (IC50 was calculated to be 141 µg/mL for CBL alone and 27.7 µg/mL for CBL–G2 dendrimer; P<0.05. In addition, CBL–G2 dendrimer conjugate forestalled the growth of MCF-7 cancerous cells in addition to enhancing the number of apoptotic and necrotic cells as demonstrated by an annexin V-fluorescein isothiocyanate assay. CBL–G2 dendrimer conjugate was able to checkmate antiapoptotic Bcl-2 expression and Bcl-2/Bax ratio in a large scale compared with the control group and

  15. Molecular dynamics investigation of the influence of anionic and zwitterionic interfaces on antimicrobial peptides' structure: implications for peptide toxicity and activity

    DEFF Research Database (Denmark)

    Khandelia, Himanshu; Kaznessis, Yiannis N

    2006-01-01

    Molecular dynamics simulations of three related helical antimicrobial peptides have been carried out in zwitterionic diphosphocholine (DPC) micelles and anionic sodiumdodecylsulfate (SDS) micelles. These systems can be considered as model mammalian and bacterial membrane interfaces, respectively...

  16. Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-04-01

    Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from − 3.4 ± 0.3 to − 4.3 ± 0.3 ‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from − 7.0 ± 0.4 to − 13.6 ± 1.2 ‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO{sub 4}·{sup −}). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO). - Highlights: • Significant C isotope fractionation for TCE degradation by Fe{sup 0} activated persulfate. • The enrichment factors was independent of Fe{sup 0}, SO{sub 4}{sup 2−}, or HCO{sub 3}{sup −} concentration. • Cl{sup −} significantly influenced the carbon isotope fractionation.

  17. Local membrane deformations activate Ca2+-dependent K+ and anionic currents in intact human red blood cells

    DEFF Research Database (Denmark)

    Dyrda, Agnieszka; Cytlak, Urszula; Ciuraszkiewicz, Anna

    2010-01-01

    by such flow, as well as the local membrane deformations generated in certain pathological conditions, such as sickle cell anemia, have been shown to increase membrane permeability, based largely on experimentation with red cell suspensions. We attempted here the first measurements of membrane currents......-activated transient PCa observed here under local membrane deformation is a likely contributor to the Ca(2+)-mediated effects observed during the normal aging process of red blood cells, and to the increased Ca(2+) content of red cells in certain hereditary anemias such as thalassemia and sickle cell anemia.......BACKGROUND: The mechanical, rheological and shape properties of red blood cells are determined by their cortical cytoskeleton, evolutionarily optimized to provide the dynamic deformability required for flow through capillaries much narrower than the cell's diameter. The shear stress induced...

  18. Studies on Anion Promoted Titania.1: Preparation, Characterization, and Catalytic Activity toward Alcohol and Cumene Conversion Reactions of Phosphated Titania.

    Science.gov (United States)

    Parida; Acharya; Samantaray; Mishra

    1999-09-15

    Phosphate impregnated titania samples with varying amount of phosphate have been prepared by solid-solid kneading as well as aqueous impregnation method. All the samples are characterized by XRD, TG-DTA, and N(2) adsorption-desorption isotherm. Surface area is found to increase with the increase in phosphate content up to 7.5 wt% loading and thereafter decreases. The average pore diameter and crystallite size of titania decreases with the addition of phosphate. However, total acidity (determined by base adsorption method) and the catalytic activity increases with the increase in phosphate content up to 10 wt%. Phosphated samples prepared using phosphoric acid as the source of phosphate exhibit higher acidity compared to the samples prepared using (NH(4))(3)PO(4). However, the sample prepared from (NH(4))(3)PO(4) shows the presence of both acid and basic sites. Though from the cumene conversion study it is understood that phosphated samples contain both Lewis and Brønsted acid sites, the latter predominates over the former. Copyright 1999 Academic Press.

  19. Interstratified nanohybrid assembled by alternating cationic layered double hydroxide nanosheets and anionic layered titanate nanosheets with superior photocatalytic activity.

    Science.gov (United States)

    Lin, Bizhou; Sun, Ping; Zhou, Yi; Jiang, Shaofeng; Gao, Bifen; Chen, Yilin

    2014-09-15

    Oppositely charged 2D inorganic nanosheets of ZnAl-layered double hydroxide and layered titanate were successfully assembled into an interstratified nanohybrid through simply mixing the corresponding nanosheet suspensions. Powder X-ray diffraction and high-resolution transmission electron microscope clearly revealed that the component nanosheets in the as-obtained nanohybrid ZnAl-Ti3O7 retain the 2D sheet skeletons of the pristine materials and that the two kinds of nanosheets are well arranged in a layer-by-layer alternating fashion with a basal spacing of about 1.3 nm, coincident with the thickness summation of the two component nanosheets. The effective interfacial heterojunction between them and the high specific surface area resulted in that the nanohybrid exhibits a superior photocatalytic activity in the degradation of methylene blue with a reaction constant k of 2.81 × 10(-2)min(-1), which is about 9 and 4 times higher than its precursors H2Ti3O7 and ZnAl-LDH, respectively. Based on UV-vis, XPS and photoelectrochemical measurements, a proposed photoexcitation model was provided to understand its photocatalytic behavior.

  20. Soft-chemical synthesis and catalytic activity of Ni-Al and Co-Al layered double hydroxides (LDHs intercalated with anions with different charge density

    Directory of Open Access Journals (Sweden)

    Takahiro Takei

    2014-09-01

    Full Text Available Co-Al and Ni-Al layered double hydroxides (LDHs intercalated with three types of anionic molecules, dodecylsulfate (C12H25SO4−, DS, di-2-ethylsulfosuccinate ([COOC2H3EtBu]2C2H3SO3−, D2ES, and polytungstate (H2W12O4210−, HWO were prepared by means of ion-exchange and co-precipitation processes. With the use of DS and D2ES as intercalation agents, high crystallinity was maintained after intercalation into the LDHs. In the case of HWO, the intercalated LDHs could be obtained by ion-exchange as well as co-precipitation with a decline in the crystallinity; however, unreacted LDH was detected in the ion-exchange samples, and some unwanted phases such as hydroxide and pyrochlore were generated by the co-precipitation process. The maximum specific surface area and pore volume of the Ni-Al sample with intercalated HWO, prepared by the ion-exchange process were 74 m2/g and 0.174 mL/g, respectively. The occupancies of DS, D2ES, and HWO within the interlayer space were approximately 0.3–0.4, 0.5–0.6, and 0.1–0.2, respectively, in the Co-Al and Ni-Al LDHs. Analysis of the catalytic activity demonstrated that the DS-intercalated Ni-Al LDH sample exhibited relatively good catalytic activity for conversion of cyclohexanol to cyclohexanone.

  1. Potentiometric anion selective sensors

    NARCIS (Netherlands)

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

    1999-01-01

    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

  2. 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.

    Science.gov (United States)

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

    2009-06-01

    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.

  3. Organic Anion Transporting Polypeptide (OATP)2B1 Contributes to Gastrointestinal Toxicity of Anticancer Drug SN-38, Active Metabolite of Irinotecan Hydrochloride.

    Science.gov (United States)

    Fujita, Daichi; Saito, Yoshimasa; Nakanishi, Takeo; Tamai, Ikumi

    2016-01-01

    Gastrointestinal toxicity, such as late-onset diarrhea, is a significant concern in irinotecan hydrochloride (CPT-11)-containing regimens. Prophylaxis of late-onset diarrhea has been reported with use of Japanese traditional (Kampo) medicine containing baicalin and with the antibiotic cefixime, and this has been explained in terms of inhibition of bacterial deconjugation of SN-38-glucuronide since unconjugated SN-38 (active metabolite of CPT-11) is responsible for the gastrointestinal toxicity. It is also prerequisite for SN-38 to be accumulated in intestinal tissues to exert toxicity. Based on the fact that liver-specific organic anion transporting polypeptide (OATP)1B1, a member of the same family as OATP2B1, is known to be involved in hepatic transport of SN-38, we hypothesized that intestinal transporter OATP2B1 contributes to the accumulation of SN-38 in gastrointestinal tissues, and its inhibition would help prevent associated toxicity. We found that uptake of SN-38 by OATP2B1-expressing Xenopus oocytes was significantly higher than that by control oocytes. OATP2B1-mediated uptake of SN-38 was saturable, pH dependent, and decreased in the presence of baicalin, cefixime, or fruit juices such as apple juice. In vivo gastrointestinal toxicity of SN-38 in mice caused by oral administration for consecutive 5 days was prevented by coingestion of apple juice. Thus, OATP2B1 contributes to the uptake of SN-38 by intestinal tissues, triggering gastrointestinal toxicity. So, in addition to the reported inhibition of bacterial β-glucuronidase by cefixime or baicalin, inhibition of OATP2B1 may also contribute to prevention of gastrointestinal toxicity. Apple juice may be helpful for prophylaxis of late-onset diarrhea observed in CPT-11 therapy without disturbance of the intestinal microflora.

  4. Templating irreversible covalent macrocyclization by using anions.

    Science.gov (United States)

    Kataev, Evgeny A; Kolesnikov, Grigory V; Arnold, Rene; Lavrov, Herman V; Khrustalev, Victor N

    2013-03-11

    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.

  5. Aggregation-Induced Emission Active Metal-Free Chemosensing Platform for Highly Selective Turn-On Sensing and Bioimaging of Pyrophosphate Anion.

    Science.gov (United States)

    Gogoi, Abhijit; Mukherjee, Sandipan; Ramesh, Aiyagari; Das, Gopal

    2015-07-07

    We report the synthesis of a metal-free chemosensor for highly selective sensing of pyrophosphate (PPi) anion in physiological medium. The novel phenylbenzimidazole functionalized imine containing chemosensor (L; [2,6-bis(((4-(1H-benzo[d]imidazol-2-yl)phenyl)imino) methyl)-4 methyl phenol]) could sense PPi anion through "turn-on" colorimetric and fluorimetric responses in a very competitive environment. The overall sensing mechanism is based on the aggregation-induced emission (AIE) phenomenon. Moreover, a real time in-field device application was demonstrated by sensing PPi in paper strips coated with L. Interestingly, detection of intracellular PPi ions in model human cells could also be possible by fluorescence microscopic studies without any toxicity to these cells.

  6. Anion-Channel Blockers Inhibit S-Type Anion Channels and Abscisic Acid Responses in Guard Cells.

    Science.gov (United States)

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

    1995-10-01

    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.

  7. Anion conductance of the human red cell is carried by a maxi-anion channel

    DEFF Research Database (Denmark)

    Glogowska, Edyta; Dyrda, Agnieszka; Cueff, Anne

    2010-01-01

    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...... channels proper has never been clarified, and the informations obtained by different groups of electrophysiologists are rather badly matched. This study, using the cell-attached configuration of the patch-clamp technique, rationalizes and explains earlier confusing results by demonstrating...... 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...

  8. Resonant spectra of quadrupolar anions

    CERN Document Server

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

    2016-01-01

    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...

  9. Improving the Enzyme Catalytic Efficiency Using Ionic Liquids with Kosmotropic Anions

    Institute of Scientific and Technical Information of China (English)

    ZHAO, Hua; CAMPBELL, Sophia; SOLOMON, Jonathan; SONG, Zhi-Yan; OLUBAJO, Olarongbe

    2006-01-01

    The kosmotropicity of cations and anions in ionic liquids has a strong influence on the enzyme catalytic efficiency in aqueous environments. The kosmotropic anion CF3COO- seemed to activate the protease, and the chaotropic anions tended to destabilize the enzyme.

  10. Synthesis and Characterization of Two Novel Organic-Inorganic Compounds Based on Tetrahexyl and Tetraheptyl Ammonium Ions and the Preyssler Anion and Their Catalytic Activities in the Synthesis of 4-Aminopyrazolo[3,4-d]- Pyrimidines

    Directory of Open Access Journals (Sweden)

    Fatemeh Farrash Bamoharram

    2010-04-01

    Full Text Available Two novel organic–inorganic compounds based on tetrahexylammonium (THA and tetraheptylammonium (THPA ions and the Preyssler anion, [NaP5W30O110]14-, were synthesized and formulated as (THA7.7H6.3 [NaP5W30O110] (A and (THPA7.5 H6.5[N aP5W30O110] (B. The synthesized compounds were characterized by IR, UV, and TGA and used for the catalytic synthesis of 4-aminopyrazolo[3,4,-d]pyrimidine derivatives 2a-2d. Our findings showed efficient catalytic activities for A and B.

  11. Anionic surface binders

    Directory of Open Access Journals (Sweden)

    Aljaž-Rožič Mateja

    2004-01-01

    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.

  12. Superoxide generated by pyrogallol reduces highly water-soluble tetrazolium salt to produce a soluble formazan: a simple assay for measuring superoxide anion radical scavenging activities of biological and abiological samples.

    Science.gov (United States)

    Xu, Chen; Liu, Shu; Liu, Zhiqiang; Song, Fengrui; Liu, Shuying

    2013-09-02

    Superoxide anion radical (O2(˙-)) plays an important role in several human diseases. The xanthine/xanthine oxidase system is frequently utilized to produce O2(˙-). However, false positive results are easily got by using this system. The common spectrophotometric probes for O2(˙-) are nitroblue tetrazolium (NBT) and cytochrome c. Nevertheless, the application of NBT method is limited because of the water-insolubility of NBT formazan and the assay using cytochrome c lacks sensitivity and is not suitable for microplate measurement. We overcome these problems by using 1,2,3-trihydroxybenzene (pyrogallol) as O2(˙-)-generating system and a highly water-soluble tetrazolium salt, 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium sodium salt (WST-1) which can be reduced by superoxide anion radical to a stable water-soluble formazan with a high absorbance at 450 nm. The method is simple, rapid and sensitive. Moreover, it can be adapted to microplate format. In this study, the O2(˙-) scavenging activities of superoxide dismutase (SOD), L-ascorbic acid, N-acetyl-L-cysteine (NAC), albumin from human serum, flavonoids and herbal extracts were assessed by using this method. Meanwhile, the activities of tissue homogenates and serum were determined by using this validated method. This method, applicable to tissue homogenates, serum and herbal extracts, proved to be efficient for measuring O2(˙-) scavenging activities of biological and abiological samples.

  13. Resonant spectra of quadrupolar anions

    Science.gov (United States)

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

    2016-09-01

    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.

  14. The role of lipophilicity in transmembrane anion transport

    NARCIS (Netherlands)

    Saggiomo, Vittorio; Otto, Sijbren; Marques, Igor; Felix, Vitor; Torroba, Tomas; Quesada, Roberto

    2012-01-01

    The transmembrane anion transport activity of a series of synthetic molecules inspired by the structure of tambjamine alkaloids can be tuned by varying the lipophilicity of the receptor, with carriers within a certain log P range performing best.

  15. 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.

    Science.gov (United States)

    Datta, Shubhashis; Halder, Mintu

    2014-01-05

    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.

  16. Recycling of agricultural solid waste, coir pith: Removal of anions, heavy metals, organics and dyes from water by adsorption onto ZnCl{sub 2} activated coir pith carbon

    Energy Technology Data Exchange (ETDEWEB)

    Namasivayam, C. [Environmental Chemistry Division, Department of Environmental Sciences, Bharathiar University, Coimbatore 641 046 (India)]. E-mail: cnamasi@yahoo.com; Sangeetha, D. [Environmental Chemistry Division, Department of Environmental Sciences, Bharathiar University, Coimbatore 641 046 (India)

    2006-07-31

    The abundant lignocellulosic agricultural waste, coir pith is used to develop ZnCl{sub 2} activated carbon and applied to the removal of toxic anions, heavy metals, organic compounds and dyes from water. Sorption of inorganic anions such as nitrate, thiocyanate, selenite, chromium(VI), vanadium(V), sulfate, molybdate, phosphate and heavy metals such as nickel(II) and mercury(II) has been studied. Removal of organics such as resorcinol, 4-nitrophenol, catechol, bisphenol A, 2-aminophenol, quinol, O-cresol, phenol and 2-chlorophenol has also been investigated. Uptake of acidic dyes such as acid brilliant blue, acid violet, basic dyes such as methylene blue, rhodamine B, direct dyes such as direct red 12B, congo red and reactive dyes such as procion red, procion orange were also examined to assess the possible use of the adsorbent for the treatment of contaminated ground water. Favorable conditions for maximum removal of all adsorbates at the adsorbate concentration of 20 mg/L were used. Results show that ZnCl{sub 2} activated coir pith carbon is effective for the removal of toxic pollutants from water.

  17. Copper(I) nitro complex with an anionic [HB(3,5-Me2Pz)3]− ligand: a synthetic model for the copper nitrite reductase active site.

    Science.gov (United States)

    Hsu, Sodio C N; Chang, Yu-Lun; Chuang, Wan-Jung; Chen, Hsing-Yin; Lin, I-Jung; Chiang, Michael Y; Kao, Chai-Lin; Chen, Hsuan-Ying

    2012-09-03

    The new copper(I) nitro complex [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))] (2), containing the anionic hydrotris(3,5-dimethylpyrazolyl)borate ligand, was synthesized, and its structural features were probed using X-ray crystallography. Complex 2 was found to cocrystallize with a water molecule, and X-ray crystallographic analysis showed that the resulting molecule had the structure [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))]·H(2)O (3), containing a water hydrogen bonded to an oxygen of the nitrite moiety. This complex represents the first example in the solid state of an analogue of the nitrous acid intermediate (CuNO(2)H). A comparison of the nitrite reduction reactivity of the electron-rich ligand containing the CuNO(2) complex 2 with that of the known neutral ligand containing the CuNO(2) complex [Cu(HC(3,5-Me(2)Pz)(3))(NO(2))] (1) shows that reactivity is significantly influenced by the electron density around the copper and nitrite centers. The detailed mechanisms of nitrite reduction reactions of 1 and 2 with acetic acid were explored by using density functional theory calculations. Overall, the results of this effort show that synthetic models, based on neutral HC(3,5-Me(2)Pz)(3) and anionic [HB(3,5-Me(2)Pz)(3)](-) ligands, mimic the electronic influence of (His)(3) ligands in the environment of the type II copper center of copper nitrite reductases (Cu-NIRs).

  18. Pentaarylfullerenes as noncoordinating cyclopentadienyl anions

    NARCIS (Netherlands)

    Bouwkamp, Marco W.; Meetsma, Auke

    2009-01-01

    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.

  19. Bound anionic states of adenine

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-03-20

    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

  20. Anion exchange polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-23

    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.

  1. 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)

    2004-01-01

    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.

  2. Adsorption of inorganic anionic contaminants on surfactant modified minerals

    Directory of Open Access Journals (Sweden)

    MAGDALENA TOMASEVIC-CANOVIC

    2003-11-01

    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.

  3. Naked-eye detection of biologically important anions by a new chromogenic azo-azomethine sensor.

    Science.gov (United States)

    Rezaeian, Khatereh; Khanmohammadi, Hamid

    2014-12-10

    A new chromogenic azo-azomethine sensor, containing active phenolic sites, has been designed and synthesized via condensation reaction of N,N,N',N'-tetrakis(2-aminoethyl)-2,2-dimethyl propane-1,3-diamine with 1-(3-formyl-4-hydroxyphenylazo)-4-nitrobenzene. The anion recognition ability of the synthesized receptor was evaluated using UV-Vis spectroscopy and (1)H NMR technique. The anion recognition studies exhibited that the receptor acts as a sensor for biologically important anions such as F(-), AcO(-) and H2PO4(-) over other anions. The binding stoichiometry between sensor and anions was found to be 1:2. (1)H NMR experiment revealed that sensor recognizes anions via H-bonds and subsequent deprotonation to elicit a vivid color change. Interestingly, the sensory system not only let for the naked eye detection without any spectroscopic instrumentation but also helped to discriminate between anions.

  4. Repair effect of thymine radical anion by echinocoside using pulse radiolysis

    Institute of Scientific and Technical Information of China (English)

    李雯艳; 郑荣梁; 赵松岭; 姜岳; 林念芸

    1996-01-01

    Repair activities of thymine radical anion by echinocoside, isolated from Pedicularis plicata. were studied using pulse radiolysis technique. The thymine radical anion was produced by the reaction of hydrated electron with thymine. Echinocoside. one of the polyphenols of phenylpropanoid glycoside, was added to the thymine aqueous solution saturated with N2. Kinetic analysis by transient absorption spectrum showed that thymine radical anion was formed at first, and then after several decades of microseconds of pulse radiolysis. the spectrum of thymine radical anion was changed to that of echinocoside radical anion. The evidence indicated that thymine radical anion was repaired through one-electron-transfer between the DNA base radical anion and echinocoside. The rate constant of electron transfer by echinocoside was 1.45× 109 dm3 · mol1 · s 1.

  5. Neutral and anionic superhalogen hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Swierszcz, Iwona [Department of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Anusiewicz, Iwona, E-mail: iwonaa@chem.univ.gda.pl [Department of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)

    2011-05-26

    Graphical abstract: The energy profile for the Na(OH){sub 2}{sup -} anionic hydroxide formation according to the NaOH+OH{sup -}{yields}Na(OH){sub 2}{sup -} reaction. Display Omitted Highlights: {yields} The superhalogen hydroxides and their anions were studied at the CCSD(T)/6-311++G(3df,3pd) level. {yields} All anionic superhalogen hydroxides were found to be thermodynamically stable. {yields} The VDE values calculated for the M(OH){sub k+1}{sup -} anions exceed 4 eV in all cases. {yields} The largest VDEs were found for the Al(OH){sub 4}{sup -} (6.07 eV) and Ga(OH){sub 4}{sup -} (6.21 eV). - Abstract: The properties of superhalogen M(OH){sub k+1}{sup -} anions and their M(OH){sub k+1} neutral parents (where M = Li, Na, K, Be, Mg, Ca, B, Al, Ga) were investigated at the ab initio CCSD(T)/6-311++G(3df,3pd)//MP2/6-311++G(d,p) level of theory. All the M(OH){sub k+1}{sup -} anions and some of their M(OH){sub k+1} neutral parents (k is the maximal formal valence of M) were found to be thermodynamically stable against the fragmentations (OH, OH{sup -}, O{sub 2} or H{sub 2}O loss). The vertical electron detachment energies (VDE) of the M(OH){sub k+1}{sup -} anions were calculated with the OVGF method and using the 6-311++G(3df,3pd) basis sets. The VDE values calculated for the anions studied exceed 4 eV in all cases, whereas the largest values of the electron binding energies were found for the Al(OH){sub 4}{sup -} (6.07 eV) and Ga(OH){sub 4}{sup -} anions (6.21 eV). Finally, formation of most of the species considered was predicted to be spontaneous due to the lack of kinetic barriers for these processes and their thermodynamic favorability.

  6. Anions in Nucleic Acid Crystallography.

    Science.gov (United States)

    D'Ascenzo, Luigi; Auffinger, Pascal

    2016-01-01

    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.

  7. 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)

    2015-10-08

    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.

  8. Extraction of monoclonal antibodies (IgG1) using anionic and anionic/nonionic reverse micelles.

    Science.gov (United States)

    George, Daliya A; Stuckey, David C

    2010-01-01

    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.

  9. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

    Science.gov (United States)

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian

    2016-01-01

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

  10. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Michael Rajamathi; Grace S Thomas; P Vishnu Kamath

    2001-10-01

    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.

  11. Pd and Pt-Ru anode electrocatalysts supported on multi-walled carbon nanotubes and their use in passive and active direct alcohol fuel cells with an anion-exchange membrane (alcohol = methanol, ethanol, glycerol)

    Science.gov (United States)

    Bambagioni, Valentina; Bianchini, Claudio; Marchionni, Andrea; Filippi, Jonathan; Vizza, Francesco; Teddy, Jacques; Serp, Philippe; Zhiani, Mohammad

    Palladium and platinum-ruthenium nanoparticles supported on multi-walled carbon nanotubes (MWCNT) are prepared by the impregnation-reduction procedure. The materials obtained, Pd/ MWCNT and Pt-Ru/ MWCNT, are characterized by TEM, ICP-AES and XRPD. Electrodes coated with Pd/ MWCNT are scrutinized for the oxidation of methanol, ethanol or glycerol in 2 M KOH solution in half cells. The catalyst is very active for the oxidation of all alcohols, with glycerol providing the best performance in terms of specific current density and ethanol showing the lowest onset potential. Membrane-electrode assemblies have been fabricated using Pd/ MWCNT anodes, commercial cathodes and anion-exchange membrane and evaluated in both single passive and active direct alcohol fuel cells fed with aqueous solutions of 10 wt.% methanol, 10 wt.% ethanol or 5 wt.% glycerol. Pd/ MWCNT exhibits unrivalled activity as anode electrocatalyst for alcohol oxidation. The analysis of the anode exhausts shows that ethanol is selectively oxidized to acetic acid, detected as acetate ion in the alkaline media of the reaction, while methanol yields carbonate and formate. A much wider product distribution, including glycolate, glycerate, tartronate, oxalate, formate and carbonate, is obtained from the oxidation of glycerol. The results obtained with Pt-Ru/ MWCNT anodes in acid media are largely inferior to those provided by Pd/ MWCNT electrodes in alkaline media.

  12. 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: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    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.

  13. Anion binding in biological systems

    Science.gov (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.

    2009-11-01

    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.

  14. Inhibition of formyl peptide-stimulated superoxide anion generation by Fal-002-2 occurs mainly through the blockade of the p21-activated kinase and protein kinase C signaling pathways in ratneutrophils.

    Science.gov (United States)

    Tsai, Ya-Ru; Huang, Li-Jiau; Lin, Hui-Yi; Hung, Yun-Jie; Lee, Miau-Rong; Kuo, Sheng-Chu; Hsu, Mei-Feng; Wang, Jih-Pyang

    2013-02-15

    In formyl-Met-Leu-Phe (fMLP)-stimulated rat neutrophils, a synthetic compound, 6-chloro-2-(2-chlorophenyl)-4-oxo-1,4-dihydroquinoline-3-carboxylate (Fal-002-2), inhibited superoxide anion (O2(•-)) generation with an IC50 value of about 11μM, which was not mediated by scavenging the generated O2(•-) or by a cytotoxic effect on neutrophils. Fal-002-2 effectively attenuated the phosphorylation of Ser residues in p47(phox) and the association between p47(phox) and p22(phox) in fMLP-stimulated neutrophils. The interaction of p47(phox) with protein kinase C (PKC) isoforms (α, βI, βII, δ and ζ) was attenuated by Fal-002-2 with a similar IC50 value to that required for inhibition of O2(•-) generation, whereas Fal-002-2 had no prominent effect on PKC isoform membrane translocation and did not affect the kinase activity. Moreover, Fal-002-2 had no effect on the phosphorylation of Akt and downstream glycogen synthase kinase-3β, only slightly affected the intracellular free Ca(2+) concentration, phosphorylation of extracellular signal-regulated kinase and p38 mitogen-activated protein kinase (MAPK), but effectively attenuated the downstream MAPK-activated protein kinase-2 phosphorylation. The interaction of p21-activated kinase (PAK) 1with p47(phox), phosphorylation of PAK1 (Thr423/Ser144) and the membrane recruitment of PAK1 were effectively inhibited by Fal-002-2. Fal-002-2 also blocked the activation of Rac1 and Cdc42 in a concentration range that effectively inhibited PAK activation. Taken together, these results suggest that Fal-002-2 inhibits fMLP-stimulated O2(•-) generation in neutrophils mainly through the blockade of PKC and PAK signaling pathways and partly through p38 MAPK signaling.

  15. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

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

    2006-01-01

    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. 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

    2005-01-01

    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.

  17. Binding Hydrated Anions with Hydrophobic Pockets.

    Science.gov (United States)

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

    2016-01-13

    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.

  18. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad

    2016-08-18

    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.

  19. Laser Cooling of Molecular Anions

    CERN Document Server

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

    2015-01-01

    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.

  20. Polymerization of anionic wormlike micelles.

    Science.gov (United States)

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

    2006-01-31

    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.

  1. Laser cooling of molecular anions.

    Science.gov (United States)

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

    2015-05-29

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarize 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 photodetachment 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.

  2. The interaction of certain inorganic anions with clays and soils

    NARCIS (Netherlands)

    Haan, de F.A.M.

    1965-01-01

    Interaction between anions and soil colloids was governed by 2 antagonistic processes, anion exclusion and positive anion adsorption. The predominantly negative charge on the colloids caused anion repulsion; positively charged sites and chemisorption resulted in positive

  3. Ionol (BHT) produces superoxide anion.

    Science.gov (United States)

    Smirnova, E G; Lyubimov, Yu I; Malinina, T G; Lyubimova, E Yu; Alexandrushkina, N I; Vanyushin, B F; Kolesova, G M; Yaguzhinsky, L S

    2002-11-01

    In aqueous medium etiolated wheat seedlings release superoxide anion (O2*-). Interaction of a synthetic antioxidant, butylated hydroxytoluene (BHT, ionol), with oxygen in the aqueous medium is accompanied by O2*- formation. This suggests that under certain conditions BHT behaves as a prooxidant. A natural antioxidant, superoxide dismutase (SOD), and also a wound healing preparation, emulsified denatured placenta (EDP), do not exhibit the prooxidant properties. In contrast to BHT, they reduce O2*- production by the etiolated wheat seedling system.

  4. Hosting anions. The energetic perspective.

    Science.gov (United States)

    Schmidtchen, Franz P

    2010-10-01

    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).

  5. Unraveling the toxicity mechanisms of the herbicide diclofop-methyl in rice: modulation of the activity of key enzymes involved in citrate metabolism and induction of cell membrane anion channels.

    Science.gov (United States)

    Ding, Haiyan; Lu, Haiping; Lavoie, Michel; Xie, Jun; Li, Yali; Lv, Xiaolu; Fu, Zhengwei; Qian, Haifeng

    2014-11-01

    Residual soil concentrations of the herbicide diclofop-methyl (DM) can be toxic to other nontarget plant species, but the toxicity mechanisms at play are not fully understood. In the present study, we analyzed the toxic effect of DM on root growth and metabolism in the rice species Oryza sativa. The results show that a 48-h exposure to a trace level (5 μg/L) of DM inhibits rice root growth by almost 70%. A 48-h exposure to 5 μg/L DM also leads to an ≈2.5-fold increase in citrate synthase (CS) activity (and CS gene transcription) and an ≈2-fold decrease in the citrate lyase gene transcripts, which lead to an increase in the intracellular concentration of citrate and in citrate exudation rate. Addition of a specific inhibitor of cell membrane anion channel, anthracene-9-carboxylic acid, decreased citrate release in the culture, suggesting that DM-induced citrate loss from the cells is mediated by a specific membrane-bound channel protein. This study brings new insights into the key biochemical mechanisms leading to DM toxicity in rice.

  6. A comparative examination of the adsorption mechanism of an anionic textile dye (RBY 3GL) onto the powdered activated carbon (PAC) using various the isotherm models and kinetics equations with linear and non-linear methods

    Science.gov (United States)

    Açıkyıldız, Metin; Gürses, Ahmet; Güneş, Kübra; Yalvaç, Duygu

    2015-11-01

    The present study was designed to compare the linear and non-linear methods used to check the compliance of the experimental data corresponding to the isotherm models (Langmuir, Freundlich, and Redlich-Peterson) and kinetics equations (pseudo-first order and pseudo-second order). In this context, adsorption experiments were carried out to remove an anionic dye, Remazol Brillant Yellow 3GL (RBY), from its aqueous solutions using a commercial activated carbon as a sorbent. The effects of contact time, initial RBY concentration, and temperature onto adsorbed amount were investigated. The amount of dye adsorbed increased with increased adsorption time and the adsorption equilibrium was attained after 240 min. The amount of dye adsorbed enhanced with increased temperature, suggesting that the adsorption process is endothermic. The experimental data was analyzed using the Langmuir, Freundlich, and Redlich-Peterson isotherm equations in order to predict adsorption isotherm. It was determined that the isotherm data were fitted to the Langmuir and Redlich-Peterson isotherms. The adsorption process was also found to follow a pseudo second-order kinetic model. According to the kinetic and isotherm data, it was found that the determination coefficients obtained from linear method were higher than those obtained from non-linear method.

  7. Effect of Several Anions on Fe-Based Catalyst for Fischer-Tropsch Synthesis

    Institute of Scientific and Technical Information of China (English)

    Jingchang Zhang; Xuehua Guo; Weiliang Cao

    2007-01-01

    The influence of several anions on Fe-based Fischer-Tropsch catalyst, used in the synthesis of light olefins from synthesis gas, was studied. The results indicated that the addition of anions resulted in the reduction of catalytic activity. When the anion content in the catalyst was 500 ppm, the influence of different anions on the catalysis activity was as follows: S2->Cl->SO42->NO3-. The addition of S2- improved the selectivity of total hydrocarbons in the products, and Cl- reduced this selectivity but increased the olefin content in the total hydrocarbons at the same time. When the contents of S2- and Cl- in the catalyst were less than 50 ppm, their influence could be ignored. The XRD results indicated that the addition of anions reduced the contents of a-Fe and Fe3C, which were the active components in the catalyst.

  8. Corticosteroids increase superoxide anion production by rat liver microsomes.

    Science.gov (United States)

    Nelson, D H; Ruhmann-Wennhold, A

    1975-01-01

    Superoxide anion production by liver microsomes from intact, adrenalectomized, and cortisoltreated adrenalectomized rats has been determined. The amount formed was roughly proportionate to the amount of cortisol given, and a similar response was seen in the activity of NADPH-cytochrome c reductase. The amount of measurable superoxide anion was markedly reduced by the addition of superoxide dismutase. The increased production of this potent free radical with cortisol therapy suggests that its formation may contribute to some of the harmful effects of corticosteroids given in more than physiologic amounts. PMID:239969

  9. Phthalocyanine as a chemically inert, redox-active ligand: structural and electronic properties of a Nb(IV)-oxo complex incorporating a highly reduced phthalocyanine(4-) anion.

    Science.gov (United States)

    Wong, Edwin W Y; Walsby, Charles J; Storr, Tim; Leznoff, Daniel B

    2010-04-05

    This report describes the reduction of a niobium(V) phthalocyanine complex and investigation of the electronic structure of the resulting products. The reduction of PcNbCl(3) (Pc = phthalocyanine dianion) with 5.5 equiv of potassium graphite in 1,2-dimethoxyethane (DME) resulted in the isolation of K(2)PcNbO.5DME (1a). Addition of 18-crown-6 to 1a gave [K(18-crown-6)](2)(mu-DME)PcNbO (1b). Both 1a and 1b were structurally characterized by single-crystal X-ray diffraction analysis. In both complexes, the niobium center adopts a square pyramidal geometry and is coordinated by four basal Pc nitrogen atoms and an apical oxo ligand. Notably, the Pc ligand in 1a is saddle-shaped, with significant bond length alternation, rather than flat with delocalized bonding. The production of ethylene during the reduction of PcNbCl(3), detected by gas chromatography/mass spectrometry (GC/MS), suggests that the oxo ligand likely results from double C-O bond activation of DME solvent. A combination of spectroscopic techniques and density functional theory (DFT) calculations were used to establish the electronic structure of 1a. The close correspondence of the electronic absorption spectrum of 1a to that of [PcZn](2-) with a di-reduced Pc(4-) ligand, indicates a similar electronic structure for the two complexes. Evaluation of the electronic transitions for 1a and [PcZn](2-) by time-dependent DFT calculations further suggests a similar electronic structure for both complexes, indicating that differences in symmetry between 1a and [PcZn](2-) do not significantly affect the nature of the electronic transitions. Electron paramagnetic resonance (EPR) spectroscopy of 1a in solution at room temperature gave a 10-line spectrum, while frozen-solution X- and Q-band EPR spectra are consistent with powder-pattern spectra defined by uniaxial g and (93)Nb hyperfine tensors: these imply the presence of a d(1) Nb(IV) metal center. EPR and electron nuclear double resonance spectroscopy suggests that

  10. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan

    2003-01-01

    . 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.

  11. 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).

    Science.gov (United States)

    Vafaei, Fatemeh; Movafeghi, Ali; Khataee, Alireza

    2013-11-01

    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.

  12. Surfactant behavior of "ellipsoidal" dicarbollide anions: a molecular dynamics study.

    Science.gov (United States)

    Chevrot, G; Schurhammer, R; Wipff, G

    2006-05-18

    We report a molecular dynamics study of cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)X(3))(2)Co](-) (XCD(-)) commonly used in liquid-liquid extraction (X = H, Me, Cl, or Br), showing that these anions, although lacking the amphiphilic topology, behave as anionic surfactants. In pure water, they display "hydrophobic attractions", leading to the formation of aggregates of different sizes and shapes depending on the counterions. When simulated at a water/"oil" interface, the different anions (HCD(-), MeCD(-), CCD(-), and BrCD(-)) are found to be surface active. As a result, the simulated M(n+) counterions (M(n+) = Na(+), K(+), Cs(+), H(3)O(+), UO(2)(2+), Eu(3+)) concentrate on the aqueous side of the interface, forming a "double layer" whose characteristics are modulated by the hydrophobic character of the anion and by M(n+). The highly hydrophilic Eu(3+) or UO(2)(2+) cations that are generally "repelled" by aqueous interfaces are attracted by dicarbollides near the interface, which is crucial as far as the mechanism of assisted cation extraction to the oil phase is concerned. These cations interact with interfacial XCD(-) in their fully hydrated Eu(H(2)O)(9)(3+) and UO(2)(H(2)O)(5)(2+) forms, whereas the less hydrophilic monocharged cations display intimate contacts via their X substituents. The results obtained with the TIP3P and OPLS models for the solvents are confirmed with other water models (TIP5P or a polarizable 4P-Pol water) and with more polar "oil" models. The importance of interfacial phenomena is further demonstrated by simulations with a high oil-water ratio, leading to the formation of a micelle covered with CCD's. We suggest that the interfacial activity of dicarbollides and related hydrophobic anions is an important feature of synergism in liquid-liquid extraction of hard cations (e.g., for nuclear waste partitioning).

  13. Vibrational Autodetachment in Nitroalkane Anions

    Science.gov (United States)

    Adams, Christopher L.; Weber, J. Mathias

    2010-06-01

    Nitroalkanes have electron affinities ge 1370 cm-1, well below the excitation energies for CH stretching modes, with the excess charge localized on the nitro group. Upon absorption of an IR photon in a CH stretching vibrational mode, the absorbed energy is redistributed in the molecule. If enough energy is transferred to the NO2 stretching/wagging modes, the excess electron residing on the nitro group is emitted. Vibrational autodetachment (VAD) spectra encode information regarding intramolecular vibrational relaxation (IVR) processes leading up to electron emission. We present VAD photoelectron spectroscopy of polyatomic molecular anions and discuss how a VAD photoelectron spectrum can be modeled.

  14. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    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.

  15. Anion channelrhodopsins for inhibitory cardiac optogenetics

    Science.gov (United States)

    Govorunova, Elena G.; Cunha, Shane R.; Sineshchekov, Oleg A.; Spudich, John L.

    2016-01-01

    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

  16. Superoxide anion-induced pain and inflammation depends on TNFα/TNFR1 signaling in mice.

    Science.gov (United States)

    Yamacita-Borin, Fabiane Y; Zarpelon, Ana C; Pinho-Ribeiro, Felipe A; Fattori, Victor; Alves-Filho, Jose C; Cunha, Fernando Q; Cunha, Thiago M; Casagrande, Rubia; Verri, Waldiceu A

    2015-09-25

    Inhibition of tumor necrosis factor-alpha (TNFα) and superoxide anion production reduces inflammation and pain. The present study investigated whether superoxide anion-induced pain depends on TNFα signaling and the role of superoxide anion in TNFα-induced hyperalgesia to clarify the interrelation between these two mediators in the context of pain. Intraplantar injection of a superoxide anion donor (potassium superoxide) induced mechanical hyperalgesia (0.5-5h after injection), neutrophil recruitment (myeloperoxidase activity), and overt pain-like behaviors (paw flinching, paw licking, and abdominal writhings) in wild-type mice. Tumor necrosis factor receptor 1 deficiency (TNFR1-/-) and treatment of wild-type mice with etanercept (a soluble TNFR2 receptor that inhibits TNFα actions) inhibited superoxide anion-induced pain-like behaviors. TNFR1(-/-) mice were also protected from superoxide anion donor-induced oxidative stress, suggesting the role of this pathway in the maintenance of oxidative stress. Finally, we demonstrated that Apocynin (an NADPH oxidase inhibitor) or Tempol (a superoxide dismutase mimetic) treatment inhibited TNFα-induced paw mechanical hyperalgesia and neutrophil recruitment (myeloperoxidase activity). These results demonstrate that TNFα/TNFR1 signaling is important in superoxide anion-triggered pain and that TNFα/TNFR1 signaling amplifies the oxidative stress triggered by superoxide anion, which contributes to sustaining pain and inflammation.

  17. Effect of divalent anions on photodegradation kinetics and pathways of riboflavin in aqueous solution.

    Science.gov (United States)

    Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Vaid, Faiyaz H M; Ansari, Izhar A

    2010-05-10

    The present investigation is based on a study of the effect of buffer and non-buffer divalent anions (phosphate, sulphate, tartrate, succinate, malonate) on the kinetics, product distribution and photodegradation pathways of riboflavin (RF) at pH 6.0-8.0. RF solutions (5x10(-5)M) were photodegraded in the presence of divalent anions (0.2-1.0M) using a visible light source and the photoproducts, cyclodehydroriboflavin (CDRF), formylmethylflavin (FMF), lumichrome (LC) and lumiflavin (LF) were assayed by a specific multicomponent spectrophotometric method. RF degradation in the presence of divalent anions follows parallel first-order kinetics to give CDRF and LC as the final products through photoaddition and photoreduction reactions, respectively. The divalent anion-catalysed CDRF formation is affected in the order: phosphate>sulphate>tartrate>succinate>malonate, showing maximum activity of the anions around pH 7. The divalent anions cause deviation of the photoreduction pathway in favour of the photoaddition pathway to form CDRF. The first- and second-order rate constants for the reactions involved in the photodegradation of RF have been determined and the rate-pH profiles and pathway relationships discussed. The catalytic activity of the divalent anions appears to be a function of the relative strength and chemical reactivity of the RF-divalent anion complex acting as a mediator in the photoaddition reaction.

  18. Tunable electronic interactions between anions and perylenediimide.

    Science.gov (United States)

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

    2013-08-07

    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.

  19. Adsorption affinity of anions on metal oxyhydroxides

    Science.gov (United States)

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

    2013-03-01

    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-}.

  20. The anionic biosurfactant rhamnolipid does not denature industrial enzymes

    Directory of Open Access Journals (Sweden)

    Jens Kvist Madsen

    2015-04-01

    Full Text Available Biosurfactants (BS are surface-active molecules produced by microorganisms. Their combination of useful properties and sustainable production make them promising industrial alternatives to petrochemical and oleochemical surfactants. Here we compare the impact of the anionic BS rhamnolipid (RL and the conventional/synthetic anionic surfactant sodium dodecyl sulfate (SDS on the structure and stability of three different commercially used enzymes, namely the cellulase Carezyme® (CZ, the phospholipase Lecitase Ultra® (LT and the α-amylase Stainzyme® (SZ. Our data reveal a fundamental difference in their mode of interaction. SDS shows great diversity of interaction towards the different enzymes. It efficiently unfolds both LT and CZ, but LT is unfolded by SDS through formation of SDS clusters on the protein well below the cmc, while CZ is only unfolded by bulk micelles and on average binds significantly less SDS than LT. SDS binds with even lower stoichiometry to SZ and leads to an increase in thermal stability. In contrast, RL does not affect the tertiary or secondary structure of any enzyme at room temperature, has little impact on thermal stability and only binds detectably (but at low stoichiometries to SZ. Furthermore all enzymes maintain activity at both monomeric and micellar concentrations of RL. We conclude that RL, despite its anionic charge, is a surfactant that does not compromise the structural integrity of industrially relevant proteins. This makes RL a promising alternative to current synthetic anionic surfactants in a wide range of commercial applications.

  1. pH triggered superior selective adsorption and separation of both cationic and anionic dyes and photocatalytic activity on a fully exfoliated titanate layer-natural polymer based nanocomposite.

    Science.gov (United States)

    Sarkar, Amit Kumar; Saha, Arka; Panda, Asit Baran; Pal, Sagar

    2015-11-18

    A fully exfoliated titanate layer-natural polymer amylopectin based nanocomposite, with pH responsive superior selective adsorption, separation of both cationic (MB: 599 mg g(-1) at pH 9) and anionic (MO: 558 mg g(-1) at pH 3) dyes and photodegradation properties, has been realized through simultaneous in situ layered titanate formation, exfoliation and polymerization.

  2. Switching between Anion-Binding Catalysis and Aminocatalysis with a Rotaxane Dual-Function Catalyst.

    Science.gov (United States)

    Eichstaedt, Katarzyna; Jaramillo-Garcia, Javier; Leigh, David A; Marcos, Vanesa; Pisano, Simone; Singleton, Thomas A

    2017-07-12

    The "off" state for aminocatalysis by a switchable [2]rotaxane is shown to correspond to an "on" state for anion-binding catalysis. Conversely, the aminocatalysis "on" state of the dual-function rotaxane is inactive in anion-binding catalysis. Switching between the different states is achieved through the stimuli-induced change of position of the macrocycle on the rotaxane thread. The anion-binding catalysis results from a pair of triazolium groups that act together to CH-hydrogen-bond to halide anions when the macrocycle is located on an alternative (ammonium) binding site, stabilizing the in situ generation of benzhydryl cation and oxonium ion intermediates from activated alkyl halides. The aminocatalysis and anion-binding catalysis sites of the dual-function rotaxane catalyst can be sequentially concealed or revealed, enabling catalysis of both steps of a tandem reaction process.

  3. Ursodeoxycholic acid and superoxide anion

    Institute of Scientific and Technical Information of China (English)

    Predrag Ljubuncic; Omar Abu-Salach; Arieh Bomzon

    2005-01-01

    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. Comparative DNA binding abilities and phosphatase-like activities of mono-, di-, and trinuclear Ni(II) complexes: the influence of ligand denticity, metal-metal distance, and coordinating solvent/anion on kinetics studies.

    Science.gov (United States)

    Bhardwaj, Vimal K; Singh, Ajnesh

    2014-10-06

    Six novel Ni(II) complexes, namely, [Ni2(HL(1))(OAc)2] (1), [Ni3L(1)2]·H2O·2CH3CN (2), [Ni2(L(2))(L(3))(CH3CN)] (3), [Ni2(L(2))2(H2O)2] (4), [Ni2(L(2))2(DMF)2]2·2H2O (5), and [Ni(HL(2))2]·H2O (6), were synthesized by reacting nitrophenol-based tripodal (H3L(1)) and dipodal (H2L(2)) Schiff base ligands with Ni(II) metal salts at ambient conditions. All the complexes were fully characterized with different spectroscopic techniques such as elemental analyses, IR, UV-vis spectroscopy, and electrospray ionization mass spectrometry. The solid-state structures of 2, 3, 5, and 6 were determined using single-crystal X-ray crystallography. The compounds 1, 3, 4, and 5 are dinuclear complexes where the two Ni(II) centers have octahedral geometry with bridging phenoxo groups. Compound 2 is a trinuclear complex with two different types of Ni(II) centers. In compound 3 one of the Ni(II) centers has a coordinated acetonitrile molecule, whereas in compound 4, a water molecule has occupied one coordination site of each Ni(II) center. In complex 5, the coordinated water of complex 4 was displaced by the dimethylformamide (DMF) during its crystallization. Complex 6 is mononuclear with two amine-bis(phenolate) ligands in scissorlike fashion around the Ni(II) metal center. The single crystals of 1 and 4 could not be obtained; however, from the spectroscopic data and physicochemical properties (electronic and redox properties) it was assumed that the structures of these complexes are quite similar to other analogues. DNA binding abilities and phosphatase-like activities of all characterized complexes were also investigated. The ligand denticity, coordinated anions/solvents (such as acetate, acetonitrile, water, and DMF), and cooperative action of two metal centers play a significant role in the phosphate ester bond cleavage of 2-hydroxypropyl-p-nitropenylphosphate by transesterification mechanism. Complex 3 exhibits highest activity among complexes 1-6 with 3.86 × 10(5) times

  5. Antimicrobial Ionic Liquids with Fumarate Anion

    Directory of Open Access Journals (Sweden)

    Biyan He

    2013-01-01

    Full Text Available The shortage of new antimicrobial drugs and increasing resistance of microbe to antimicrobial agents have been of some concern. The formulation studies of new antibacterial and antifungal agents have been an active research field. Ionic liquids are known as designed liquids with controllable physical/chemical/biological properties and specific functions, which have been attracting considerable interest over recent years. However, no attention has been made towards the preparation of ionic liquids with antimicrobial activities. In this paper, a new class of ionic liquids (ILs with fumarate anion was synthesized by neutralization of aqueous 1-butyl-3-methylimidazolium hydroxide with equimolar monoester fumarate and characterized using NMR and thermal gravimetric analysis. The ILs are soluble in water and polar organic solvents and also soluble in the common ILs. The antimicrobial activities of the ILs are more active than commercially available potassium sorbate and are greatly affected by the alkyl chain length. The significant antimicrobial properties observed in this research suggest that the ILs may have potential applications in the modern biotechnology.

  6. CO{sub 2} binding in the (quinoline-CO{sub 2}){sup −} anionic complex

    Energy Technology Data Exchange (ETDEWEB)

    Graham, Jacob D.; Buytendyk, Allyson M.; Wang, Yi; Bowen, Kit H., E-mail: kbowen@jhu.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Kim, Seong K. [Department of Chemistry, Seoul National University, Seoul 151-747 (Korea, Republic of)

    2015-06-21

    We have studied the (quinoline-CO{sub 2}){sup −} anionic complex by a combination of mass spectrometry, anion photoelectron spectroscopy, and density functional theory calculations. The (quinoline-CO{sub 2}){sup −} anionic complex has much in common with previously studied (N-heterocycle-CO{sub 2}){sup −} anionic complexes both in terms of geometric structure and covalent bonding character. Unlike the previously studied N-heterocycles, however, quinoline has a positive electron affinity, and this provided a pathway for determining the binding energy of CO{sub 2} in the (quinoline-CO{sub 2}){sup −} anionic complex. From the theoretical calculations, we found CO{sub 2} to be bound within the (quinoline-CO{sub 2}){sup −} anionic complex by 0.6 eV. We also showed that the excess electron is delocalized over the entire molecular framework. It is likely that the CO{sub 2} binding energies and excess electron delocalization profiles of the previously studied (N-heterocycle-CO{sub 2}){sup −} anionic complexes are quite similar to that of the (quinoline-CO{sub 2}){sup −} anionic complex. This class of complexes may have a role to play in CO{sub 2} activation and/or sequestration.

  7. Anionic fructose-related conformational and positional isomers assigned through PES experiments and DFT calculations.

    Science.gov (United States)

    Zeng, Zhen; Bernstein, Elliot R

    2017-08-30

    Gas phase, isolated fructose anionic species, fructose(-), (fructose-H)(-), (fructose-OH)(-), and (fructose-H2O)(-), are investigated employing anionic photoelectron spectroscopy (PES) combined with density functional theory (DFT) calculations. The PES vertical detachment energies (VDEs) for these anions are determined and, based on these experimental values, their calculated anionic structures are assigned. Generation of these four species through the matrix assisted laser desorption ionization (MALDI) process is sample desorption substrate dependent. The parent anion fructose(-) exists as a single, dominant open chain structure in the gas phase, with substrate dependent specific conformational isomers. (Fructose-H)(-) and (fructose-OH)(-) are mainly produced from the laser ablation process rather than from fragmentation reaction pathways associated with the parent anion species. Both conformational and positional isomers are identified in the gas phase for these latter anions. (Fructose-H2O)(-) has two types of positional isomers, both of which contribute to two different components of the observed PES feature. The fixed positions for losing an OH group and an H atom, in addition to thermodynamic calculations, provide reaction pathways for generating a dehydration product (open chain structures) from the parent anion (open chain and furanose structures), further demonstrating the active nature of fructose upon capturing an extra electron.

  8. Vibrational Spectroscopy of Microhydrated Conjugate Base Anions

    NARCIS (Netherlands)

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

    2012-01-01

    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

  9. Anion stripping as a general method to create cationic porous framework with mobile anions.

    Science.gov (United States)

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

    2014-05-28

    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.

  10. Evidence for the interaction between (t)BuOK and 1,10-phenanthroline to form the 1,10-phenanthroline radical anion: a key step for the activation of aryl bromides by electron transfer.

    Science.gov (United States)

    Yi, Hong; Jutand, Anny; Lei, Aiwen

    2015-01-11

    Electron paramagnetic resonance and electrochemistry are used to evidence the interaction between 1,10-phenanthroline (Phen) and KO(t)Bu to form the 1,10-phenanthroline radical anion, Phen˙(-), and the (t)BuO˙ radical via an inner-sphere electron transfer. In addition, electrochemistry is also used to explain the formation of aryl radicals from aryl bromides via outer-sphere electron transfer from the key intermediate Phen˙(-).

  11. Molecular anions sputtered from fluorides

    CERN Document Server

    Gnaser, H

    2002-01-01

    The emission of negatively charged ions from different fluoride samples (LiF, CaF sub 2 , LaF sub 3 and HfF sub 4) induced by sputtering with a 14.5-keV Cs sup + ion beam was studied. Sputtered ions were detected in a high-sensitivity double-focusing mass spectrometer. In particular, the possible existence of small doubly charged negative molecular ions was investigated. But whereas singly charged species of the general type MF sub n sup - (where M represents a metal atom) were detected with high abundances, stable dianions were observed in an unambiguous way only for one molecule: HfF sub 6 sup 2 sup -. The flight time through the mass spectrometer of approx 35 mu s establishes a lower limit with respect to the intrinsic lifetime of this doubly charged ion. For singly charged anions abundance distributions and, in selected cases, emission-energy spectra were recorded. For two ion species (Ca sup - and HfF sub 5 sup -) isotopic fractionation effects caused by the (velocity dependent) ionization process were d...

  12. Off-On-Off fluorescence behavior of an intramolecular charge transfer probe toward anions and CO2

    Science.gov (United States)

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

    2016-11-01

    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.

  13. Anion photoelectron imaging spectroscopy of glyoxal

    Science.gov (United States)

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

    2016-09-01

    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.

  14. Anionic peroxidase production by Arnebia euchroma callus.

    Science.gov (United States)

    Farhadi, Sahar; Haghbeen, Kamahldin; Marefatjo, Mohammad-Javad; Hoor, Marjan Ghiyami; Zahiri, Hossein Shahbani; Rahimi, Karim

    2011-01-01

    Arnebia euchroma callus, obtained from the root cell culture of an Iranian native specimen, has gained a doubling time of 63 H after regular subculturing on Linsmaier-Skoog (LS) medium containing sugar (50 g/L), 2,4-dichlorophenoxyacetic acid (10(-6) M), and kinetin (10(-5) M) under darkness at 25°C. Despite the observed somaclonal variations, peroxidase production by the A. euchroma calli has been stable over 4 years under the aforementioned conditions. Isoelectric focusing experiments revealed that the partially purified A. euchroma peroxidases (AePoxs) are mainly anionic with pI values of about 5.5 and 6.6. AePox reaches its optimal activity at 55°C and pH 7.5. Results of the various kinetic studies suggest that AePox belongs to the type III plant peroxidases with no activity for the oxidation of 3-indoleacetic acid, but seems to play a role in the lignin biosynthesis and H(2) O(2) regulation during the proliferation of the A. euchroma cells on LS medium. Comparing the biochemical properties of AePox with horseradish peroxidase and in view of the ease of solid cell culture, the A. euchroma callus could be considered as a source of plant peroxidase for some biotechnological applications. Copyright © 2011 International Union of Biochemistry and Molecular Biology, Inc.

  15. Endomorphins 1 and 2 modulate chemotaxis, phagocytosis and superoxide anion production by microglia.

    Science.gov (United States)

    Azuma, Y; Ohura, K; Wang, P L; Shinohara, M

    2001-09-03

    We evaluate the role of endomorphins 1 and 2 on microglial functions. Endomorphins 1 and 2 blocked phagocytosis of Escherichia coli. In addition, both markedly inhibited chemotaxis toward zymosan-activated serum. In contrast, when microglia was preincubated with these endomorphins, followed by incubation with LPS before stimulation with phorbol 12-myristate 13-acetate (PMA) at 200 nM, they potentiated superoxide anion production. Furthermore, when microglia was preincubated with these endomorphins together with PMA at 20 nM, followed by stimulation with PMA at 200 nM, superoxide anion production was potentiated. These results suggest that endomorphins 1 and 2 modulate phagocytosis, chemotaxis and superoxide anion production by microglia.

  16. Renal elimination of organic anions in cholestasis

    Institute of Scientific and Technical Information of China (English)

    Adriana Mónica Tortes

    2008-01-01

    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.

  17. 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...

  18. Anion release and uptake kinetics: structural changes of layered 2-dimensional ZnNiHN upon uptake of acetate and chlorinated acetate anions.

    Science.gov (United States)

    Machingauta, Cleopas; Hossenlopp, Jeanne M

    2013-12-01

    X-ray diffraction and UV-vis spectroscopy were used for the investigation of ion exchange reaction kinetics of nitrates with acetate (Ac), chloro acetate (ClAc), dichloro acetate (dClAc) and trichloro acetate (tClAc) anions, using zinc nickel hydroxy nitrate (ZnNiHN) as the exchange precursor. The exchange reactions conducted at 24, 30, 40 and 50°C revealed that rate constants were inversely related to the calculated anion electronic spatial extent (ESE), while a direct relationship between rate constants and the average oxygen charges was observed. Temporal solid phase structural transformations were shown to be affected by the nature of the guest anions. The amount of nitrates released into solution has been shown to decrease as the guest anions became more chlorinated. Use of isoconversional approach revealed that activation energies changed significantly with α during dClAc intercalation than for the other anions. The topotactic intercalation of the guest anions, except dClAc, followed the Avrami-Erofe'ev kinetic model for the entire reaction progress.

  19. A new class of organocatalysts: sulfenate anions.

    Science.gov (United States)

    Zhang, Mengnan; Jia, Tiezheng; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J

    2014-09-26

    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.

  20. Fluorescence-lifetime-based sensors for anions

    Science.gov (United States)

    Teichmann, Maria; Draxler, Sonja; Kieslinger, Dietmar; Lippitsch, Max E.

    1997-05-01

    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.

  1. Thermal Properties of Anionic Polyurethane Composition for Leather Finishing

    Directory of Open Access Journals (Sweden)

    Olga KOVTUNENKO

    2016-09-01

    Full Text Available Thermal properties of anionic polyurethane composition mixed with collagen product and hydrophilic sodium form of montmorillonite for use in the finishing of leather were studied by thermogravimetric method. The thermal indices of processes of thermal and thermo-oxidative destruction depending on the polyurethane composition were determined. The influence of anionic polyurethane composition on thermal behavior of chromium tanned gelatin films that imitate the leather were studied. APU composition with natural compounds increases their thermal stability both in air and in nitrogen atmosphere due to the formation of additional bonds between active groups of APU, protein and chrome tanning agent as the result of chemical reactions between organic and inorganic parts with the new structure formation.DOI: http://dx.doi.org/10.5755/j01.ms.22.3.10043

  2. Thermal Properties of Anionic Polyurethane Composition for Leather Finishing

    Directory of Open Access Journals (Sweden)

    Olga KOVTUNENKO

    2016-09-01

    Full Text Available Thermal properties of anionic polyurethane composition mixed with collagen product and hydrophilic sodium form of montmorillonite for use in the finishing of leather were studied by thermogravimetric method. The thermal indices of processes of thermal and thermo-oxidative destruction depending on the polyurethane composition were determined. The influence of anionic polyurethane composition on thermal behavior of chromium tanned gelatin films that imitate the leather were studied. APU composition with natural compounds increases their thermal stability both in air and in nitrogen atmosphere due to the formation of additional bonds between active groups of APU, protein and chrome tanning agent as the result of chemical reactions between organic and inorganic parts with the new structure formation.DOI: http://dx.doi.org/10.5755/j01.ms.22.3.10043

  3. Continuous beds for microchromatography: chromatofocusing and anion exchange chromatography.

    Science.gov (United States)

    Li, Y M; Liao, J L; Zhang, R; Henriksson, H; Hjertén, S

    1999-02-01

    A method was developed for the preparation of continuous beds derivatized with polyethyleneimine (PEI) for chromatofocusing and anion exchange chromatography in the capillary mode. First, a continuous bed activated by epoxy groups was synthesized inside a fused silica capillary and became at the same time covalently attached to the inner wall of the capillary. A PEI solution was then pumped through the continuous bed to allow the imine groups in PEI to react with the epoxy groups in the bed. Efficient immobilization of PEI was indicated by the high-resolution separation of standard proteins (hemoglobins C, S, F, and A) in both chromatofocusing and anion exchange chromatography on a capillary column prepared by this method. Copyright 1999 Academic Press.

  4. Gallium based low-interaction anions

    Science.gov (United States)

    King, Wayne A.; Kubas, Gregory J.

    2000-01-01

    The present invention provides: a composition of the formula M.sup.+x (Ga(Y).sub.4.sup.-).sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R).sub.x Q.sup.+ Ga(Y).sub.4.sup.- where Q is selected from the group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M.sup.+x.sub.y [X(Ga(Y.sub.3).sub.z ].sup.-y.sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.

  5. Quasielastic neutron scattering study of tetrahydroborate anion dynamical perturbations in sodium borohydride due to partial halide anion substitution

    Energy Technology Data Exchange (ETDEWEB)

    Verdal, Nina [NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102 (United States); Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742-2115 (United States); Udovic, Terrence J. [NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102 (United States); Rush, John J. [NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102 (United States); Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742-2115 (United States); Skripov, Alexander V. [Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990 (Russian Federation)

    2015-10-05

    Highlights: • NaBH{sub 4}–NaX (X = Cl, I) solutions were made by ball-milling/annealing pure compounds. • BH{sub 4}{sup −} reorientational motions were studied by quasielastic neutron scattering. • Mobility increased from X = Cl to NaBH{sub 4} to X = I, consistent with expanding lattices. • Near 400 K, BH{sub 4}{sup −} favored cubic tumbling for X = Cl and tetrahedral tumbling for X = I. • Activation energies were in the range of 11–12 kJ mol{sup −1} for both compounds. - Abstract: Equimolar NaBH{sub 4}–NaX (X = Cl and I) solid solutions were synthesized to study, via quasielastic neutron scattering, the effect of partial halide anion substitution on the reorientational dynamics of tetrahydroborate (BH{sub 4}{sup −}) anions in NaBH{sub 4}. The BH{sub 4}{sup −} reorientational mobility increased in the order of NaBH{sub 4}–NaCl, NaBH{sub 4}, and NaBH{sub 4}–NaI, which corresponded with expanding face-centered-cubic lattices accommodating the respective increasing sizes of the Cl{sup −}, BH{sub 4}{sup −}, and I{sup −} anions. The BH{sub 4}{sup −} anions in NaBH{sub 4}–NaCl were found (at least above 400 K) to undergo ‘cubic’ tumbling motions with the four H atoms per anion visiting all eight corners of a cube, similar to what was previously observed for NaBH{sub 4}. In contrast, the BH{sub 4}{sup −} anions in NaBH{sub 4}–NaI were found to undergo something more akin to ‘tetrahedral’ tumbling motions, where the H atoms visit all four corners of a tetrahedron. Despite a noticeable softening of the BH{sub 4}{sup −} torsional energies with increasing lattice constant amongst NaBH{sub 4} and the two solid solutions, all three compounds exhibited similar activation energies for reorientation of about 11–12 kJ mol{sup −1}.

  6. Assessing the reactivation efficacy of hydroxylamine anion towards VX-inhibited AChE: a computational study.

    Science.gov (United States)

    Khan, Md Abdul Shafeeuulla; Ganguly, Bishwajit

    2012-05-01

    Oximate anions are used as potential reactivating agents for OP-inhibited AChE because of they possess enhanced nucleophilic reactivity due to the α-effect. We have demonstrated the process of reactivating the VX-AChE adduct with formoximate and hydroxylamine anions by applying the DFT approach at the B3LYP/6-311 G(d,p) level of theory. The calculated results suggest that the hydroxylamine anion is more efficient than the formoximate anion at reactivating VX-inhibited AChE. The reaction of formoximate anion and the VX-AChE adduct is a three-step process, while the reaction of hydroxylamine anion with the VX-AChE adduct seems to be a two-step process. The rate-determining step in the process is the initial attack on the VX of the VX-AChE adduct by the nucleophile. The subsequent steps are exergonic in nature. The potential energy surface (PES) for the reaction of the VX-AChE adduct with hydroxylamine anion reveals that the reactivation process is facilitated by the lower free energy of activation (by a factor of 1.7 kcal mol(-1)) than that of the formoximate anion at the B3LYP/6-311 G(d,p) level of theory. The higher free energy of activation for the reverse reactivation reaction between hydroxylamine anion and the VX-serine adduct further suggests that the hydroxylamine anion is a very good antidote agent for the reactivation process. The activation barriers calculated in solvent using the polarizable continuum model (PCM) for the reactivation of the VX-AChE adduct with hydroxylamine anion were also found to be low. The calculated results suggest that V-series compounds can be more toxic than G-series compounds, which is in accord with earlier experimental observations.

  7. 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

    2016-01-01

    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−.

  8. A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides.

    Science.gov (United States)

    Theiss, Frederick L; Couperthwaite, Sara J; Ayoko, Godwin A; Frost, Ray L

    2014-03-01

    The application of layered double hydroxides (LDHs) and thermally activated LDHs for the removal of various fluorine (F(-),BF4(-)), chlorine (Cl(-),ClO4(-)), bromine (Br(-),BrO3(-)) and iodine (I(-),IO3(-)) species from aqueous solutions has been reviewed in this article. LDHs and thermally activated LDHs were able to significantly reduce the concentration of selected anions in laboratory scale experiments. The M(2+):M(3+) cation ratio of the LDH adsorbent was an important factor which influenced anion uptake. Though LDHs were able to remove some target anion species through anion exchange and surface adsorption thermal activation and reformation generally produced better results. The presence of competing anions including carbonate, phosphate and sulphate had a significant impact on uptake of the target anion as LDHs typically exhibit lower affinity towards monovalent anions compared to anions with multiple charges. The removal of fluoride and perchlorate from aqueous solution by a continuous flow system utilising fixed bed columns packed with LDH adsorbents has also been investigated. The adsorption capacity of the columns at breakpoint was heavily dependent on the flow rate and lower than result reported for the corresponding batch methods. There is still considerable scope for future research on numerous topics summarised in this article.

  9. IMPACT OF CRITICAL ANION SOIL SOLUTION CONCENTRATION ON ALUMINUM ACTIVITY IN ALPINE TUNDRA SOIL Andrew Evans, Jr.1 , Michael B. Jacobs2, and Jason R. Janke1, (1) Metropolitan State University of Denver, Dept. of Earth and Atmospheric Sciences, (2) Dept. of Chemistry, Denver, CO, United States.

    Science.gov (United States)

    Evans, A.

    2015-12-01

    Soil solution anionic composition can impact both plant and microbial activity in alpine tundra soils by altering biochemical cycling within the soil, either through base cation leaching, or shifts in aluminum controlling solid phases. Although anions play a critical role in the aqueous speciation of metals, relatively few high altitude field studies have examined their impact on aluminum controlling solid phases and aluminum speciation in soil water. For this study, thirty sampling sites were selected on Trail Ridge Road in Rocky Mountain National Park, Estes Park, CO, and sampled during July, the middle of the growing season. Sampling elevations ranged from approximately 3560 - 3710 m. Soil samples were collected to a depth of 15.24 cm, and the anions were extracted using a 2:1 D.I. water to soil ratio. Filtered extracts were analyzed using IC and ICP-MS. Soil solution NO3- concentrations were significantly higher for sampling locations east of Iceberg Pass (EIBP) (mean = 86.94 ± 119.8 mg/L) compared to locations west of Iceberg Pass (WIBP) (mean 1.481 ± 2.444 mg/L). Both F- and PO43- soil solution concentrations, 0.533 and 0.440 mg/L, respectively, were substantially lower, for sampling sites located EIBP, while locations WIBP averaged 0.773 and 0.829 mg/L respectively, for F- and PO43-. Sulfate concentration averaged 3.869 ± 3.059 mg/L for locations EIBP, and 3.891 ± 3.1970 for locations WIBP. Geochemical modeling of Al3+ in the soil solution indicated that a suite of aluminum hydroxyl sulfate minerals controlled Al3+ activity in the alpine tundra soil, with shifts between controlling solid phases occurring in the presence of elevated F- concentrations.

  10. Studies of anions sorption on natural zeolites.

    Science.gov (United States)

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    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.

  11. Anion exchange kinetics of nanodimensional layered metal hydroxides: use of isoconversional analysis.

    Science.gov (United States)

    Majoni, Stephen; Hossenlopp, Jeanne M

    2010-12-16

    Anion exchange reactions of nanodimensional layered metal hydroxide compounds are utilized to create materials with targeted physical and chemical properties and also as a means for controlled release of intercalated anions. The kinetics of this important class of reaction are generally characterized by model-based approaches. In this work, a different approach based on isothermal, isoconversional analysis was utilized to determine effective activation energies with respect to extent of reaction. Two different layered metal hydroxide materials were chosen for reaction with chloride anions, using a temperature range of 30-60 °C. The concentrations of anions released into solution and the changes in polycrystalline solid phases were evaluated using model-based (Avrami-Erofe'ev nucleation-growth model) and model-free (integral isoconversional) methods. The results demonstrate the utility of the isoconversional approach for identifying when fitting to a single model is not appropriate, particularly for characterizing the temperature dependence of the reaction kinetics.

  12. Cellulose Anionic Hydrogels Based on Cellulose Nanofibers As Natural Stimulants for Seed Germination and Seedling Growth.

    Science.gov (United States)

    Zhang, Hao; Yang, Minmin; Luan, Qian; Tang, Hu; Huang, Fenghong; Xiang, Xia; Yang, Chen; Bao, Yuping

    2017-05-17

    Cellulose anionic hydrogels were successfully prepared by dissolving TEMPO-oxidized cellulose nanofibers in NaOH/urea aqueous solution and being cross-linked with epichlorohydrin. The hydrogels exhibited microporous structure and high hydrophilicity, which contribute to the excellent water absorption property. The growth indexes, including the germination rate, root length, shoot length, fresh weight, and dry weight of the seedlings, were investigated. The results showed that cellulose anionic hydrogels with suitable carboxylate contents as plant growth regulators could be beneficial for seed germination and growth. Moreover, they presented preferable antifungal activity during the breeding and growth of the sesame seed breeding. Thus, the cellulose anionic hydrogels with suitable carboxylate contents could be applied as soilless culture mediums for plant growth. This research provided a simple and effective method for the fabrication of cellulose anionic hydrogel and evaluated its application in agriculture.

  13. Transmembrane anion transport and cytotoxicity of synthetic tambjamine analogs.

    Science.gov (United States)

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

    2014-03-21

    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.

  14. Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism.

    Science.gov (United States)

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

    2014-04-05

    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.

  15. Conformational equilibrium of talin is regulated by anionic lipids.

    Science.gov (United States)

    Ye, Xin; McLean, Mark A; Sligar, Stephen G

    2016-08-01

    A critical step in the activation of integrin receptors is the binding of talin to the cytoplasmic domain of the β subunits. This interaction leads to separation of the integrin α and β transmembrane domains and significant conformational changes in the extracellular domains, resulting in a dramatic increase in integrin's affinity for ligands. It has long been shown that the membrane bilayer also plays a critical role in the talin-integrin interaction. Anionic lipids are required for proper interaction, yet the specificity for specific anionic headgroups is not clear. In this report, we document talin-membrane interactions with bilayers of controlled composition using Nanodiscs and a FRET based binding and structural assay. We confirm that recruitment of the talin head domain to the membrane surface is governed by charge in the absence of other adapter proteins. In addition, measurement of the donor-acceptor distance is consistent with the hypothesis that anionic lipids promote a conformational change in the talin head domain allowing interaction of the F3 domain with the phospholipid bilayer. The magnitude of the F3 domain movement is altered by the identity of the phospholipid headgroup with phosphatidylinositides promoting the largest change. Our results suggest that phoshpatidylinositol-4,5-bisphosphate plays key a role in converting talin head domain to a conformation optimized for interactions with the bilayer and subsequently integrin cytoplasmic tails.

  16. Specific adsorption of perchlorate anions on Pt{hkl} single crystal electrodes.

    Science.gov (United States)

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

    2014-07-21

    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

  17. Vibrational spectroscopy of microhydrated conjugate base anions.

    Science.gov (United States)

    Asmis, Knut R; Neumark, Daniel M

    2012-01-17

    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

  18. An anionic surfactant for EOR applications

    Science.gov (United States)

    Sagir, Muhammad; Tan, Isa M.; Mushtaq, Muhammad

    2014-10-01

    This work is to investigate the new anionic surfactants for the Enhanced Oil Recovery (EOR) application. Sulfonated anionic surfactant was produced by attaching SO3 to an ethoxylated alcohol to increase the performance of the surfactant. Methallyl chloride and ethoxylated alcohol was reacted followed by the reaction with sodium bisulfite to produce anionic sulfonated surfactant in 80.3 % yield. The sulfonation reaction parameters such as reactants mole ratio, reaction temperature and catalyst amount were optimized. The generation and stability of foam from the synthesized surfactant is also tested and results are reported. The synthesized novel surfactant was further investigated for the effect on the CO2 mobility in porous media and the findings are presented here. This in house developed surfactant has a great potential for CO2- EOR applications.

  19. Syntheses and structural characterizations of anionic borane-capped ammonia borane oligomers: evidence for ammonia borane H2 release via a base-promoted anionic dehydropolymerization mechanism.

    Science.gov (United States)

    Ewing, William C; Marchione, Allegra; Himmelberger, Daniel W; Carroll, Patrick J; Sneddon, Larry G

    2011-10-26

    Studies of the activating effect of Verkade's base, 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (VB), on the rate and extent of H(2) release from ammonia borane (AB) have led to the syntheses and structural characterizations of three anionic aminoborane chain-growth products that provide direct support for anionic dehydropolymerization mechanistic steps in the initial stages of base-promoted AB H(2) release reactions. The salt VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(3)](-) (1) containing a linear five-membered anionic aminoborane chain was produced in 74% yield via the room-temperature reaction of a 3:1 AB/VB mixture in fluorobenzene solvent, while the branched and linear-chain seven-membered anionic aminoborane oligomers VBH(+)[HB(NH(2)BH(3))(3)](-) (2a) and VBH(+)[H(3)BNH(2)BH(2)NH(2)BH(2)NH(2)BH(3)](-) (2b) were obtained from VB/AB reactions carried out at 50 °C for 5 days when the AB/VB ratio was increased to 4:1. X-ray crystal structure determinations confirmed that these compounds are the isoelectronic and isostructural analogues of the hydrocarbons n-pentane, 3-ethylpentane, and n-heptane, respectively. The structural determinations also revealed significant interionic B-H···H-N dihydrogen-bonding interactions in these anions that could enhance dehydrocoupling chain-growth reactions. Such mechanistic pathways for AB H(2) release, involving the initial formation of the previously known [H(3)BNH(2)BH(3)](-) anion followed by sequential dehydrocoupling of B-H and H-N groups of growing borane-capped aminoborane anions with AB, are supported by the fact that 1 was observed to react with an additional AB equivalent to form 2a and 2b.

  20. Enhanced electrochemical performance and manganese redox activity of LiFe0.4Mn0.6PO4 by iodine anion substitution as cathode material for Li-ion battery

    Science.gov (United States)

    Sin, Byung Cheol; Singh, Laxman; An, JiEun; Lee, Hansol; Lee, Hyung-il; Lee, Youngil

    2016-05-01

    For the first time, an attempt has been made for the possible augmentation and exploration of iodine substitution into LiFe0.4Mn0.6PO4 (LFMP) material is assessed as a cathode material for lithium ion batteries. Iodine substituted LiFe0.4Mn0.6(PO4)1-xIx (LFMPI, x = 0, 0.01, 0.015, and 0.02) have been synthesized by a solid-state reaction without any external carbon source. X-ray diffraction shows that the LFMP and LFMPI cathode materials have formed the same single crystalline phase; the values of lattice parameters and unit cell volume have been insignificantly changed by I- anion substitution. Uniformly distributed grains of the LFMPI samples with grain sizes in the range of 250 nm to 0.9 μm have been obtained by scanning electron microscopy. X-ray photoelectron spectroscopy for the LFMPI with x = 0.02 have clearly observed at 619.5 and 630.7 eV for I 3d5/2 and I 3d3/2, respectively. The electrochemical properties of the pure LFMP cathode material have been compared with those of I- anion substituted LFMPI samples. LFMPI with x = 0.015 has delivered the highest discharge capacity of 141.5 mAh g-1 at 0.1C, and LFMPI with x = 0.01 has 102.1 mAh g-1 at high rate of 3C. Iodine substituted LFMPI have demonstrated improved electrochemical properties with excellent reversible cycling.

  1. 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)

    2010-05-24

    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.

  2. Cytosolic nucleotides block and regulate the Arabidopsis vacuolar anion channel AtALMT9.

    Science.gov (United States)

    Zhang, Jingbo; Martinoia, Enrico; De Angeli, Alexis

    2014-09-12

    The aluminum-activated malate transporters (ALMTs) form a membrane protein family exhibiting different physiological roles in plants, varying from conferring tolerance to environmental Al(3+) to the regulation of stomatal movement. The regulation of the anion channels of the ALMT family is largely unknown. Identifying intracellular modulators of the activity of anion channels is fundamental to understanding their physiological functions. In this study we investigated the role of cytosolic nucleotides in regulating the activity of the vacuolar anion channel AtALMT9. We found that cytosolic nucleotides modulate the transport activity of AtALMT9. This modulation was based on a direct block of the pore of the channel at negative membrane potentials (open channel block) by the nucleotide and not by a phosphorylation mechanism. The block by nucleotides of AtALMT9-mediated currents was voltage dependent. The blocking efficiency of intracellular nucleotides increased with the number of phosphate groups and ATP was the most effective cellular blocker. Interestingly, the ATP block induced a marked modification of the current-voltage characteristic of AtALMT9. In addition, increased concentrations of vacuolar anions were able to shift the ATP block threshold to a more negative membrane potential. The block of AtALMT9-mediated anion currents by ATP at negative membrane potentials acts as a gate of the channel and vacuolar anion tune this gating mechanism. Our results suggest that anion transport across the vacuolar membrane in plant cells is controlled by cytosolic nucleotides and the energetic status of the cell.

  3. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    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.

  4. Krebs cycle anions in metabolic acidosis.

    Science.gov (United States)

    Bowling, Francis G; Morgan, Thomas J

    2005-10-05

    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.

  5. The effect of anions on the human P2X7 receptor.

    Science.gov (United States)

    Kubick, Christoph; Schmalzing, Günther; Markwardt, Fritz

    2011-12-01

    P2X7 receptors (P2X7Rs) are nonselective cation channels that are opened by the binding of extracellular ATP and are involved in the modulation of epithelial secretion, inflammation and nociception. Here, we investigated the effect of extracellular anions on channel gating and permeation of human P2X7Rs (hP2X7Rs) expressed in Xenopus laevis oocytes. Two-microelectrode voltage-clamp recordings showed that ATP-induced hP2X7R-mediated currents increased when extracellular chloride was substituted by the organic anions glutamate or aspartate and decreased when chloride was replaced by the inorganic anions nitrate, sulfate or iodide. ATP concentration-response comparisons revealed that substitution of chloride by glutamate decreased agonist efficacy, while substitution by iodide increased agonist efficacy at high ATP concentrations. Meanwhile, the ATP potency remained unchanged. Activation of the hP2X7R at low ATP concentrations via the high-affinity ATP effector site was not affected by the replacement of chloride by glutamate or iodide. To analyze the anion effect on the hP2X7R at the single-molecule level, we performed single-channel current measurements using the patch-clamp technique in the outside-out configuration. Chloride substitution did not affect the single-channel conductance, but the probability that the P2X7R channel was open increased when chloride was replaced by glutamate and decreased when chloride was replaced by iodide. This effect was due to an influence of the anions on the mean closed times of the hP2X7R channel. We conclude that hP2X7R channels are not anion-permeable in physiological Na+-based media and that external anions allosterically affect ion channel opening in the fully ATP4-liganded P2X7R through an extracellular anion binding site.

  6. Solvent-dependent enthalpic versus entropic anion binding by biaryl substituted quinoline based anion receptors.

    Science.gov (United States)

    Sun, Zhan-Hu; Albrecht, Markus; Raabe, Gerhard; Pan, Fang-Fang; Räuber, Christoph

    2015-01-08

    Anion receptors based on an 8-thiourea substituted quinoline with pentafluorinated (1a) or nonfluorinated (1b) biarylamide groups in the 2-position show similar binding of halide anions with somewhat higher association constants for the more acidic fluorinated derivative. Surprisingly, binding affinities for the halides in the case of the nonfluorinated 1b are similar in nonpolar chloroform or polar DMSO as solvent. Thorough thermodynamic investigations based on NMR van't Hoff analysis show that anion binding in chloroform is mainly enthalpically driven. In DMSO, entropy is the driving force for the binding of the ions with replacement of attached solvent.

  7. Anionic/cationic complexes in hair care.

    Science.gov (United States)

    O'Lenick, Tony

    2011-01-01

    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.

  8. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Ruel, Bianca H.M.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    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

  9. Wigner photoemission time delay from endohedral anions

    Science.gov (United States)

    Kumar, Ashish; Varma, Hari R.; Deshmukh, Pranawa C.; Manson, Steven T.; Dolmatov, Valeriy K.; Kheifets, Anatoli

    2016-10-01

    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.

  10. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Ruel, Bianca H.M.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    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

  11. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;

    2003-01-01

    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...

  12. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.;

    2005-01-01

    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...

  13. Donnan Membrane Technique (DMT) for Anion Measurement

    NARCIS (Netherlands)

    Alonso Vega, M.F.; Weng, L.P.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2010-01-01

    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-

  14. Neutral Resonant Ionization in Hydrogen Anion Production

    Science.gov (United States)

    Vogel, John

    2013-09-01

    Dissociative ionization of molecules causes gas phase H- but fails to explain anion intensity. Atomic collisions on surfaces with reduced work function give anions, but also fail to explain intensity, lowered electron density, and diagnostics. Neutral resonant ionization of H(2s) atoms to ion pairs is here predicted with a very high cross section. H(2s,p) atoms are resonant with numerous short-lived excited states (``resonances'') of H- as well as the putative doubly-excited stable state of H- which resists production by other means. This state decays through 1Σu+ (2s σu2) to a singly excited ion pair, leaving both proton and anion with 3.8 eV energy. H(2s,p) atoms arise from dissociative recombination of trihydrogen ion (H3+)which dominates ion content of hydrogen plasmas. Initial H(2s,p) are resonantly produced by ground state Cs atoms or excited Ar, Kr, and Xe atoms, but these initiators are not needed to sustain anion production. This theory may explain the intense ion source at Cal Tech that produced 1.5 mA/cm2 H3 in the mid-1980's (1). A full CRM calculation is not complete, but equilibrium calculations suggest that >1 mA/cm2 H- may be predicted.

  15. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

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

    1998-01-01

    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

  16. Anionic phospholipids modulate peptide insertion into membranes.

    Science.gov (United States)

    Liu, L P; Deber, C M

    1997-05-06

    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

  17. Biological Role of Anions (Sulfate, Nitrate , Oxalate and Acetate) on the Antibacterial Properties of Cobalt (II) and Nickel(II) Complexes With Pyrazinedicarboxaimide Derived, Furanyl and Thienyl Compounds

    OpenAIRE

    Chohan, Zahid H.; Praveen, M.

    1999-01-01

    A number of biologically active complexes of cobalt(II) and nickel(II) with pyrazinedicarboxaimido derived thienyl and furanyl compounds having the same metal ion but different anions such as sulphate, nitrate, oxalate and acetate have been synthesized and characterized on the basis of their physical, spectral and analytical data. In order to evaluate the role of anions on their antibacterial properties, these ligands and their synthesized metal complexes with various anions have been screene...

  18. Purification and Characterization of Two Voltage-Dependent Anion Channel Isoforms from Plant Seeds1

    Science.gov (United States)

    Abrecht, Helge; Wattiez, Ruddy; Ruysschaert, Jean-Marie; Homblé, Fabrice

    2000-01-01

    Mitochondria were isolated from imbibed seeds of lentil (Lens culinaris) and Phaseolus vulgaris. We copurified two voltage-dependent anion channel from detergent solubilized mitochondria in a single purification step using hydroxyapatite. The two isoforms from P. vulgaris were separated by chromatofocusing chromatography in 4 m urea without any loss of channel activity. Channel activity of each isoform was characterized upon reconstitution into diphytanoyl phosphatidylcholine planar lipid bilayers. Both isoforms form large conductance channels that are slightly anion selective and display cation selective substates. PMID:11080295

  19. Anion-π interactions involving [MX(n)](m-) anions: a comprehensive theoretical study.

    Science.gov (United States)

    Estarellas, Carolina; Quiñonero, David; Deyà, Pere M; Frontera, Antonio

    2013-01-14

    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.

  20. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    Energy Technology Data Exchange (ETDEWEB)

    Jonathan L. Sessler

    2007-09-21

    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.

  1. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins.

    Science.gov (United States)

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S

    2014-07-01

    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.

  2. Three hydroxy aurone compounds as chemosensors for cyanide anions.

    Science.gov (United States)

    Chen, Huihui; Sun, Yunhui; Zhou, Chuanjian; Cao, Duxia; Liu, Zhiqiang; Ma, Lin

    2013-12-01

    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.

  3. 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

    2005-01-01

    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.

  4. Anion transport and GABA signaling

    Directory of Open Access Journals (Sweden)

    Christian Andreas Huebner

    2013-10-01

    Full Text Available Whereas activation of GABAA receptors by GABA usually results in a hyperpolarizing influx of chloride into the neuron, the reversed chloride driving force in the immature nervous system results in a depolarizing efflux of chloride. This GABAergic depolarization is deemed to be important for the maturation of the neuronal network. The concept of a developmental GABA switch has mainly been derived from in vitro experiments and reliable in vivo evidence is still missing. As GABAA receptors are permeable for both chloride and bicarbonate, the net effect of GABA also critically depends on the distribution of bicarbonate. Whereas chloride can either mediate depolarizing or hyperpolarizing currents, bicarbonate invariably mediates a depolarizing current under physiological conditions. Intracellular bicarbonate is quickly replenished by cytosolic carbonic anhydrases. Intracellular bicarbonate levels also depend on different bicarbonate transporters expressed by neurons. The expression of these proteins is not only developmentally regulated but also differs between cell types and even subcellular regions. In this review we will summarize current knowledge about the role of some of these transporters for brain development and brain function.

  5. Functional role of anion channels in cardiac diseases

    Institute of Scientific and Technical Information of China (English)

    Da-yue DUAN; Luis LH LIU; Nathan BOZEAT; Z Maggie HUANG; Sunny Y XIANG; Guan-lei WANG; Linda YE; Joseph R HUME

    2005-01-01

    In comparison to cation (K+, Na+, and Ca2+) channels, much less is currently known about the functional role of anion (Cl-) channels in cardiovascular physiology and pathophysiology. Over the past 15 years, various types of Cl- currents have been recorded in cardiac cells from different species including humans. All cardiac Cl- channels described to date may be encoded by five different Cl- channel genes: the PKA- and PKC-activated cystic fibrosis tansmembrane conductance regulator (CFTR), the volume-regulated ClC-2 and ClC-3, and the Ca2+-activated CLCA or Bestrophin. Recent studies using multiple approaches to examine the functional role of Cl- channels in the context of health and disease have demonstrated that Cl- channels might contribute to: 1) arrhythmogenesis in myocardial injury; 2) cardiac ischemic preconditioning; and 3) the adaptive remodeling of the heart during myocardial hypertrophy and heart failure. Therefore,anion channels represent very attractive novel targets for therapeutic approaches to the treatment of heart diseases. Recent evidence suggests that Cl- channels,like cation channels, might function as a multiprotein complex or functional module.In the post-genome era, the emergence of functional proteomics has necessitated a new paradigm shift to the structural and functional assessment of integrated Cl- channel multiprotein complexes in the heart, which could provide new insight into our understanding of the underlying mechanisms responsible for heart disease and protection.

  6. Natural minerals and synthetic materials for sorption of radioactive anions

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Mun Ja; Chun, Kwan Sik; Kim, Seung Soo

    1998-07-01

    Technetium-99 and iodine-129 are fission products with long half-lives, and exist as highly soluble anionic species. Studies on natural and synthetic materials sorbing TcO{sub 4} and/or I have been performed by several researchers. The application of these materials as an additive in the high-level waste disposal has been considered. The iron- or sulfide-containing minerals such as metal iron, iron powder, stibnite and pyrrhotite show a high capacity for TcO{sub 4} sorption. And the small amounts of activated carbon are reported to have high distribution coefficients recently. In the iodine sorption studies, sulfide-, copper-, lead- or mercury-containing minerals can be a candidate. Pyrite, chalcopyrite, galena, Cu{sub 2}S and CuS reveal a high capacity for I sorption. The synthetic materials were found to have high sorption capacity and compensate the defects of natural minerals, which contain hydrous oxides such as zirconium oxide, aluminium oxide and mercarbide. The mercarbide has the high distribution coefficients for the sorption of TcO{sub 4} and I. Recently it was proposed that the synthetic clay, hydrotalcite, could be useful for the fixation of anion. However, to determine the applicability of those natural and synthetic materials as an additive to a buffer or backfill material for sorption of TcO{sub 4} and/or I, the sorption behavior of the anions on those materials under the repository conditions should be identified. (author). 32 refs., 21 tabs., 10 figs

  7. Investigation of cation (Sn2+) and anion (N3-) substitution in favor of visible light photocatalytic activity in the layered perovskite K2La2Ti3O10.

    Science.gov (United States)

    Kumar, Vinod; Govind; Uma, S

    2011-05-15

    Noticeable lowering of the energy gaps have been achieved for the layered perovskite K(2)La(2)Ti(3)O(10) as a result of the attempts made to incorporate Sn(2+) and N(3-) ions. Incorporation of Sn(2+) ions was carried out by the ion-exchange reaction of K(2)La(2)Ti(3)O(10) with aqueous tin(II) chloride solution. Nitrogen incorporation was attempted by the solid state reaction of the parent oxide with urea around 400 °C in air. The resultant oxides have been characterized by power X-ray diffraction, UV-visible diffuse reflectance spectroscopy, and Fourier transform infrared spectroscopy. Room temperature ion-exchange was sufficient to introduce Sn(2+) ions with the resulting product of composition (Sn(0.45)K(0.2)H(0.9))La(2)Ti(3)O(10) · H(2)O. Visible light absorption was observed with the absorption edge red shift of ∼ 100 nm from that of the parent K(2)La(2)Ti(3)O(10). The lowering of the band gap was as expected by the contribution of Sn 5s orbitals to the O 2p orbitals in the formation of the valence band. Nitridation using urea resulted not only in nitrogen doping but with the additional sensitization by the presence of carbon nitride (CN) polymers, which again resulted in visible light absorption. The product oxides obtained as a result of cation and anion intended substitutional studies have been found to be useful for the visible light photocatalytic decomposition of organic dyes such as rhodamine B.

  8. 酶法制备鲽鱼鱼皮胶原蛋白肽及其清除超氧阴离子自由基的研究%Study on the Enzymatic Preparation and Superoxide Anion Radical Scavenging Activity of Collagen Peptide from Plaice Skin

    Institute of Scientific and Technical Information of China (English)

    王群; 郑海涛; 葛尧; 何计国

    2011-01-01

    采用碱性蛋白酶酶解鲽鱼鱼皮胶原蛋白制备胶原蛋白肽,对其清除超氧阴离子自由基的能力进行研究.通过单因素试验和响应面法分析不同酶解条件对超氧阴离子自由基清除率的影响,优化得到最佳酶解工艺条件:pH 9.5,加酶量158l U/g,底物浓度10 mg/mL,酶解时间为6h,酶解温度60℃,最高清除率为75.51%,半数清除浓度(IC5o)为7.98 mg/mL.%Alcalase was used to hydrolyze plaice skin for preparing collagen peptide, and the superoxide anion radical scavenging activity of this collagen peptide was studied. Effect of the different enzymatic hydrolysis conditions on superoxide anion radical scavenging activity were analyzed by single factor experiment and response surface method. The optimal hydrolytic conditions of plaice skin collagen using Alcalase with high scavenging rate were pH=9.5, enzyme dosage 1581 U/g, concentration of substrate 10 mg/mL, hydrolysis time 6 h, temperature 60℃. The maximum scavenging rate of 75.51% and half scavenging concentration (IC50) of 7.98 mg/mL were obtained.

  9. Electron anions and the glass transition temperature

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo

    2016-08-24

    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.

  10. Specific anion effects in Artemia salina.

    Science.gov (United States)

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero

    2015-09-01

    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.

  11. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... 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...

  12. Stability and Characteristics of the Halogen Bonding Interaction in an Anion-Anion Complex: A Computational Chemistry Study.

    Science.gov (United States)

    Wang, Guimin; Chen, Zhaoqiang; Xu, Zhijian; Wang, Jinan; Yang, Yang; Cai, Tingting; Shi, Jiye; Zhu, Weiliang

    2016-02-04

    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.

  13. Bosentan, a mixed endothelin receptor antagonist, inhibits superoxide anion-induced pain and inflammation in mice.

    Science.gov (United States)

    Serafim, Karla G G; Navarro, Suelen A; Zarpelon, Ana C; Pinho-Ribeiro, Felipe A; Fattori, Victor; Cunha, Thiago M; Alves-Filho, Jose C; Cunha, Fernando Q; Casagrande, Rubia; Verri, Waldiceu A

    2015-11-01

    Bosentan is a mixed endothelin receptor antagonist widely used to treat patients with pulmonary arterial hypertension, and the emerging literature suggests bosentan as a potent anti-inflammatory drug. Superoxide anion is produced in large amounts during inflammation, stimulates cytokine production, and thus contributes to inflammation and pain. However, it remains to be determined whether endothelin contributes to the inflammatory response triggered by the superoxide anion. The present study investigated the effects of bosentan in a mouse model of inflammation and pain induced by potassium superoxide, a superoxide anion donor. Male Swiss mice were treated with bosentan (10-100 mg/kg) by oral gavage, 1 h before potassium superoxide injection, and the inflammatory response was evaluated locally and at spinal cord (L4-L6) levels. Bosentan (100 mg/kg) inhibited superoxide anion-induced mechanical and thermal hyperalgesia, overt pain-like behavior (abdominal writhings, paw flinching, and licking), paw edema, myeloperoxidase activity (neutrophil marker) in the paw skin, and leukocyte recruitment in the peritoneal cavity. Bosentan also inhibited superoxide anion-induced interleukin-1 beta (IL-1β) and tumor necrosis factor alpha (TNF-α) production, while it enhanced IL-10 production in the paw skin and spinal cord. Bosentan inhibited the reduction of antioxidant capacity (reduced glutathione, ferric reducing antioxidant power, and ABTS radical scavenging ability) induced by the superoxide anion. Finally, we demonstrated that intraplantar injection of potassium superoxide induces the mRNA expression of prepro-endothelin-1 in the paw skin and spinal cord. In conclusion, our results demonstrated that superoxide anion-induced inflammation, pain, cytokine production, and oxidative stress depend on endothelin; therefore, these responses are amenable to bosentan treatment.

  14. Politseiuuringud kooskõlastamisele / Liivia Anion

    Index Scriptorium Estoniae

    Anion, Liivia

    2003-01-01

    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

  15. Lowest autodetachment state of the water anion

    Science.gov (United States)

    Houfek, Karel; Čížek, Martin

    2016-05-01

    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.

  16. Designing New Electrolytes for Lithium Ion Batteries Using Superhalogen Anions

    OpenAIRE

    Srivastava, Ambrish Kumar; Misra, Neeraj

    2016-01-01

    The electrolytes used in Lithium Ion Batteries (LIBs) such as LiBF4, LiPF6 etc. are Li-salts of some complex anions, BF4-, PF6- etc. The investigation shows that the vertical detachment energy (VDE) of these anions exceeds to that of halogen, and therefore they behave as superhalogen anions. Consequently, it might be possible to design new electrolytic salts using other superhalogen anions. We have explored this possibility using Li-salts of various superhalogen anions such as BO2-, AlH4-, Ti...

  17. Donnan membrane technique (DMT) for anion measurement.

    Science.gov (United States)

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

    2010-04-01

    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.

  18. Bound anions differentially stabilize multiprotein complexes in the absence of bulk solvent.

    Science.gov (United States)

    Han, Linjie; Hyung, Suk-Joon; Mayers, Jonathan J S; Ruotolo, Brandon T

    2011-07-27

    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

  19. Scavenging of superoxide anions by lecithinized superoxide dismutase in HL-60 cells.

    Science.gov (United States)

    Ishihara, Tsutomu; Shibui, Misaki; Hoshi, Takaya; Mizushima, Tohru

    2016-01-01

    Superoxide dismutase covalently bound to four lecithin molecules (PC-SOD) has been found to have beneficial therapeutic effects in animal models of various diseases. However, the mechanism underlying these improved therapeutic effects has not yet been elucidated. It has previously been shown that PC-SOD localizes on the plasma membrane and in the lysosomes of cells. In this study, we evaluated the superoxide anion-scavenging activity of PC-SOD in HL-60 human promyelocytic leukemia cells. Compared to SOD, PC-SOD had only 17% scavenging activity in cell-free systems. Nevertheless, by analyzing enzyme activities in cell suspensions containing PC-SOD or SOD, PC-SOD and SOD showed almost equal activity for scavenging extracellular superoxide anions produced by HL-60 cells. Furthermore, the activity for scavenging extracellular superoxide anions increased with increased amount of PC-SOD on the plasma membrane. Moreover, PC-SOD exhibited no obvious inhibitory effect on the scavenging of intracellular superoxide anions. These results suggested that the association of PC-SOD with the plasma membrane plays a key role in its beneficial therapeutic effects. Thus, this finding may provide a rationale for selecting target diseases for PC-SOD treatment.

  20. Anion order in perovskites: a group-theoretical analysis.

    Science.gov (United States)

    Talanov, M V; Shirokov, V B; Talanov, V M

    2016-03-01

    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.

  1. Developing principles for predicting ionic liquid effects on reaction outcome. The importance of the anion in controlling microscopic interactions.

    Science.gov (United States)

    Keaveney, Sinead T; Haines, Ronald S; Harper, Jason B

    2015-03-28

    A series of ionic liquids containing anions of differing coordination strength were investigated as solvents for the condensation reaction of an alkyl amine and an aromatic aldehyde. As predicted, the rate constant of the process was found to increase with the proportion of the ionic liquid in the reaction mixture. Temperature-dependent kinetic analyses demonstrated that by varying the ability of the anion to interact with the cation the magnitude of both the enthalpy and entropy of activation could be controlled in a predictable manner, with the activation parameters being linearly dependent on the ionic liquid basicity. Interestingly, the unexpected trend in the rate constants observed when altering the anion of the ionic liquid highlighted the presence of more subtle secondary microscopic interactions involving the anion, further emphasizing the fragility of the enthalpy - entropy balance.

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

    Indian Academy of Sciences (India)

    M Sudha Swaraga; M Adinarayana

    2003-04-01

    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.

  3. Synthesis of anionic phosphorus-containing heterocycles by intramolecular cyclizations involving N-functionalized phosphinecarboxamides.

    Science.gov (United States)

    Robinson, Thomas P; Goicoechea, Jose M

    2015-04-07

    We report that the 2-phosphaethynolate anion (PCO(-)) reacts with propargylamines in the presence of a proton source to afford novel N-derivatized phosphinecarboxamides bearing alkyne functionalities. Deprotonation of these species gives rise to novel five- and six-membered anionic heterocycles resulting from intramolecular nucleophilic attack of the resulting phosphide at the alkyne functionality (via 5-exo-dig or 6-endo-dig cyclizations, respectively). The nature of the substituents on the phosphinecarboxamide can be used to influence the outcome of these reactions. This strategy represents a unique approach to phosphorus-containing heterocylic systems that are closely related to known organic molecules with interesting bio-active properties.

  4. Effect of superoxide anion scavenger on rat hearts with chronic intermittent hypoxia.

    Science.gov (United States)

    Pai, Peiying; Lai, Ching Jung; Lin, Ching-Yuang; Liou, Yi-Fan; Huang, Chih-Yang; Lee, Shin-Da

    2016-04-15

    Only very limited information regarding the protective effects of the superoxide anion scavenger on chronic intermittent hypoxia-induced cardiac apoptosis is available. The purpose of this study is to evaluate the effects of the superoxide anion scavenger on cardiac apoptotic and prosurvival pathways in rats with sleep apnea. Forty-two Sprague-Dawley rats were divided into three groups, rats with normoxic exposure (Control, 21% O2, 1 mo), rats with chronic intermittent hypoxia exposure (Hypoxia, 3-7% O2vs. 21% O2per 40 s cycle, 8 h per day, 1 mo), and rats with pretreatment of the superoxide anion scavenger and chronic intermittent hypoxia exposure (Hypoxia-O2 (-)-Scavenger, MnTMPyP pentachloride, 1 mg/kg ip per day; 3-7% O2vs. 21% O2per 40 s cycle, 8 h per day, 1 mo) at 5-6 mo of age. After 1 mo, the protein levels and apoptotic cells of excised hearts from three groups were measured by Western blotting and terminal deoxynucleotide transferase-mediated dUTP nick end labeling (TUNEL) assay. The superoxide anion scavenger decreased hypoxia-induced myocardial architecture abnormalities, left ventricular hypertrophy, and TUNEL-positive apoptosis. The superoxide anion scavenger decreased hypoxia-induced Fas ligand, Fas death receptors, Fas-associated death domain (FADD), activated caspase-8, and activated caspase-3 (Fas-dependent apoptotic pathway) as well as Bad, activated caspase-9 and activated caspase-3 (mitochondria-dependent apoptotic pathway), endonuclease G (EndoG), apoptosis-inducing factor (AIF), and TUNEL-positive apoptosis. The superoxide anion scavenger increased IGF-1, IGF-1R, p-PI3k, p-Akt, p-Bad, Bcl-2, and Bcl-xL (survival pathway). Our findings imply that the superoxide anion scavenger might prevent cardiac Fas-mediated and mitochondrial-mediated apoptosis and enhance the IGF-1-related survival pathway in chronic intermittent hypoxia. The superoxide anion scavenger may prevent chronic sleep apnea-enhanced cardiac apoptotic pathways and enhances

  5. Preparation of anionic polyurethane nanoparticles and blood compatible behaviors.

    Science.gov (United States)

    Zhu, Qinshu; Wang, Yan; Zhou, Min; Mao, Chun; Huang, Xiaohua; Bao, Jianchun; Shen, Jian

    2012-05-01

    The anionic polyurethane nanoparticles (APU-NPs) were obtained by an emulsion polymerization method. It was found that the average size of the prepared APU-NPs is about 84 nm, and the APU-NPs have zeta-potential of -38.9 mV. The bulk characterization of synthesized APU-NPs was investigated by FTIR. The blood compatibility of APU-NPs was characterized by in vitro for coagulation tests, complement activation, platelet activation, cytotoxicity experiments, and hemolysis assay. The results showed that the APU-NPs synthesized in this paper are blood compatible with low level of cell cytotoxicity, and the results were significant for their potential use in vivo.

  6. Explaining Ionic Liquid Water Solubility in Terms of Cation and Anion Hydrophobicity

    Directory of Open Access Journals (Sweden)

    Johannes Ranke

    2009-03-01

    Full Text Available The water solubility of salts is ordinarily dictated by lattice energy and ion solvation. However, in the case of low melting salts also known as ionic liquids, lattice energy is immaterial and differences in hydrophobicity largely account for differences in their water solubility. In this contribution, the activity coefficients of ionic liquids in water are split into cation and anion contributions by regression against cation hydrophobicity parameters that are experimentally determined by reversed phase liquid chromatography. In this way, anion hydrophobicity parameters are derived, as well as an equation to estimate water solubilities for cation-anion combinations for which the water solubility has not been measured. Thus, a new pathway to the quantification of aqueous ion solvation is shown, making use of the relative weakness of interactions between ionic liquid ions as compared to their hydrophobicities.

  7. Anion channels/transporters in plants: from molecular bases to regulatory networks.

    Science.gov (United States)

    Barbier-Brygoo, Hélène; De Angeli, Alexis; Filleur, Sophie; Frachisse, Jean-Marie; Gambale, Franco; Thomine, Sébastien; Wege, Stefanie

    2011-01-01

    Anion channels/transporters are key to a wide spectrum of physiological functions in plants, such as osmoregulation, cell signaling, plant nutrition and compartmentalization of metabolites, and metal tolerance. The recent identification of gene families encoding some of these transport systems opened the way for gene expression studies, structure-function analyses of the corresponding proteins, and functional genomics approaches toward further understanding of their integrated roles in planta. This review, based on a few selected examples, illustrates that the members of a given gene family exhibit a diversity of substrate specificity, regulation, and intracellular localization, and are involved in a wide range of physiological functions. It also shows that post-translational modifications of transport proteins play a key role in the regulation of anion transport activity. Key questions arising from the increasing complexity of networks controlling anion transport in plant cells (the existence of redundancy, cross talk, and coordination between various pathways and compartments) are also addressed.

  8. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

    Science.gov (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

    2015-06-24

    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.

  9. Superoxide Anion Radical Scavenging Ability of Quaternary Ammonium Salt of Chitosan

    Institute of Scientific and Technical Information of China (English)

    Xiao Yan ZHU; Jian Min WU; Zhi Shen JIA

    2004-01-01

    A series of N-alkyl or N-aryl chitosan quaternary ammonium salt were prepared using 96% deacetylated chitosan. Their scavenging activities against superoxide anion radical were investigated by chemiluminescence. The IC50 values of these compounds range from 280 to 880 μg/mL, which should be attributed to their different substitutes.

  10. Interaction of anions with a newly characterized alpha carbonic anhydrase from Halomonas sp.

    Science.gov (United States)

    Orhan, Furkan; Şentürk, Murat; Supuran, Claudiu T

    2016-12-01

    The inhibition and characterization of the α-class carbonic anhydrase (CA, EC 4.2.1.1) from the Halomonas sp. are reported for the first time. The enzyme was purified 91-fold with a yield of 39%, and a specific activity of 600 U/mg proteins was obtained. It has an optimum pH at 7.5, an optimum ionic strength at 20 mM and an optimum temperature at 20 °C. The following anions, SCN(-), Br(-), Cl(-), I(-), [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] showed inhibitory effects on the hydratase activity of the enzyme. Sulfate, sulfide, azide, nitrate, nitrite and iodide exhibited the strongest inhibitory activity, in the micromolar range (KI-s of 5.5-15.5 µM). SCN(-), Br(-), Cl(-), [Formula: see text] were moderate inhibitors, whereas other anions showed only weak activities. Our findings indicate that these anions inhibit the Halomonas sp. CA (HmCA) enzyme in a similar manner to other α-CAs from mammals investigated earlier, but the susceptibility to various anions differs significantly between the Halomonas sp. and other organism CAs.

  11. Efficient encapsulation of plasmid DNA in anionic liposomes by a freeze/thaw extrusion procedure

    NARCIS (Netherlands)

    Schoen, P; Bijl, L; Wilschut, J

    1998-01-01

    In this study we investigated whether intact plasmid DNA can be efficiently encapsulated in anionic liposomes prepared by freeze/thaw and extrusion techniques. There is controversy about this method of DNA encapsulation, especially as to whether DNA remains intact and retains its biological activity

  12. Interaction of anions with substituted buckybowls. The anion's nature and solvent effects.

    Science.gov (United States)

    Campo-Cacharrón, Alba; Cabaleiro-Lago, Enrique M; González-Veloso, Iván; Rodríguez-Otero, Jesús

    2014-08-07

    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.

  13. Organic superconductors with an incommensurate anion structure

    Directory of Open Access Journals (Sweden)

    Tadashi Kawamoto and Kazuo Takimiya

    2009-01-01

    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.

  14. 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)

    1994-02-03

    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.

  15. Probes for anionic cell surface detection

    Science.gov (United States)

    Smith, Bradley D.

    2013-03-05

    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.

  16. Electroculture for crop enhancement by air anions

    Science.gov (United States)

    Pohl, H. A.; Todd, G. W.

    1981-12-01

    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.

  17. Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds.

    Science.gov (United States)

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

    2004-11-01

    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.

  18. Strong and Selective Halide Anion Binding by Neutral Halogen-Bonding [2]Rotaxanes in Wet Organic Solvents.

    Science.gov (United States)

    Lim, Jason Y C; Bunchuay, Thanthapatra; Beer, Paul D

    2017-04-03

    The design and construction of neutral interlocked host molecules for anion recognition are rare. Using an active-metal template approach, the preparation of a family of neutral halogen bonding (XB) rotaxanes containing two, three and four iodotriazole groups integrated into the macrocycle and axle components is achieved. In spite of the interlocked hosts' neutrality, such rotaxane systems are capable of binding halide anions strongly and selectively in wet organic solvent mixtures. Importantly, halide-binding strength and selectivity can be modulated by varying the number and position of the halogen bond donor iodotriazole groups within the interlocked cavity; the rotaxane containing the largest number of halogen bond donor groups exhibits the highest halide anion-binding affinities. By varying the percentage of water content in the solvent, neutral XB donor-mediated anion-binding strength is also demonstrated to be highly sensitive to solvent polarity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Li-Wei [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan (China); Luo, Tzuoo-Tsair [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China); Wang, Chih-Min [Department of Bioscience and Biotechnology, National Taiwan Ocean University, Keelung 202, Taiwan (China); Lee, Gene-Hsiang; Peng, Shie-Ming [Department of Chemistry, National Taiwan University, Taipei 107, Taiwan (China); Liu, Yen-Hsiang [Department of Chemistry, Fu Jen Catholic University, New Taipei City 242, Taiwan (China); Lee, Sheng-Long [Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan (China); Lu, Kuang-Lieh [Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan (China)

    2016-07-15

    A Cd(II)–organic framework {[Cd_2(tpim)_4(SO_4)(H_2O)_2]·(SO_4)·21H_2O}{sub n} (1) was synthesized by reacting CdSO{sub 4}·8/3H{sub 2}O and 2,4,5-tri(4-pyridyl)imidazole (tpim) under hydrothermal conditions. A structural analysis showed that compound 1 adopts a layered structure in which the [Cd(tpim){sub 2}]{sub n} chains are linked by sulfate anions. These 2D layers are further packed into a 3D supramolecular framework via π–π interactions. The structure contains two types of SO{sub 4}{sup 2−} anions, i.e., bridging SO{sub 4}{sup 2−} and free SO{sub 4}{sup 2−} anions, the latter of which are included in the large channels of the framework. Compound 1 exhibits interesting anion exchange behavior. In the presence of SCN{sup −} anions, both the bridging and free SO{sub 4}{sup 2−} anions in 1 were completely exchanged by SCN{sup −} ligands to form a 1D species [Cd(tpim){sub 2}(SCN){sub 2}] (1A), in which the SCN{sup –} moieties function as a monodentate ligand. On the other hand, when compound 1 was ion exchanged with N{sub 3}{sup −} anions in aqueous solution, the bridging SO{sub 4}{sup 2−} moieties remained intact, and only the free guest SO{sub 4}{sup 2−} were replaced by N{sub 3}{sup −} anions. The gas adsorption behavior of the activated compound 1 was also investigated. - Highlights: • An interesting anion-induced structural transformation of a sulfate-incorporated 2D Cd(II)–organic framework is reported. • The sulfate-incorporated 2D layer compound exhibits very different anion exchange behavior with respect to SCN{sup −} and N{sub 3}{sup −}. • Both the bridging and free SO{sub 4}{sup 2−} anions in the 2D structure were completely exchanged by SCN{sup −} ligands, resulting in the formation of a 1D species. However, in the case of N{sub 3}{sup −} anions, only the free guest SO{sub 4}{sup 2−} in the structure was replaced.

  20. EPAC1 activation by cAMP stabilizes CFTR at the membrane by promoting its interaction with NHERF1.

    Science.gov (United States)

    Lobo, Miguel J; Amaral, Margarida D; Zaccolo, Manuela; Farinha, Carlos M

    2016-07-01

    Cyclic AMP (cAMP) activates protein kinase A (PKA) but also the guanine nucleotide exchange factor 'exchange protein directly activated by cAMP' (EPAC1; also known as RAPGEF3). Although phosphorylation by PKA is known to regulate CFTR channel gating - the protein defective in cystic fibrosis - the contribution of EPAC1 to CFTR regulation remains largely undefined. Here, we demonstrate that in human airway epithelial cells, cAMP signaling through EPAC1 promotes CFTR stabilization at the plasma membrane by attenuating its endocytosis, independently of PKA activation. EPAC1 and CFTR colocalize and interact through protein adaptor NHERF1 (also known as SLC9A3R1). This interaction is promoted by EPAC1 activation, triggering its translocation to the plasma membrane and binding to NHERF1. Our findings identify a new CFTR-interacting protein and demonstrate that cAMP activates CFTR through two different but complementary pathways - the well-known PKA-dependent channel gating pathway and a new mechanism regulating endocytosis that involves EPAC1. The latter might constitute a novel therapeutic target for treatment of cystic fibrosis.

  1. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)

    2015-07-28

    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.

  2. Zero-point energy effects in anion solvation shells.

    Science.gov (United States)

    Habershon, Scott

    2014-05-21

    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.

  3. Preorganized anion traps for exploiting anion-π interactions: an experimental and computational study.

    Science.gov (United States)

    Bretschneider, Anne; Andrada, Diego M; Dechert, Sebastian; Meyer, Steffen; Mata, Ricardo A; Meyer, Franc

    2013-12-09

    1,3-Bis(pentafluorophenyl-imino)isoindoline (A(F)) and 3,6-di-tert-butyl-1,8-bis(pentafluorophenyl)-9H-carbazole (B(F)) have been designed as preorganized anion receptors that exploit anion-π interactions, and their ability to bind chloride and bromide in various solvents has been evaluated. Both receptors A(F) and B(F) are neutral but provide a central NH hydrogen bond that directs the halide anion into a preorganized clamp of the two electron-deficient appended arenes. Crystal structures of host-guest complexes of A(F) with DMSO, Cl(-), or Br(-) (A(F):DMSO, A(F):Cl(-), and A(2)(F):Br(-)) reveal that in all cases the guest is located in the cleft between the perfluorinated flaps, but NMR spectroscopy shows a more complex situation in solution because of E,Z/Z,Z isomerism of the host. In the case of the more rigid receptor B(F), Job plots evidence 1:1 complex formation with Cl(-) and Br(-), and association constants up to 960 M(-1) have been determined depending on the solvent. Crystal structures of B(F) and B(F):DMSO visualize the distinct preorganization of the host for anion-π interactions. The reference compounds 1,3-bis(2-pyrimidylimino)isoindoline (A(N)) and 3,6-di-tert-butyl-1,8-diphenyl-9H-carbazole (B(H)), which lack the perfluorinated flaps, do not show any indication of anion binding under the same conditions. A detailed computational analysis of the receptors A(F) and B(F) and their host-guest complexes with Cl(-) or Br(-) was carried out to quantify the interactions in play. Local correlation methods were applied, allowing for a decomposition of the ring-anion interactions. The latter were found to contribute significantly to the stabilization of these complexes (about half of the total energy). Compounds A(F) and B(F) represent rare examples of neutral receptors that are well preorganized for exploiting anion-π interactions, and rare examples of receptors for which the individual contributions to the binding energy have been quantified. Copyright

  4. A point mutation associated with episodic ataxia 6 increases glutamate transporter anion currents.

    Science.gov (United States)

    Winter, Natalie; Kovermann, Peter; Fahlke, Christoph

    2012-11-01

    Episodic ataxia is a human genetic disease characterized by paroxysmal cerebellar incoordination. There are several genetically and clinically distinct forms of this disease, and one of them, episodic ataxia type 6, is caused by mutations in the gene encoding a glial glutamate transporter, the excitatory amino acid transporter-1. So far, reduced glutamate uptake by mutant excitatory amino acid transporter-1 has been thought to be the main pathophysiological process in episodic ataxia type 6. However, excitatory amino acid transporter-1 does not only mediate secondary-active glutamate transport, but also functions as an ion channel. Here, we examined the effects of a disease-associated point mutation, P290R, on glutamate transport, anion current as well as on the subcellular distribution of excitatory amino acid transporter-1 using heterologous expression in mammalian cells. P290R reduces the number of excitatory amino acid transporter-1 in the surface membrane and impairs excitatory amino acid transporter-1-mediated glutamate uptake. Cells expressing P290R excitatory amino acid transporter-1 exhibit larger anion currents than wild-type cells in the absence as well as in the presence of external l-glutamate, despite a lower number of mutant transporters in the surface membrane. Noise analysis revealed unaltered unitary current amplitudes, indicating that P290R modifies opening and closing, and not anion permeation through mutant excitatory amino acid transporter-1 anion channels. These findings identify gain-of-function of excitatory amino acid transporter anion conduction as a pathological process in episodic ataxia. Episodic ataxia type 6 represents the first human disease found to be associated with altered function of excitatory amino acid transporter anion channels and illustrates possible physiological and pathophysiological impacts of this functional mode of this class of glutamate transporters.

  5. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    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.

  6. Isatin phenylhydrazones: anion enhanced photochromic behaviour.

    Science.gov (United States)

    Cigáň, M; Jakusová, K; Gáplovský, M; Filo, J; Donovalová, J; Gáplovský, A

    2015-11-01

    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.

  7. 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)

    2015-10-15

    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.

  8. Isobar Separator for Anions: Current status

    Energy Technology Data Exchange (ETDEWEB)

    Alary, Jean-François, E-mail: alaryjf@isobarex.ca [Isobarex Corp., 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Javahery, Gholamreza [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Kieser, William; Zhao, Xiao-Lei [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada); Litherland, Albert [IsoTrace Laboratory, Department of Physics, University of Toronto, 60 St. George Street, Toronto, ON M5S 3B1 (Canada); Cousins, Lisa [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Charles, Christopher [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada)

    2015-10-15

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of {sup 36}S from {sup 36}Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion–molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  9. Modeling Carbon Chain Anions in L1527

    CERN Document Server

    Harada, Nanase

    2008-01-01

    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-...

  10. Ion-selective electrode and anion gap range: What should the anion gap be?

    Directory of Open Access Journals (Sweden)

    Sadjadi SA

    2013-06-01

    Full Text Available Seyed-Ali Sadjadi, Rendell Manalo, Navin Jaipaul, James McMillan Jerry L Pettis Memorial Veterans Medical Center, Loma Linda University School of Medicine, Loma Linda, CA, USA Background: Using flame photometry technique in the 1970s, the normal value of anion gap (AG was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE, the anion gap value has fallen to lower levels. Methods: A retrospective study of US veterans from a single medical center was performed to determine the value of the anion gap in subjects with normal renal function and normal serum albumin and in patients with lactic acidosis and end-stage renal disease on dialysis. Results: In 409 patients with an estimated glomerular filtration rate ≥60 mL/min/1.73 m2 body surface area and serum albumin ≥4 g/dL, the mean AG was 7.2 ± 2 (range 3–11 meq/L. In 299 patients with lactic acidosis (lactate level ≥4 meq/L and 68 patients with end-stage renal disease on dialysis, the mean AG was 12.5 meq/L and 12.4 meq/L, respectively. A value <2 meq/L should be considered a low anion gap and a possible clue to drug intoxication and paraproteinemic disorders. Conclusion: With the advent of ISE for measurement of analytes, the value of the anion gap has fallen. Physicians need to be aware of the normal AG value in their respective institutions, and laboratories need to have an established value for AG based on the type of instrument they are using. Keywords: acidosis, electrolytes, ESRD

  11. A model for underpotential deposition in the presence of anions

    Science.gov (United States)

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

    2010-05-01

    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.

  12. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.

    2012-01-01

    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....

  13. Hydrazone derivatives appended to diphenylphosphine oxide as anion sensors

    Indian Academy of Sciences (India)

    MARUTHAI KUMARAVEL; JOEL T MAGUE; MARAVANJI S BALAKRISHNA

    2017-04-01

    Phosphine substituted hydrazones with or without nitro substituents were synthesized and characterized by multinuclear NMR, FT-IR, UV-Vis spectroscopy and single crystal X-ray diffraction. The anion recognition properties of phosphine oxides {Ph₂P(O)C₆H₄CHNNHPh} (2) and {Ph₂P(O)C₆H₄CHNNHC₆H₃ (2,4-NO₂) ₂} (4) with anions (F⁻, Cl⁻, Br⁻, I⁻, CH₃COO⁻ and H₂PO⁻ ₄ ) were investigated. The selectivity towards these anions is attributed to the hydrogen bonding capability of the NH bond. Competitive titrations have shown that the binding ability of fluoride with 4 is not influenced by the presence of other anions.

  14. 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.

    2001-07-30

    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.

  15. Biology of SLAC1-type anion channels - from nutrient uptake to stomatal closure.

    Science.gov (United States)

    Hedrich, Rainer; Geiger, Dietmar

    2017-10-01

    Contents 46 I. 46 II. 47 III. 50 IV. 53 V. 56 VI. 57 58 58 References 58 SUMMARY: Stomatal guard cells control leaf CO2 intake and concomitant water loss to the atmosphere. When photosynthetic CO2 assimilation is limited and the ratio of CO2 intake to transpiration becomes suboptimal, guard cells, sensing the rise in CO2 concentration in the substomatal cavity, deflate and the stomata close. Screens for mutants that do not close in response to experimentally imposed high CO2 atmospheres identified the guard cell-expressed Slowly activating anion channel, SLAC1, as the key player in the regulation of stomatal closure. SLAC1 evolved, though, before the emergence of guard cells. In Arabidopsis, SLAC1 is the founder member of a family of anion channels, which comprises four homologues. SLAC1 and SLAH3 mediate chloride and nitrate transport in guard cells, while SLAH1, SLAH2 and SLAH3 are engaged in root nitrate and chloride acquisition, and anion translocation to the shoot. The signal transduction pathways involved in CO2 , water stress and nutrient-sensing activate SLAC/SLAH via distinct protein kinase/phosphatase pairs. In this review, we discuss the role that SLAC/SLAH channels play in guard cell closure, on the one hand, and in the root-shoot continuum on the other, along with the molecular basis of the channels' anion selectivity and gating. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  16. Anionic Regulated NiFe (Oxy)Sulfide Electrocatalysts for Water Oxidation.

    Science.gov (United States)

    Li, Bo-Quan; Zhang, Shu-Yuan; Tang, Cheng; Cui, Xiaoyang; Zhang, Qiang

    2017-07-01

    The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, rechargeable metal-air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS-2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm(-2) and the fastest kinetics being 56.3 mV dec(-1) to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in-depth understanding of electrocatalysis at the electronic and atomic level. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Experimental evidence for the functional relevance of anion-π interactions

    Science.gov (United States)

    Dawson, Ryan E.; Hennig, Andreas; Weimann, Dominik P.; Emery, Daniel; Ravikumar, Velayutham; Montenegro, Javier; Takeuchi, Toshihide; Gabutti, Sandro; Mayor, Marcel; Mareda, Jiri; Schalley, Christoph A.; Matile, Stefan

    2010-07-01

    Attractive in theory and confirmed to exist, anion-π interactions have never really been seen at work. To catch them in action, we prepared a collection of monomeric, cyclic and rod-shaped naphthalenediimide transporters. Their ability to exert anion-π interactions was demonstrated by electrospray tandem mass spectrometry in combination with theoretical calculations. To relate this structural evidence to transport activity in bilayer membranes, affinity and selectivity sequences were recorded. π-acidification and active-site decrowding increased binding, transport and chloride > bromide > iodide selectivity, and supramolecular organization inverted acetate > nitrate to nitrate > acetate selectivity. We conclude that anion-π interactions on monomeric surfaces are ideal for chloride recognition, whereas their supramolecular enhancement by π,π-interactions appears perfect to target nitrate. Chloride transporters are relevant to treat channelopathies, and nitrate sensors to monitor cellular signaling and cardiovascular diseases. A big impact on organocatalysis can be expected from the stabilization of anionic transition states on chiral π-acidic surfaces.

  18. A rapid phospholipase D assay using zirconium precipitation of anionic substrate phospholipids

    DEFF Research Database (Denmark)

    Petersen, G.; Hansen, Harald S.; Chapman, K.D.

    2000-01-01

    Activation of phospholipase D (PLD) is involved in a number of signal transduction pathways in eukaryotic cells. The most common method for determination of PLD activity in vitro involves incubation with a radiolabeled substrate and lipid extraction followed by thin-layer chromatography in order ...... biochemical characterization of this anandamide-generating enzyme. - Petersen, G., K. D. Chapman, and H. S. Hansen. A rapid phospholipase D assay using zirconium precipitation of anionic substrate phospholipids: Application to N-acylethanolamine formation in vitro....

  19. Effects of common inorganic anions on the rates of photocatalytic degradation of sodium dodecylbenzenesulfonate over illuminated titanium dioxide

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Experiments were carried out to study the effects of several anions on the photocatalytic degradation rates of sodium dodecylbenzene sulphonate (DBS) with TiO2 as catalyst. The anions were added as Na2 SO4, NaNO3, NaCl, NaHCO3, NaH2 PO4 and Na3 PO4, and two levels of anion content, i.e. 12 mmol/L and 36 mmol/L in terms of Na+ , were studied. The results revealed that: Cl , SO24- , NO-3 and HCO3-retarded the rates of DBS degradation to different degrees; PO43 - increased the DBS degradation rate at low concentration and decreased the rate at high concentration; H2PO-4 accelerated the rate of DBS degradation. The mechanism of the effects of anions on DBS degradation was concluded as the following three aspects: anions compete for the radicals; anions are absorbed on the surface of catalyst and block the active site catalyst.

  20. Once upon Anion: A Tale of Photodetachment

    Science.gov (United States)

    Lineberger, W. Carl

    2013-04-01

    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!

  1. Anion permselective membrane. [For redox fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, S.S.; Hodgdon, R.B.

    1978-01-01

    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.

  2. 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: detlef.schooss@kit.edu [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)

    2015-01-14

    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.

  3. 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)

    1997-11-01

    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.

  4. 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

    2001-12-01

    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.

  5. A comparative study of structural and electrochemical properties of high-density aluminum substituted α-nickel hydroxide containing different interlayer anions

    Science.gov (United States)

    Shangguan, Enbo; Li, Jing; Guo, Dan; Guo, Litan; Nie, Mengzhen; Chang, Zhaorong; Yuan, Xiao-Zi; Wang, Haijiang

    2015-05-01

    Al-substituted α-type nickel hydroxides (α-Ni(OH)2) containing different interlayer anions (NO3-, SO42- , Cl-, CO32- , OH-) are synthesized via a polyacrylamide (PAM) assisted two-step drying method. The effects of interlayer anions on the microstructure, morphology and electrochemical performance of Al-substituted α-Ni(OH)2 are investigated by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. The results demonstrate that the intercalated anions have a critical effect on the basal plane spacing, degree of crystallinity, and electrochemical properties of the end products. Especially, the intercalated anions have a marked impact on the activation process of the nickel electrodes. The Cl- intercalated α-Ni(OH)2 sample exhibits better high-rate discharge ability and cycle stability than samples with other interlayer anions. This is attributed to the higher crystallinity, better exchange ability and smaller anion size of Cl-. The anion exchange ability and the size of anions also play an important role in the proton diffusion rate, which directly affects the electrochemical properties of α-Ni(OH)2. The relationships between the specific capacity and basal spacing are also discussed in details for the five samples.

  6. Solvent Extraction of Calcium into Nitrobenzene by Using an Anionic Ligand Based on Cobalt Bis(Dicarbollide) Anion with Covalently Bonded CMPO Function.

    Science.gov (United States)

    Makrlík, Emanuel; Selucký, Pavel; Vaňura, Petr

    2012-06-01

    From extraction experiments and γ-activity measurements, the exchange extraction constantcorresponding to the general equilibrium Ca2+(aq) + 2HL(nb) CaL2(nb) + 2H+(aq) taking place in the two-phase water-nitrobenzene (L- = anionic ligand based on cobalt bis(dicarbollide) anion with covalently bonded CMPO function; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log Kex (Ca2+, 2HL) = 0.0 ± 0.1. Further, the stability constant of the electroneutral complex species CaL2 in water-saturated nitrobenzene was calculated for a temperature of 25 °C : log βnb (CaL2) = 11.0 ± 0.2.

  7. Diffuse neutron scattering from anion-excess strontium chloride

    DEFF Research Database (Denmark)

    Goff, J.P.; Clausen, K.N.; Fåk, B.

    1992-01-01

    The defect structure and diffusional processes have been studied in the anion-excess fluorite (Sr, Y)Cl2.03 by diffuse neutron scattering techniques. Static cuboctahedral clusters found at ambient temperature break up at temperatures below 1050 K, where the anion disorder is highly dynamic...

  8. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    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...

  9. Regulation of organic anion transport in the liver

    NARCIS (Netherlands)

    Roelofsen, H; Jansen, PLM

    1997-01-01

    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

  10. Electron transfer from alpha-keggin anions to dioxygen

    Science.gov (United States)

    Yurii V. Geletii; Rajai H. Atalla; Craig L. Hill; Ira A. Weinstock

    2004-01-01

    Polyoxometalates (POMs), of which alpha-Keggin anions are representative, are a diverse and rapidly growing class of water-soluble cluster-anion structures with applications ranging from molecular catalysis to materials. [1] POMs are inexpensive, minimally or non-toxic, negatively charged clusters comprised of early transition-metals, usually in their do electronic...

  11. Modulation of FXYD interaction with Na,K-ATPase by anionic phospholipids and protein kinase phosphorylation

    DEFF Research Database (Denmark)

    Cornelius, Flemming; Mahmmoud, Yasser Ahmed

    2007-01-01

    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...

  12. Interaction of immunosuppressive drugs with human organic anion transporter (OAT) 1 and OAT3, and multidrug resistance-associated protein (MRP) 2 and MRP4

    NARCIS (Netherlands)

    El-Sheikh, A.A.K.; Greupink, R.; Wortelboer, H.M.; Heuvel, J.J.M.W. van den; Schreurs, M.; Koenderink, J.B.; Masereeuw, R.; Russel, F.G.M.

    2013-01-01

    Renal proximal tubule transporters can play a key role in excretion, pharmacokinetic interactions, and toxicity of immunosuppressant drugs. Basolateral organic anion transporters (OATs) and apical multidrug resistance-associated proteins (MRPs) contribute to the active tubular uptake and urinary eff

  13. ARE MODELS OF ANION HYDRATION OVERBOUND ? THE SOLVATION OF THE ELECTRON AND CHLORIDE ANION COMPARED

    OpenAIRE

    Sprik, M.

    1991-01-01

    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. Removal of anionic reactive dyes from water using anion exchange membranes as adsorbers.

    Science.gov (United States)

    Liu, Chia-Hung; Wu, Jeng-Shiou; Chiu, Hsin-Chieh; Suen, Shing-Yi; Chu, Khim Hoong

    2007-04-01

    Two commercial anion exchange membranes, strong basic (SB6407) and weak basic (DE81), were evaluated for the removal of anionic reactive dyes, Cibacron blue 3GA (three sulfonic acid groups per dye molecule) and Cibacron red 3BA (four sulfonic acid groups per dye molecule), from water in this study. The adsorption isotherm results show that the Langmuir maximum adsorption capacities of Cibacron blue 3GA (31.5mg/cm(3) for SB6407 and 25.5mg/cm(3) for DE81) were greater than those of Cibacron red 3BA (24.5mg/cm(3) for SB6407 and 18.5mg/cm(3) for DE81). For each reactive dye, the capacity for SB6407 was higher than DE81 based on the same membrane volume. However, consideration of the number of ion exchange sites interacting with a dye molecule indicates that the DE81 results are close to the theoretical values while the SB6407 membrane had some unused binding sites. In addition, Cibacron red 3BA demonstrated faster and stronger binding with both anion exchange membranes than Cibacron blue 3GA. Both dyes could bind with strong basic SB6407 more quickly and stronger. In the batch desorption process, different desorption solutions were tested and the mixtures of salt, acid, or base in methanol solution (e.g. 1N KSCN in 60% methanol or 1N HCl in 60% methanol) achieved better performance. Finally, in the flow process with one piece of anion exchange membrane (initial dye concentration of 0.05g/L), SB6407 was found superior to DE81 in dye recovery and both membranes retained their original uptake capacities over three cycles of adsorption, washing, and desorption.

  15. Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles.

    Science.gov (United States)

    Pan, Bingcai; Xu, Jingsheng; Wu, Bing; Li, Zhigang; Liu, Xitong

    2013-08-20

    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.

  16. Review on anionic redox for high-capacity lithium- and sodium-ion batteries

    Science.gov (United States)

    Zhao, Chenglong; Wang, Qidi; Lu, Yaxiang; Hu, Yong-Sheng; Li, Baohua; Chen, Liquan

    2017-05-01

    Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A2MO3-family layered compounds (A  =  Li, Na; M  =  Mn4+, Ru4+, etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible.

  17. 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

    2003-01-01

    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.

  18. Nucleophilic reactivities of the anions of nucleobases and their subunits.

    Science.gov (United States)

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

    2012-01-02

    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.

  19. 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: duxiacao@ujn.edu.cn [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: mse_guanrf@ujn.edu.cn [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)

    2015-07-01

    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.

  20. Anionic clusters in dusty hydrocarbon and silane plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Hollenstein, C.; Schwarzenbach, W.; Howling, A.A.; Courteille, C.; Dorier, J.L.; Sansonnens, L. [Ecole Polytechnique Federale, Lausanne (Switzerland). Centre de Recherche en Physique des Plasma (CRPP)

    1995-10-01

    Measurements of anions and cations are reported for hydrocarbon and silane rf capacitive glow discharges. Series of anions were observed by quadrupole mass spectrometry using power-modulated plasmas and their structures are interpreted from the form of the mass spectra. Various experiments in silane plasmas show that anion confinement results in particles and conversely, anion de-trapping can inhibit particle formation. In contrast, the polymerized neutral flux magnitudes, mass spectra and dynamics are independent of the powder formation. Powder is known to form readily in deposition plasmas containing electronegative free radicals, and the general role of anions in particle formation is discussed in the light of these experiments. (author) 6 figs., 21 refs.

  1. Pyrrolidine dithiocarbamate inhibits superoxide anion-induced pain and inflammation in the paw skin and spinal cord by targeting NF-κB and oxidative stress.

    Science.gov (United States)

    Pinho-Ribeiro, Felipe A; Fattori, Victor; Zarpelon, Ana C; Borghi, Sergio M; Staurengo-Ferrari, Larissa; Carvalho, Thacyana T; Alves-Filho, Jose C; Cunha, Fernando Q; Cunha, Thiago M; Casagrande, Rubia; Verri, Waldiceu A

    2016-06-01

    We evaluated the effect of pyrrolidine dithiocarbamate (PDTC) in superoxide anion-induced inflammatory pain. Male Swiss mice were treated with PDTC and stimulated with an intraplantar or intraperitoneal injection of potassium superoxide, a superoxide anion donor. Subcutaneous PDTC treatment attenuated mechanical hyperalgesia, thermal hyperalgesia, paw oedema and leukocyte recruitment (neutrophils and macrophages). Intraplantar injection of superoxide anion activated NF-κB and increased cytokine production (IL-1β, TNF-α and IL-10) and oxidative stress (nitrite and lipid peroxidation levels) at the primary inflammatory foci and in the spinal cord (L4-L6). PDTC treatment inhibited superoxide anion-induced NF-κB activation, cytokine production and oxidative stress in the paw and spinal cord. Furthermore, intrathecal administration of PDTC successfully inhibited superoxide anion-induced mechanical hyperalgesia, thermal hyperalgesia and inflammatory response in peripheral foci (paw). These results suggest that peripheral stimulus with superoxide anion activates the local and spinal cord oxidative- and NF-κB-dependent inflammatory nociceptive mechanisms. PDTC targets these events, therefore, inhibiting superoxide anion-induced inflammatory pain in mice.

  2. Role of phosphate and other proton-donating anions in respiration-coupled transport of Ca2+ by mitochondria.

    Science.gov (United States)

    Lehninger, A L

    1974-04-01

    Measurements of extra oxygen consumption, (45)Ca(2+) uptake, and the osmotic expansion of the matrix compartment show that not all permeant anions are capable of supporting and accompanying the energy-dependent transport of Ca(2+) from the medium into the matrix in respiring rat-liver mitochondria. Phosphate, arsenate, acetate, butyrate, beta-hydroxybutyrate, lactate, and bicarbonate + CO(2) supported Ca(2+) uptake, whereas the permeant anions, nitrate, thiocyanate, chlorate, and perchlorate, did not. The active anions share a common denominator, the potential ability to donate a proton to the mitochondrial matrix; the inactive anions lack this capacity. Phosphate and the other active permeant anions move into the matrix in response to the alkaline-inside electrochemical gradient of protons generated across the mitochondrial membrane by electron transport, thus forming a negative-inside anion gradient. It is postulated that the latter gradient is the immediate "pulling" force for the influx of Ca(2+) on the electrogenic Ca(2+) carrier in respiring mitochondria under intracellular conditions. Since mitochondria in the cell are normally exposed to an excess of phosphate (and the bicarbonate-CO(2) system), particularly in state 4, inward transport of these proton-yielding anions probably precedes and is necessary for inward transport of Ca(2+) and other cations under biological conditions. These observations indicate that a negative-inside gradient of phosphate generated by electron transport is a common step and provides the immediate motive power not only for (a) the inward transport of dicarboxylates and tricarboxylates and (b) the energy-dependent exchange of external ADP(3-) for internal ATP(4-) during oxidative phosphorylation, as has already been established, but also for (c) the inward transport of Ca(2+), K(+), and other cations.

  3. Study on the Anion Recognition Properties of Synthesized Receptors (Ⅲ): Convenient Synthesis and Anion Recognition Property of Bisthiosemicarbazone Derivative

    Institute of Scientific and Technical Information of China (English)

    ZHANG You-Ming; XU Wei-Xia; YAO Hong; WEI Tai-Bao

    2006-01-01

    A new series of bisthiosemicarbazone derivative receptors (1, 2 and 3) have been synthesized by simple steps in good yields. Their anion recognition properties were studied by UV-Vis and 1H NMR spectroscopy. The result showed that the receptors 1, 2 and 3 all had a better selectivity to F-, CH3COO- and H2PO4-, but no evident binding with Cl-, Br-, I-, NO3- and HSO4. Upon addition of the three anions to the receptors in DMSO, the solution acquired a color change from colorless to dark yellow that can be observed by the naked-eyes, thus the receptors can act as fluoride ion sensors even in the presence of other halide ions. The data showed that it was regular that the three receptors had different binding ability with the three anions. For the same anion, the association conformed through hydrogen bonding interactions between compound 1, 2 or 3 and anions.

  4. Rapid and high-capacity ultrasonic assisted adsorption of ternary toxic anionic dyes onto MOF-5-activated carbon: Artificial neural networks, partial least squares, desirability function and isotherm and kinetic study.

    Science.gov (United States)

    Askari, Hanieh; Ghaedi, Mehrorang; Dashtian, Kheibar; Azghandi, Mohammad Hossein Ahmadi

    2017-07-01

    The present paper focused on the ultrasonic assisted simultaneous removal of fast green (FG), eosin Y (EY) and quinine yellow (QY) from aqueous media following using MOF-5 as a metal organic framework and activated carbon hybrid (AC-MOF-5). The structure and morphology of AC-MOF-5 was identified by SEM, FTIR and XRD analysis. The interactive and main effects of variables such as pH, initial dyes concentration (mgL(-1)), adsorbent dosage (mg) and sonication time (min) on removal percentage were studied by central composite design (CCD), subsequent desirability function (DF) permit to achieved real variable experimental condition. Optimized values were found 7.06, 5.68, 7.59 and 5.04mgL(-1), 0.02g and 2.55min for pH, FG, EY and QY concentration, adsorbent dosage and sonication time, respectively. Under this conditions removal percentage were obtained 98.1%, 98.1% and 91.91% for FG, EY and QY, respectively. Two models, namely partial least squares (PLS) and multi-layer artificial neural network (ANN) model were used for building up to construct an empirical model to predict the dyes under study removal behavior. The obtained results show that ANN and PLS model is a powerful tool for prediction of under-study dyes adsorption by AC-MOF-5. The evaluation and estimation of equilibrium data from traditional isotherm models display that the Langmuir model indicated the best fit to the equilibrium data with maximum adsorption capacity of 21.230, 20.242 and 18.621mgg(-1), for FG, EY and QY, respectively, while the adsorption rate efficiently follows the pseudo-second-order model. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

  6. Selection and evaluation of adsorbents for the removal of anionic surfactants from laundry rinsing water.

    Science.gov (United States)

    Schouten, Natasja; van der Ham, Louis G J; Euverink, Gert-Jan W; de Haan, André B

    2007-10-01

    Low-cost adsorbents were tested to remove anionic surfactants from laundry rinsing water to allow re-use of water. Adsorbents were selected corresponding to the different surfactant adsorption mechanisms. Equilibrium adsorption studies of linear alkyl benzene sulfonate (LAS) show that ionic interaction results in a high maximum adsorption capacity on positively charged adsorbents of 0.6-1.7 gLAS/g. Non-ionic interactions, such as hydrophobic interactions of LAS with non-ionic resins or activated carbons, result in a lower adsorption capacity of 0.02-0.6 gLAS/g. Negatively charged materials, such as cation exchange resins or bentonite clay, have negligible adsorption capacities for LAS. Similar results are obtained for alpha olefin sulfonate (AOS). Cost comparison of different adsorbents shows that an inorganic anion exchange material (layered double hydroxide) and activated carbons are the most cost-effective materials in terms of the amount of surfactant adsorbed per dollar worth of adsorbent.

  7. Designing New Electrolytes for Lithium Ion Batteries Using Superhalogen Anions

    CERN Document Server

    Srivastava, Ambrish Kumar

    2016-01-01

    The electrolytes used in Lithium Ion Batteries (LIBs) such as LiBF4, LiPF6 etc. are Li-salts of some complex anions, BF4-, PF6- etc. The investigation shows that the vertical detachment energy (VDE) of these anions exceeds to that of halogen, and therefore they behave as superhalogen anions. Consequently, it might be possible to design new electrolytic salts using other superhalogen anions. We have explored this possibility using Li-salts of various superhalogen anions such as BO2-, AlH4-, TiH5- and VH6- as well as hyperhalogen anions, BH4-y(BH4)y-(y = 1 to 4). Our density functional calculations show that Li-salts of these complex anions possess similar characteristics as those of electrolytic salts in LIBs. Note that they all are halogen free and hence, non-toxic and safer than LiBF4, LiPF6 etc. In particular, LiB4H13 and LiB5H16 are two potential candidates for electrolytic salt due to their smaller Li-dissociation energy ({\\Delta}E) than those of LiBF4, LiPF6 etc. We have also noticed that {\\Delta}E of Li...

  8. SLAH3-type anion channel expressed in poplar secretory epithelia operates in calcium kinase CPK-autonomous manner.

    Science.gov (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

    2016-05-01

    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.

  9. Characterization and anions inhibition studies of an α-carbonic anhydrase from the teleost fish Dicentrarchus labrax.

    Science.gov (United States)

    Ekinci, Deniz; Ceyhun, Saltuk Buğrahan; Sentürk, Murat; Erdem, Deryanur; Küfrevioğlu, Omer İrfan; Supuran, Claudiu T

    2011-01-15

    Carbonic anhydrase (CA; EC 4.2.1.1) 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.

  10. Pyruvate anions neutralize peritoneal dialysate cytotoxicity.

    Science.gov (United States)

    Mahiout, A; Brunkhorst, R

    1995-01-01

    A new peritoneal dialysate containing pyruvate anions was developed in order to avoid cytotoxic effect of conventional lactate-based dialysate. The dialysate has a final pH of 5.4 to 5.6 and is composed of 1.36-3.86% glucose-monohydrate; 132 mmol/l sodium; 1.75 mmol/l calcium; 0.75 mmol/l magnesium; 102 mmol/l chloride and 35 mmol/l pyruvate. For cytotoxicity testing peritoneal macrophages, and mesothelial cells (MC) were exposed to conventional lactate dialysate, and pyruvate dialysate. We investigated the O2- generation and cytokine synthesis after endotoxin stimulation in peritoneal macrophages and the proliferation of mesothelial cells of cultured human MC. After exposure to lactate dialysate O2- generation and cytokine synthesis in peritoneal macrophages and proliferation of mesothelial cells were inhibited when compared to solution containing pyruvate and the control solution. After preincubation with 3.86% glucose containing solutions, all negative effects became even more pronounced in the lactate group whereas after pre-exposure to pyruvate containing solution the toxic effects were absent. These results suggest that the acute toxic effects of commercially available peritoneal dialysates can be avoided by the use of sodium pyruvate instead of sodium lactate.

  11. Helix-Sense-Selective Polymerization of N,N-Diphenyl(Meth)acrylamide by Anionic Catalysts

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diphenyl methacrylamide(DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too.It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

  12. Simultaneous determination of inorganic and organic anions by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yang Soon; Joe, Ki Soo; Han, Sun Ho; Park, Soon Dal; Choi, Kwang Soon

    1999-06-01

    Four methods were investigated for the simultaneous determination of several inorganic and organic anions in aqueous solution by ion chromatography. The first is two columns coupled system. The second is the gradient elution system with an anion exchange column. The third is the system with a mixed-mode stationary phase. The fourth is the system with an anion exchange column and the eluant of low conductivity without ion suppressor. The advantages and disadvantages of individual systems were discussed. The suitable methods were proposed for the application to the samples of the nuclear power industry and the environment. (author)

  13. A Quick Reference on High Anion Gap Metabolic Acidosis.

    Science.gov (United States)

    Funes, Silvia; de Morais, Helio Autran

    2017-03-01

    High anion gap (AG) metabolic acidoses can be identified by a decrease in pH, decrease in HCO3(-) or base excess, and an increased AG. The AG represents the difference between unmeasured cations and unmeasured anions; it increases secondary to the accumulation of anions other than bicarbonate and chloride. The most common causes of high AG acidosis are renal failure, diabetic ketoacidosis, and lactic acidosis. Severe increases in concentration of phosphorus can cause hyperphosphatemic acidosis. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Determination of Anions in Landifll Leachate Water by Activated Carbon Adsorption-Solid Phase Extraction-Ion Chromatography%活性炭吸附-固相萃取-离子色谱法快速测定垃圾渗滤液中的阴离子

    Institute of Scientific and Technical Information of China (English)

    黄朝颜; 孟洁; 吴艳芬

    2014-01-01

    建立了活性炭吸附–固相萃取–离子色谱法快速测定垃圾渗滤液中F–,Cl-,NO3–,PO43–,SO42–5种阴离子的方法。100 mL样品先经10 g预先洗涤烘干的活性炭吸附,然后通过吸附特性不同的ENVI–18(C18小柱)、PSA固相萃取小柱。利用C18小柱对水中有机污染物的萃取及键合相有双齿配体的PSA小柱对金属离子的螯合,除去渗滤液中大量的有机物和重金属,再经离子色谱检测。5种离子的质量浓度在1~10 mg/L范围内与其色谱峰面积呈良好的线性关系,线性相关系数大于0.999,F–,Cl-,NO3–,PO43–,SO42–的检出限分别为0.02,0.02,0.08,0.15,0.09 mg/L。5种离子的平均加标回收率为96%~105%,测定结果的相对标准偏差小于6%(n=6)。该方法简便快捷,测定结果准确可靠,可用于垃圾渗滤液中F–,Cl-,NO3–,PO43–,SO42–5种阴离子的测定。%A method based on activated carbon adsorption–solid phase extraction–ion chromatography for the determination of anions (F–,Cl–,NO3–,PO43–,SO42–) in landfill leachate water was developed. 100 mL landfill leachate water was enriched by 10 g activated carbon, two different kinds of solid phase extraction column: ENVI–18 and PSA. After the pretreatment,much of the organic matter and high heavy metal content have been removed. Then the sample was analyzed by ion chromatography. The concentration offive aions had good linear relationship with the chromatography peak area in the range of 1–10 mg/L. The recoveries were 96%–105%,with coefficients of variation below 5%(n=6). The method is simple,reliable and suitable for determining anions in landfill leachate water.

  15. Biological activity of palladium(II) and platinum(II) complexes of the acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate and the X-ray crystal structure of the [Pd(asme)2] (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) complex.

    Science.gov (United States)

    Akbar Ali, Mohammad; Mirza, Aminul Huq; Butcher, Raymond J; Tarafder, M T H; Keat, Tan Boon; Ali, A Manaf

    2002-11-25

    Palladium(II) and platinum(II) complexes of general empirical formula, [M(NS)(2)] (NS=uninegatively charged acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate; M=Pt(II) and Pd(II)) have been prepared and characterized by a variety of physicochemical techniques. Based on conductance, IR and electronic spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(asme)(2)] complex (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted cis-square planar structure with the ligands coordinated to the palladium(II) ions as uninegatively charged bidentate NS chelating agents via the azomethine nitrogen and the mercaptide sulfur atoms. The distortion from a regular square-planar geometry is attributed to the restricted bite angles of the ligands. Antimicrobial tests indicate that the Schiff bases exhibit strong activities against the pathogenic bacteria, Bacillus subtilis (mutant defective DNA repair), methicillin-resistant Staphylococcus aureus, B. subtilis (wild type) and Pseudomonas aeruginosa and the fungi, Candida albicans (CA), Candida lypotica (2075), Saccharomyces cerevisiae (20341) and Aspergillus ochraceous (398)-the activities exhibited by these compounds being greater than that of the standard antibacterial and antifungal drugs, streptomycin and nystatin, respectively. The palladium(II) and platinum(II) complexes are inactive against most of these organisms but, the microbe, Pseudomonas aeruginosa shows strong sensitivity to the platinum(II) complexes. Screening of the compounds for their cytotoxicities against T-lymphoblastic leukemia cancer cells has shown that the acetone Schiff base of S-methyldithiocarbazate (Hasme) exhibits a very weak activity, whereas the S-benzyl derivative (Hasbz) is inactive. However, the palladium(II) complexes exhibit strong cytotoxicities against this cancer; their

  16. Gas-phase infrared multiple photon dissociation spectroscopy of isolated SF6- and SF5- anions.

    Science.gov (United States)

    Steill, Jeffrey D; Oomens, Jos; Eyler, John R; Compton, Robert N

    2008-12-28

    Resonantly enhanced multiple photon dissociation of gas-phase SF(6) (-) and SF(5) (-) is studied using tunable infrared light from the FELIX free electron laser. The photodissociation spectrum of the sulfur hexafluoride anion, producing SF(5) (-), is recorded over the spectral range of 250-1650 cm(-1). The infrared multiple photon dissociation cross section exhibits a strong, broad resonance enhancement at 675 cm(-1) in agreement with the calculated value of nu(3), one of the two IR-active fundamental vibrational modes predicted for the O(h)-symmetry ion. Much weaker absorption features are observed in the spectral region of 300-450 cm(-1) as well as at 580 cm(-1) that are not easily assigned to the other IR-active fundamental of SF(6) (-) since these resonances are observed at a much higher energy than the calculated values for the IR-active nu(4) mode. The potential role of binary combination bands is considered. Photodissociation from the sulfur pentafluoride anion produced only F(-), but photodetachment was also observed through SF(6) associative electron capture. The IR multiple photon dissociation spectrum of SF(5) (-) shows multiple resonances within the region of 400-900 cm(-1) and agreement with calculations is clear, including the observation of three fundamental frequencies: nu(1) at 780 cm(-1), nu(7) at 595 cm(-1), and nu(8) at 450 cm(-1). Comparisons of the measured frequencies with ab initio and density functional theory calculations confirm an SF(5) (-) anion of C(4v) symmetry. Similar comparisons for SF(6) (-) are not inconsistent with an anion of O(h) symmetry.

  17. Activation of the Estrogen Receptor-Alpha by Novel Anions

    Science.gov (United States)

    2011-04-01

    National
Institutes
of
Health
R21ES015160‐02
awarded
to
 MBM 
DOD
 BCRP
Predoctoral
Traineeship
Award
BC073599
awarded
to
GBS
 
 
 
 
 
 
 
 11
 Supporting

  18. Effect of anionic macromolecules on intestinal permeability of furosemide.

    Science.gov (United States)

    Valizadeh, Hadi; Fahimfar, Hadi; Ghanbarzadeh, Saeed; Islambulchilar, Ziba; Zakeri-Milani, Parvin

    2015-02-01

    Furosemide is an anionic molecule and has very low absorption in gastro intestinal tract. The aim of this study was to investigate the effect of anionic macromolecules on the intestinal permeability of Furosemide. The intestinal permeability of Furosemide was determined using single-pass intestinal perfusion technique in rats. Briefly a jejunal segment of ∼10 cm was isolated and cannulated in both ends for inlet and outlet solution. The perfusate was collected every 10 min and samples were analyzed using the RP-HPLC method. Test samples containing furosemide and two anionic macromolecules, sodium carboxy methyl cellulose and sodium alginate, at different concentrations were used. The obtained data showed that existence of Sodium carboxy methyl cellulose significantly increased the Peff values in all three investigated concentrations (p macromolecules at specific concentrations could alter the permeability of anionic drugs across the biological membranes. Donnan phenomenon and chelating property of macromolecules could be attributed to the observed effect.

  19. Two benzoyl coumarin amide fluorescence chemosensors for cyanide anions

    Science.gov (United States)

    Wang, Zian; Wu, Qianqian; Li, Jiale; Qiu, Shuang; Cao, Duxia; Xu, Yongxiao; Liu, Zhiqiang; Yu, Xueying; Sun, Yatong

    2017-08-01

    Two new benzoyl coumarin amide derivatives with ortho hydroxyl benzoyl as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions in acetonitrile have also been examined. The influence of electron donating diethylamino group in coumarin ring and hydroxyl in benzoyl group on recognition properties was explored. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectral change and high sensitivity. The import of diethylamine group increases smartly the absorption ability and fluorescence intensity of the compound, which allows the recognition for cyanide anions can be observed by naked eyes. The in situ hydrogen nuclear magnetic resonance spectra combining photophysical properties change and job's plot data confirm that Michael addition between the chemosensors and cyanide anions occurs. Molecular conjugation is interrupted, which leads to fluorescence quenching. At the same time, there is a certain extent hydrogen bond reaction between cyanide and hydroxyl group in the compounds, which is beneficial to the recognition.

  20. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    Energy Technology Data Exchange (ETDEWEB)

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju [Dept. of Chemistry, Sunchon National University, Suncheon (Korea, Republic of)

    2016-10-15

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN{sup -} selective, colorimetric sensor either without or with UV irradiation.

  1. Two independent anion transport systems in rabbit mandibular salivary glands

    DEFF Research Database (Denmark)

    Novak, I; Young, J A

    1986-01-01

    Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion in the foll......Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion...... stimulated secretion by about 30%, but when infused in addition to furosemide (0.1 mmol/l), it inhibited by about 20%. Amiloride (1.0 mmol/l) caused no inhibition. The results suggest that there are at least three distinct carriers in the rabbit mandibular gland. One is a furosemide-sensitive Na-coupled Cl...

  2. 北方某典型大气污染城市冬季降水的阴离子成分及对发光菌活性的影响%Analysis on Anionic Composition of Atmospheric Water of a Typical Air Pollution City in Northern China in Winter and its Effect to the Activity of Luminescent Bacteria

    Institute of Scientific and Technical Information of China (English)

    张建江; 贾继民; 王君; 马永红; 田华; 邱尔臣; 宋远新

    2013-01-01

    Objective To analyze the anionic composition of atmospheric water of a typical air pollution city (M city) in northern China in winter and its impact on biological activity in vitro of luminescent bacteria. Methods Atmospheric water samples were collected in the winter heating period from 2011 to 2012. The water samples were detected and analyzed respectively by pH meter, conductivity meter, and ion chromatography. The impact of atmospheric water on biological activity of Photo-bacterium phosphoreum T3 variants in vitro was observed using intelligent biological toxicity testing instrument. Results Among atmospheric water samples collected in 11 winters, pH changing ranges were between 6.51 and 8.38, with the average value of 7.26. The changing ranges of conductivity were between 192.2 and 1,343.0 μS/cm, with the average value of 803.0 μS/cm. The average values of SO42- , Cl- , NO3- , and F- were 69.20 mg/L, 16.20 mg/L, 2.28 mg/L, andl.24mg/L, respectively. The anion concentrations in order of size were SO42- > Cl- > NO3- > F- . The luminescent loss rates resulted from atmospheric water in winter among luminescent bacteria were between 4.31% and 16.09 % , with the average rate of 10.12%. Conclusions Atmospheric water of M city in 11 winters basically maintains neutral and slightly alkaline character. The main anion is SO42- , and fuel combustion of winter heating may be an important source. Atmospheric water in winter produces a slight inhibition to the biological activity of luminescent bacteria.%目的 分析北方某典型大气污染城市(M市)冬季降水的阴离子成分及对发光菌生物活性的影响.方法于2011-2012年冬季采暖期采集冬季降水,分别采用酸度计、电导率仪、离子色谱仪对样品进行指标检测.并用智能生物毒性测试仪观察降水对明亮发光杆菌(Photobacterium phosphoreum)T3变种生物活性的影响.结果 采集到的11次冬季降水的pH变化范围为6.51~8.38,平均值为7.26,

  3. Core-modified octaphyrins: Syntheses and anion-binding properties

    Indian Academy of Sciences (India)

    Rajneesh Misra; Venkataramanarao G Anand; Harapriya Rath; Tavarekere K Chandrashekar

    2005-03-01

    In this paper, a brief review of the syntheses, characterization and anion-binding properties of core-modified octaphyrins is presented. It has been shown that the core-modified octaphyrins exhibit aromaticity both in solution and in solid state, confirming the validity of the (4 + 2) Huckel rule for larger -electron systems. Solid-state binding characteristics of TFA anions of two core-modified octaphyrins are also described.

  4. Intestinal transporters for endogenic and pharmaceutical organic anions

    DEFF Research Database (Denmark)

    Grandvuinet, Anne Sophie; Vestergaard, Henrik Tang; Rapin, Nicolas

    2012-01-01

    This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations.......This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations....

  5. Local impermeant anions establish the neuronal chloride concentration

    DEFF Research Database (Denmark)

    Glykys, J; Dzhala, V; Egawa, K

    2014-01-01

    , but accumulating evidence suggests factors other than the bulk concentrations of transported ions determine [Cl(-)](i). Measurement of [Cl(-)](i) in murine brain slice preparations expressing the transgenic fluorophore Clomeleon demonstrated that cytoplasmic impermeant anions ([A](i)) and polyanionic extracellular...... anions determine the homeostatic set point for [Cl(-)], and hence, neuronal volume and the polarity of local GABA(A)R signaling....

  6. Photoelectron spectroscopic study of carbon aluminum hydride cluster anions

    Science.gov (United States)

    Zhang, Xinxing; Wang, Haopeng; Ganteför, Gerd; Eichhorn, Bryan W.; Kiran, Boggavarapu; Bowen, Kit H.

    2016-10-01

    Numerous previously unknown carbon aluminum hydride cluster anions were generated in the gas phase, identified by time-of-flight mass spectrometry and characterized by anion photoelectron spectroscopy, revealing their electronic structure. Density functional theory calculations on the CAl5-9H- and CAl5-7H2- found that several of them possess unusually high carbon atom coordination numbers. These cluster compositions have potential as the basis for new energetic materials.

  7. Synthesis of Pyridoacridines through Anionic Cascade Ring Closure

    DEFF Research Database (Denmark)

    Petersen, I.N.; Kristensen, Jesper Langgaard

    2014-01-01

    A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin. © Georg Thieme Verlag.......A new synthesis of 13-deazaascididemin (AK-37) based on a recently developed anionic cascade ring closure is presented. Although the isolated yields are modest, the approach provides ready access to new substituted derivatives of 13-deazaascididemin. © Georg Thieme Verlag....

  8. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  9. Migration of Cations and Anions in Amorphous Polymer Electrolytes

    Institute of Scientific and Technical Information of China (English)

    N.A.Stolwijk; S.H.Obeidi; M.Wiencierz

    2007-01-01

    1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...

  10. Thin Robust Anion Exchange Membranes for Fuel Cell Applications

    Science.gov (United States)

    2014-01-01

    provide inexpensive compact power from a wider variety of fuels than is possible with a proton exchange membrane (PEM) fuel cell, has continued to...in aqueous solution. Interestingly though, while the proton transfer events in the anion exchange membrane are more frequent as would be ECS...release; distribution is unlimited. (Invited) Thin Robust Anion Exchange Membranes for Fuel Cell Applications The views, opinions and/or findings

  11. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  12. Site-Specific Description of the Enhanced Recognition Between Electrogenerated Nitrobenzene Anions and Dihomooxacalix[4]arene Bidentate Ureas.

    Science.gov (United States)

    Martínez-González, Eduardo; Armendáriz-Vidales, Georgina; Ascenso, José R; Marcos, Paula M; Frontana, Carlos

    2015-05-01

    Electron transfer controlled hydrogen bonding was studied for a series of nitrobenzene derivative radical anions, working as large guest anions, and substituted ureas, including dihomooxacalix[4]arene bidentate urea derivatives, in order to estimate binding constants (Kb) for the hydrogen-bonding process. Results showed enhanced Kb values for the interaction with phenyl-substituted bidentate urea, which is significantly larger than for the remaining compounds, e.g., in the case of 4-methoxynitrobenzene a 28-fold larger Kb value was obtained for the urea bearing a phenyl (Kb ∼ 6888) vs tert-butyl (Kb ∼ 247) moieties. The respective nucleophilic and electrophilic characters of the participant anion radical and urea hosts were parametrized with global and local electrodonating (ω(-)) and electroaccepting (ω(+)) powers, derived from DFT calculations. ω(-) data were useful for describing trends in structure–activity relationships when comparing nitrobenzene radical anions. However, ω(+) for the host urea structures lead to unreliable explanations of the experimental data. For the latter case, local descriptors ωk(+)(r) were estimated for the atoms within the urea region in the hosts [∑kωk(+)(r)]. By compiling all the theoretical and experimental data, a Kb-predictive contour plot was built considering ω(-) for the studied anion radicals and ∑kωk(+)(r) which affords good estimations.

  13. Grain boundary mobility in anion doped MgO

    Science.gov (United States)

    Kapadia, C. M.; Leipold, M. H.

    1973-01-01

    Certain anions OH(-), F(-) and Gl(-) are shown to enhance grain growth in MgO. The magnitude of their effect decreases in the order in which the anions are listed and depends on their location (solid-solution, second phase) in the MgO lattice. As most anions exhibit relatively high vapor pressures at sintering temperatures, they retard densification and invariably promote residual porosity. The role of anions on grain growth rates was studied in relation to their effect on pore mobility and pore removal; the atomic process controlling the actual rates was determined from observed kinetics in conjunction with the microstructural features. With respect to controlling mechanisms, the effects of all anions are not the same. OH(-) and F(-) control behavior through creation of a defect structure and a grain boundary liquid phase while Cl(-) promotes matter transport within pores by evaporation-condensation. Studies on an additional anion, S to the minus 2nd power gave results which were no different from undoped MgO, possibly because of evaporative losses during hot pressing. Hence, the effect of sulphur is negligible or undetermined.

  14. Counterion-mediated pattern formation in membranes containing anionic lipids.

    Science.gov (United States)

    Slochower, David R; Wang, Yu-Hsiu; Tourdot, Richard W; Radhakrishnan, Ravi; Janmey, Paul A

    2014-06-01

    Most lipid components of cell membranes are either neutral, like cholesterol, or zwitterionic, like phosphatidylcholine and sphingomyelin. Very few lipids, such as sphingosine, are cationic at physiological pH. These generally interact only transiently with the lipid bilayer, and their synthetic analogs are often designed to destabilize the membrane for drug or DNA delivery. However, anionic lipids are common in both eukaryotic and prokaryotic cell membranes. The net charge per anionic phospholipid ranges from -1 for the most abundant anionic lipids such as phosphatidylserine, to near -7 for phosphatidylinositol 3,4,5 trisphosphate, although the effective charge depends on many environmental factors. Anionic phospholipids and other negatively charged lipids such as lipopolysaccharides are not randomly distributed in the lipid bilayer, but are highly restricted to specific leaflets of the bilayer and to regions near transmembrane proteins or other organized structures within the plane of the membrane. This review highlights some recent evidence that counterions, in the form of monovalent or divalent metal ions, polyamines, or cationic protein domains, have a large influence on the lateral distribution of anionic lipids within the membrane, and that lateral demixing of anionic lipids has effects on membrane curvature and protein function that are important for biological control. Copyright © 2014. Published by Elsevier B.V.

  15. Astronomical identification of CN-, the smallest observed molecular anion

    CERN Document Server

    Agundez, M; Guelin, M; Kahane, C; Roueff, E; Klos, J; Aoiz, F J; Lique, F; Marcelino, N; Goicoechea, J R; Garcia, M Gonzalez; Gottlieb, C A; McCarthy, M C; Thaddeus, P

    2010-01-01

    We present the first astronomical detection of a diatomic negative ion, the cyanide anion CN-, as well as quantum mechanical calculations of the excitation of this anion through collisions with para-H2. CN- is identified through the observation of the J = 2-1 and J = 3-2 rotational transitions in the C-star envelope IRC +10216 with the IRAM 30-m telescope. The U-shaped line profiles indicate that CN-, like the large anion C6H-, is formed in the outer regions of the envelope. Chemical and excitation model calculations suggest that this species forms from the reaction of large carbon anions with N atoms, rather than from the radiative attachment of an electron to CN, as is the case for large molecular anions. The unexpectedly large abundance derived for CN-, 0.25 % relative to CN, makes likely its detection in other astronomical sources. A parallel search for the small anion C2H- remains so far unconclusive, despite the previous tentative identification of the J = 1-0 rotational transition. The abundance of C2H...

  16. Evidence for functional interaction of plasma membrane electron transport, voltage-dependent anion channel and volume-regulated anion channel in frog aorta

    Indian Academy of Sciences (India)

    Rashmi P Rao; J Prakasa Rao

    2010-12-01

    Frog aortic tissue exhibits plasma membrane electron transport (PMET) owing to its ability to reduce ferricyanide even in the presence of mitochondrial poisons, such as cyanide and azide. Exposure to hypotonic solution (108 mOsmol/kg H2O) enhanced the reduction of ferricyanide in excised aortic tissue of frog. Increment in ferricyanide reductase activity was also brought about by the presence of homocysteine (100 M dissolved in isotonic frog Ringer solution), a redox active compound and a potent modulator of PMET. Two plasma-membrane-bound channels, the volume regulated anion channel (VRAC) and the voltage-dependent anion channel (VDAC), are involved in the response to hypotonic stress. The presence of VRAC and VDAC antagonists–tamoxifen, glibenclamide, fluoxetine and verapamil, and 4,4′-diisothiocyanatostilbene-2,2′-disulphonic acid (DIDS), respectively–inhibited this enhanced activity brought about by either hypotonic stress or homocysteine. The blockers do not affect the ferricyanide reductase activity under isotonic conditions. Taken together, these findings indicate a functional interaction of the three plasma membrane proteins, namely, ferricyanide reductase (PMET), VDAC and VRAC.

  17. 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

    2011-12-31

    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.

  18. Equine digital veins are more sensitive to superoxide anions than digital arteries.

    Science.gov (United States)

    Lapo, Rock Allister; Gogny, Marc; Chatagnon, Gérard; Lalanne, Valérie; Harfoush, Khaled; Assane, Moussa; Desfontis, Jean-Claude; Mallem, Mohamed Yassine

    2014-10-05

    This work was designed to investigate (i) the effect of superoxide dismutase (SOD) inhibition on endothelial function and (ii) the free radical-induced endothelial dysfunction in equine digital veins (EDVs) and equine digital arteries (EDAs) isolated from healthy horses. EDV and EDA rings were suspended in a 5 ml organ bath containing Krebs solution. After a 60 min equilibration period, EDV and EDA rings were contracted with phenylephrine. Then, cumulative concentration-response curves (CCRCs) to acetylcholine were performed. In both EDVs and EDAs, acetylcholine (1 nM to 10 µM) produced concentration-dependent relaxation. We investigated the influence of SOD inhibition by diethyldithiocarbamate (DETC; 100 µM), a CuZnSOD inhibitor, on EDAs and EDVs relaxant responses to acetylcholine. Acetylcholine -mediated relaxation was impaired by DETC only in EDVs. SOD activity assayed by a xanthine-xanthine oxidase method was higher in EDAs compared with EDVs (Psuperoxide anions generating systems showed that in both EDVs and EDAs, the acetylcholine-mediated relaxation was significantly impaired by pyrogallol and homocysteine. This impairment was more pronounced in EDVs than in EDAs. Moreover, the pyrogallol-induced impairment of acetylcholine-mediated relaxation was potentiated by DETC to a greater extent in EDVs. We concluded that due to the lower activity of SOD, EDVs are more sensitive to superoxide anions than EDAs. So, any alteration of superoxide anions metabolism is likely to have a more important impact on venous rather than arterial relaxation.

  19. Cn-AMP2 from green coconut water is an anionic anticancer peptide.

    Science.gov (United States)

    Prabhu, Saurabh; Dennison, Sarah R; Mura, Manuela; Lea, Robert W; Snape, Timothy J; Harris, Frederick

    2014-12-01

    Globally, death due to cancers is likely to rise to over 20 million by 2030, which has created an urgent need for novel approaches to anticancer therapies such as the development of host defence peptides. Cn-AMP2 (TESYFVFSVGM), an anionic host defence peptide from green coconut water of the plant Cocos nucifera, showed anti-proliferative activity against the 1321N1 and U87MG human glioma cell lines with IC50 values of 1.25 and 1.85 mM, respectively. The membrane interactive form of the peptide was found to be an extended conformation, which primarily included β-type structures (levels > 45%) and random coil architecture (levels > 45%). On the basis of these and other data, it is suggested that the short anionic N-terminal sequence (TES) of Cn-AMP2 interacts with positively charged moieties in the cancer cell membrane. Concomitantly, the long hydrophobic C-terminal sequence (YFVFSVGM) of the peptide penetrates the membrane core region, thereby driving the translocation of Cn-AMP2 across the cancer cell membrane to attack intracellular targets and induce anti-proliferative mechanisms. This work is the first to demonstrate that anionic host defence peptides have activity against human glioblastoma, which potentially provides an untapped source of lead compounds for development as novel agents in the treatment of these and other cancers.

  20. Imidiazolium based ionic liquids: effects of different anions and alkyl chains lengths on the barley seedlings.

    Science.gov (United States)

    Cvjetko Bubalo, Marina; Hanousek, Karla; Radošević, Kristina; Gaurina Srček, Višnja; Jakovljević, Tamara; Radojčić Redovniković, Ivana

    2014-03-01

    We studied the effects of five imidiazolium based ionic liquids with different anions and length of alkyl chains linked to imidazolium ring on the early development of barley (Hordeum vulgare). The inhibitory effect depends on the ionic liquids concentration and chemical structure, whereby the most toxic one was [C10mim][Br], followed by [C7mim][Br], [C4mim][Br], [C4mim][CH3CO2] and [C4mim][BF4]. Both anion and cation structures affected the toxicity of ionic liquid indicating that selection of more biocompatible anions such as [CH3CO2] does not necessarily indicate lower toxicity. Alternation in the extent of oxidative stress and antioxidant enzymes activities were found in barley plants due to ionic liquid treatments. When seedlings were exposed to higher concentrations of ionic liquids, antioxidant system could not effectively remove reactive oxidative species, leading to lipid peroxidation and damage of the photosynthetic system. However, overall data indicated that the performance of barley seedling was improved when all measured enzymes involved in scavenging of reactive oxygen species (ROS) were increased with special emphasis on GPX activities. Since there are no studies about ionic liquid (IL) toxicity in plants, that simultaneously evaluates the antioxidative enzyme system in response to different ILs, this work is valuable for gaining knowledge about the protection mechanism of plants from oxidative stress caused by IL exposure.

  1. Synthetic ion transporters can induce apoptosis by facilitating chloride anion transport into cells.

    Science.gov (United States)

    Ko, Sung-Kyun; Kim, Sung Kuk; Share, Andrew; Lynch, Vincent M; Park, Jinhong; Namkung, Wan; Van Rossom, Wim; Busschaert, Nathalie; Gale, Philip A; Sessler, Jonathan L; Shin, Injae

    2014-10-01

    Anion transporters based on small molecules have received attention as therapeutic agents because of their potential to disrupt cellular ion homeostasis. However, a direct correlation between a change in cellular chloride anion concentration and cytotoxicity has not been established for synthetic ion carriers. Here we show that two pyridine diamide-strapped calix[4]pyrroles induce coupled chloride anion and sodium cation transport in both liposomal models and cells, and promote cell death by increasing intracellular chloride and sodium ion concentrations. Removing either ion from the extracellular media or blocking natural sodium channels with amiloride prevents this effect. Cell experiments show that the ion transporters induce the sodium chloride influx, which leads to an increased concentration of reactive oxygen species, release of cytochrome c from the mitochondria and apoptosis via caspase activation. However, they do not activate the caspase-independent apoptotic pathway associated with the apoptosis-inducing factor. Ion transporters, therefore, represent an attractive approach for regulating cellular processes that are normally controlled tightly by homeostasis.

  2. 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

    2006-05-01

    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.

  3. Nitro radical anion formation from nitrofuryl substituted 1,4-dihydropyridine derivatives in mixed and non-aqueous media.

    Science.gov (United States)

    Argüello, J; Núñez-Vergara, L J; Bollo, S; Squella, J A

    2006-09-01

    Three new nitrofuryl substituted 1,4-dihydropyridine derivatives were electrochemically tested in the scope of newly found compounds useful as chemotherapeutic alternative to the Chagas' disease. All the compounds were capable to produce nitro radical anions sufficiently stabilized in the time window of the cyclic voltammetric experiment. In order to quantify the stability of the nitro radical anion we have calculated the decay constant, k2. Furthermore, from the voltammetric results, some parameters of biological significance as E7(1) (indicative of in vivo nitro radical anion formation) and KO2 (thermodynamic indicator of oxygen redox cycling) have been calculated. From the comparison of E7(1), KO2 and k2 values between the studied nitrofuryl 1,4-DHP derivatives and well-known current drugs an auspicious activity for one of the studied compounds i.e. FDHP2, can be expected.

  4. Inactivation of Bacillus Subtilis by Atomic Oxygen Radical Anion

    Institute of Scientific and Technical Information of China (English)

    LI Longchun; WANG Lian; YU Zhou; LV Xuanzhong; LI Quanxin

    2007-01-01

    UAtomic oxygen radical anion (O- ) is one of the most active oxygen species, and has extremely high oxidation ability toward small-molecules of hydrocarbons. However, to our knowledge, little is known about the effects of O- on cells of micro-organisms. This work showed that O- could quickly react with the Bacillus subtilis cells and seriously damage the cell walls a s well as their other contents, leading to a fast and irreversible inactivation. SEM micrographs revealed that the cell structures were dramatically destroyed by their exposure to O-. The inactivation efficiencies of B. subtilis depend on the O-- intensity, the initial population of cells and the treatment temperature, but not on the pH in the range of our investigation. For a cell concentration of 106 cfu/ml, the number of survived cells dropped from 106 cfu/ml to 103 cfu/ml after about five-minute irradiation by an O- flux in an intensity of 233 nA/cm2 under a dry argon environment (30 ℃, 1 atm, exposed size: 1.8 cm2). The inactivation mechanism of micro-organisms induced by O- is also discussed.

  5. Photoinduced Dynamics of Neutral, Cationic, and Anionic Species

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup

    In contrast to ground state (thermal) chemistry where internal energy is statistically distributed among the molecular degrees of freedom, photo-activation of a reaction entails initial localization of the internal energy in a highly non-statistical manner. The result is often reaction rates fast...... impact on the evolution of the ensuing reaction. The diversity of the processes studied illustrates the versatility of the experimental method as a means to increase knowledge on the complex interplay between structural dynamics and (photo)-reactivity....... than those predicted by statistical models, but also a more critical dependence between molecular structure and (photo)-reactivity. This thesis presents a collection of studies of various types of photoinduced processes in neutral, anionic, or cationic molecular species as introduced below....... The investigations have primarily employed femtosecond time-resolved photoionization or photodetachment techniques. Intersystem crossing (ISC) in neutral organic species is conventionally assumed to be slow due to the spin-forbidden nature of the process; this assumption has been challenged during the past decade...

  6. Determination of trace inorganic anions in anionic surfactants by single-pump column-switching ion chromatography

    Institute of Scientific and Technical Information of China (English)

    Jia Jie Zhang; Hai Bao Zhu; Yan Zhu

    2012-01-01

    An ion chromatography method has been proposed for the determination of three common inorganic anions (chloride,nitrate and sulfate) in anionic surfactants using a single pump system.The new system consists of an ion exclusion column,a concentrator column,and an anion exchange column connected in series via two 6-ports valves in a Dionex ICS-2000 ion chromatograph.The valves were switched several times for removing surfactants,concentrating and separating the three anions.The chromatographic conditions were optimized.Detection limits (S/N =3) were in the range of 0.10-0.68 μg/L.The relative standard deviations (RSDs)of peak area were less than 4.6%.The recoveries were in the range of 84.1-112.6%.

  7. Enhanced anion electroadsorption into carbon molecular sieve electrodes in acidic media.

    Science.gov (United States)

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

    2005-11-08

    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.

  8. Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

    Science.gov (United States)

    2015-01-15

    capacities (IECs). Solution cast membranes were thermally cross- linked to form anion exchange membranes. Cross-linking was achieved by taking advantage...distribution is unlimited. Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers The views...Box 12211 Research Triangle Park, NC 27709-2211 Anion Exchnage Membrane, Polymer synthesis, Morphology, Anion Conductivity REPORT DOCUMENTATION PAGE

  9. Demonstration of organic anion transport in T lymphocytes. L-lactate and fluo-3 are target molecules.

    Science.gov (United States)

    Sommer, F; Bischof, S; Röllinghoff, M; Lohoff, M

    1994-10-15

    In this paper, we describe for the first time the existence of organic anion transport in T lymphocytes, exemplified by the transmembrane transport of the anions L-lactate and the Ca2+ indicator fluo-3. The transport of either anion was found to be inhibitable by probenecid, a common blocker of organic anion transport. Transport of L-lactate was observed in long-term cultured T cell lines, as well as in freshly ex vivo isolated T cells, and occurred via a saturable, pH-dependent, and stereospecific process. L-Lactate uptake was dependent on the activation state of the T cells, because activation of T cells by Con A strongly enhanced accumulation of L-lactate from the medium. Because L-lactate may be transported bidirectionally through the T cell membrane in vivo, different physiologic roles of L-lactate transport are discussed. L-Lactate uptake may serve as an alternative source of energy in an inflamed, glucose-deficient tissue or may represent a prerequisite for the earlier-published immunoregulatory function of this molecule on T cells. On the other hand, release of L-lactate emerging from glycolysis could be necessary to avoid acidification of the cell. The fact that the Ca2+ indicator fluo-3 is also transported through the cellular membranes of long-term cultured T cells via organic anion transport has important implications for the determination of Ca2+ influx into T cells. Even though the transport of both molecules, L-lactate and fluo-3, represents organic anion transport, evidence is presented that confirms that the respective transport systems are different.

  10. Tetravalent metal complexation by Keggin and lacunary phosphomolybdate anions.

    Science.gov (United States)

    Copping, Roy; Jonasson, Leif; Gaunt, Andrew J; Drennan, Dennis; Collison, David; Helliwell, Madeleine; Pirttijarvi, Ross J; Jones, Chris J; Huguet, Anne; Apperley, David C; Kaltsoyannis, Nikolas; May, Iain

    2008-07-07

    We report the synthesis, spectroscopic and structural characterization, and computational analysis of a series of phosphomolybdate complexes with tetravalent metal cations. The reaction between Ce (IV) and Th (IV) with phosphomolybdate at the optimum pH for the stabilization of the lacunary heteropolyoxometalate anion, [PMo 11O 39] (7-), results in the formation of compounds containing the anions [Ce(PMo 11O 39) 2] (10-) and [Th(PMo 11O 39) 2] (10-), respectively. Single crystal X-ray diffraction analysis was performed on salts of both species, Cs 10[Ce(PMo 11O 39) 2].20H 2O and (NH 4) 10[Th(PMo 11O 39) 2].22H 2O. In both anionic complexes the f-block metal cation is coordinated to the four unsaturated terminal lacunary site oxygens of each [PMo 11O 39] (7-) anion, yielding 8 coordinate sandwich complexes, analogous to previously prepared related complexes. Spectroscopic characterization points to the stability of these complexes in solution over a reasonably wide pH range. Density functional analysis suggests that the Ce-O bond strength in [Ce(PMo 11O 39) 2] (10-) is greater than the Th-O bond strength in [Th(PMo 11O 39) 2] (10-), with the dominant bonding interaction being ionic in both cases. In contrast, under similar reaction conditions, the dominant solid state Zr (IV) and Hf (IV) complexes formed contain the anions [Zr(PMo 12O 40)(PMo 11O 39)] (6-) and [Hf(PMo 12O 40)(PMo 11O 39)] (6-), respectively. In these complexes the central Group 4 d-block metal cations are coordinated to the four unsaturated terminal lacunary site oxygens of the [PMo 11O 39] (7-) ligand and to four bridging oxygens of a plenary Keggin anion, [PMo 12O 40] (3-). In addition, (NH 4) 5{Hf[PMo 12O 40][(NH 4)PMo 11O 39]}.23.5H 2O can be crystallized as a minor product. The structure of the anion, {Hf[PMo 12O 40][(NH 4)PMo 11O 39]} (5-), reveals coordination of the central Hf (IV) cation via four bridging oxygens on both the coordinated [PMo 11O 39] (7-) and [PMo 12O 40] (3-) anions

  11. Anion separation by selective crystallization of metal-organic frameworks.

    Science.gov (United States)

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

    2006-08-07

    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.

  12. Discovery of Interstellar Anions in Cepheus and Auriga

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.; Buckle, J. V.; Walsh, C.

    2011-01-01

    We report the detection of microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H in the star-forming region LI251 A (in Cepheus), and the pre-stellar core LI512 (in Auriga). The carbon chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for LI5l2. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

  13. RedOx-controlled sorption of iodine anions by hydrotalcite composites

    Energy Technology Data Exchange (ETDEWEB)

    Levitskaia, Tatiana G.; Chatterjee, Sayandev; Arey, Bruce W.; Campbell, Emily L.; Hong, Yongchun; Kovarik, Libor; Peterson, James M.; Pence, Natasha K.; Romero, Jesus; Shutthanandan, Vaithialingam; Schwenzer, Birgit; Varga, Tamas

    2016-01-01

    The radioactive contaminant iodine-129 (I-129) is one of the top risk drivers at radiological waste disposal and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. Currently there are very few options available to treat I-129 in the groundwater, which is partially related to its complex biogeochemical behavior in the subsurface and occurrence in the multiple chemical forms. We hypothesize that layered hydrotalcite materials containing redox active transition metal ions offer a potential solution, benefiting from the simultaneous adsorption of iodate (IO3-) and iodide (I-) anions, which exhibit different electronic and structural properties and therefore may require dissimilar hosts. To test this hypothesis, Cr3+- based materials were selected based on the rationale that Cr3+ readily reduces IO3- in solution. It was combined with either redox-active Co2+ or redox-inactive Ni2+ so that two model materials were prepared by hydrothermal synthesis including Co2+-Cr3+ and Ni2+-Cr3+(M-Cr). Obtained M-Cr materials comprised of Co2+-Cr3+ or Ni2+-Cr3+ layered hydrotalcite and small fractions of Co3O4 spinel or Ni(OH)2 theophrastite phases were structurally characterized before and after uptake of periodate (IO4-), IO3-, and I- anions. It was found that the IO3- uptake is driven by its chemical reduction to I2 and I-. Interestingly, in the Co2+-Cr3+ hydrotalcite, Co2+ and not Cr3+ serves as a reductant while in the Ni2+-Cr3+ hydrotalcite Cr3+ is responsible for the reduction of IO3-. A different uptake mechanism was identified for the IO4- anion. The Co2+-Cr3+ hydrotalcite phase efficiently uptakes IO4- by a diffusion-limited ion exchange mechanism and is not accompanied by the redox process, while Cr3+ in the Ni2+-Cr3+ hydrotalcite reduces IO4- to IO3-, I2 and I-. Iodide exhibited high affinity only to the Co-Cr material. The Co-Cr material performed remarkably well for the removal of IO3-, I- and total iodine from the groundwater

  14. Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions

    Directory of Open Access Journals (Sweden)

    Carlos J. Gómez-García

    2012-04-01

    Full Text Available Up to five different crystalline radical salts have been prepared with the organic donor BEDT-TTF and three different polynitrile anions. With the polynitrile dianion tcpd2− (=C[C(CN2]32−, two closely related radical salts: α'-(ET4tcpd·THF (1 (THF = tetrahydrofurane and α'-(ET4tcpd·H2O (2 have been prepared, depending on the solvent used in the synthesis. With the mono-anion tcnoetOH− (=[(NC2CC(OCH2CH2OHC(CN2]− two polymorphs with similar physical properties but different crystal packings have been synthesized: θ-(ET2(tcnoetOH (3 and β''-(ET2(tcnoetOH (4. Finally, with the mono-anion tcnoprOH− (=[(NC2CC(OCH2CH2CH2OHC(CN2]− we have prepared a metallic radical salt: β''-(ET2(tcnoprOH(CH2Cl2CH3Cl0.5 (5. Salts 1‑4 are semiconductors with high room temperature conductivities and activation energies in the range 0.1–0.5 eV, whereas salt 5 is metallic down to 0.4 K although it does not show any superconducting transition above this temperature.

  15. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

    Science.gov (United States)

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

    2015-11-03

    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.

  16. Involvement of anion channels in mediating elicitor-induced ATP efflux in Salvia miltiorrhiza hairy roots.

    Science.gov (United States)

    Wu, Shu-Jing; Siu, Ka-Chai; Wu, Jian-Yong

    2011-01-15

    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.

  17. Synthesis, Structure, and Reactivity of Anionic sp(2) -sp(3) Diboron Compounds: Readily Accessible Boryl Nucleophiles.

    Science.gov (United States)

    Pietsch, Sabrina; Neeve, Emily C; Apperley, David C; Bertermann, Rüdiger; Mo, Fanyang; Qiu, Di; Cheung, Man Sing; Dang, Li; Wang, Jianbo; Radius, Udo; Lin, Zhenyang; Kleeberg, Christian; Marder, Todd B

    2015-05-04

    Lewis base adducts of tetra-alkoxy diboron compounds, in particular bis(pinacolato)diboron (B2 pin2 ), have been proposed as the active source of nucleophilic boryl species in metal-free borylation reactions. We report the isolation and detailed structural characterization (by solid-state and solution NMR spectroscopy and X-ray crystallography) of a series of anionic adducts of B2 pin2 with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents. The B(sp(2) )-B(sp(3) ) adducts exhibit two distinct boron environments in the solid-state and solution NMR spectra, except for [(4-tBuC6 H4 O)B2 pin2 ](-) , which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles-namely, aryl halides and diazonium salts-demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.

  18. o-Tolidine: A new reagent for a simple nephelometric determination of anionic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    March, J.G. [Department of Analytical Chemistry, University of the Balearic Islands, 07122-Palma de Mallorca (Spain)]. E-mail: joan.march@uib.es; Gual, M. [Department of Analytical Chemistry, University of the Balearic Islands, 07122-Palma de Mallorca (Spain); Frontera, A.D. [Department of Analytical Chemistry, University of the Balearic Islands, 07122-Palma de Mallorca (Spain)

    2005-05-10

    Simple light scattering methods (batch, flow injection, sequential injection) for the determination of anionic active matter in detergents based on a novel reaction are reported. The methods are based on formation of a solid phase by association of anionic surfactants and protonated o-tolidine. Measurements were carried out with a conventional spectrofluorimeter at 400 nm, and dodecylbenzene sulfonic acid (DBS) was selected as the reference anionic surfactant. Influence of the main parameters affecting the characteristics of the methods was studied by the univariate method. The optimized methods provided linear ranges from 1.6 to 300 mg l{sup -1} DBS with a repeatability within the 1.2-2.6% range. Reaction time for the manual method is 45 s and sampling frequency for FIA and SIA were estimated as 68 and 20 h{sup -1}, respectively. The methods were applied to commercial samples and results successfully compared with a volumetric recommended method. The proposed methods are simple, fast and neither require sample preparation nor any organic solvent.

  19. Anion channels and the stimulation of anthocyanin accumulation by blue light in Arabidopsis seedlings

    Science.gov (United States)

    Noh, B.; Spalding, E. P.; Evans, M. H. (Principal Investigator)

    1998-01-01

    Activation of anion channels by blue light begins within seconds of irradiation in seedlings and is related to the ensuing growth inhibition. 5-Nitro-2-(3-phenylpropylamino)-benzoic acid (NPPB) is a potent, selective, and reversible blocker of these anion channels in Arabidopsis thaliana. Here we show that 20 microM NPPB blocked 72% of the blue-light-induced accumulation of anthocyanin pigments in seedlings. Feeding biosynthetic intermediates to wild-type and tt5 seedlings provided evidence that NPPB prevented blue light from up-regulating one or more steps between and including phenylalanine ammonia lyase and chalcone isomerase. NPPB was found to have no significant effect on the blue-light-induced increase in transcript levels of PAL1, CHS, CHI, or DFR, which are genes that encode anthocyanin-biosynthetic enzymes. Immunoblots revealed that NPPB also did not inhibit the accumulation of the chalcone synthase, chalcone isomerase, or flavanone-3-hydroxylase proteins. This is in contrast to the reduced anthocyanin accumulation displayed by a mutant lacking the HY4 blue-light receptor, as hy4 displayed reduced expression of the above enzymes. Taken together, the data indicate that blue light acting through HY4 leads to an increase in the amount of biosynthetic enzymes but blue light must also act through a separate, anion-channel-dependent system to create a fully functional biosynthetic pathway.

  20. First evidence of epithelial transport in tardigrades: a comparative investigation of organic anion transport.

    Science.gov (United States)

    Halberg, Kenneth Agerlin; Møbjerg, Nadja

    2012-02-01

    We investigated transport of the organic anion Chlorophenol Red (CPR) in the tardigrade Halobiotus crispae using a new method for quantifying non-fluorescent dyes. We compared the results acquired from the tardigrade with CPR transport data obtained from Malpighian tubules of the desert locust Schistocerca gregaria. CPR accumulated in the midgut lumen of H. crispae, indicating that organic anion transport takes place here. Our results show that CPR transport is inhibited by the mitochondrial un-coupler DNP (1 mmol l(-1); 81% reduction), the Na(+)/K(+)-ATPase inhibitor ouabain (10 mmol l(-1); 21% reduction) and the vacuolar H(+)-ATPase inhibitor bafilomycin (5 μmol l(-1); 21% reduction), and by the organic anions PAH (10 mmol l(-1); 44% reduction) and probenecid (10 mmol l(-1); 61% reduction, concentration-dependent inhibition). Transport by locust Malpighian tubules exhibits a similar pharmacological profile, albeit with markedly higher concentrations of CPR being reached in S. gregaria. Immunolocalization of the Na(+)/K(+)-ATPase α-subunit in S. gregaria revealed that this transporter is abundantly expressed and localized to the basal cell membranes. Immunolocalization data could not be obtained from H. crispae. Our results indicate that organic anion secretion by the tardigrade midgut is transporter mediated with likely candidates for the basolateral entry step being members of the Oat and/or Oatp transporter families. From our results, we cautiously suggest that apical H(+) and possibly basal Na(+)/K(+) pumps provide the driving force for the transport; the exact coupling between electrochemical gradients generated by the pumps and transport of ions, as well as the nature of the apical exit step, are unknown. This study is, to our knowledge, the first to show active epithelial transport in tardigrades.

  1. Poly-anion production in Penning and RFQ ion traps

    Energy Technology Data Exchange (ETDEWEB)

    Bandelow, Steffi; Martinez, Franklin; Marx, Gerrit; Schweikhard, Lutz [Institute for Physics, Ernst-Moritz-Arndt University, 17487 Greifswald (Germany)

    2014-07-01

    The poly-anion production is being investigated in Penning and linear radio-frequency quadrupole (RFQ) traps at the ClusterTrap setup. The range of anionic charge states produced with the electron-bath technique in a Penning trap is restricted by the upper mass limit of this trap. By installation of a cylindrical Penning trap with a 12-Tesla superconducting magnet, the mass and thus cluster-size range is enhanced by a factor of 20 compared to the previously used hyperbolic 5-Tesla Penning trap. For first experimental tests with the 12-Tesla cylindrical Penning trap, gold cluster mono-anions Au{sup n-1}, n=330-350, have been exposed to an electron bath. As a result, higher negative charge states up to hexa-anionic clusters have been observed for the first time. In a parallel effort, di- and tri-anionic gold clusters have been produced in an RFQ-trap. To this end, an electron beam is guided through the RFQ-trap, which is operated by 2- or 3-state digital driving voltages. In addition, both polyanion-production techniques have been combined by pre-charging clusters in the RFQ-trap, transferring the resulting dianions into the Penning trap and applying the electron-bath technique to produce higher charge states.

  2. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    Science.gov (United States)

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

    2015-11-19

    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.

  3. Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

    Science.gov (United States)

    West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

    2007-01-01

    We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

  4. Treatment of acute non-anion gap metabolic acidosis.

    Science.gov (United States)

    Kraut, Jeffrey A; Kurtz, Ira

    2015-02-01

    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.

  5. Deflocculation of Cellulosic Suspensions with Anionic High Molecular Weight Polyelectrolytes

    Directory of Open Access Journals (Sweden)

    Markus Heikki Juhani Korhonen

    2014-04-01

    Full Text Available Pulp fibers have a strong tendency to form flocs in water suspensions, which may cause their undesirable distribution in the paper sheets. This flocculation can be controlled by adding, e.g., an anionic high molecular weight polyelectrolyte in the fiber suspension. The objective of this study was to investigate the effect of anionic polyelectrolytes on deflocculation kinetics, dewatering, and rheology of cellulosic suspensions. The results showed that both microfibrillated cellulose (MFC and macroscopic pulp fibers can be dispersed using anionic polyacrylamides (APAM. The higher the molecular weight of APAM, the higher is its effect. Adsorption experiments illustrate that anionic polyelectrolytes do not strongly attach to cellulose surfaces but they can be partly entrapped or can disperse nanocellulose fibrils (increase the swelling. Based on rheological experiments, the MFC network became weaker with APAM addition. Similar to the flocculation mechanism of cellulosic materials with polymers, deflocculation is also time dependent. Deflocculation occurs very rapidly, and the maximum deflocculation level is achieved within a few seconds. When mixing is continued, the floc size starts to increase again. Also dewatering was found to be strongly dependent on the contact time with the APAMs. These results indicate that the positive effects of anionic deflocculants are quickly diminished due to shear forces, and therefore, the best deflocculating effect is achieved using as short a contact time as possible.

  6. Vertical detachment energies of anionic thymidine: Microhydration effects

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F.

    2010-10-01

    Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N1H hydrogen of thymine has been replaced by a 2'-deoxyribose ring, are greater by ˜0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

  7. Metal-Oxide Film Conversions Involving Large Anions

    Energy Technology Data Exchange (ETDEWEB)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C. [The University of Western Ontario, Chemistry Department, 1151 Richmond St., N6A 5B7, London, Ontario (Canada)

    2008-07-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I{sup -}, Br{sup -}, S{sup 2-}). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag{sub 2}O to (1) AgI and (2) AgBr. (authors)

  8. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Senent, M. L. [Departamento de Quimica y Fisica Teoricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Hochlaf, M., E-mail: senent@iem.cfmac.csic.es, E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallee (France)

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  9. Determination of inorganic anions in papermaking waters by ion chromatography

    Directory of Open Access Journals (Sweden)

    DARJA ŽARKOVIĆ

    2009-03-01

    Full Text Available A suppressed ion chromatography (IC method for the determination of inorganic anions in process water from paperboard production was developed and validated. Common inorganic anions (Cl-, NO3-, PO43- and SO42- were detected in fresh and process water samples collected from a paperboard production system at 16 characteristic points. It was shown that the use of an IonPac®-AS14 column under isocratic conditions with Na2CO3/NaHCO3 as the eluent and a suppression device proved to be a reliable analytical solution for the separation of the inorganic anions present in papermaking waters. This IC method is quite satisfactory concerning selectivity and sensitivity, and enables the determination of several inorganic anions over a wide concentration range. According to the obtained results, the total amount of analyzed inorganic anions was below 0.1 g/L, i.e., below the critical value which may trigger operational problems in paper production.

  10. A Spectral-SAR Model for the Anionic-Cationic Interaction in Ionic Liquids: Application to Vibrio fischeri Ecotoxicity

    Directory of Open Access Journals (Sweden)

    Vasile Ostafe

    2007-08-01

    Full Text Available Within the recently launched the spectral-structure activity relationship (S-SARanalysis, the vectorial anionic-cationic model of a generic ionic liquid is proposed, alongwith the associated algebraic correlation factor in terms of the measured and predictedactivity norms. The reliability of the present scheme is tested by assessing the Hanschfactors, i.e. lipophylicity, polarizability and total energy, to predict the ecotoxicityendpoints of wide types of ionic liquids with ammonium, pyridinium, phosphonium,choline and imidazolium cations on the aquatic bacteria Vibrio fischeri. The results, whileconfirming the cationic dominant influence when only lipophylicity is considered,demonstrate that the anionic effect dominates all other more specific interactions. It wasalso proved that the S-SAR vectorial model predicts considerably higher activity for theionic liquids than for its anionic and cationic subsystems separately, in all consideredcases. Moreover, through applying the least norm-correlation path principle, the completetoxicological hierarchies are presented, unfolding the ecological rules of combined cationicand anionic influences in ionic liquid toxicity.

  11. Solubility and transport of cationic and anionic patterned nanoparticles

    Science.gov (United States)

    Su, Jiaye; Guo, Hongxia; Olvera de La Cruz, Monica

    2012-02-01

    Diffusion and transport of nanoparticles (NPs) though nanochannels is important for desalination, drug delivery, and biomedicine. Their surface composition dictate their efficiency separating them by reverse osmosis, delivering into into cells, as well as their toxicity. We analyze bulk diffusion and transport through nanochannels of NPs with different hydrophobic-hydrophilic patterns achieved by coating a fraction of the NP sites with positive or negative charges via explicit solvent molecular dynamics simulations. The cationic NPs are more affected by the patterns, less water soluble, and have higher diffusion constants and fluxes than their anionic NPs counterparts. The NP-water interaction dependence on surface pattern and field strength explains these observations. For equivalent patterns, anionic NPs solubilize more than cationic NPs since the Coulomb interaction of free anionic NPs, which are much stronger than hydrophobic NP-water interactions, are about twice that of cationic NPs.

  12. Analysis of anions in geological brines using ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Merrill, R.M.

    1985-03-01

    Ion chromatographic procedures for the determination of the anions bromide, sulfate, nitrite, nitrate, phosphate, and iodide in brine samples have been developed and are described. The techniques have been applied to the analysis of natural brines, and geologic evaporites. Sample matrices varied over a range from 15,000 mg/L to 200,000 mg/L total halogens, nearly all of which is chloride. The analyzed anion concentrations ranged from less than 5 mg/L in the cases of nitrite, nitrate, and phosphate, to 20,000 mg/L in the case of sulfate. A technique for suppressing chloride and sulfate ions to facilitate the analysis of lower concentration anions is presented. Analysis times are typically less than 20 minutes for each procedure and the ion chromatographic results compare well with those obtained using more time consuming classical chemical analyses. 10 references, 14 figures.

  13. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  14. Effect of anions on the electrochemistry of zinc tetraphenylporphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Seely, G.R.; Gust, D.; Moore, T.A.; Moore, A.L. (Arizona State Univ., Tempe, AZ (United States))

    1994-10-13

    Accurate measurements of porphyrin redox potentials are essential for the prediction and rationalization of the rates of electron transfer reactions involving these biologically important electron-donating and accepting chromophores. The present work describes a survey of redox potentials of zinc tetraphenylporphyrin obtained by cyclic voltammetry in dichloromethane, with tetrabutylammonium salts containing a variety of anions as electrolytes. Of the anions tested, hexafluorophosphate appears to have the least ability to ligate the metal, so that potentials measured in its presence as electrolyte should most closely approach those of the unligated porphyrin. With perchlorate electrolyte, the potential for one-electron oxidation is approximately 80 mV lower, enough to affect the interpretation of photochemical electron transfer rates. In general, anions bind much more strongly to the cation radical than to zinc tetraphenylporphyrin itself. The use of reference redox systems based on thymoquinone and ferrocene carboxylate enabled comparison of potentials measured with different electrolytes. 30 refs., 2 tabs.

  15. Cell wall bound anionic peroxidases from asparagus byproducts.

    Science.gov (United States)

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  16. J774 macrophages secrete antibiotics via organic anion transporters.

    Science.gov (United States)

    Cao, C X; Silverstein, S C; Neu, H C; Steinberg, T H

    1992-02-01

    Mouse macrophages and J774 macrophage-like cells express probenecid-inhibitable organic anion transporters that remove anionic dyes from the cells' cytoplasmic matrix and secrete these dyes into the extracellular medium. The present studies show that these transporters also secrete antibiotics from J774 macrophages. Penicillin G permeates J774 cells poorly, but after it was introduced into the cell cytoplasm, it was secreted in a probenecid-inhibitable fashion. The quinolone norfloxacin enters macrophages readily. Probenecid retarded the secretion of intracellular norfloxacin by J774 cells and enhanced norfloxacin accumulation three- to fourfold. Thus the intracellular accumulation of norfloxacin is regulated in part by organic anion transporters that secrete norfloxacin (and penicillin G) from J774 cells. This transport process may have clinical significance, as fluoroquinolones inhibit growth of intracellular pathogens such as mycobacteria and Brucella organisms in vitro but fail to arrest infections with these organisms in vivo.

  17. Organization and function of anionic phospholipids in bacteria.

    Science.gov (United States)

    Lin, Ti-Yu; Weibel, Douglas B

    2016-05-01

    In addition to playing a central role as a permeability barrier for controlling the diffusion of molecules and ions in and out of bacterial cells, phospholipid (PL) membranes regulate the spatial and temporal position and function of membrane proteins that play an essential role in a variety of cellular functions. Based on the very large number of membrane-associated proteins encoded in genomes, an understanding of the role of PLs may be central to understanding bacterial cell biology. This area of microbiology has received considerable attention over the past two decades, and the local enrichment of anionic PLs has emerged as a candidate mechanism for biomolecular organization in bacterial cells. In this review, we summarize the current understanding of anionic PLs in bacteria, including their biosynthesis, subcellular localization, and physiological relevance, discuss evidence and mechanisms for enriching anionic PLs in membranes, and conclude with an assessment of future directions for this area of bacterial biochemistry, biophysics, and cell biology.

  18. Determination of arsenate in water by anion selective membrane electrode using polyurethane–silica gel fibrous anion exchanger composite

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Asif Ali, E-mail: asifkhan42003@yahoo.com; Shaheen, Shakeeba, E-mail: shakeebashaheen@ymail.com

    2014-01-15

    Highlights: • PU–Si gel is new anion exchanger material synthesized and characterized. • This material used as anion exchange membrane is applied for electroanalytical studies. • The method for detection and determination of AsO{sub 4}{sup 3−} in traces amounts discussed. • The results are also verified from arsenic analyzer. -- Abstract: Polyurethane (PU)–silica (Si gel) based fibrous anion exchanger composites were prepared by solid–gel polymerization of polyurethane in the presence of different amounts of silica gel. The formation of PU–Si gel fibrous anion exchanger composite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTA), scanning electron microscopy (SEM) and elemental analysis. The membrane having a composition of 5:3 (PU:Si gel) shows best results for water content, porosity, thickness and swelling. Our studies show that the present ion selective membrane electrode is selective for arsenic, having detection limit (1 × 10{sup −8} M to 1 × 10{sup −1} M), response time (45 s) and working pH range (5–8). The selectivity coefficient values for interfering ions indicate good selectivity for arsenate (AsO{sub 4}{sup 3−}) over interfering anions. The accuracy of the detection limit results was compared by PCA-Arsenomat.

  19. Anionic fluoroquinolones as antibacterials against biofilm-producing Pseudomonas aeruginosa.

    Science.gov (United States)

    Long, Timothy E; Keding, Lexie C; Lewis, Demetria D; Anstead, Michael I; Withers, T Ryan; Yu, Hongwei D

    2016-02-15

    Pseudomonas aeruginosa is a common biofilm-forming bacterial pathogen implicated in diseases of the lungs. The extracellular polymeric substances (EPS) of respiratory Pseudomonas biofilms are largely comprised of anionic molecules such as rhamnolipids and alginate that promote a mucoid phenotype. In this Letter, we examine the ability of negatively-charged fluoroquinolones to transverse the EPS and inhibit the growth of mucoid P. aeruginosa. Anionic fluoroquinolones were further compared with standard antibiotics via a novel microdiffusion assay to evaluate drug penetration through pseudomonal alginate and respiratory mucus from a patient with cystic fibrosis. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions

    Science.gov (United States)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.

    2016-04-01

    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.

  1. Solution Properties of Dissymmetric Sulfonate-type Anionic Gemini Surfactants.

    Science.gov (United States)

    Yoshimura, Tomokazu; Akiba, Kazuki

    2016-01-01

    Dissymmetric and symmetric anionic gemini surfactants, N-alkyl-N'-alkyl-N,N'dipropanesulfonylethylenediamine (CmCnSul, where m and n represent alkyl chain lengths of m-n = 4-16, 6-14, 8-12, 10-10, and 12-12), were synthesized by two- or three-step reactions. Their physicochemical properties were characterized by equilibrium surface tension measurements, steady-state fluorescence spectroscopy of pyrene, and dynamic light scattering. The critical micelle concentration (CMC) of the dissymmetric surfactants C4C16Sul, C6C14Sul, and C8C12Sul was slightly lower than that of the symmetric surfactant C10C10Sul. The occupied area per molecule (A) of C8C12Sul was smaller than that of C10C10Sul, indicating that C8C12Sul has a high surface activity. However, the increase in the degree of dissymmetry from C8C12Sul to C6C14Sul and then to C4C16Sul resulted in high surface tension and large A. Based on the surface tension, the standard free energies of micellization (∆G°mic) and adsorption (∆G°ads), the efficiency of surface adsorption (pC20), and the effectiveness of surface adsorption (CMC/C20) were obtained. These parameters suggested that C8C12Sul formed micelles more readily than the other surfactants. The properties determined from the surface tension indicated that C8C12Sul's ability is intermediate between those of C10C10Sul and C12C12Sul. The pyrene fluorescence and dynamic light scattering results revealed that the micelle size depends on the longer of the two alkyl chains in dissymmetric surfactants.

  2. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Directory of Open Access Journals (Sweden)

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  3. Electron Photodetachment from Aqueous Anions. I. Quantum Yields for Generation of Hydrated Electron by 193 and 248 nm Laser Photoexcitation of Miscellaneous Inorganic Anions

    CERN Document Server

    Sauer, M C; Shkrob, I A; Sauer, Myran C.; Shkrob, Ilya A.

    2004-01-01

    Time resolved transient absorption spectroscopy has been used to determine quantum yields for electron photodetachment in 193 nm and (where possible) 248 nm laser excitation of miscellaneous aqueous anions, including hexacyanoferrate(II), sulfate, sulfite, halide anions (Cl-, Br-, and I-), pseudohalide anions (OH-, HS-, CNS-), and several common inorganic anions for which no quantum yields have been reported heretofore: SO3=, NO2-, NO3-, ClO3- and ClO4-. Molar extinction coefficients for these anions and photoproducts of electron detachment from these anions at the excitation wavelengths were also determined. These results are discussed in the context of recent ultrafast kinetic studies and compared with the previous data obtained by product analyses. We suggest using electron photodetachment from the aqueous halide and pseudohalide anions as actinometric standard for time-resolved studies of aqueous photosystems in the UV.

  4. Human organic anion transporter 2 is an entecavir, but not tenofovir, transporter.

    Science.gov (United States)

    Furihata, Tomomi; Morio, Hanae; Zhu, Meiyan; Suzuki, Yuki; Ide, Hideyuki; Tsubota, Akihito; Fu, Zhongguo; Anzai, Naohiko; Chiba, Kan

    2017-02-01

    Entecavir (ETV) and tenofovir (TFV) are essential nucleoside analogues in current hepatitis B virus (HBV) treatments. Since these drugs target the HBV polymerase that is localized within human hepatocytes, determining of their cellular uptake process is an important step in fully understanding their pharmacological actions. However, the human hepatic transporters responsible for their uptake have remained unidentified. Therefore, this study aimed at identifying the primary ETV and TFV uptake transporter(s) in human hepatocytes. In transport assays, temperature-sensitive ETV and TFV uptake by human hepatocytes were observed, and their uptake were strongly inhibited by bromosulfophthalein, which is an inhibitor of organic anion transporters/organic anion transporting polypeptides (OATs/OATPs). Given these results, ETV and TFV uptake activities in several human OAT/OATP expression systems were examined. The results showed that, among the transporters tested, only OAT2 possessed ETV transport activity. On the other hand, none of the transporters showed any TFV uptake activity. To summarize, our results identify that human OAT2 is an ETV transporter, thereby suggesting that it plays an important part in the mechanisms underlying ETV antiviral activity. Furthermore, although the hepatic TFV transporters remain unknown, our results have, at least, clarified that these two anti-HBV drugs have different hepatocyte entry routes. Copyright © 2016 The Japanese Society for the Study of Xenobiotics. Published by Elsevier Ltd. All rights reserved.

  5. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    Science.gov (United States)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

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

    OpenAIRE

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

    2005-01-01

    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...

  7. 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

    2001-01-01

    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.

  8. Na+ Modulates Anion Permeation and Blockade of P2X7 Receptors from Mouse Parotid Glands

    OpenAIRE

    Reyes, Juan Pablo; Pérez-Cornejo, Patricia; Hernández-Carballo, Carmen Y.; Srivastava, Alaka; Romanenko, Victor G.; Gonzalez, Mireya; Melvin, James E.; Arreola, Jorge

    2008-01-01

    We previously reported that mouse parotid acinar cells display an anion conductance (IATPCl) when stimulated by external ATP in Na+-free extracellular solutions. It has been suggested that the P2X7 receptor channel (P2X7R) might underlie IATPCl. In this work we show that IATPCl can be activated by ATP, ADP, AMP-PNP, ATPγS and CTP. This is consistent with the nucleotide sensitivity of P2X7R. Accordingly, acinar cells isolated from P2X7R−/− mice lacked IATPCl. Experiments with P2X7R heterologou...

  9. Selection and evaluation of adsorbents for the removal of anionic surfactants from laundry rinsing water

    OpenAIRE

    2007-01-01

    Low-cost adsorbents were tested to remove anionic surfactants from laundry rinsing water to allow re-use of water. Adsorbents were selected corresponding to the different surfactant adsorption mechanisms. Equilibrium adsorption studies of linear alkyl benzene sulfonate (LAS) show that ionic interaction results in a high maximum adsorption capacity on positively charged adsorbents of 0.6–1.7 g LAS/g. Non-ionic interactions, such as hydrophobic interactions of LAS with non-ionic resins or activ...

  10. Parthenolide induces superoxide anion production by stimulating EGF receptor in MDA-MB-231 breast cancer cells.

    Science.gov (United States)

    D'Anneo, A; Carlisi, D; Emanuele, S; Buttitta, G; Di Fiore, R; Vento, R; Tesoriere, G; Lauricella, M

    2013-12-01

    The sesquiterpene lactone parthenolide (PN) has recently attracted considerable attention because of its anti-microbial, anti-inflammatory and anticancer effects. However, the mechanism of its cytotoxic action on tumor cells remains scarcely defined. We recently provided evidence that the effect exerted by PN in MDA-MB-231 breast cancer cells was mediated by the production of reactive oxygen species (ROS). The present study shows that PN promoted the phosphorylation of EGF receptor (phospho-EGFR) at Tyr1173, an event which was observed already at 1 h of incubation with 25 µM PN and reached a peak at 8-16 h. This effect seemed to be a consequence of ROS production, because N-acetylcysteine (NAC), a powerful ROS scavenger, prevented the increment of phospho-EGFR levels. In addition fluorescence analyses performed using dihydroethidium demonstrated that PN stimulated the production of superoxide anion already at 2-3 h of incubation and the effect further increased prolonging the time of treatment, reaching a peak at 8-16 h. Superoxide anion production was markedly hampered by apocynin, a well known NADPH oxidase (NOX) inhibitor, suggesting that the effect was dependent on NOX activity. The finding that AG1478, an EGFR kinase inhibitor, substantially blocked both EGFR phosphorylation and superoxide anion production strongly suggested that phosphorylation of EGFR can be responsible for the activation of NOX with the consequent production of superoxide anion. Therefore, EGFR phosphorylation can exert a key role in the production of superoxide anion and ROS induced by PN in MDA-MB-231 cells.

  11. MinD and MinE interact with anionic phospholipids and regulate division plane formation in Escherichia coli.

    Science.gov (United States)

    Renner, Lars D; Weibel, Douglas B

    2012-11-09

    The Min proteins (MinC, MinD, and MinE) form a pole-to-pole oscillator that controls the spatial assembly of the division machinery in Escherichia coli cells. Previous studies identified that interactions of MinD with phospholipids positioned the Min machinery at the membrane. We extend these studies by measuring the affinity, kinetics, and ATPase activity of E. coli MinD, MinE, and MinDE binding to supported lipid bilayers containing varying compositions of anionic phospholipids. Using quartz crystal microbalance measurements, we found that the binding affinity (K(d)) for the interaction of recombinant E. coli MinD and MinE with lipid bilayers increased with increasing concentration of the anionic phospholipids phosphatidylglycerol and cardiolipin. The K(d) for MinD (1.8 μM) in the presence of ATP was smaller than for MinE (12.1 μM) binding to membranes consisting of 95:5 phosphatidylcholine/cardiolipin. The simultaneous binding of MinD and MinE to membranes revealed that increasing the concentration of anionic phospholipid stimulates the initial rate of adsorption (k(on)). The ATPase activity of MinD decreased in the presence of anionic phospholipids. These results indicate that anionic lipids, which are concentrated at the poles, increase the retention of MinD and MinE and explain its dwell time at this region of bacterial cells. These studies provide insight into interactions between MinD and MinE and between these proteins and membranes that are relevant to understanding the process of bacterial cell division, in which the interaction of proteins and membranes is essential.

  12. The Determination of Anionic Surfactants in Natural and Waste Waters.

    Science.gov (United States)

    Crisp, P. T.; And Others

    1983-01-01

    Background information, procedures, and results of an experiment suitable for measuring subpart per million concentrations of anionic surfactants in natural waters and waste effluents are provided. The experiment required only a spectrophotometer or filter photometer and has been successfully performed by students in an undergraduate environmental…

  13. Physicochemical treatments of anionic surfactants wastewater: Effect on aerobic biodegradability.

    Science.gov (United States)

    Aloui, Fathi; Kchaou, Sonia; Sayadi, Sami

    2009-05-15

    The effect of different physicochemical treatments on the aerobic biodegradability of an industrial wastewater resulting from a cosmetic industry has been investigated. This industrial wastewater contains 11423 and 3148mgL(-1) of chemical oxygen demand (COD) and anionic surfactants, respectively. The concentration of COD and anionic surfactants were followed throughout the diverse physicochemical treatments and biodegradation experiments. Different pretreatments of this industrial wastewater using chemical flocculation process with lime and aluminium sulphate (alum), and also advanced oxidation process (electro-coagulation (Fe and Al) and electro-Fenton) led to important COD and anionic surfactants removals. The best results were obtained using electro-Fenton process, exceeding 98 and 80% of anionic surfactants and COD removals, respectively. The biological treatment by an isolated strain Citrobacter braakii of the surfactant wastewater, as well as the pretreated wastewater by the various physicochemical processes used in this study showed that the best results were obtained with electro-Fenton pretreated wastewater. The characterization of the treated surfactant wastewater by the integrated process (electro-coagulation or electro-Fenton)-biological showed that it respects Tunisian discharge standards.

  14. Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

    Science.gov (United States)

    Nadarajah, Arunan

    1996-01-01

    Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

  15. Molecular Anions in Protostars, Prestellar Cores and Dark Clouds

    Science.gov (United States)

    Cordiner, Martin; Charnley, Steven; Buckle, Jane; Wash, Catherine; Millar, Tom

    2011-01-01

    From our recent survey work using the Green Bank Telescope, microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H have been detected in six new sources. Using HC3N = 10(exp -9) emission maps, we targeted the most carbon-chain-rich sources for our anion survey, which included the low-mass Class 0 protostar L1251A-IRS3, the prestellar cores L1389-SMM1 and L1512, and the interstellar clouds Ll172A, TMC-1C and L1495B. Derived [C6H(-)]/[C6H] anion-to-neutral ratios are approximately 1-10. The greatest C6H(-) column densities are found in the quiescent clouds TMC-1C and L1495B, but the anion-to-neutral ratios are greatest in the prestellar cores and protostars. These results are interpreted in terms of the physical and chemical properties of the sources, and the implications for molecular cloud chemistry are discussed.

  16. The Determination of Anionic Surfactants in Natural and Waste Waters.

    Science.gov (United States)

    Crisp, P. T.; And Others

    1983-01-01

    Background information, procedures, and results of an experiment suitable for measuring subpart per million concentrations of anionic surfactants in natural waters and waste effluents are provided. The experiment required only a spectrophotometer or filter photometer and has been successfully performed by students in an undergraduate environmental…

  17. Anion effects on the cyclobis(paraquat-p-phenylene) host

    DEFF Research Database (Denmark)

    Andersen, Sissel Stenbæk; Jensen, Morten; Sørensen, Anne;

    2012-01-01

    Binding studies between the electron accepting host cyclobis(paraquat-p-phenylene) and a series of electron donors in the presence of differently sized counteranions reveal that both the nature and the concentration of the anion have a large impact on the association strength of the resulting host...

  18. Photocatalytic Anion Oxidation and Applications in Organic Synthesis.

    Science.gov (United States)

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

    2016-08-19

    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.

  19. Sheathless capillary electrophoresis-mass spectrometry for anionic metabolic profiling

    NARCIS (Netherlands)

    Gulersonmez, M.C.; Lock, S.; Hankemeier, T.; Ramautar, R.

    2016-01-01

    The performance of CE coupled on-line to MS via a sheathless porous tip sprayer was evaluated for anionic metabolic profiling. A representative metabolite mixture and biological samples were used for the evaluation of various analytical parameters, such as peak efficiency (plate numbers), migration

  20. Synthesis and Anion Recognition of a Novel Heterocyclic Organotin Complex

    Institute of Scientific and Technical Information of China (English)

    Li Xin ZHANG; Gui Zhi LI; Zhi Qiang LI

    2004-01-01

    A novel heterocyclic hexacoordinate organotin(IV) complex, bis(O-vanillin)-semi ethylenediamino dibenzyltin (VEDBT) was synthesized by the reaction of dibenzyltin dichloride with bis(O-vanillin)-semiethyenediamine, its structure has been characterized by spectral methods.The electrodes using VEDBT as a neutral carrier show high selectivity for salicylate anions.

  1. On the Adsorption of Some Anionic Collectors on Fluoride Minerals

    DEFF Research Database (Denmark)

    Sørensen, Emil

    1973-01-01

    Test flotations have been carried out in a small apparatus under standardized conditions in order to determine the dependence of the flotation yield on the reagent concentration for certain minerals and anionic collectors. The results suggest that a special adsorption mechanism is operating...

  2. Comment on "Local impermeant anions establish the neuronal chloride concentration".

    Science.gov (United States)

    Voipio, Juha; Boron, Walter F; Jones, Stephen W; Hopfer, Ulrich; Payne, John A; Kaila, Kai

    2014-09-05

    Glykys et al. (Reports, 7 February 2014, p. 670) conclude that, rather than ion transporters, "local impermeant anions establish the neuronal chloride concentration" and thereby determine "the magnitude and direction of GABAAR currents at individual synapses." If this were possible, perpetual ion-motion machines could be constructed. The authors' conclusions conflict with basic thermodynamic principles.

  3. Modelling the Effects of Competing Anions on Fluoride Removal by ...

    African Journals Online (AJOL)

    NICOLAAS

    Effects of each two anions exist simultaneously in aqueous solution on ... precipitation,6,7 membrane processes,8 electrochemical treat- ... is significantly dependent on the physico-chemical properties ... X-ray diffraction (XRD) measurements of the catalyst .... fluoride concentration (mg L–1) and X2 is the time of reaction.

  4. Spectral modulation through controlling anions in nanocaged phosphors

    NARCIS (Netherlands)

    H. Bian; Y. Liu; D. Yan; H. Zhu; C. Liu; C.S. Xu; Y. Liu; H. Zhang; X. Wang

    2013-01-01

    A new approach has been proposed and validated to modulate the emission spectra of europium-doped 12CaO center dot 7Al(2)O(3) phosphors by tuning the nonradiative and radiative transition rates, realized by controlling the sort and amount of the encaged anions. A single wavelength at 255 nm can exci

  5. Anion-exchange membranes in electrochemical energy systems

    NARCIS (Netherlands)

    Antanassov, Plamen B.; Dekel, Dario R.; Herring, Andrew M.; Hickner, Michael A.; Kohl, Paul A.; Kucernak, Anthony R.; Mustain, William E.; Nijmeijer, Kitty; Scott, Keith; Varcoe, John R.; Xu, Tongwen; Zhuang, Lin

    2014-01-01

    This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current stat

  6. Oxidation of silicon surface with atomic oxygen radical anions

    Institute of Scientific and Technical Information of China (English)

    Wang Lian; Song Chong-Fu; Sun Jian-Qiu; Hou Ying; Li Xiao-Guang; Li Quan-Xin

    2008-01-01

    The surface oxidation of silicon (Si) wafers by atomic oxygen radical anions (O- anions) and the preparation of metal-oxide-semiconductor (MOS) capacitors on the O--oxidized Si substrates have been examined for the first time. The O- anions are generated from a recently developed O- storage-emission material of [Ca24Al28O64]4+.4O- (C12A7-O- for short). After it has been irradiated by an O- anion beam (0.5 μA/cm2) at 300℃ for 1-10 hours, the Si wafer achieves an oxide layer with a thickness ranging from 8 to 32 nm. X-ray photoelectron spectroscopy (XPS) results reveal that the oxide layer is of a mixture of SiO2, Si2O3, and Si2O distributed in different oxidation depths. The features of the MOS capacitor of are investigated by measuring capacitance-voltage (C - V) and current-voltage (Ⅰ - Ⅴ) curves. The oxide charge density is about 6.0×1011 cm-2 derived from the C - V curves. The leakage current density is in the order of 10-6 A/cm2 below 4 MV/cm, obtained from the Ⅰ - Ⅴ curves. The Oanions formed by present method would have potential applications to the oxidation and the surface-modification of materials together with the preparation of semiconductor devices.

  7. 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

    2005-07-01

    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.

  8. Nuclear magnetic resonance studies of atomic motion in borohydride-based materials: Fast anion reorientations and cation diffusion

    Energy Technology Data Exchange (ETDEWEB)

    Skripov, A.V., E-mail: skripov@imp.uran.ru; Soloninin, A.V.; Babanova, O.A.; Skoryunov, R.V.

    2015-10-05

    Highlights: • Solid solutions LiBH{sub 4}–LiI: extremely fast BH{sub 4} reorientations down to low T. • LiLa(BH{sub 4}){sub 3}Cl: Li-ion diffusive jumps and BH{sub 4} reorientations at the same frequency scale. • Dramatic acceleration of B{sub 12}H{sub 12} reorientations in the disordered phase of Na{sub 2}B{sub 12}H{sub 12}. • Fast Na-ion diffusion in the disordered phase of Na{sub 2}B{sub 12}H{sub 12}. - Abstract: Two basic types of thermally activated atomic jump motion are known to exist in solid borohydrides and the related systems: the reorientations of complex anions ([BH{sub 4}]{sup −}, [B{sub 12}H{sub 12}]{sup 2−}) and the translational diffusion of metal cations or complex anions. This paper reviews recent progress in nuclear magnetic resonance (NMR) studies of these jump processes in complex hydrides, such as solid solutions of halide anions in borohydrides, bimetallic borohydrides and borohydride–chlorides, borohydride–amides, and B{sub 12}H{sub 12}-based compounds. The emphasis is put on the systems showing fast-ion conductivity. For these systems, we discuss a possible relation between the reorientational motion of complex anions and the translational motion of metal cations.

  9. Ferrous Ion Chelating, Superoxide Anion Radical Scavenging and Tyrosinase Inhibitory Properties of Pure and Commercial Essential Oils of Anetrhum Graveolens

    Directory of Open Access Journals (Sweden)

    Sh Darvish Alipour Astaneh

    2013-04-01

    Full Text Available Introduction: Despite slight toxicities of essential oils, they are not under strict control in many countries. Anethum graveolens is widely consumed and its essential oils are at public reach. This study was designed to study essential oils of Anethum graveolens. Methods: The biological properties of pure and commercial essential oils of Anethum graveolens were investigated. In fact, Ferrous ion chelating activity, superoxide anion radical scavenging property, tyrosinase inhibition and total flavonoids of the oils were determined. Results: Chelating activity of 7.8 µg of EDTA was equivalent to 2 µg of the pure oil. The oils had superoxide anion radical scavenging activities which may be related to their total phenol and flavonoid contents. IC50 of ferrous ion chelating, antityrosiase and superoxide anion radical scavenging activities of pure and commercial oils were 1.3, 1.4, 1 and (171.6, 589, 132 µg respectively. Antityrosiase activity of 6.4 µg pure oil was equal to 1000 µg of the commercial oil. Conclusion: Anethum possesses antioxidative and free radical scavenging properties. This oil chelates ferrous ions and superoxide radicals. It is effective in formation of reactive toxic products. Anethum has good potentials regarding its applications in food and drug industries.

  10. Structures and energetics of hydrated oxygen anion clusters.

    Science.gov (United States)

    Chipman, Daniel M; Bentley, John

    2005-08-25

    Hydration of the atomic oxygen radical anion is studied with computational electronic structure methods, considering (O(-))(H(2)O)(n) clusters and related proton-transferred (OH(-))(OH)(H(2)O)(n)(-)(1) clusters having n = 1-5. A total of 67 distinct local-minimum structures having various interesting hydrogen bonding motifs are obtained and analyzed. On the basis of the most stable form of each type, (O(-))(H(2)O)(n)) clusters are energetically favored, although for n > or = 3, there is considerable overlap in energy between other members of the (O(-))(H(2)O)(n) family and various members of the (OH(-))(OH)(H(2)O)(n)(-)(1) family. In the lower-energy (O(-))(H(2)O)(n) clusters, the hydrogen bonding arrangement about the oxygen anion center tends to be planar, leaving the oxygen anion p-like orbital containing the unpaired electron uninvolved in hydrogen bonding with any water molecule. In (OH(-))(OH)(H(2)O)(n)(-)(1) clusters, on the other hand, nonplanar arrangements are the rule about the anionic oxygen center that accepts hydrogen bonds. No instances are found of OH(-) acting as a hydrogen bond donor. Those OH bonds that form hydrogen bonds to an anionic O(-) or OH(-) center are significantly stretched from their equilibrium value in isolated water or hydroxyl. A quantitative inverse correlation is established for all hydrogen bonds between the amount of the OH bond stretch and the distance to the other oxygen involved in the hydrogen bond.

  11. Synthesis of Novel Anionic Receptors with (Thio)urea and Amide Binding Sites and the Recognition Properties for Anions

    Institute of Scientific and Technical Information of China (English)

    吴进龙; 隗兰华; 曾振亚; 刘顺英; 龚睿; 孟令芝; 何永炳

    2003-01-01

    Two new neutral receptors (1 and 2) containing (thio)urea and amide groups were synthesized by simple steps in good yields.The binding properties for anions of 1 and 2 were characterized by UV-vis and fluorescence spectra. Receptor 1 had an excellent selectivity for AcO- in comparison with other anions. The association constants of 1·AcO- and 2·p-NO2PhOPO32- were higher than those of other anions (Cl-, Br-,I-, H2PO4- and p-NO2PhO-). In particular, an obvious color change was observed from light yellow to golden yellow upon addition of AcO- to the solution of 1 in DMSO. The results of non-linear curve fitting by UV-vis and fluorescence spectral data indicate that a 1:1 stoichiometry complex is formed between compound 1 or 2 and anions through a hydrogen bonding interaction.

  12. Anion Transport in a Chemically Stable, Sterically Bulky alpha-C Modified Imidazolium Functionalized Anion Exchange Membrane

    Science.gov (United States)

    2014-06-24

    comparison of benzyltrimethylammonium and 1-benzyl-3-methylimidazolium cationic groups with the same poly( ethylene -co-tetrafluoroethylene) (ETFE...12) Simone, P. M.; Lodge, T. P. Phase Behavior and Ionic Conductivity of Concentrated Solutions of Polystyrene-Poly( Ethylene Oxide) Diblock Copolymers...1514515144 Herring, A. M. Preparation and Characterization of an Alkaline Anion Exchange Membrane from Chlorinated Poly (Propylene) Aminated with

  13. Anion Exchange on Cationic Surfactant Micelles, and a Speciation Model for Estimating Anion Removal on Micelles during Ultrafiltration of Water.

    Science.gov (United States)

    Chen, Ming; Jafvert, Chad T

    2017-07-05

    Surfactant micelles combined with ultrafiltration can partially, or sometimes nearly completely, separate various ionic and nonionic pollutants from water. To this end, the selectivity of aqueous micelles composed of either cetyltrimethylammonium (CTA(+)) bromide or cetylpyridinium (CP(+)) chloride toward many environmentally relevant anions (IO3(-), F(-), Cl(-), HCO3(-), NO2(-), Br(-), NO3(-), H2PO4(-), HPO4(2-), SO4(2-), and CrO4(2-)) was investigated. Selectivity coefficients of CTA(+) micelles (with respect to Br(-)) and CP(+) micelle (with respect to Cl(-)) for these anions were evaluated using a simple thermodynamic ion exchange model. The sequence of anion affinity for the CTA(+) micelles and for the CP(+) micelles were the same, with decreasing affinity occurring in the order of: CrO4(2-) > SO4(2-) > HPO4(2-) > NO3(-) > Br(-) > NO2(-) > Cl(-) > HCO3(-) > H2PO4(-) ≈ F(-). From the associated component mass balance and ion exchange (i.e., mass action) equations, an overall speciation model was developed to predict the distribution of all anions between the aqueous and micellar pseudophase for complex ionic mixtures. Experimental results of both artificial and real surface waters were in good agreement to model predictions. Further, the results indicated that micelles combined with ultrafiltration may be a potential technology for nutrient and other pollutant removal from natural or effluent waters.

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

    KAUST Repository

    Wallack, Maxwell J.

    2015-01-01

    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.

  15. 76 FR 2130 - Prospective Grant of Exclusive License: Inhibitors of the Plasmodial Surface Anion Channel as...

    Science.gov (United States)

    2011-01-12

    ... Plasmodial Surface Anion Channel as Antimalarials AGENCY: National Institutes of Health, Public Health... January 28, 2010, both applications entitled ``Inhibitors of the Plasmodial Surface Anion Channel As...: The subject technologies are antimalarial small molecule inhibitors of the plasmodial surface...

  16. A dual-emissive ionic liquid based on an anionic platinum(II) complex

    OpenAIRE

    Ogawa, Tomohiro; Yoshida, Masaki; Ohara, Hiroki; Kobayashia, Atsushi; Kato, Masako

    2015-01-01

    An ionic liquid fabricated froman anionic cyclometalated platinum(II) complex and an imidazolium cation exhibits dual emission from the monomeric and aggregated forms of the platinum complex anions, leading to temperature-dependent color changes of luminescence.

  17. A dual-emissive ionic liquid based on an anionic platinum(ii) complex.

    Science.gov (United States)

    Ogawa, Tomohiro; Yoshida, Masaki; Ohara, Hiroki; Kobayashi, Atsushi; Kato, Masako

    2015-09-07

    An ionic liquid fabricated from an anionic cyclometalated platinum(ii) complex and an imidazolium cation exhibits dual emission from the monomeric and aggregated forms of the platinum complex anions, leading to temperature-dependent color changes of luminescence.

  18. Cholangiocyte anion exchange and biliary bicarbonate excretion

    Institute of Scientific and Technical Information of China (English)

    Jesús M Banales; Jesús Prieto; Juan F Medina

    2006-01-01

    Primary canalicular bile undergoes a process of fluidization and alkalinization along the biliary tract that is influenced by several factors including hormones, innervation/neuropeptides, and biliary constituents. Theexcretion of bicarbonate at both the canaliculi and the bile ducts is an important contributor to the generation of the so-called bile-salt independent flow. Bicarbonate is secreted from hepatocytes and cholangiocytes through parallel mechanisms which involve chloride efflux through activation of Cl- channels, and further bicarbonate secretion via AE2/SLC4A2-mediated Cl-/HCO3-exchange. Glucagon and secretin are two relevant hormones which seem to act very similarly in their target cells (hepatocytes for the former and cholangiocytes for the latter). These hormones interact with their specific G protein-coupled receptors, causing increases in intracellular levels of cAMP and activation of cAMP-dependent Cl- and HCO3- secretory mechanisms. Both hepatocytes and cholangiocytes appear to have cAMP-responsive intracellular vesicles in which AE2/SLC4A2 colocalizes with cell specific Cl- channels (CFTR in cholangiocytes and not yet determined in hepatocytes) and aquaporins (AQP8 in hepatocytes and AQP1 in cholangiocytes). cAMP-induced coordinated trafficking of these vesicles to either canalicular or cholangiocyte lumenal membranes and further exocytosis results in increased osmotic forces and passive movement of water with net bicarbonate-rich hydrocholeresis.

  19. A Novel Benzimidazolyl based Receptor for the recognition of Fluoride and Cyanide Anion

    Indian Academy of Sciences (India)

    ERAMONI SAIKIA; PANKAJ DUTTA; BOLIN CHETIA

    2017-01-01

    A novel benzimidazole based ligand (1) has been synthesized and studied its anion recognition properties. The binding of anion with 1 was studied using UV-Visible spectroscopy, fluorescence spectroscopy and ¹H-NMR techniques at very low concentrations. The results obtained from the spectroscopic studies indicatethat ligand 1 is an efficient anion receptor providing changes in chemical shift and optical signals for the detection of two most environmentally important anions, fluoride and cyanide.

  20. Synthesis of an Anionic Receptor Based on Phenylhydrazone Group and Its Recognition Property for Acetate

    Institute of Scientific and Technical Information of China (English)

    WANG, Yue-Hong; LIN, Hai; LIN, Hua-Kuan

    2007-01-01

    A colorimetric anion receptor was synthesized by a simple method where the phenylhydrazone moiety was need as binding sites. The anion recognition via hydrogen-bonding interactions can be easily monitored by anion complexation induced changes in UV-vis absorption spectra. Moreover, the hydrogen bond formation between the phenylhydrazone N-H and acetate or fluoride anion was described on the basis of 1H NMR experiments.

  1. Formation and cleavage of aromatic disulfide radical anions.

    Science.gov (United States)

    Antonello, Sabrina; Daasbjerg, Kim; Jensen, Henrik; Taddei, Ferdinando; Maran, Flavio

    2003-12-03

    The electron transfer (ET) to a series of para-substituted diaryl disulfides, having the general formula (X-C(6)H(4)S-)(2), has been studied. The X groups were selected as to have a comprehensive variation of the substituent effect, being X = NH(2), MeO, H, F, Cl, CO(2)Et, CN, and NO(2). The reduction was carried out experimentally, using N,N-dimethylformamide as the solvent, and by molecular orbital (MO) ab initio calculations. The ET was studied heterogeneously, by voltammetric reduction and convolution analysis, and homogeneously, by using electrogenerated radical anions as the solution electron donors. The reduction is dissociative, leading to the cleavage of the S-S bond in a stepwise manner. Both experimental approaches led us to estimate the E degrees and the intrinsic barrier values for the formation of the radical anions. Comparison of the independently obtained results allowed obtaining, for the first time, a quantitative description of the correlation between heterogeneous and homogeneous rate constants of ETs associated with significant inner reorganization energy. The experimental outcome was fully supported by the theoretical calculations, which provided information about the disulfide lowest unoccupied MOs (LUMOs) and singly occupied MO (SOMO), the bond dissociation energies, and the most significant structural modifications associated with radical anion formation. With disulfides bearing electron-donating or mildly electron-withdrawing groups, the inner reorganization is particularly large, which reflects the significant stretching of the S-S bond experienced by the molecule upon ET. The process entails formation of loose radical anion species in which the SOMO is heavily localized, as the LUMO, onto the frangible bond. As a consequence of the formation of these sigma-radical anions, the S-S bond energy of the latter is rather small and the cleavage rate constant is very large. With electron-withdrawing groups, the extent of delocalization of the

  2. Effect of alterations in glomerular charge on deposition of cationic and anionic antibodies to fixed glomerular antigens in the rat.

    Science.gov (United States)

    Adler, S; Baker, P; Pritzl, P; Couser, W G

    1985-07-01

    Reduction of the negative charge of the glomerular capillary wall alters its charge- and size-selective properties. To investigate the effect of alteration in glomerular charge properties on antibody localization, we prepared cationic and anionic fractions of antibodies to subepithelial and glomerular basement membrane (GBM) antigens, and compared their deposition in normal rats and rats treated with protamine sulfate or aminonucleoside of puromycin to reduce capillary wall charge. IgG antibodies were eluted from kidneys of rats with active Heymann's nephritis (AICN), passive Heymann's nephritis (PHN), or anti-GBM nephritis (NTN), separated into cationic and anionic fractions, and radiolabeled with iodine 125 or iodine 131. Relative antibody content of each fraction was determined by incubation with an excess of glomerular antigen. Varying amounts of cationic and anionic IgG eluted from kidneys of rats with AICN or PHN were injected into 24 normal or protamine sulfate-treated rats. Glomerular binding of all antibodies was highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 4 hours was 1.08 +/- 0.07 for AICN eluate and 0.37 +/- 0.04 for PHN eluate. The ratios were not significantly different in animals pretreated with protamine sulfate (1.15 +/- 0.06 and 0.44 +/- 0.06, respectively; P greater than 0.05). Varying amounts of cationic and anionic IgG eluted from kidneys of rats with NTN were injected into 10 normal rats and four rats treated with aminonucleoside of puromycin. Glomerular binding of antibody was again highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 1 hour was 1.03 +/- 0.06, and was not significantly altered in rats treated with aminonucleoside of puromycin (1.05 +/- 0.03, P greater than 0.5). Proteinuria in PHN rats was also unaffected by treatment with protamine sulfate for

  3. Silent S-Type Anion Channel Subunit SLAH1 Gates SLAH3 Open for Chloride Root-to-Shoot Translocation.

    Science.gov (United States)

    Cubero-Font, Paloma; Maierhofer, Tobias; Jaslan, Justyna; Rosales, Miguel A; Espartero, Joaquín; Díaz-Rueda, Pablo; Müller, Heike M; Hürter, Anna-Lena; Al-Rasheid, Khaled A S; Marten, Irene; Hedrich, Rainer; Colmenero-Flores, José M; Geiger, Dietmar

    2016-08-22

    Higher plants take up nutrients via the roots and load them into xylem vessels for translocation to the shoot. After uptake, anions have to be channeled toward the root xylem vessels. Thereby, xylem parenchyma and pericycle cells control the anion composition of the root-shoot xylem sap [1-6]. The fact that salt-tolerant genotypes possess lower xylem-sap Cl(-) contents compared to salt-sensitive genotypes [7-10] indicates that membrane transport proteins at the sites of xylem loading contribute to plant salinity tolerance via selective chloride exclusion. However, the molecular mechanism of xylem loading that lies behind the balance between NO3(-) and Cl(-) loading remains largely unknown. Here we identify two root anion channels in Arabidopsis, SLAH1 and SLAH3, that control the shoot NO3(-)/Cl(-) ratio. The AtSLAH1 gene is expressed in the root xylem-pole pericycle, where it co-localizes with AtSLAH3. Under high soil salinity, AtSLAH1 expression markedly declined and the chloride content of the xylem sap in AtSLAH1 loss-of-function mutants was half of the wild-type level only. SLAH3 anion channels are not active per se but require extracellular nitrate and phosphorylation by calcium-dependent kinases (CPKs) [11-13]. When co-expressed in Xenopus oocytes, however, the electrically silent SLAH1 subunit gates SLAH3 open even in the absence of nitrate- and calcium-dependent kinases. Apparently, SLAH1/SLAH3 heteromerization facilitates SLAH3-mediated chloride efflux from pericycle cells into the root xylem vessels. Our results indicate that under salt stress, plants adjust the distribution of NO3(-) and Cl(-) between root and shoot via differential expression and assembly of SLAH1/SLAH3 anion channel subunits.

  4. Contribution of various metabolites to the "unmeasured" anions in critically ill patients with metabolic acidosis.

    NARCIS (Netherlands)

    Moviat, M.; Terpstra, A.M.; Ruitenbeek, W.; Kluijtmans, L.A.J.; Pickkers, P.; Hoeven, J.G. van der

    2008-01-01

    OBJECTIVE: The physicochemical approach, described by Stewart to investigate the acid-base balance, includes the strong ion gap (SIG), a quantitative measure of "unmeasured" anions, which strongly correlates to the corrected anion gap. The chemical nature of these anions is for the most part

  5. Contact transfer of anions from hands as a function of the use of hand lotions

    Science.gov (United States)

    Welker, R. W.; Schulman, M.

    2001-01-01

    Contact transfer of anions from human hands can result in contamination of materials, increasing their rate of corrosion. Two types of hand lotion were applied to the hands: one was specially formulated for cleanroom use and the other was a popular commercial lotion. The effect on contact transfer of anions was measured versus anion transfer from washed hands without lotions.

  6. Removal of anionic and nonionic surfactants in a wastewater treatment plant with anaerobic digestion: a comparative study

    OpenAIRE

    Prats Rico, Daniel; Ruiz Beviá, Francisco; Vázquez, Beatriz; Rodríguez Pastor, Manuel

    1995-01-01

    This paper presents a comparative study of the elimination of anionic surfactants (linear alkylbenzene sulphonates, LAS) and nonionic surfactants in a conventional municipal activated sludge plant. The LAS were analysed by high performance liquid chromatography, after extraction and purification. The nonionic surfactants was analysed by the Wickbold method. The elimination of the surl4actants in water, suspended solids and sludges were determined in the different stages of the ...

  7. Helix—Sense—Selective Polymerization of N,N—Diphenyl (Meth) acrylamide by Anionic Catalysts

    Institute of Scientific and Technical Information of China (English)

    HongXUE; YongAnXU; 等

    2002-01-01

    In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diphenyl methacrylamide (DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

  8. Ginkgolide X is a potent antagonist of anionic Cys-loop receptors with a unique selectivity profile at glycine receptors

    DEFF Research Database (Denmark)

    Jensen, Anders Asbjørn; Bergmann, Marianne Lerbæk; Sander, Tommy

    2010-01-01

    identified as the primary molecular determinant of the selectivity profile of ginkgolide X, and a 6' M2 ring consisting of five Thr residues was found to be of key importance for its activity at the GABAAR. Conformational analysis and docking of low-energy conformations of the native ginkgolide...... arise from different flexibility and thus different binding modes to the ion channel of the anionic Cys-loop receptor....

  9. Comparative characteristics of two anion-channel rhodopsins and prospects of their use in optogenetics.

    Science.gov (United States)

    Dolgikh, D A; Malyshev, A Yu; Roshchin, M V; Smirnova, G R; Nekrasova, O V; Petrovskaya, L E; Feldman, T B; Balaban, P M; Kirpichnikov, M P; Ostrovsky, M A

    2016-11-01

    Anion-selective opsins slow ChloC and ACR2 were expressed in rat brain cortical neurons by electroporation in utero. It is shown that the light-activated channel ACR2 has pronounced advantages in terms of both the inactivation kinetics and the neuron inhibition intensity, which is associated with a more negative value of the light-activated current reversal potential compared to the slow ChloC channel. The identified properties of opsin ACR2 indicate that it can be used for strictly controlled suppression of neuronal activity in optogenetic experiments, including the expression in the retinal ganglionic cells for reconstituting the OFF-component of their receptive field, which is essential for optogenetic prosthetics of degenerative retina.

  10. Stabilization of {alpha}-amylase by using anionic surfactant during the immobilization process

    Energy Technology Data Exchange (ETDEWEB)

    El-Batal, A.I. [National Center for Radiation Research and Technology, P.O. Box 29, Nasr City, Cairo (Egypt); Atia, K.S. [Nuclear Research Center, Radioisotopes Applications Division, Abo-Zable, P.O. Box 13759, Cairo (Egypt)]. E-mail: ks_atia@yahoo.com; Eid, M. [National Center for Radiation Research and Technology, P.O. Box 29, Nasr City, Cairo (Egypt)

    2005-10-01

    This work describes the entrapment of {alpha}-amylase into butylacrylate-acrylic acid copolymer (BuA/AAc) using {gamma} irradiation. The effect of an anionic surfactant (AOT), the reuse efficiency, and kinetic behavior of immobilized {alpha}-amylase were studied. Covering of {alpha}-amylase with bis-(2-ethylhexyl)sulfosuccinate sodium salt (AOT) made the enzyme more stable than the uncovered form. The hydrolytic activity of the pre-coated immobilized {alpha}-amylase was increased below the critical micelle concentration (cmc) (10mmol/L). The results showed an increase in the relative activity with increase in the degree of hydration. The pre-coated immobilized {alpha}-amylase showed a higher k{sub cat}/K{sub m} and lower activation energy compared to the free and uncoated-immobilized preparation, respectively. The results suggest that the immobilization of {alpha}-amylase is a potentially useful approach for commercial starch hydrolysis in two-phase systems.

  11. Characterization of the anion sensitive ATPase in intact vacuoles of Kalanchoe diagremontiana

    Energy Technology Data Exchange (ETDEWEB)

    Kobza, J.; Uribe, E.G.

    1986-04-01

    A method for the isolation of intact vacuoles from K. daigremontiana was developed which produced high yields of relatively pure vacuoles as determined by marker enzyme contamination. Upon isolation, the vacuoles were stabilized by the inclusion of 5% (w/v) ficoll. Enzyme activity was insensitive to vanadate and azide but was strongly inhibited by DCCD. Enzyme activity was strictly dependent on the inclusion of Mg/sup 2 +/ and was stimulated by anions as depicted by the series, NO/sub 3//sup -/ < Br/sup -/ < SO/sub 4//sup -/ < HCO/sub 3//sup -/ < Cl/sup -/. It was found that in intact vacuoles the ATPase activity was stimulated by phosphate to a level equivalent to that found with the chloride. The enzyme exhibited Michaelis-Menten kinetics with a Km for Mg-ATP complex of 0.51 mM.

  12. Stabilization of α-amylase by using anionic surfactant during the immobilization process

    Science.gov (United States)

    El-Batal, A. I.; Atia, K. S.; Eid, M.

    2005-10-01

    This work describes the entrapment of α-amylase into butylacrylate-acrylic acid copolymer (BuA/AAc) using γ irradiation. The effect of an anionic surfactant (AOT), the reuse efficiency, and kinetic behavior of immobilized α-amylase were studied. Covering of α-amylase with bis-(2-ethylhexyl)sulfosuccinate sodium salt (AOT) made the enzyme more stable than the uncovered form. The hydrolytic activity of the pre-coated immobilized α-amylase was increased below the critical micelle concentration (cmc) (10 mmol/L). The results showed an increase in the relative activity with increase in the degree of hydration. The pre-coated immobilized α-amylase showed a higher k/K and lower activation energy compared to the free and uncoated-immobilized preparation, respectively. The results suggest that the immobilization of α-amylase is a potentially useful approach for commercial starch hydrolysis in two-phase systems.

  13. 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

    2012-01-01

    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.

  14. Coumarin Based Neutral Sensor for Biologically Important Anions

    Institute of Scientific and Technical Information of China (English)

    SHAO Jie

    2011-01-01

    A coumarin Shiff-base derivative,salicylaldehyde-N-(6-phenylazo-coumarin-3-formyl)-hydrazone(1),was obtained by simple organic synthesis from cheap and commercially available starting materials.Sensor 1 exhibits a very weak fluorescence emission,however,in the presence of acetate ions “turn-on” fluorescence is observed,which results from binding-induced conformational restriction of the fluorophore.Importantly,sensor 1 can also be used as colorimetric chemosensor for the anions with strong basicity,which is easily observed from yellow to red by naked eyes.Consequently,compound l can behave as a colorimetric and fluorescence sensor for biologically important F,CH3COO and H2PO4- in the presence of the other anions tested such as Cl-,Br- and I- in dimethyl sulfoxide(DMSO).

  15. Electronic spectra of anions intercalated in layered double hydroxides

    Indian Academy of Sciences (India)

    S Radha; P Vishnu Kamath

    2013-10-01

    Transition metal complexes intercalated in layered double hydroxides have a different electronic structure as compared to their free state owing to their confinement within the interlayer gallery. UV–Vis absorptions of the intercalated complex anions show a significant shift as compared to their free state. The ligand to metal charge transfer transitions of the ferricyanide anion show a red shift on intercalation. The ferrocyanide ion shows a significant blue shift of – bands due to the increased separation between 2g and g levels on intercalation. MnO$^{-}_{4}$ ion shows a blue shift in its ligand to metal charge transfer transition since the non-bonding 1 level of oxygen from which the transition arises is stabilized.

  16. Anionic reagents with silicon-containing double bonds.

    Science.gov (United States)

    Scheschkewitz, David

    2009-03-02

    E=Si transfer: Anionic compounds capable of transferring a silicon-containing double bond are reviewed (see figure), particularly reagents with Si=Si moieties (Tip=2,4,6-iPr(3)C(6)H(2), M=Li, Na, K) and their applications towards main-group and transition-metal electrophiles, as well as their reactivity towards organic compounds. A few recently reported derivatives with Si=C (Ad=1-adamantyl) and Si=P moieties are included for completeness.Anionic compounds capable of transferring a silicon double bond are summarized following an introduction to the differences between alkenes and their heavier homologues. The main focus is on reagents with Si=Si moieties and their applications towards main-group and transition-metal electrophiles, as well as their reactivity towards organic compounds, but a few recently reported derivatives with Si=C and Si=P bonds are also included.

  17. Molecular dynamics simulation of anionic clays containing glutamic acid

    Science.gov (United States)

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

    2010-08-01

    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.

  18. Anion-switchable supramolecular gels for controlling pharmaceutical crystal growth

    Science.gov (United States)

    Foster, Jonathan A.; Piepenbrock, Marc-Oliver M.; Lloyd, Gareth O.; Clarke, Nigel; Howard, Judith A. K.; Steed, Jonathan W.

    2010-12-01

    We describe the use of low-molecular-weight supramolecular gels as media for the growth of molecular crystals. Growth of a range of crystals of organic compounds, including pharmaceuticals, was achieved in bis(urea) gels. Low-molecular-weight supramolecular gelators allow access to an unlimited range of solvent systems, in contrast to conventional aqueous gels such as gelatin and agarose. A detailed study of carbamazepine crystal growth in four different bis(urea) gelators, including a metallogelator, is reported. The crystallization of a range of other drug substances, namely sparfloxacin, piroxicam, theophylline, caffeine, ibuprofen, acetaminophen (paracetamol), sulindac and indomethacin, was also achieved in supramolecular gel media without co-crystal formation. In many cases, crystals can be conveniently recovered from the gels by using supramolecular anion-triggered gel dissolution; however, crystals of substances that themselves bind to anions are dissolved by them. Overall, supramolecular gel-phase crystallization offers an extremely versatile new tool in pharmaceutical polymorph screening.

  19. Dihydrogen Phosphate Selective Anion Receptor Based on Acylhydrazone

    Energy Technology Data Exchange (ETDEWEB)

    Senthil Pandian, T.; Kang, Jongmin [Sejong Univ., Seoul (Korea, Republic of)

    2014-07-15

    Anion receptor based on acylhydrazone has been designed and synthesized. UV-vis and {sup 1}H NMR titration showed that receptor is selective receptor for dihydrogen phosphate (H{sub 2}PO{sub 4}{sup -}). Dihydrogen phosphate was complexed by the receptor via at least 4 hydrogen bonding interactions, contributing from two amide N-Hs and two imine C-Hs. In addition, nitrogen in the aromatic ring could make 2 additional hydrogen bondings with OH groups in the dihydrogen phosphate. However, the receptor could make only 4 hydrogen bonds with halides. Therefore, receptor could bind anions through hydrogen bonds with a selectivity in the order of H{sub 2}PO{sub 4}{sup -} > Br{sup -} > Cl{sup -} in highly polar solvent such as DMSO.

  20. Carbonate and Bicarbonate Ion Transport in Alkaline Anion Exchange Membranes

    Science.gov (United States)

    2013-06-25

    Bicarbonate Ion Transport in Alk Block 13: Supplementary Note © 2013 . Published in Journal of the Electrochemical Society , Vol. Ed. 0 160, (9) (2013...for public release; distribution is unlimited. ... 60325.7-CH-II F994 Journal of The Electrochemical Society , 160 (9) F994-F999 (2013) 0013-4651/2013...160(9)/F994/6/$31.00 © The Electrochemical Society Carbonate and Bicarbonate Ion Transport in Alkaline Anion Exchange Membranes Andrew M. Kiss,a

  1. Assessment Of Suitability Of Anionic Synthetic Detergents In Sri Lanka

    OpenAIRE

    Sunethra Gunatilake; Sarath Malavipathirana

    2015-01-01

    This research was focused on the understanding of the biodegradability of synthetic anionic detergent powder available in Sri Lankan market. Eight different types of synthetic detergent powders were selected. LAS contents of the selected products were measured according to ASTM D 3049-89 standard. The biodegradability was measured as the reduction percentage of LAS initially present within a specific period. The phosphate content in the detergents were measured by SLS 760 1986 method and the...

  2. Comment on "Local impermeant anions establish the neuronal chloride concentration".

    Science.gov (United States)

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

    2014-09-01

    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.

  3. Separation of multiply charged anions by capillary electrophoresis using alkyl phosphonium pairing agents.

    Science.gov (United States)

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

    2012-04-01

    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.

  4. Indirect photometric detection of boron cluster anions electrophoretically separated in methanol.

    Science.gov (United States)

    Vítová, Lada; Fojt, Lukáš; Vespalec, Radim

    2014-04-18

    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.

  5. Effect of Anion on Adsorption of Rare Earth Elements on Kaolinite

    Institute of Scientific and Technical Information of China (English)

    Wan Yingxin; Liu Jianjun

    2007-01-01

    For a better understanding the adsorption of rare earth elements (REEs) on minerals and its controlling factors, adsorption experiments were performed with kaolin in a matrix of various concentration of anion (Cl-, ClO4-, SO42-) in the pH 6.5. The adsorption of REEs onto the kaolin increase with increasing anion concentration, especially in the presence of SO42-, which is ascribe to the Na+ mass effect and anion complexation. furthermore, the heavy REEs are more adsorbed onto kaolin in presence of higher concentration of anion, especially for Cl- and SO42-, presumably due to the difference of anion complexation with light REE and heavy REEs.

  6. 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

    2003-01-01

    @@ 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).

  7. Ammoniated electron as a solvent stabilized multimer radical anion

    CERN Document Server

    Shkrob, I A

    2005-01-01

    The excess electron in liquid ammonia ("ammoniated electron") is commonly viewed as a cavity electron in which the s-type wave function fills the interstitial void between 6-9 ammonia molecules. Herewith an alternative model is examined in which the ammoniated electron is regarded as a solvent stabilized multimer radical anion, as was originally suggested by Symons [Chem. Soc. Rev. 1976, 5, 337]. In this model, most of the excess electron density resides in the frontier orbitals of N atoms in the ammonia molecules forming the solvation cavity; a fraction of this spin density is transferred to the molecules in the second solvation shell. The cavity is formed due to the repulsion between negatively charged solvent molecules. Using density functional theory calculations for small ammonia cluster anions in the gas phase, it is demonstrated that such core anions would quantitatively account for the observed pattern of Knight shifts for 1H and 14N nuclei as observed by NMR spectroscopy and the downshifted stretchin...

  8. Coumarin benzothiazole derivatives as chemosensors for cyanide anions.

    Science.gov (United States)

    Wang, Kangnan; Liu, Zhiqiang; Guan, Ruifang; Cao, Duxia; Chen, Hongyu; Shan, Yanyan; Wu, Qianqian; Xu, Yongxiao

    2015-06-05

    Four coumarin benzothiazole derivatives, N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (1), (Z)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide (2), 7-(diethylamino)-N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (3) and (Z)-7-(diethylamino)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide) (4), have been synthesized. Their crystal structures, photophysical properties in acetonitrile and recognition properties for cyanide anions have been investigated. All the compounds are generally planar, especially compound 1 exhibits perfect planarity with dihedral angle between benzothiazolyl group and coumarin group being only 3.63°. Coumarin benzothiazole compounds 1 and 3 can recognize cyanide anions by Michael addition reaction and compound 3 exhibits color change from yellow to colorless and green fluorescence was quenched completely, which can be observed by naked eye. Coumarin benzothiazolyliden compound 4 can recognize cyanide anions with fluorescence turn-on response based on the copper complex ensemble displacement mechanism.

  9. Cassini observations of carbon-based anions in Titan's ionosphere

    Science.gov (United States)

    Desai, Ravindra; Lewis, Gethyn; Waite, J. Hunter; Kataria, Dhiren; Wellbrock, Anne; Jones, Geraint; Coates, Andrew

    2016-07-01

    Cassini observations of Titan's ionosphere revealed an atmosphere rich in positively and negatively charged ions and organic molecules. The detection of large quantities of negatively charged ions was particularly surprising and adds Titan to the growing list of locations where anion chemistry has been observed to play an important role. In this study we present updated analysis on these negatively charged ions through an enhanced understanding of the Cassini CAPS Electron Spectrometer (CAPS-ELS) instrument response. The ionisation of Titan's dominant atmospheric constituent, N2, by the HeII Solar line, results in an observable photoelectron population at 24.1eV which we use to correct for differential spacecraft charging. Correcting for further energy-angle signatures within this dataset, we use an updated fitting procedure to show how the ELS mass spectrum, previously grouped into broad mass ranges, can be resolved into specific peaks at multiples of carbon-based anion species up to over 100amu/q. These peaks are shown to be ubiquitous within Titan's upper atmosphere and reminiscent of carbon-based anions identified in dense molecular clouds beyond our Solar System. It is thus shown how the moon Titan in the Outer Solar System can be used as an analogue to study these even more remote and exotic astrophysical environments.

  10. Photostability enhancement of anionic natural dye by intercalation into hydrotalcite.

    Science.gov (United States)

    Kohno, Yoshiumi; Totsuka, Koichi; Ikoma, Shuji; Yoda, Keiko; Shibata, Masashi; Matsushima, Ryoka; Tomita, Yasumasa; Maeda, Yasuhisa; Kobayashi, Kenkichiro

    2009-09-01

    The aim of this study is the improvement of the photostability of several natural anionic dyes, carmine (CM), carthamus yellow (CY), and annatto dye (ANA), by complexation with hydrotalcite. The composite of the dyes and hydrotalcite is prepared by the coprecipitation method. CM is successfully intercalated in the hydrotalcite layer when the amount of introduced CM is large. The photostability of CM in CM/HT composites is superior to the CM adsorbed on silica surface. The effect of the stability enhancement is larger when the amount of introduced CM exceeds 0.23 g/g-host, or when the layer charge density of the hydrotalcite is larger. CY is also stabilized by complexation with hydrotalcite, whereas ANA is not stabilized by complexation with hydrotalcite. The photostability of an anionic natural dye can be improved by intercalation into the hydrotalcite layer, if the dye has a hydrophilic nature and a rather planar structure. The intercalated dye is stabilized by the protection from the attack of the atmospheric oxygen. In addition, contribution of the electrostatic interaction between the positively charged hydrotalcite layer and the intercalated anionic dye is also proposed.

  11. Anion composition of açaı́ extracts.

    Science.gov (United States)

    Liao, Hongzhu; Shelor, C Phillip; Chen, Yongjing; Sabaa-Srur, Armando U O; Smith, Robert E; Dasgupta, Purnendu K

    2013-06-26

    Many products labeled açaı́ are presently marketed as natural supplements with various claimed health benefits. Authentic açaı́ is expensive; as a result, numerous products labeled as containing açaı́ are being sold that actually contain little or no açaı́. Authentic açaı́ samples from Brazil and Florida as well as several reputed açaı́ products were analyzed by suppressed conductometric anion chromatography. Columns with different selectivities were used to obtain a complete separation of all anions. Tandem mass spectrometry was used for confirmation of the less common ions. Quinate, lactate, acetate, formate, galacturonate, chloride, sulfate, malate, oxalate, phosphate, citrate, isocitrate, and myo-inositol hexakisphosphate (phytate) were found. Only the Florida açaı́ had detectable levels of hexanoate. No açaı́ sample had any detectable levels of tartrate, which is present in abundance in grape juice, the most common adulterant. The highly characteristic anion profile and in particular the absence of tartrate can readily be used to identify authentic açaı́ products. Açaı́ from Florida had a 6 times greater level of phytate. The present analytical approach for phytate may be superior to extant methods.

  12. [Chromatographic separation of plasmid DNA by anion-exchange cryogel].

    Science.gov (United States)

    Guo, Yantao; Shen, Shaochuan; Yun, Junxian; Yao, Kejian

    2012-08-01

    Plasmid DNA (pDNA) is used as an important vector for gene therapy, and its wide application is restricted by the purity and yield. To obtain high-purity pDNA, a chromatographic method based on anion-exchange supermacroporous cryogel was explored. The anion-exchange cryogel was prepared by grafting diethylaminoethyl-dextran to the epoxide groups of polyacrylamide-based matrix and pUC19 plasmid was used as a target to test the method. The plasmid was transferred into Escherichia coli DH5alpha, cultivated, harvested and lysed. The obtained culture was centrifuged and the supernatant was used as the plasmid feedstock, which was loaded into the anion-exchange cryogel bed for chromatographic separation. By optimizing the pH of running buffer and the elution conditions, high-purity pDNA was obtained by elution with 0.5 mol/L sodium chloride solution at pH 6.6. Compared to the traditional methods for purification of pDNA, animal source enzymes and toxic reagents were not involved in the present separation process, ensuring the safety of both the purification operations and the obtained pDNA.

  13. Coumarin benzothiazole derivatives as chemosensors for cyanide anions

    Science.gov (United States)

    Wang, Kangnan; Liu, Zhiqiang; Guan, Ruifang; Cao, Duxia; Chen, Hongyu; Shan, Yanyan; Wu, Qianqian; Xu, Yongxiao

    2015-06-01

    Four coumarin benzothiazole derivatives, N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (1), (Z)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide (2), 7-(diethylamino)-N-(benzo[d]thiazol-2-yl)-2-oxo-2H-chromene-3-carboxamide (3) and (Z)-7-(diethylamino)-N-(3-methylbenzo[d]thiazol-2(3H)-ylidene)-2-oxo-2H-chromene-3-carboxamide) (4), have been synthesized. Their crystal structures, photophysical properties in acetonitrile and recognition properties for cyanide anions have been investigated. All the compounds are generally planar, especially compound 1 exhibits perfect planarity with dihedral angle between benzothiazolyl group and coumarin group being only 3.63°. Coumarin benzothiazole compounds 1 and 3 can recognize cyanide anions by Michael addition reaction and compound 3 exhibits color change from yellow to colorless and green fluorescence was quenched completely, which can be observed by naked eye. Coumarin benzothiazolyliden compound 4 can recognize cyanide anions with fluorescence turn-on response based on the copper complex ensemble displacement mechanism.

  14. Stability of atoms in the anionic domain (Z

    CERN Document Server

    Gil, G

    2013-01-01

    We study the stability and universal behaviour of the ionization energy of N-electron atoms with nuclear charge Z in the anionic domain (Zanionic instability threshold. As testing systems we choose inert gases (He-like, Ne-like and Ar-like isoelectronic sequences) and alkali metals (Li-like, Na-like, K-like sequences). From the results, it is apparent that, for inert gases case, the stability relation with N is completely inverted in the singly-charged anion region (Z=N-1) with respect to the neutral atom region (Z=N), i.e. larger systems are more stable than the smaller ones. We devised a semi-analytical model (inspired by the zero-range forces theory) which lead us to establish the ionization energy dependence on the nuclear charge n...

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

    Directory of Open Access Journals (Sweden)

    Neus Mesquida

    2012-04-01

    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.

  16. Anionic markers for the forensic identification of Chemical Ignition Molotov Cocktail composition.

    Science.gov (United States)

    Martín-Alberca, C; Ferrando, J L; García-Ruiz, C

    2013-03-01

    An improved version of the famous Molotov cocktail is the Chemical Ignition Molotov Cocktail (CIMC). This incendiary device contains chemical reagents that enable its self-ignition. The analysis of anions from CIMC residues by capillary electrophoresis (CE) allows the identification of the reagents used to produce the device, and provides forensic analysts with valuable information. Although, sulfate, chlorate, chloride, and perchlorate anions have been recently proposed in the literature as target anions to determine the CIMC composition, the identification of some of them could be controversial due to their presence in the environment. Therefore, the purpose of this study was to identify highly reliable anions capable of indicating the components used to prepare these self-initiated devices. The relationship among the detected anions in CIMC residues and the reagents employed in their elaboration is discussed. Some anions have been proposed as anionic markers of CIMC as incendiary devices. Additionally, the viability of different CIMC compositions was studied.

  17. Relative partial cross sections for anions formed upon electron attachment to nitrotoluene

    Science.gov (United States)

    Aleem, A.; Mauracher, A.; Sulzer, P.; Denifl, S.; Zappa, F.; Bacher, A.; Wendt, N.; Märk, T. D.; Scheier, P.

    2008-04-01

    Free electron attachment to the three different isomers of mono-nitrotoluene molecules in the gas phase is studied using a crossed electron-molecule beams technique. For the molecule 2-nitrotoluene 77 products anions are measured. The ion yield of the different anions spans a range of more than six orders of magnitude. The total anion yield of the three different isomers of mono-nitrotoluene is compared and shows remarkable differences mainly resulting from the different contributions of the NO2- fragment anions. The anion efficiency curves show six resonances that we assign to different transient negative ions. Competition of decay reactions is forming a series of fragment anions from each isomeric transient negative anion.

  18. A fluorescent coumarin-thiophene hybrid as a ratiometric chemosensor for anions: Synthesis, photophysics, anion sensing and orbital interactions

    Science.gov (United States)

    Yanar, Ufuk; Babür, Banu; Pekyılmaz, Damla; Yahaya, Issah; Aydıner, Burcu; Dede, Yavuz; Seferoğlu, Zeynel

    2016-03-01

    A colorimetric and fluorimetric fluorescent chemosensor (CT-2), having a coumarin ring as a signaling unit and an acetamido thiophene ring as an H-donor receptor, has been synthesized from amino derivative (CT-1) of CT-2 for the purpose of recognition of anions in DMSO. The absorption and emission maxima were both determined for the fluorescent dye in different solvents. Both hypsochromic shift at the absorption maximum, and quenching of fluorescence after interactions between the anions and the receptoric part, were observed. This phenomenon was explained using orbital interactions based on quantum chemical calculations. The selectivity and sensitivity of CT-2 for F-, Cl-, Br-, I-, AcO-, CN-, H2PO4-, HSO4- and ClO4- anions were determined with spectrophotometric, fluorimetric and 1H NMR titration techniques and it was found that CT-2 be utilized for the detection of CN-, F- and AcO- in the presence of other ions as competitors. Color and fluorescence changes visible to the naked eye and under UV (365 nm) were observed upon addition of CN-, F- and AcO- to the solution of chemosensor (CT-2) in DMSO. The sensor showed no colorimetric and fluorimetric response for the anions such as Cl-, Br-, I-, H2PO4-, HSO4-, and ClO4-. However, 1H NMR titration shows that the chemosensor was more sensitive to CN-, than F- and AcO- at the stochiometric ratio of 1:2.5 respectively. Additionally, the compounds CT-1 and CT-2 showed good thermal stability for practical applications.

  19. An S-type anion channel SLAC1 is involved in cryptogein-induced ion fluxes and modulates hypersensitive responses in tobacco BY-2 cells.

    Directory of Open Access Journals (Sweden)

    Takamitsu Kurusu

    Full Text Available Pharmacological evidence suggests that anion channel-mediated plasma membrane anion effluxes are crucial in early defense signaling to induce immune responses and hypersensitive cell death in plants. However, their molecular bases and regulation remain largely unknown. We overexpressed Arabidopsis SLAC1, an S-type anion channel involved in stomatal closure, in cultured tobacco BY-2 cells and analyzed the effect on cryptogein-induced defense responses including fluxes of Cl(- and other ions, production of reactive oxygen species (ROS, gene expression and hypersensitive responses. The SLAC1-GFP fusion protein was localized at the plasma membrane in BY-2 cells. Overexpression of SLAC1 enhanced cryptogein-induced Cl(- efflux and extracellular alkalinization as well as rapid/transient and slow/prolonged phases of NADPH oxidase-mediated ROS production, which was suppressed by an anion channel inhibitor, DIDS. The overexpressor also showed enhanced sensitivity to cryptogein to induce downstream immune responses, including the induction of defense marker genes and the hypersensitive cell death. These results suggest that SLAC1 expressed in BY-2 cells mediates cryptogein-induced plasma membrane Cl(- efflux to positively modulate the elicitor-triggered activation of other ion fluxes, ROS as well as a wide range of defense signaling pathways. These findings shed light on the possible involvement of the SLAC/SLAH family anion channels in cryptogein signaling to trigger the plasma membrane ion channel cascade in the plant defense signal transduction network.

  20. Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

    Science.gov (United States)

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

    2016-11-01

    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.

  1. Determination of arsenate in water by anion selective membrane electrode using polyurethane-silica gel fibrous anion exchanger composite.

    Science.gov (United States)

    Khan, Asif Ali; Shaheen, Shakeeba

    2014-01-15

    Polyurethane (PU)-silica (Si gel) based fibrous anion exchanger composites were prepared by solid-gel polymerization of polyurethane in the presence of different amounts of silica gel. The formation of PU-Si gel fibrous anion exchanger composite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTA), scanning electron microscopy (SEM) and elemental analysis. The membrane having a composition of 5:3 (PU:Si gel) shows best results for water content, porosity, thickness and swelling. Our studies show that the present ion selective membrane electrode is selective for arsenic, having detection limit (1×10(-8)M to 1×10(-1)M), response time (45s) and working pH range (5-8). The selectivity coefficient values for interfering ions indicate good selectivity for arsenate (AsO4(3-)) over interfering anions. The accuracy of the detection limit results was compared by PCA-Arsenomat.

  2. Dependency of the hydrogen bonding capacity of the solvent anion on the thermal stability of feruloyl esterases in ionic liquid systems

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Ståhlberg, Tim; Nguyen van Buu, Olivier

    2011-01-01

    acid with glycerol in four ionic liquid (IL) systems. The IL systems were systematically composed of two selected pairs of cations and anions, respectively: [BMIm][PF6], [C2OHMIm][PF6], [BMIm][BF4], and [C2OHMIm][BF4]. AnFaeA had activity in [PF6]--based ILs, whereas the AndFaeC and the FAE in Ultraflo...... rapid inactivation of AnFaeA, while [PF6]- did not. The cation did not have a similar effect. These observations could be explained in terms of the hydrogen bonding capacity of IL cations and anions via COSMO-RS simulations....

  3. Electronic relaxations of radiative defects of the anion sublattice in cesium bromide crystals and exoemission of electrons

    CERN Document Server

    Galyij, P V

    2002-01-01

    The paper presents the results of investigations of thermostimulated exoelectron emission (TSEE) from CsBr crystal, excited by moderate doses (D <= 10 sup 4 Gy) of ultraviolet (h nu <= 7 eV) that selectively creates anion excitons and radiative defects in the anion sublattice. Having used the previously established connection between thermoactivated processes such as thermostimulated exoemission, electroconductivity, and luminescence in the irradiated crystal lattice, the concentrations of exoemission-active centers (EAC) and kinetics parameters of TSEE are calculated. The EAC concentration calculated on a base of the bulk, thermoactivated-recombinational, and band-gap Auger-like exoemission mechanisms, are in satisfactory agreement with the concentration of electron color centers in the irradiated crystals.

  4. Formation and decay of fluorobenzene radical anions affected by their isomeric structures and the number of fluorine atoms.

    Science.gov (United States)

    Higashino, Saki; Saeki, Akinori; Okamoto, Kazumasa; Tagawa, Seiichi; Kozawa, Takahiro

    2010-08-12

    Aryl fluoride has attracted much attention as a resist component for extreme ultraviolet (EUV) lithography, because of the high absorption cross section of fluorine for EUV photons; however, less is known about electron attachment to fluorobenzene (FBz) and the stability of the reduced state. Picosecond and nanosecond pulse radiolysis of tetrahydrofuran solutions of FBz from mono-, di-, tri-, tetra-, penta-, and hexafluorobenzene was performed, and the effects of isomeric structure and number of fluorine atoms were examined. Scavenging of solvated electrons was found to correlate with the electron affinity obtained by density functional theory in the gas phase, whereas the decay of FBz radical anions was dominated by the activation energy of fluorine anion dissociation calculated using a polarized continuum model (PCM). A sharp contrast in the lifetimes of ortho-, meta-, and para-position difluorobenzene was observed, which could provide information on the molecular design of functional materials.

  5. Model of a vanadium redox flow battery with an anion exchange membrane and a Larminie-correction

    Science.gov (United States)

    Wandschneider, F. T.; Finke, D.; Grosjean, S.; Fischer, P.; Pinkwart, K.; Tübke, J.; Nirschl, H.

    2014-12-01

    Membranes are an important part of vanadium redox flow battery cells. Most cell designs use Nafion®-type membranes which are cation exchange membranes. Anion exchange membranes are reported to improve cell performance. A model for a vanadium redox flow battery with an anion exchange membrane is developed. The model is then used to calculate terminal voltages for open circuit and charge-discharge conditions. The results are compared to measured data from a laboratory test cell with 40 cm2 active membrane area. For higher charge and discharge currents, an empirical correction for the terminal voltage is proposed. The model geometry comprises the porous electrodes and the connected pipes, allowing a study of the flow in the entrance region for different state-of-charges.

  6. Azide anions inhibit GH-18 endochitinase and GH-20 Exo β-N-acetylglucosaminidase from the marine bacterium Vibrio harveyi.

    Science.gov (United States)

    Sirimontree, Paknisa; Fukamizo, Tamo; Suginta, Wipa

    2016-02-01

    Vibrio harveyi is a bioluminescent marine bacterium that utilizes chitin as its sole source of energy. In the course of chitin degradation, the bacterium primarily secretes an endochitinase A (VhChiA) to hydrolyze chitin, generating chitooligosaccharide fragments that are readily transported into the cell and broken down to GlcNAc monomers by an exo β-N-acetylglucosaminidase (VhGlcNAcase). Here we report that sodium salts, especially sodium azide, inhibit two classes of these chitin-degrading enzymes (VhChiA and VhGlcNAcase) with distinct modes of action. Kinetic analysis of the enzymatic hydrolysis of pNP-glycoside substrates reveals that sodium azide inhibition of VhChiA has a mixed-type mode, but that it inhibits VhGlcNAcase competitively. We propose that azide anions inhibit chitinase activity by acting as strong nucleophiles that attack Cγ of the catalytic Glu or Cβ of the neighbouring Asp residues. Azide anions may bind not only to the catalytic centre, but also to the other subsites in the substrate-binding cleft of VhChiA. In contrast, azide anions may merely occupy the small-binding pocket of VhGlcNAcase, thereby blocking the accessibility of its active site by short-chain substrates.

  7. A BTT-Based Colorimetric Dual Sensor for Hg(II and Selected Anions with Molecular Logic Operations

    Directory of Open Access Journals (Sweden)

    Veikko Uahengo

    2016-01-01

    Full Text Available A benzotrithiophenes (BTT based colorimetric sensor (2 was synthesized via a simple one-step reaction process, and its recognition properties towards several biologically important anions and cations were investigated by naked eye observation and spectroscopic methods of UV-vis and 1H NMR analysis in DMSO. The molar addition of anions such as F−, AcO−, and H2PO4- induced a marked red shift of the charge transfer band (Δλ=94 nm, from 440 nm to 534 nm concomitant with a clearly visible “naked eye” detectable colorimetric activities (from orange to pink. However, the molar addition of H2PO4- did not induce significant spectral changes, compared to F− and AcO−. Furthermore, the molar addition of Hg2+ to 2 resulted in hypochromic shift at 440 nm and the eventual disappearance of a low energy band at 534 nm, concomitant with the colorimetric activities (from orange to yellow. Moreover, both spectral and color changes induced by the addition of anions (F− and AcO− were all reversible by the molar addition of metal cations of 3d5–10. The reversibility properties triggered the logic operation studies, and, subsequently, the complementary IMP/INH logic functions based on color and spectral switching (ON/OFF were confirmed. Conclusively, 2 can thus be utilized as a colorimetric molecular switch modulated by AcO−/MII.

  8. Cloning, characterization and anion inhibition studies of a γ-carbonic anhydrase from the Antarctic cyanobacterium Nostoc commune.

    Science.gov (United States)

    De Luca, Viviana; Del Prete, Sonia; Carginale, Vincenzo; Vullo, Daniela; Supuran, Claudiu T; Capasso, Clemente

    2015-11-01

    We report the cloning and catalytic activity of a γ-carbonic anhydrase (CA, EC 4.2.1.1) isolated from the Antarctic cyanobacterium Nostoc commune, NcoCA. The enzyme has a significant catalytic activity for the physiologic reaction, CO2 hydration to bicarbonate and protons, with a k(cat) of 9.5×10(5) s(-1) and a k(cat)/K(m) of 8.3×10(7) M(-1) × s(-1), being the most catalytically efficient γ-CA investigated so far. An anion inhibition study of NcoCA with inorganic/organic anions is also reported here. Fluoride, sulfate, perchlorate and tetrafluoroborate did not inhibit appreciably NcoCA, whereas the other halides, pseudohalides, bicarbonate, nitrate, nitrite and many complex inorganic anions showed inhibition in the millimolar range. The best NcoCA inhibitors detected so far were diethyldithiocarbamate (K(I) of 0.80 mM) as well as sulfamide, sulfamate, phenylboronic acid and phenylarsonic acid (K(I)s in the range of 70-90 μM). Since γ-CAs are present in carboxysomes, being involved in photosynthesis, this study may be relevant for a better understanding of such processes in some Antarctic organisms. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Insights in the radical scavenging mechanism of syringaldehyde and generation of its anion

    Science.gov (United States)

    Yancheva, D.; Velcheva, E.; Glavcheva, Z.; Stamboliyska, B.; Smelcerovic, A.

    2016-03-01

    The ability of syringaldehyde, a naturally occurring phenolic antioxidant and medicinally important compound, to scavenge free radicals according different mechanisms was elucidated by computing the respective reaction enthalpies at DFT B3LYP/6-311++G** level. Bond dissociation enthalpy, ionization potentials and proton affinities were calculated in gas phase, benzene, water and DMSO in order to account for different environment (nonpolar lipid membranes and polar physiological liquids) where the antioxidant action in the living organism could take place and various experimental in vitro conditions. Molecular and electronic properties influencing the reactivity of syringaldehyde according to the different mechanisms were discussed in the light of the reported radical scavenging activities in crocin bleaching, oxidation potential of the first anodic peak and DPPH test. According to the calculated reaction enthalpies, in polar environment the syringaldehyde reacts preferably by sequential proton loss electron transfer which is related to the formation of a phenoxy anion. Such phenoxy anion was generated in DMSO solution and the changes in the force field, steric and electronic structure, resulting from the conversion, were described in detail based on the IR spectral data and DFT computations.

  10. Oxidation of caffeine by phosphate radical anion in aqueous solution under anoxic conditions

    Indian Academy of Sciences (India)

    Maram Ravi Kumar; Mundra Adinarayana

    2000-10-01

    The photooxidation of caffeine in presence of peroxydiphosphate (PDP) in aqueous solution at natural H (∼7 5) has been carried out in a quantum yield reactor using a high-pressure mercury lamp. The reactions were followed spectrophotometrically by measuring the absorbance of caffeine at max (272 nm). The rates of reaction were calculated under different experimental conditions. The quantum yields were calculated from the rates of oxidation of caffeine and the intensity of light at 254 nm which was measured by using peroxydisulphate solution as a standard chemical actinometer. The reaction rates of oxidation of caffeine by PDP increase with increase in [PDP] as well as with increase in light intensity, while they are independent of [caffeine]. The quantum yields of oxidation of caffeine by PDP are independent of [PDP] as well as light intensity. However, quantum yields of oxidation of caffeine by PDP increase with increase in caffeine concentration. On the basis of these experimental results and product analysis, a probable mechanism has been suggested in which PDP is activated to phosphate radical anions (PO$_{4}^{\\bullet 2-}$) by direct photolysis of PDP and also by the sensitizing effect of caffeine. The phosphate radical anions thus produced react with caffeine by electron transfer reaction, resulting in the formation of caffeine radical cation, which deprotonates in a fast step to produce C8OH adduct radicals. These radicals might react with PDP to give final product 1,3,7-trimethyluric acid and PO$_{4}^{\\bullet 2-}$ radicals, the latter propagates the chain reaction.

  11. Major anion and cation fluxes from the Central SiberianPlateau watersheds with underlying permafrost

    Science.gov (United States)

    Kolosov, Roman R.; Prokushkin, Anatoly S.; Pokrovsky, Oleg S.

    2016-11-01

    The subarctic rivers of the Central Siberian Plateau have specific fed-characteristics due to the permafrost distribution and the active layer thawing dynamics. Two watersheds with different types of permafrost (from insular to continuous) are studied. Different data sources (Roshydromet and our own observations) are used for receiving anions’ (HCO3-, SO4 2-, Cl-) and cations’ (Ca2+, Mg2+) fluxes from the Nizhnyaya Tunguska river (1960-2011) and the Tembenchi river (1970-2011). The annual discharge of N. Tunguska for 1939-2011 is characterized by an increase of 0.3 km3/year/year, and for Tembenchi, 0.04 km3/year/year. The major part of the increase (about 60%) is due to spring flooding (May - June). The volume-weighted mean concentrations of major anions and cations in the N. Tunguska river water increased three times in the spring period (40.7 - 116.8 mg/l) and in the summer-fall period (74-212.9 mg/l). On the contrary, such concentrations decreased sharply during the winter mean water period. Due to these results, the total export of main anions and cations from the N. Tunguska river basin rose more than 4,5 times. Two possible reasons can be identified: 1) a water discharge increase of the Subarctic rivers (Peterson et al., 2002); 2) permafrost degradation induced by global climate warming (Frey and McClelland 2009).

  12. Hydrolysis of fish oil by hyperactivated Rhizomucor miehei lipase immobilized by multipoint anion exchange.

    Science.gov (United States)

    Filice, Marco; Marciello, Marzia; Betancor, Lorena; Carrascosa, Alfonso V; Guisan, Jose M; Fernandez-Lorente, Gloria

    2011-07-01

    Rhizomucor miehei lipase (RML) is greatly hyperactivated (around 20- to 25-fold toward small substrates) in the presence of sucrose laurate. Hyperactivation appears to be an intramolecular process because it is very similar for soluble enzymes and covalently immobilized derivatives. The hyperactivated enzyme was immobilized (in the presence of sucrose laurate) on cyanogen bromide-activated Sepharose (very mild covalent immobilization through the amino terminal residue), on glyoxyl Sepharose (intense multipoint covalent immobilization through the region with the highest amount of Lys residues), and on different anion exchangers (by multipoint anionic exchange through the region with the highest density of negative charges). Covalent immobilization does not promote the fixation of the hyperactivated enzyme, but immobilization on Sepharose Q retains the hyperactivated enzyme even in the absence of a detergent. The hydrolysis of fish oils by these hyperactivated enzyme derivatives was sevenfold faster than by covalently immobilized derivatives and three and a half times faster than by the enzyme hyperactivated on octyl-Sepharose. The open structure of the hyperactivated lipase is fairly exposed to the medium, and no steric hindrance should interfere with the hydrolysis of large substrates. These new hyperactivated derivatives seem to be more suitable for hydrolysis of oils by RML immobilized inside porous supports. In addition, the hyperactivated derivatives are fairly stable against heat and organic cosolvents.

  13. A highly selective and sensitive fluorescence probe for the hypochlorite anion.

    Science.gov (United States)

    Chen, Xinqi; Wang, Xiaochun; Wang, Shujuan; Shi, Wen; Wang, Ke; Ma, Huimin

    2008-01-01

    A new rhodamine B-based fluorescent probe for the hypochlorite anion (OCl(-)) has been designed, synthesized, and characterized. The probe comprises a spectroscopic unit of rhodamine B and an OCl(-)-specific reactive moiety of dibenzoylhydrazine. The probe itself is nearly nonfluorescent because of its spirolactam structure. Upon reaction with OCl(-), however, a largely enhanced fluorescence is produced due to the opening of the spirolactam ring by the oxidation of the exocyclic hydrazide and subsequently the formation of the hydrolytic product rhodamine B. Most notably, the fluorescence-on reaction shows high sensitivity and extremely high selectivity for OCl(-) over other common ions and oxidants, which makes it possible for OCl(-) to be detected directly in their presence. In addition, the reaction mechanism has been investigated and proposed. The OCl(-) anion selectively oxidizes the hydrazo group in the probe, and forms the analogue of dibenzoyl diimide, which in turn hydrolyzes and releases the fluorophore. The reaction mechanism that is described here might be useful in developing excellent spectroscopic probes with cleavable active bonds for other species.

  14. Augmentation of sarcolemmal Ca by anionic amphiphile: contractile response of three ventricular tissues.

    Science.gov (United States)

    Langer, G A; Rich, T L

    1986-02-01

    The anionic amphiphile dodecyl sulfate was used at the concentration of 100 microM, below the concentration at which membrane permeability is compromised. In rat myocardial tissue culture dodecyl sulfate induced a large increase in Ca uptake in the intact cells, of which 84% was distributed in a rapidly exchangeable (t1/2 less than 18 s) and 16% in a slowly exchangeable (t1/2 = 17 min) compartment. Dodecyl sulfate induced a large increase in Ca bound to isolated sarcolemmal membrane of these cells. This increase in membrane binding and the distribution in whole cells is consistent with insertion of dodecyl sulfate in the sarcolemma (SL) with subsequent Ca binding to its anionic head group. With perfusate extracellular calcium concentration ([Ca]o) equal to 1 mM, dodecyl sulfate produced greater than 60% increase in active force in ventricular tissue from adult rabbit and neonatal rat but virtually no increase in adult rat ventricle. Preperfusion with 0.1 mM [Ca]o or 10(-6) M ryanodine markedly increased the relative response of adult rat ventricle to dodecyl sulfate. After a quiescent period in rabbit ventricle, dodecyl sulfate caused a progressive increase of force of each beat compared with control; i.e., the treppe response was increased at each successive beat. This did not occur in adult rat ventricle. These results further clarify the different quantitative role of SL-bound versus sarcotubular Ca in the hearts of different species.

  15. Spectroscopy and computational studies on the interaction of octyl, dodecyl, and hexadecyl derivatives of anionic and cationic surfactants with adenosine deaminase.

    Science.gov (United States)

    Ajloo, Davood; Mahmoodabadi, Najmeh; Ghadamgahi, Maryam; Saboury, Ali Akbar

    2016-07-01

    Effects of sodium (octyl, dodecyl, hexadecyl) sulfate and their cationic analogous on the structure of adenosine deaminase (ADA) were investigated by fluorescence and circular dichroism spectroscopy as well as molecular dynamics simulation and docking calculation. Root-mean-square derivations, radius of gyration, solvent accessible surface area, and radial distribution function were obtained. The results showed that anionic and cationic surfactants reduce protein stability. Cationic surfactants have more effect on the ADA structure in comparison with anionic surfactants. More concentration and longer surfactants are parallel to higher denaturation. Furthermore, aggregation in the presence of anionic surfactants is more than cationic surfactants. Docking data showed that longer surfactants have more interaction energy and smaller ones bound to the active site.

  16. Simultaneous quantification of sinigrin, sinalbin, and anionic glucosinolate hydrolysis products in Brassica juncea and Sinapis alba seed extracts using ion chromatography.

    Science.gov (United States)

    Popova, Inna E; Morra, Matthew J

    2014-11-01

    Although mustards such as Sinapis alba and Brassica juncea contain glucosinolates (sinalbin and sinigrin, respectively) that hydrolyze to form biopesticidal products, routine quality control methods to measure active ingredients in seed and seed meals are lacking. We present a simple and fast ion chromatography method for the simultaneous quantification of sinigrin, sinalbin, and anionic hydrolysis products in mustard seed to assess biological potency. Optimum conditions include isocratic elution with 100 mM NaOH at a flow rate of 0.9 mL/min on a 4 × 210 mm hydroxide-selective anion-exchange column. All anion analytes including sinigrin, sinalbin, SO4(2-), and SCN(-) yielded recoveries ranging from 83 to 102% and limits of detection ≤0.04 mM, with samples displaying little interference from plant matrix components. Sample preparation is minimized and analysis times are shortened to <90 min as compared with previous methods that took days and multiple instruments.

  17. Kinetics of Ca2+- and ATP-dependent, voltage-controlled anion conductance in the plasma membrane of mesophyll cells of Pisum sativum

    NARCIS (Netherlands)

    Elzenga, J.T.M.; van Volkenburgh, E.

    1997-01-01

    Whole-cell patch-clamp techniques were used to measure anion currents through the plasma membrane of protoplasts of mesophyll cells of expanding pea (Pisum sativum L.) leaves. Voltage-induced changes of the currents could be modelled with single exponential activation and deactivation kinetics. The

  18. Gluconic acid production in bioreactor with immobilized glucose oxidase plus catalase on polymer membrane adjacent to anion-exchange membrane.

    Science.gov (United States)

    Godjevargova, Tzonka; Dayal, Rajeshwar; Turmanova, Sevdalina

    2004-10-20

    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.

  19. PCL assay application in superoxide anion-radical scavenging capacity of tea Camellia sinensis extracts

    Directory of Open Access Journals (Sweden)

    Anna Gramza-Michałowska

    2015-12-01

    Full Text Available Background. Plant polyphenols are known for their limiting of adverse effects on reactive oxygen species (ROS in biological systems. The photochemiluminescence (PCL assay allows to evaluate the antiradical activity of a compound in the presence of a superoxide anion-radical (O •-, which is one of the ROS directly associated with the human body. In this work, determination of the superoxide anion radical scavenging ac- tivity of different tea extracts using the PCL assay was performed. Material and methods. Investigations were conducted on different tea leaves extracts. The study included five kinds of tea leaves subjected to aqueous and ethanol extraction procedure. Catechins content was evalu- ated using HPLC. Antiradical activity of the samples was conducted with use of Photochem assay. Results. Analysis of total catechins content in tea aqueous extracts enabled them to be arranged as follows: yellow > green > white > red > black, while for ethanol extracts it was: yellow = green > white > red > black. The examined tea extracts were ranked from highest to lowest water-soluble antioxidative capacity (ACW values as follows: yellow > green > white > red > black. The results of lipid-soluble antioxidative capacity (ACL values for aqueous extracts were similar; however, were approximately 50% lower than those pre- sented as ACW. The second examined group were ethanol extracts, which ranked for ACW values: yellow > green = red = white > black, while ACL values ranked as follows: yellow > white = black = red > green. PCL assay results were correlated with total catechin content in aqueous extracts. Conclusions. Antiradical activity of different tea leaves extracts in PCL assay, showed that the highest activ- ity was found in extracts of yellow tea; the lowest, however, was identified in black tea extracts.

  20. Predicting the Strength of Anion-π Interactions of Substituted Benzenes: the Development of Anion-π Binding Substituent Constants.

    Science.gov (United States)

    Bagwill, Christina; Anderson, Christa; Sullivan, Elizabeth; Manohara, Varun; Murthy, Prithvi; Kirkpatrick, Charles C; Stalcup, Apryll; Lewis, Michael

    2016-11-23

    A computational study aimed at accurately predicting the strength of the anion-π binding of substituted benzenes is presented. The anion-π binding energies (Ebind) of 37 substituted benzenes and the parent benzene, with chloride or bromide were investigated at the MP2(full)/6-311++G** level of theory. In addition, energy decomposition analysis was performed on 27 selected chloride-arene complexes via symmetry adapted perturbation theory (SAPT), using the SAPT2+ approach. Initial efforts aimed to correlate the anion-π Ebind values with the sum of the Hammett constants σp (Σσp) or σm (Σσm), as done by others. This proved a decent approach for predicting the binding strength of aromatics with electron-withdrawing substituents. For the Cl(-)-substituted benzene Ebind values, the correlation with the Σσp and Σσm values of aromatics with electron-withdrawing groups had r(2) values of 0.89 and 0.87 respectively. For the Br(-)-substituted benzene Ebind values, the correlation with the Σσp and Σσm values of aromatics with electron-withdrawing groups had r(2) values of 0.90 and 0.87. However, adding aromatics with electron-donating substituents to the investigation caused the correlation to deteriorate. For the Cl(-)-substituted benzene complexes the correlation between Ebind values and the Hammett constants had r(2) = 0.81 for Σσp and r(2) = 0.84 for Σσm. For the Br(-)-substituted benzene complexes, the respective r(2) values were 0.71 for Σσp and 0.79 for Σσm. The deterioration in correlation upon consideration of substituted benzenes with electron-donating substituents is due to the anion-π binding energies becoming more attractive regardless of what type of substituent is added to the aromatic. A similar trend has been reported for parallel face-to-face substituted benzene-benzene binding. This is certainly counter to what electrostatic arguments would predict for trends in anion-π binding energies, and this discrepancy is further highlighted

  1. N-acetylglyoxylic amide bearing a nitrophenyl group as anion receptors: NMR and X-ray investigations on anion binding and selectivity

    Science.gov (United States)

    Suryanti, Venty; Bhadbhade, Mohan; Black, David StC; Kumar, Naresh

    2017-10-01

    N-Nitrophenylglyoxylic amides 1 and 2 in presence of tetrabutylammonium cation (TBA) act as receptors for anions HSO4-, Cl-, Br- and NO3- as investigated by NMR studies. The receptors formed 1:1 host-guest complexes in solution. X-ray structure of 1 along with TBA that bind a chloride anion is reported. Molecule 1 showed the highest selectivity for HSO4- anion over others measured. X-ray structure of the bound Cl- revealed a pocket containing the anion making strong (Nsbnd H⋯Cl) and weak hydrogen bonds (Csbnd H⋯Cl) that contribute to the recognition of the chloride anion. Nsbnd H and Csbnd H hydrogen bonds resulted in a relatively strong binding for chloride ions.

  2. Simultaneous determination of NH4+, NO2(-) and NO3(-) by ion-exclusion/anion-exchange chromatography on a strongly basic anion-exchange resin with basic eluent.

    Science.gov (United States)

    Mori, Masanobu; Hironaga, Takahiro; Itabashi, Hideyuki; Nakatani, Nobutake; Kozaki, Daisuke; Tanaka, Kazuhiko

    2012-04-01

    Ion-exclusion/anion-exchange chromatography (IEC/AEC) on a combination of a strongly basic anion-exchange resin in the OH(-)-form with basic eluent has been developed. The separation mechanism is based on the ion-exclusion/penetration effect for cations and the anion-exchange effect for anions to anion-exchange resin phase. This system is useful for simultaneous separation and determination of ammonium ion (NH4+), nitrite ion (NO2(-)), and nitrate ion (NO3(-)) in water samples. The resolution of analyte ions can be manipulated by changing the concentration of base in eluent on a polystyrene-divinylbenzene based strongly basic anion-exchange resin column. In this study, several separation columns, which consisted of different particle sizes, different functional groups and different anion-exchange capacities, were compared. As the results, the separation column with the smaller anion-exchange capacity (TSKgel Super IC-Anion) showed well-resolved separation of cations and anions. In the optimization of the basic eluent, lithium hydroxide (LiOH) was used as the eluent and the optimal concentration was concluded to be 2 mmol/L, considering the resolution of analyte ions and the whole retention times. In the optimal conditions, the relative standard deviations of the peak areas and the retention times of NH4+, NO2(-), and NO3(-) ranged 1.28% - 3.57% and 0.54% - 1.55%, respectively. The limits of detection at signal-to-noise of 3 were 4.10 micromol/L for NH4+, 1.87 micromol/L for NO2(-) and 2.83 micromol/L for NO3(-).

  3. Lysozyme stability and amyloid fibrillization dependence on Hofmeister anions in acidic pH.

    Science.gov (United States)

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

    2015-09-01

    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.

  4. Ternary Complexation on Bacterial Surfaces: Implications for Subsurface Anion Transport

    Science.gov (United States)

    Maclean, L. C.; Higginbottom, C. M.; Fowle, D. A.

    2002-12-01

    The physical, chemical, and biological controls on contaminant mobilities in aquatic ecosystems must be determined to establish the threat that contamination poses to the environment. Quantitative models of contaminant mobilities are required as a prerequisite to guide remediation efforts and to prioritize the potential hazard to the ecosystem of each contaminated site. It is well established that mineral surface adsorption is an important control on contaminant mobilities, and many studies have utilized thermodynamics to quantify metal/organic adsorption in order to yield predictive models of contaminant transport. However, these models of contaminant transport may not be representative of the reactions which control contaminant mobilities as most mineral surfaces are coated with organic acids, bacteria, and extracellular polymers. Numerous laboratory studies have demonstrated that bacterial cell walls have a high affinity for binding metal cations, and field studies indicate that a significant proportion of bacteria cells and associated extracellular matrices are coated with small scale hydrous metal oxides. The small size of bacteria, and in many cases the nanoscale of their associated mineral phases, suggests these bacteria-mineral composites may represent a large proportion of surface area exposed to fluid flow. Therefore, due to the affinity of bacterial cell walls for cations and biominerals, bacteria may also have a significant impact on anionic contaminant mobility in many natural systems. The extent of metal-bacteria adsorption reactions varies drastically as a function of pH and solution chemistry. Current adsorption models have focused on the interactions of positively charged metal cations with bacterial surfaces, however in many oxidizing environments metals such as Cr exist as anions or anionic complexes. We have studied the ability of non-metabolizing cells of the bacterial species Bacillus subtilis and Shewanella putrifaciens to adsorb aqueous Cr

  5. Chemistry of nitrile anions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Carles, S.; Le Garrec, J.-L.; Biennier, L. [Institut de Physique de Rennes, Département de Physique Moléculaire, Astrophysique de Laboratoire, UMR CNRS 6251, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France); Guillemin, J.-C. [Institut des Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837,35708 Rennes Cedex 7 (France)

    2015-12-31

    Despite the extreme conditions of temperature (down to 10K) and density (down to 100 molecules/cm{sup 3}), the giant molecular clouds and the circumstellar envelopes present a rich and complex chemistry. To date, more than 180 molecules have been detected in the InterStellar Medium (ISM) with a large abundance of nitriles (RC≡N). In addition, several anions have been recently observed in this medium: C{sub 4}H{sup ¯}, C{sub 6}H{sup ¯}, C{sub 8}H{sup ¯}, CN{sup ¯}, C{sub 3}N{sup ¯} and C{sub 5}N{sup ¯}. These last species should play a key role in the molecular growth towards complexity. To explore this hypothesis, their reactivity must be studied in the laboratory. The FALP-MS and the CRESU experimental apparatuses of the Rennes University are able to measure absolute rate coefficient of various chemical reactions, including the ion – molecule reactions, in gas phase at low temperature (from 300K for the FALP-MS down to 15K for the CRESU). Therefore, these experimental tools are particularly adapted to the kinetic studies of reactions potentially involved in the Interstellar Medium. One of the difficulties encountered in experiments with anions is their generation. We describe here the formation of the CN{sup ¯} and C{sub 3}N{sup ¯} anions by dissociative electron attachment on the molecular precursors BrCN and BrC{sub 3}N.

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

    KAUST Repository

    Oburger, E.

    2011-07-26

    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

  7. Minority anion substitution by Ni in ZnO

    CERN Document Server

    Pereira, Lino Miguel da Costa; Correia, João Guilherme; Amorim, Lígia Marina; Silva, Daniel José; David-Bosne, Eric; Decoster, Stefan; da Silva, Manuel Ribeiro; Temst, Kristiaan; Vantomme, André

    2013-01-01

    We report on the lattice location of implanted Ni in ZnO using the $\\beta$− emission channeling technique. In addition to the majority substituting for the cation (Zn), a significant fraction of the Ni atoms occupy anion (O) sites. Since Ni is chemically more similar to Zn than it is to O, the observed O substitution is rather puzzling. We discuss these findings with respect to the general understanding of lattice location of dopants in compound semiconductors. In particular, we discuss potential implications on the magnetic behavior of transition metal doped dilute magnetic semiconductors.

  8. Methylglyoxal as a scavenger for superoxide anion-radical.

    Science.gov (United States)

    Shumaev, K B; Lankin, V Z; Konovalova, G G; Grechnikova, M A; Tikhaze, A K

    2016-07-01

    Methylglyoxal at a concentration of 5 mM caused a significant inhibition of superoxide anion radical (O2 (·-)) comparable to the effect of Tirone. In the process of O2 (·-) generation in the system of egg phosphatidylcholine liposome peroxidation induced by the azo-initiator AIBN, a marked inhibition of chemiluminescence in the presence of 100 mM methylglyoxal was found. At the same time, methylglyoxal did not inhibit free radical peroxidation of low-density lipoprotein particles, which indicates the absence of interaction with methylglyoxal alkoxyl and peroxyl polyenoic lipid radicals. These findings deepen information about the role of methylglyoxal in the regulation of free radical processes.

  9. Modeling Donnan Dialysis Separation for Carboxylic Anion Recovery

    DEFF Research Database (Denmark)

    Prado Rubio, Oscar Andres; Møllerhøj, Martin; Jørgensen, Sten Bay

    2010-01-01

    dynamic model for transport of multiple ions through an anion exchange membrane is derived based on an irreversible thermodynamics approach. This model accounts for the convective transport of the dissociated and undissociated species in the channels with diffusion and migration across the boundary...... layers and membranes. Donnan equilibrium, flux continuity of the transported ions, the electroneutrality condition and Faraday's law are employed to describe the electrical potential and concentration discontinuities at the interfaces. The Nernst-Planck equation is used to model the ion transport though...

  10. Predicting Carbonate Ion Transport in Alkaline Anion Exchange Materials

    Science.gov (United States)

    2012-01-01

    Electrochemical Society , 2013. 2. Wilson K. S. Chiu, "Part 1. Role of the 3-D Electrode Microstructure on Charge Transfer, Mass Transfer, and Electrochemical Reactions in Solid Oxide Fuel Cells; Part 2. Ion and Water Transport in Alkaline Anion Exchange Membranes," technical seminar for the Army Research Laboratory (host: Dr. Deryn Chu), Adelphi, MD, August 13, 2012. (c) Presentations Number of Presentations: 2.00 Non Peer-Reviewed Conference Proceeding publications (other than abstracts): Received Paper TOTAL: Number of Non Peer-Reviewed

  11. On the real structure of profiled anion-deficient corundum

    Science.gov (United States)

    Maksimov, V. I.; Sokolov, V. I.; Surdo, A. I.; Abashev, R. M.; Yushkova, E. N.

    2017-02-01

    Profiled Al2O3 single crystals grown by Stepanov’s method to obtain anion-deficient composition were characterized by neutron diffraction at T=300 K for the first time. Whereas the main structure motif of investigated crystals is checked to be of corundum-type, the scattering pictures of as-grown crystal demonstrate pronounced anomalies being probably indications on substructure forming. However, neutron scanning of synthesised crystal taken after annealing under restoring conditions reveals additional effects associated with displacement type superstructure.

  12. Anion and Cation Ionic Conductivity of Dragon Fruit

    Science.gov (United States)

    Hajar, Nadya; Asiah, M. N.; Abdullah, S.; Rusop, M.

    2010-07-01

    The separation of all ions in a synthetic solution was achieved with an anion eluent containing 0.3392 g Na2CO3 and 0.084 g NaHCO2 and the run around 20 min. Cation eluent containing 0.60 g Tartaric acid and 0.125 g Dipicolinic acid and the run around 16 min. This method was applied to dragon fruit juice with success and has shown sensitivity. Moreover, sample preparation was a simple 1:1, 1:10, 1:100 and 1:1000 ppm with 0.20 mm filtration and direct injection without prior sample clean-up. Due to the use of eluent generator, very low conductance background conductivity can be obtained and sensitivity of dragon fruit has been greatly improved. Under the experimental condition, several inorganic anions, such as F-, NO3-, NO2-, Br- and PO43- obtained from dragon fruit. For cation, inorganic ions that occurred during the experiment were NH3+, Ca+, and Mg+. Conductivity for anion of F-, NO3-, NO2-, Br- and PO43- were approximately 20, 17, 16, 16 and 20 μS/cm, respectively. Concentration for F- is 1.57 mg/l, NO3- is 1.92 mg/l, NO2- is 0.30 mg/l, Br- is 0.45 mg/l and PO43- is 4.45 mg/l. Conductivity for cation of NH3+, Ca+, and Mg+ were approximately 537, 538 and 531 μS/cm, respectively. Concentration for cation of NH3+ is 0.93 mg/l, Ca+ is 1.15 mg/l, and Mg+ 7.285 is mg/l. The method has successfully applied to the determination of inorganic ions in dragon fruit. An ion chromatography method is described for the simultaneous determination of ionic conductivity for dragon fruit juice using a selected anion and cation eluent. The detection of ionic conductivity in dragon fruit juice has been studied.

  13. Enhanced Anion Transport Using Some Expanded Porphyrins as Carriers.

    Science.gov (United States)

    1991-01-01

    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

  14. CONTROLLED ANIONIC SYNTHESIS OF FUNCTIONALIZED AND STAR-BRANCHED POLYMERS

    Institute of Scientific and Technical Information of China (English)

    RODERIC P. QUIRK; YIN Jian; GUO Shaohua; HU Xiaowei; GABRIEL SUMMERS; KIM Jungahn; ZHU Linfang; LAUREL E. SCHOCK

    1990-01-01

    The use of living, alkyllithium-initiated anionic polymerization to prepare chain-end functionalized polymers and heteroarm, star- branched polymers is discussed. The scope and limitations of specific termination reactions with a variety of electrophilic species are illustrated for carbonation, hydroxyethylation,amination, and sulfonation. The methodology of using substituted 1,1- diphenylethylenes to provide a general, quantitative functionalization procedure is outlined and illustrated with examples of amine and phenol end-functionalization. A methodology is described for the synthesis of functionalized,star-branched copolymers with compositionally heterogeneous arms of controlled molecular weight and narrow molecular weight distribution using 1, 3-bis (1-phenylethenyl) benzene.

  15. Mechanisms of pH-gradient driven transport mediated by organic anion polypeptide transporters.

    Science.gov (United States)

    Leuthold, Simone; Hagenbuch, Bruno; Mohebbi, Nilufar; Wagner, Carsten A; Meier, Peter J; Stieger, Bruno

    2009-03-01

    Organic anion transporting polypeptides (humans OATPs, rodents Oatps) are expressed in most mammalian tissues and mediate cellular uptake of a wide variety of amphipathic organic compounds such as bile salts, steroid conjugates, oligopeptides, and a large list of drugs, probably by acting as anion exchangers. In the present study we aimed to investigate the role of the extracellular pH on the transport activity of nine human and four rat OATPs/Oatps. Furthermore, we aimed to test the concept that OATP/Oatp transport activity is accompanied by extrusion of bicarbonate. By using amphibian Xenopus laevis oocytes expressing OATPs/Oatps and mammalian cell lines stably transfected with OATPs/Oatps, we could demonstrate that in all OATPs/Oatps investigated, with the exception of OATP1C1, a low extracellular pH stimulated transport activity. This stimulation was accompanied by an increased substrate affinity as evidenced by lower apparent Michaelis-Menten constant values. OATP1C1 is lacking a highly conserved histidine in the third transmembrane domain, which was shown by site-directed mutagenesis to be critically involved in the pH dependency of OATPs/Oatps. Using online intracellular pH measurements in OATP/Oatp-transfected Chinese Hamster Ovary (CHO)-K1 cells, we could demonstrate the presence of a 4,4'-diisothiocyanatostilbene-2,2'-disulfonic acid-sensitive chloride/bicarbonate exchanger in CHO-K1 cells and that OATP/Oatp-mediated substrate transport is paralleled by bicarbonate efflux. We conclude that the pH dependency of OATPs/Oatps may lead to a stimulation of substrate transport in an acidic microenvironment and that the OATP/Oatp-mediated substrate transport into cells is generally compensated or accompanied by bicarbonate efflux.

  16. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion

    Energy Technology Data Exchange (ETDEWEB)

    Transue, Wesley J.; Velian, Alexandra; Nava, Matthew; Martin-Drumel, Marie-Aline; Womack, Caroline C.; Jiang, Jun; Hou, Gao-Lei; Wang, Xue-Bin; McCarthy, Michael C.; Field, Robert W.; Cummins, Christopher C.

    2016-06-01

    Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been characterized by molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH = 25.5 kcal/mol and ΔS = ₋2.43 e.u., and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3- , for which structural data have been obtained in a single-crystal Xray diffraction study. Negative ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3- has been assessed using nucleus-independent chemical shift (NICS), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) methods.

  17. Superoxide anion production by human spermatozoa as a part of the ionophore-induced acrosome reaction process.

    Science.gov (United States)

    Griveau, J F; Renard, P; Le Lannou, D

    1995-04-01

    The involvement of superoxide anion (O2o-) in human sperm capacitation and/or acrosome reaction was investigated. Addition of superoxide dismutase (SOD) to the medium at the beginning of the capacitation process or 15 min before induction of the acrosome reaction, decreased the level of ionophore-induced acrosome reaction. Hyperactivation was unaffected by the presence of SOD during the capacitation process. Addition of calcium ionophore to the sperm suspension increased production of O2o- by the spermatozoa by four to five-fold and induced the acrosome reaction. In the presence of SOD, superoxide anion could not be detected in the medium and the rate of induced-acrosome reaction was decreased greatly. The presence of an inhibitor of protein kinase C inhibited the production of O2o- in the medium and reduced the induced-acrosome reaction. The production of O2o- and the acrosome reaction were also increased by exposure of spermatozoa to 12-myristate 13-acetate phorbol ester, a specific activator of protein kinase C. While the level of spontaneous acrosome reaction was not increased by the direct addition of O2o- to the medium, its presence induced the release of unesterified fatty acids from membrane phospholipids. These findings suggest that the production of O2o- by spermatozoa could be involved in the ionophore-induced acrosome reaction, possibly through the de-esterification of membrane phospholipids. However, this production of superoxide anion is not sufficient on its own to induce the acrosome reaction.

  18. [Production of superoxide anion radical and nitric oxide in renal tissues sutured with different surgical suture material].

    Science.gov (United States)

    Kostenko, V O; Tsebrzhins'kii, O I

    2000-01-01

    The generation of superoxide anion radicals (in mitochondria, microsomes and under respiratory burst of leucocytes) and nitric oxide (NO) in renal tissue has been studied in the experiment with white rats, which had been carried out nephrotomy with following usage for suture such absorbable surgical threads as plain and chromic catgut, biofil (of dura mater spinalis of the cattle), Dexon II (polyglycolic acid) and biofil modified with aethonium, succinate and mexidol. The research proves the use of plai and chromic catgut leads to the development longer oxidative stress with increasing of cytotoxic agents production (superoxide anion and NO). The risk of longitudinal oxidative stress decreases under the use of biofil suture modified with biological active compounds (aethonium, succinate and mexidol). In this case, the generation of superoxide anion radicals in mitochondria and microsomes is normalised earlier. The superoxide generation with respiratory burst of leucocytes and NO production decreases in 14 day of postoperative period under the use of biofil suture modified with succinate and mexidol.

  19. Detection of anionic energetic material residues in enhanced fingermarks on porous and non-porous surfaces using ion chromatography.

    Science.gov (United States)

    Love, Catherine; Gilchrist, Elizabeth; Smith, Norman; Barron, Leon

    2013-09-10

    The ability to link criminal activity and identity using validated analytical approaches can be of great value to forensic scientists. Herein, the factors affecting the recovery and detection of inorganic and organic energetic material residues within chemically or physically enhanced fingermarks on paper and glass substrates are presented using micro-bore anion exchange chromatography with suppressed conductivity detection. Fingermarks on both surfaces were enhanced using aluminium powder or ninhydrin after spiking with model test mixtures or through contact with black-powder substitutes. A quantitative study of the effects of environmental/method interferences, the sweat matrix, the surface and the enhancement technique on the relative anion recovery of forensically relevant species is presented. It is shown that the analytical method could detect target analytes at the nanogram level even within excesses of enhancement reagents and their reaction products when using solid phase extraction and/or microfiltration. To our knowledge, this work demonstrates for the first time that ion chromatography can detect anions in energetic materials within fingermarks on two very different surfaces, after operational enhancement techniques commonly used by forensic scientists and police have been applied.

  20. Towards the Rational Design of Ionic Liquid Matrices for Secondary Ion Mass Spectrometry: Role of the Anion

    Science.gov (United States)

    Dertinger, Jennifer J.; Walker, Amy V.

    2013-08-01

    The role of the ionic liquid (IL) anion structure on analyte signal enhancements has been systematically investigated in secondary ion mass spectrometry (SIMS) using a variety of samples, including lipids, sterols, polymers, and peptides. Twenty-four ILs were synthesized. The 12 matrix acids were cinnamic acid derivatives. Two bases were employed: 1-methylimidazole and tripropylamine. Three matrices, methylimmidazolium o-coumarate, tripropylammonium o-coumarate, and tripropylammonium 3,4,5-trimethoxycinnamate, were "universal" matrices enhancing all analytes tested. The pKa of the matrix acid does not appear to have a strong effect on analyte ion intensities. Rather, it is observed that a single hydroxyl group on the anion aromatic ring leads to significantly increased molecular ion intensities. No analyte signal enhancements were observed for -CH3, -CF3 and -OCH3 groups present on the aromatic ring. The position of the -OH group on the aromatic ring also alters molecular ion intensity enhancements. As well as the chemical identity and position of substituents, the number of moieties on the aromatic ring may affect the analyte signal enhancements observed. These observations suggest that the activation of the IL anion aromatic ring is important for optimizing analyte signal intensities. The implications for SIMS imaging of complex structures, such as biological samples, are discussed.